APPROVED: William Acree, Jr., Major Professor Thomas R. Cundari, Committee Member Diana Mason, Committee Member Guido Verbeck, Committee Member Michael Richmond, Chair of the Department of
Chemistry Sandra L. Terrell, Dean of the Robert B. Toulouse
School of Graduate Studies
PREDICTING CHEMICAL AND BIOCHEMICAL PROPERTIES USING
THE ABRAHAM GENERAL SOLVATION MODEL
Christina Mintz, B.A.
Dissertation Prepared for the Degree of
DOCTOR OF PHILOSOPHY
UNIVERSITY OF NORTH TEXAS
May 2009
Mintz, Christina. Predicting Chemical and Biochemical Properties Using the Abraham
General Solvation Model. Doctor of Philosophy (Chemistry), May 2009, 361 pp., 45 tables, 35
illustrations, 547 references.
Several studies were done to illustrate the versatillity of the Abraham model in
mathematically describing the various solute-solvent interactions found in a wide range of
different chemical and biological systems. The first study focused on using the solvation model
to construct mathematical correlations describing the minimum inhibitory concentration of
organic compounds for growth inhibition towards the three bacterial strains Porphyromonas
gingivalis, Selenomonas artemidis, and Streptococcus sobrinus. The next several studies expand
the practicallity of the Abraham model by predicting free energies of partition in chemical
systems. The free energy studies expand the use of the Abraham model to other temperatures and
properties by developing correlations for the enthalpies of solvation of gaseous solutes of various
compounds dissolved in water, 1-octanol, hexane, heptane, hexadecane, cyclohexane, benzene,
toluene, carbon tetrachloride, chloroform, methanol, ethanol, 1-butanol, propylene carbonate,
dimethyl sulfoxide, 1,2-dichloroethane, N,N-dimethylformamide, tert-butanol, dibutyl ether,
ethyl acetate, acetonitrile, and acetone. Also, a generic equation for linear alkanes is created for
use when individual datasets are small. The prediction of enthalpies of solvation is furthered by
modifying the Abraham model so that experimental data measured at different temperatures can
be included into a single correlation expression. The temperature dependence is directly
included in the model by separating each coefficient into an enthalpic and entropic component.
Specifically, the final study describes the effects of temperature on the sorption coefficients of
organic gases onto humic acid. The derived predicted values for each research study show a
good correlation with experimental values.
iii
ACKNOWLEDGEMENTS
I would like to acknowledge the many people who offered their guidance and
encouragement throughout my time at the University of North Texas. First and foremost, I
gratefully and sincerely thank Dr. William Acree, Jr. for his guidance, understanding, patience,
and friendship during my graduate studies. His dedication and passion for research and teaching
continues to amaze and inspire me today. I have learned so much from him and consider myself
very lucky to have had such a compassionate advisor that made coming to school each day
something I could look forward to.
I thank all of the members of the Acree group, especially Laura Sprunger, Kaci Bowen,
Stacy Rae Payne, Katherine Burton, and Tara Ladlie who joined us through the REU program.
Thank you for all of your constant support and all of the laughter. I had a lot of great times
together, and I have truly made lifelong friends. I also thank Dr. Michael Abraham for his
collaboration and contributions with all of my publications.
My greatest gratitude is also extended to Dr. Diana Mason who was my inspiration to
further my education by attending graduate school. She showed me that there really is a fun side
to chemistry, and is the reason I became interested in this field from the very beginning.
Everyday, I miss our demonstration shows and travels to the many chemistry education
conferences. I will forever be grateful for her guidance, knowledge, enthusiasm, and friendship.
To all of my committee members, I also thank you for taking the time to work with me during
this endeavor.
Finally, and most importantly, I would like to thank my husband Ben. I could not have
gotten through graduate school without his unwavering support, patience, and love. He believed
that I could do anything even when I could not quite believe it myself. I am looking forward to
iv
our next big endeavor together with our little girl. I thank my family, especially my parents,
Robert and Jane Forsbach, and my brother, Nathan, for their unending encouragement and
support. The countless sacrifices that you made for me have gotten me where I am today. To
my grandparents, Meme and Papaw, thank you for teaching me the importance of a good
education and financially helping me through my many years of school. You taught me that
through focus and determination you can find the answers to anything. Last, but certainly not
least I thank my mother-in-law Pam Mintz. She also endured and survived the experience of
graduate school and provided me with much needed encouragement throughout the last four
years.
v
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS ............................................................................................................iii LIST OF TABLES ....................................................................................................................... .vii LIST OF ILLUSTRATIONS ........................................................................................................ .ix Chapters
1. INTRODUCTION ...................................................................................................1 2. THE ABRAHAM GENERAL SOLVATION PARAMETER MODEL ................4
2.1. Introduction ..................................................................................................4
2.2. General Principles of the Abraham’s General Solvation Model .................6
2.3. Cavity Effects...............................................................................................9 3. STATISTICAL ANALYSIS .................................................................................18
3.1. Multiple Linear Regression Analysis.........................................................18
3.1.1. Standard Deviation.........................................................................18
3.1.2. Correlation Coefficient and the Coefficient of Determination ......19
3.1.3. Average Error and Absolute Average Error ..................................20
3.1.4. Fischer Statistic ..............................................................................21
3.2. Validation Statistics ...................................................................................22
3.2.1. Test and Training Sets ...................................................................22
3.2.2. The Bootstrap Method ...................................................................22 4. CORRELATION OF MINIMUM INHIBITORY CONCENTRATIONS
TOWARD ORAL BACTERIAL GROWTH BASED ON THE ABRAHAM MODEL .................................................................................................................24
4.1. Introduction ................................................................................................24
4.2. Methods......................................................................................................26
4.3. Results and Discussion ..............................................................................27 5. ENTHALPY OF SOLVATION CORRELATIONS FOR GASEOUS SOLUTES
DISSOLVED IN WATER AND VARIOUS ORGANIC SOLVENTS ................43
5.1. Introduction ................................................................................................43
vi
5.2. Experimental Methods ...............................................................................45
5.3. Results and Discussion ..............................................................................48
5.3.1. 1-Octanol and Water ......................................................................48
5.3.2. Carbon Tetrachloride and Toluene ................................................53
5.3.3. DMSO and Propylene Carbonate...................................................60
5.3.4. Dibutyl Ether and Ethyl Acetate ....................................................65
5.3.5. Chloroform and 1,2 Dichloroethane ..............................................80
5.3.6. Benzene and Alkane Solvents ........................................................84
5.3.7. Alcohol Solvents ............................................................................97
5.3.8. Linear Alkanes .............................................................................105
5.3.9. N,N-Dimethylformamide and tert-Butanol .................................112
5.3.10. Acetonitrile and Acetone .............................................................121 6. CHARACTERIZATION OF THE PARTITIONING OF GASEOUS SOLUTES
INTO HUMIC ACID WITH THE ABRAHAM MODEL AND TEMPERATURE-INDEPENDENT EQUATION COEFFICIENTS .................127
6.1. Introduction ..............................................................................................127
6.2. Experimental Methods .............................................................................128
6.3. Results and Discussion ............................................................................131 7. SUMMARY .........................................................................................................146
APPENDIX: SUPPLEMENTAL MATERIAL ..........................................................................148 REFERENCES ............................................................................................................................336
vii
LIST OF TABLES
Table 2.1. The Abraham General Solvation Model Descriptors .................................................. 5
Table 2.2. Coefficients in the Abraham Solvation Equation ........................................................ 6
Table 4.1. Experimental minimal inhibitory concentrations of organic compounds, -log MIC (millimolar) to Porphyromonas gingivalis, Streptococcus sobrinus and Selenomonas artemidis oral bacteria. ........................................................................ 27
Table 4.2. Comparison of coefficients in Eq. 4.4 for water to solvent partitions, and for aqueous toxicity towards various organisms. ............................................................ 38
Table 5.1. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.29 ............................. 67
Table 5.2. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.30 ............................. 67
Table 5.3. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.41 ............................. 76
Table 5.4. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.42 ............................. 77
Table 5.5. Equation c oefficients f or ∆HSolv correlations ba sed on t he G oss m odified Abraham model. ........................................................................................................ 79
Table 5.6. Enthalpies of solvation of gaseous solutes in cyclohexane, ∆HSolv,Cy (kJ/mol) calculated from published water-to-cyclohexane enthalpy of transfer data. ............. 92
Table 5.7. Comparison of di rect vs . i ndirect e nthalpies of t ransfer f or a lcohol s olutes between water and cyclohexane. ............................................................................... 96
Table 5.8. Inter-correlation matrix, in R2, for solute descriptors for Eq. 5.63. ........................... 98
Table 5.9. Inter-correlation matrix, in R2, for solute descriptors for Eq. 5.64. ........................... 98
Table 5.10. Summarized c omparison of t he d escriptive ability of t he s olvent-specific Abraham model correlations for enthalpies of solvation in hexane, heptane, and hexadecane vs. the generic alkane correlation equation. .................................. 111
Table 5.11. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.78. ........................ 113
Table 5.12. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.79. ........................ 113
Table 5.13. Summary of test set computations for tert-butanol ................................................. 117
Table 5.14. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.87 ......................... 120
Table 5.15. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.88 ......................... 120
viii
Table 6.1. Equation Coefficients for the Abraham Model Correlations for Describing the Gas-to-Humic Acid Partition Coefficient Data at Different Temperatures ............. 135
Table 6.2. Temperature-Independent Equation Coefficients for Eq. 6.9 of the Abraham Model for Correlating the Gas-to-Humic Acid Partition Coefficients .................... 137
Table 6.3. Summarized C omparison of t he D escriptive A bility o f E q. 6.9 V ersus the Temperature-Specific Abraham Model Correlation Equations ............................... 139
Table 6.4. Coefficients in Eq. 2.2 for Gas-to-Solvent Phase Partitions .................................... 144
ix
LIST OF ILLUSTRATIONS
Figure 2.1. The i nfluencing f actors between a gas p hase an d s olvent can b e used t o calculate the partition between two solvent phases. Figure was reproduced in modified form from Abraham et al.2 .................................................................. 7
Figure 2.2. Illustration of the cavity effects. Figure was reproduced in modified form from Abraham et al. 2 .............................................................................................. 9
Figure 3.1. Interpretation of t he correlation c oefficient and t he c oefficient of determination. ....................................................................................................... 20
Figure 4.1. A pl ot of c alculated va lues ba sed on E q. 4.5 ve rsus obs erved va lues f or Porphyromonas gingivalis. ................................................................................... 32
Figure 4.2. A pl ot of c alculated va lues ba sed on E q. 4.7 ve rsus obs erved va lues f or Selenomonas artemidis. ........................................................................................ 34
Figure 4.3. A pl ot of c alculated va lues ba sed on E q. 4.9 ve rsus obs erved va lues fo r Streptococcus sobrinus. ........................................................................................ 35
Figure 4.4. A pl ot of t he s cores of P C2 a gainst t he s cores of P C1 f or t he pr incipal component analysis: ■ water to wet solvent partitions No 1 -19; □ water to dry s olvent pa rtitions No 20 -24; ∆ aqueous t oxicity N o 25 -40; ▲ equations found in this work No 41-43................................................................. 38
Figure 4.5. A plot of b-coefficients against v-coefficients for the systems in Table 3: ■ water to wet solvent partitions No. 1-19; □ water to dry solvent partitions No. 20-24; ∆ aqueous toxicity No. 25-40; ▲ equations found in this work No. 41-43. ............................................................................................................. 41
Figure 5.1. Plot of the calculated va lues of ∆ HSolv,W on Eq. 5.8 against the observed values. ................................................................................................................... 50
Figure 5.2. Plot o f the calculated values o f ∆ HSolv,W on Eq. 5.9 a gainst the observed values. ................................................................................................................... 51
Figure 5.3. A pl ot of t he c alculated va lues of ∆H Solv,CT in E q. 5.15 a gainst t he observed values ..................................................................................................... 55
Figure 5.4. A pl ot of the calculated v alues o f ∆H Solv,Tol in E q. 5.18 a gainst t he observed values ..................................................................................................... 57
Figure 5.5. A p lot o f t he cal culated v alues o f ∆HSolv,DMSO on E q. 5.21 a gainst t he observed values. .................................................................................................... 61
Figure 5.6. A pl ot of t he c alculated va lues of ∆HSolv,PC on E q. 5.25 a gainst t he observed values. .................................................................................................... 64
x
Figure 5.7. A plot of the calculated values of ∆HSolv,BE based on E q. 5.29 a gainst the observed values. .................................................................................................... 68
Figure 5.8. A plot of the calculated values of ∆HSolv,EA based on E q. 5.34 a gainst the observed values. .................................................................................................... 71
Figure 5.9. A pl ot of t he c alculated va lues of ∆HSolv,CFM on E q. 5.43 a gainst t he observed values. .................................................................................................... 81
Figure 5.10. A pl ot of t he c alculated va lues of ∆HSolv,DCE on E q. 5.46 a gainst t he observed values. .................................................................................................... 83
Figure 5.11. A pl ot of t he calculated va lues of ∆H Solv,Hp in E q. 5.49 a gainst t he observed values. .................................................................................................... 86
Figure 5.12. A plot of the calculated values of ∆HSolv,Cy in Eq. 5.55 against the observed values. ................................................................................................................... 89
Figure 5.13. A plot of the calculated values of ΔH Solv,MeOH on E q. 5.63 a gainst t he observed values. .................................................................................................... 99
Figure 5.14. A plot of the calculated values of ∆H solv,EtOH based on Eq. 5.66 against the observed values. .................................................................................................. 101
Figure 5.15. A plot of the calculated values of ΔHSolv,BtOH on E q. 5.69 a gainst t he observed values. .................................................................................................. 103
Figure 5.16. A plot of the calculated values of ΔHSolv,Hx from E q. 5.72 a gainst t he observed values. .................................................................................................. 107
Figure 5.17. A pl ot of t he c alculated va lues of ∆HSolv,Alk from E q. 5.76 a gainst t he observed values. .................................................................................................. 110
Figure 5.18. A plot of the calculated values of ∆H Solv,DMF based on Eq. 5.78 against the observed values ................................................................................................... 114
Figure 5.19. A plot of the calculated values of ∆H Solv,t-BTOH based on E q. 5.81 a gainst the observed values ............................................................................................. 116
Figure 5.20. A plot of the calculated values of ∆H Solv,DMF based on Eq. 5.87 against the observed values ................................................................................................... 119
Figure 5.23. A plot of the calculated values of ΔHSolv,ACN (kJ/mole) based on E q. 5.89 against the observed values. ................................................................................ 122
Figure 5.24. A plot of the calculated values of ΔHSolv,ACE (kJ/mole) based on E q. 5.92 against the observed values. ................................................................................ 124
xi
Figure 6.1. A plot of the calculated values log K LHA on Eq. 6.7 against the observed values. ................................................................................................................. 132
Figure 6.2. A plot of the calculated values log KLHA on Eq. 6.9 against the observed values. ................................................................................................................. 138
Figure 6.3. A plot of the scores of PC2 against the scores of PC1; points numbered as in T able 6.4. T he poi nt f or w ater, no. 25, i s of f-scale as s hown b y t he arrow. .................................................................................................................. 143
1
CHAPTER 1
INTRODUCTION
Accurate p rediction o f s olution-phase p roperties i s i mportant i n m any industrial
applications, r anging f rom t he de sign of c hemical s eparation pr ocesses, t o t he selection of
reaction media for opt imizing product yields, to the synthesis of potential new drug molecules
that require delivery to a specific body organ or target site. Each process involves the dissolved
solute interacting with solvent molecules in a surrounding solubilizing media. A useful approach
in describing partitioning processes in chemical and biochemical systems is to use the Abraham
general s olvation m odel. T he m odel i s ba sed on l inear free e nergy relationships of s olute
descriptors and system constants, and the model system constants provide information regarding
the various interactions between a solute and solvent. The following studies in this dissertation
illustrate th e u sefulness of the A braham m odel to mathematically describe t he va rious s olute-
solvent interactions found in a wide range of different chemical and biological systems.
In t he first p art o f this dissertation, t he ba ckground of t he A braham general s olvation
model is explored. Chapter 2 gives general background information about the Abraham model
including its solute descriptors and system coefficients. The cavity theory of solvation, which is
a b asic founding principle of t he m odel i s a lso discussed. C hapter 3 describes th e s tatistical
techniques employed in obtaining the coefficients that describe the system and the statistics used
to validate the predictive ability of the model.
The remaining chapters of this dissertation go through recent research projects. Chapter 4
illustrates the usefulness of the Abraham model to predict free energies of partition in biological
systems. Specifically, the study focuses on using the solvation model to construct mathematical
correlations describing the minimum inhibitory concentration of organic compounds for growth
2
inhibition towards the three bacterial strains Porphyromonas gingivalis, Selenomonas artemidis,
and Streptococcus sobrinus. The derived predicted mathematical correlations obtained show a
good correlation t o t he published observed inhibitory d ata. T he r esults ar e f urther an alyzed
using Principle Component Analysis to show that the three growth inhibition systems behave as
though a solute is transferred from water to an environment that is still quite water-like.
Chapters 5 and 6 illustrate the usefulness of the Abraham Model to predict free energies
of p artition in c hemical s ystems. Previous publ ications us ing t he A braham general solvation
model focused on developing correlations for both water-to-organic solvents and gas-to-organic
solvents a t 298.15 K . However, m anufacturing a nd bi ological pr operties a re not restricted t o
298.15 K. There is a growing need to estimate partitioning properties of organic solvents at other
temperatures as w ell. In C hapter 5 , I expand my considerations t o ot her t emperatures a nd
properties by developing Abraham model correlations for the enthalpies of solvation of gaseous
solutes of va rious compounds di ssolved i n water, 1 -octanol, h exane, h eptane, h exadecane,
cyclohexane, be nzene, t oluene, c arbon t etrachloride, c hloroform, m ethanol, e thanol, 1 -butanol,
propylene c arbonate, di methyl s ulfoxide, 1,2 -dichloroethane, N,N-dimethylformamide, tert-
butanol, di butyl ether, ethyl a cetate, a cetonitrile, a nd a cetone. I also e xpand the us e of t he
Abraham solvation model by creating a generic equation for linear alkanes. T he alkanes tested
were h exane, h eptane, and h exadecane. The d erived p redicted v alues f or ea ch r esearch s tudy
show a good correlation with experimental enthalpy of solvation values.
The goal of the research project described in Chapter 6 was to further my prediction of
enthalpies of solvation by modifying the Abraham model so that experimental data measured at
different t emperatures c an b e i ncluded i nto a s ingle correlation ex pression. T he t emperature
dependence is directly included in the model by separating each coefficient into an enthalpic and
3
entropic component. Specifically, the project describes the effects of temperature on the sorption
coefficients of organic gases onto humic acid. Humic acid is found in soil organic matter and
along many upland streams. Adsorption of organic compounds to humic acid plays an important
role in the transport of chemical compounds in the environment.
4
CHAPTER 2
THE ABRAHAM GENERAL SOLVATION PARAMETER MODEL
2.1. Introduction
The general s olvation parameter m odel of A braham1-8 is one of t he m ost us eful
approaches for the analysis and prediction of free energies of partition in chemical and biological
systems. T he m ethod r elies on t wo l inear f ree energy r elationships, one f or pr ocesses w ithin
condensed phases
SP = c + e·E + s·S + a·A + b·B + v·V (2.1)
and the other for processes involving gas-to-condensed phase transfer
SP = c + e·E + s·S + a·A + b·B + l·L (2.2)
The de pendent va riable, S P, i s s ome pr operty of a s eries of s olutes i n a f ixed pha se. T he
independent variables, or descriptors, are solute properties as follows: E and S refer to the excess
molar r efraction a nd di polarity/polarity de scriptors of t he s olute, r espectively, A a nd B a re
measures of the solute hydrogen-bond acidity and hydrogen-bond basicity, V is the McGowan
volume of t he s olute, a nd L i s t he l ogarithm of t he s olute g as p hase di mensionless O stwald
partition c oefficient f or hexadecane at 298 K . The f irst f our de scriptors c an be r egarded a s
measures of the tendency of the given solute to undergo various solute-solvent interactions. The
latter two descriptors, V and L, are both measures of solute size, and so will be measures of the
solvent cavity term that will accommodate the dissolved solute. General dispersion interactions
5
are also related to solute size; hence, both V and L will also describe the general solute-solvent
interactions. See Table 2.1 to see the symbols used for the solute descriptors and a description of
its contribution to the equation.
Table 2.1. The Abraham General Solvation Model Descriptors
Solute Descriptor New Old
E R2 The excess molar refraction ((cm3 mol-1)/10) represents solute polarisabilty and gives a measure of the ability of a solute to interact with a solvent through n- and π- electron pairs.
S pH2
The solute dipolar/polarisabilty parameter gives a measure of the solutes ability to stabilize a charge or dipole.
A aH2
The hydrogen bond acidity descriptor measures the extent of hydrogen bonding by the solute in a basic solvent.
B bH2
The hydrogen bond basicity descriptor measures of the extent of hydrogen bonding by the solute in an acidic solvent.
L logL16 The Otswald solubility coefficient between gas to wet solvent at 298 K, which represents cavity size and dispersion forces.
V Vx McGowan’s characteristic volume ((cm3 mol-1)/100), used to describe the transfer between water and wet solvents, reflects the three-dimensional space occupied by the solute. It is calculated from atomic size and the number of chemical bonds within the solute.
One additional note about the Abraham solute descriptors. In describing partition systems that
contain an appreciable quantity of water in the organic (or animal) phase one uses the alternative
basicity solute descriptor, Bo. For most solutes B and Bo are numerically equivalent. There are a
few solutes, ho wever, such as alkyl sulfoxides, a nilines and a lkylpyridines, for B and Bo may
differ.
The regression coefficients and constants (c, e, s, a, b, v, and l) are obtained by regression
analysis of experimental data for a s pecific process. In the case of partition coefficients, where
6
two solvent phases are involved, the c, e, s, a, b, v, and l coefficients represent differences in the
solvent phase properties.9 Each of these model system constants provide a breakdown of solute-
stationary ph ase i nteractions i n t erms of t he c ontribution t o r etention of cavity f ormation a nd
dispersion i nteractions, l one-pair electron i nteractions, i nteractions of a di pole-type, a nd
hydrogen-bonding interactions.10 See Table 2.2 for a description of each regression coefficient.
Table 2.2. Coefficients in the Abraham Solvation Equation
Regression Coefficients Description
e Describes the solvents tendency to interact with the solute through π and σ electron pairs.
s Measure of the solvent phase’s dipolarity/polarizability.
a Measure of the solvent phase’s hydrogen bond basicity.
b Measure of the solvent phase’s hydrogen bond acidity.
l Measure of both the work needed to create a solvent cavity and of dispersion forces.
v Reflects the hydrophobicity of the solvent that results from both the work need to create a solvent cavity and dispersion forces.
2.2. General Principles of the Abraham’s General Solvation Model
The m ethod of Abraham i s pr imarily concerned w ith th e p roperties of s olutes a s it
transfers from one phase to another. Figure 2.1 illustrates these types of transfer processes that
can be de fined b y t he e quilibrium t ransfer c oefficients K w (gas-to-water), K s (gas-to-solvent),
and the partition coefficient between two solvent phases P.11
7
Figure 2.1. The influencing factors between a gas phase and solvent can be used to calculate the partition between two solvent phases. Figure was reproduced in modified form from Abraham et al.2
The different partitioning processes occur at infinite dilution where solute-solute interactions are
negligible. T he r elationship be tween l og K w and l og K s can b e u sed t o calculate t he p artition
between two solvent phases using the equation:
Log P = Log KS – Log KW (2.3)
Accurate p rediction o f s olution-phase p roperties i s i mportant i n m any industrial
applications, r anging f rom t he de sign of c hemical s eparation pr ocesses t o t he s ynthesis of
potential new drug molecules that require delivery to a specific body organ or target site. Each
process i nvolves t he di ssolved s olute i nteracting w ith s olvent m olecules i n t he s urrounding
solubilizing me dia.12 The e quilibrium t ransfer f rom s olute-to-solvent i s c ontrolled by t he
standard Gibbs free energy of the compound in the two phases, which is also directly related to
the standard Gibbs free energy of solvation in a solvent and water,11 ∆Gos and ∆Go
w:
8
∆G˚s = -RTlnKs = -2.303RTLogKs (2.4)
∆G˚w = -RTlnKw = -2.303RTLogKw (2.5)
where K in each equation is the gas-to-liquid partition coefficient. Using Eqns. 2.4 and 2.5, I am
able to express the standard Gibbs free energy of transfer (∆G˚t) using the equations:
∆G˚t = -RTlnP = -2.303RTLogP (2.6)
∆G˚t = ∆G˚s - ∆G˚w (2.7)
The partition coefficient, Log P, is determined using Eq. 2.3.
In o rder f or t he A braham c orrelation equation to ha ve a ph ysical i nterpretation i t i s
necessary that each descriptor be related to Gibbs free energy. The Abraham Model of Solvation
is a l inear c orrelation equation be cause i t i s constructed s o t hat t he de scriptors us ed as
independent variables actually describe the same type of process as the dependent variable. For
example, the Abraham descriptors used as a measure for hydrogen bond strength (A and B) are
Gibbs free energy quantities derived from Log K. Therefore, the descriptors can be used in the
correlation of Gibbs free energy of transfer and the Partition Coefficient (log P) as the dependent
variables.10
9
2.3. Cavity Effects
The i nfluence of s olute s tructure on pa rtitioning pr ocesses i s de scribed b y t he c avity
theory of solution13, see Figure 2.2. The Abraham Solvation Model uses this theory to describe
the partition of a solute between the gas phase and a solvent. In the cavity theory the solvation
process is broken down into three steps10:
1) A cavity, the same size as the solute, is formed within the solvent. This process involves
the endothermic breaking of molecular interactions and, therefore, the Gibbs free energy
change is positive and is energetically unfavorable.
2) The reorganization of the bulk solvent molecules into their equilibrium position around
the n ewly created cavity, for w hich t he Gibbs f ree en ergy change i s assumed t o b e
negligable.
3) The solute is inserted into the cavity and various interactions take place between the solute
and s olvent. D epending on t he f unctional groups, t he s olute-solvent in teractions ma y
involve h ydrogen-bonding, di pole-dipole i nteractions, e tc. T his s tep i s exothermic, an d
the Gibbs free energy change is negative making this step energetically favorable.
Figure 2.2. Illustration of the cavity effects. Figure was reproduced in modified form from Abraham et al. 2
10
The theory is simplified even further by holding the solvent constant and only changing the
solute type. T herefore, the solvent properties would not need to be considered and only the
properties of t he s olute would ne ed t o be d etermined. In r elating t he cavity t heory t o t he
Abraham model, the V or L descriptor is taken as the solute size descriptor from step (1) of
the cavity theory. In step (3), because the solvent is thought to be constant, the solvent-solute
interactions s hould be r elated t o t he s olute pr operties or de scriptors us ed i n t he Abraham
Model.2
2.4 Selected Applications
In t he chemical lite rature o ne c an f ind n umerous q uantatitive s tructure-activity
relationships ( QSARs), qua ntitative s tructure-property r elationships ( QSPRs), qua ntitative
structure-toxicity r elationships ( QSTRs) a nd lin ear free energy relationships ( LFERs) for
predicting pr operties r anging f rom boi ling poi nt t emperatures, va por pressures, w ater-to-
organic solvent and gas-to-organic solvent partition coefficients, water-to-micellar surfactant
partition coefficients, gas-to-body organ and blood-to-body organic partition coefficients, gas
chromatographic r etentions of s olutes on a g iven l iquid or s olid s tationary pha se, ga s
chromatographic retention factors (defined as the ratio of the solute’s adjusted retention time
divided b y t he r etention t ime of a n unr etained s olute) of s olutes on a g iven l iquid or s olid
stationary phase, hi gh p erformance l iquid c hromatographic (HPLC) r etention t imes w ith a
given m obile pha se-stationary p hase p air, retention time s a nd s electivities o f s olutes in
micellar electrokinetic chromatographic systems, permeability of solutes through human and
animal skin from aqueous solution, adsorption of solutes onto activated carbon (carbon black,
activated c harcoal, e tc.) from a queous s olution, rat a nd hum an i ntestinal absorption data of
11
drugs and pha rmaceuticals, aqueous s olubilities, Draize e ye s cores an d eye i rritation, n asal
pungency, odor threshold, lethal toxicity of organic compounds to a given aquatic organism,
and the inhibition of growth by organic compounds against selected bacteria, algae, tumor cell
lines an d can cer cel l l ines. P ublished co rrelations h ave em ployed a w ide v ariety o f s olute
descriptors and solute properties, which are calculable from measured experimental data (such
as the Hildebrand solubility parameter, which is defined to be the square root of the energy of
vaporization at 298.15 K divided by its molar volume, δ = (ΔEvap,298 K/V)0.5 ), from molecular
structure considerations or using quantum mechanical computations. The advantage that the
Abraham model has over other published QSAR, QSPR and LFER models is that the same set
of solute descriptors i s used in every de rived correlation. O ne does not have to calculate a
different s et of s olute de scriptors f or e very pr operty t hat i s t o be c orrelated. A s di scussed
later, by using the same set of solute descriptors for every correlation, one can compare the
chemical similarity of the different processes as the calculated equation coefficients (see Eq.
2.1 and 2.2 do contain chemical information regarding the solubilizing media’s polarity and
hydrogen-bonding characteristics. One final no te, t he A braham m odel was d eveloped t o
describe partitioning processes, or properties that are directly related to partitioning processes.
The model should not be used to describe processes that are a result of chemical reactions.
To date, Abraham model correlations have been reported to describe solute partitioning
into 1-octanol14,15 from water
Log Pwet = 0.088 + 0.562 E – 1.054 S + 0.034 A – 3.460 B + 3.814 V (2.8)
Log Pdry = - 0.034 + 0.489 E – 1.044 S – 0.024 A – 4.235 B + 4.218 V (2.9)
12
and from the gas phase
Log Kwet = -0.222 + 0.088 E + 0.701 S + 3.473 A + 1.477 B + 0.851 L (2.10)
Log Kdry = -0.120 – 0.203 E + 0.560 S + 3.576 A + 0.702 B + 0.939 L (2.11)
and into other a lcohols ( methanol, e thanol, 1 -propanol, 1 -butanol, 1 -pentanol, 1 -hexanol, 1 -
heptanol, 1 -decanol, 2 -propanol, 2 -butanol, 2 -methyl-1-propanol, 2 -methyl-2-propanol, 2 -
pentanol, 3 -methyl-1-butanol),4,7,8,16,17 into alkanes ( butane, hexane, h eptane, o ctane, n onane,
decane, u ndecane, d odecane, h exadecane, c yclohexane, m ethylcyclohexane, 2 ,2,4-
trimethylpentane),18-21 in aromatic hydrocarbons (benzene, toluene),19-21 in halogenated alkanes
(dichloromethane, t richloromethane, c arbon t etrachloride, 1,2-dichloroethane, methylene
iodide),22,23 in ha logenated b enzenes ( fluorobenzene, c hlorobenzene, bromobenzene,
iodobenzene),24 in alkyl acetates (methyl acetate, ethyl acetate, butyl acetate),25 in ethers (diethyl
ether, di butyl e ther, t etrahydrofuran, 1,4 -dioxane, m ethyl tert-butyl e ther),26,27 in ke tones
(acetone, 2 -butanone, c yclohexanone)28 and i n s everal m iscellaneous s olvents ( such as
acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetate, olive oil, saline
solution).20,29-32 Correlation e quations a re pe riodically upda ted as m ore ex perimental d ata
becomes available. In total Abraham model correlations have been derived for approximately 40
different organic solvents. Most of the derived correlations for solute partitioning into organic
solvents from either water or the gas phase pertain to 298.15 K. Many industrial manufacturing
processes and chemical separations take place at temperatures other than 298.15 K. T here is a
13
growing need to be able to extrapolate measured and/or predicted partition coefficients to higher
and lower temperatures.
The Abraham model can describe practical water-to-organic partition coefficients as well
as “hypothetical” water-to-organic solvent partition coefficients. P ractical partition coefficients
refer to the equilibrium distribution of the solute between an organic solvent saturated with water
and an aqueous phase saturated with the organic solvent. Hypothetical partition coefficients, on
the ot her ha nd, r efer t o the h ypothetical pa rtition pr ocess o f s olute t ransfer f rom w ater t o t he
anhydrous ( dry) or ganic s olvent. H ypothetical pa rtition c oefficients c an be c alculated a s t he
ratio of t he s olute’s m olar s olubility i n t he a nhydrous or ganic s olvent di vided b y i ts a queous
molar solubility, ie., P = [solute]dry organic solvent/[solute]water. Even though hypothetical in nature,
these partition coefficients are valuable in that one can use the predicted values to calculate the
solute’s m olar s olubility in t he or ganic s olvent, pr ovided t hat t he s olute’s a queous m olar
solubility is known. For solvents that are partly miscible with water, such as ethyl acetate or 1-
butanol, pa rtition c alculated a s a s olubility r atio m ay not e qual t hose obt ained f rom di rect
equilibrium pa rtition measurements. T he pr esence of w ater i n t he or ganic s olvent c an ha ve a
significant effect on t he solubilizing properties of the equilibrium organic phase. Care must be
taken not to confuse the two sets of partitioning correlations. O ne will note that Eqs. 2.8 and
2.10 have b een s ubscripted “w et” t o i ndicate t hat t he co rrelations p ertain th e d irect p artition
measurement describing the equilibrium distribution of the solute between 1-octanol (saturated
with w ater) an d w ater ( saturated w ith 1 -octanol). Equations 2.9 a nd 2.11 refer t o t he
hypothetical partitioning processes, and are thus labeled as “dry.” The equation coefficients for
the “wet” and “dry” partitioning processes are not the same for 1-octanol as the water-saturated
1-octanol or ganic pha se doe s c ontain a n a ppreciable a mount of di ssolved w ater. P ublished
14
Abraham model c orrelations g enerally de note whether t he equation d escribes a p ractical o r
hypothetical p artition p rocess. F or s olvents th at a re completely mis cible w ith w ater (such a s
methanol, e thanol), t he w ater-to-organic pa rtition pr ocess i s h ypothetical and only one l og P
correlation is presented. In the case of organic solvents that are almost completely immiscible
with w ater ( such a s a lkanes, c hloroform, c arbon t etrachloride, di chloromethane, 1,2 -
dichloroethane and most nonpolar aromatic solvents) there will be only a single Abraham model
correlation as the practical water-to-organic solvent partition coefficient will be nearly identical
to th e c alculated mo lar solubility r atio. It is o nly f or p artially mis cible o rganic s olvents th at
dissolve an appreciable amount of water that one will have two log P correlation equations, one
equation for describing the practical “wet” partition process and one equation for describing the
hypothetical “dry” partition process.
In addition t o de scribing t he pa rtitioning of or ganic s olutes i nto organic solvents f rom
water and t he gas ph ase, t he A braham m odel ha s be en us ed t o de scribe t he s olubilizing
characteristics of room temperature ionic liquids (RTILs). Sprunger et al.33,34 modified the basic
Abraham solvation parameter model
Log P = cation + canion + (ecation + eanion) · E + (scation + sanion) · S + (acation + aanion) · A
+ (bcation + banion) · B + (vcation + vanion) · V (2.12)
and
Log K = cation + canion + (ecation + eanion) · E + (scation + sanion) · S + (acation + aanion) · A
+ (bcation + banion) · B + (lcation + lanion) · L (2.13)
15
by s plitting th e v arious s olute-RTIL in teractions in to a c ation-specific an d an ion-specific
contribution. The major advantage with splitting the interactions in this fashion is that one will
be able to describe far more RTILs with fewer experimental measurements. Normally 40 to 50
experimental log P or log K values are needed to develop each log P or log K correlation. The
authors r eported e quation c oefficients f or 8 cations a nd f or 4 anions ba sed on a t otal of 598
experimental lo g K and 584 e xperimental l og P v alues. The ex perimental v alues w ere
determined b y i nverse-chromatography f rom t he m easured retention t imes of s olutes on t he
RTIL stationary phase. Only 16 RTILs were contained in the databases used to calculate the ion-
specific eq uation co efficients, an d f or each R TIL t here was b etween 2 8 t o 6 0 ex perimental
values for RTIL. For several of the RTILs there was insufficient experimental data to develop
the Abraham model correlations; however, by combining all of the data for a given cation and/or
anion, the authors were able to calculate equation coefficients for 8 cat ions and 4 anions. T he
authors’ calculated equation coefficients can be combined to give 32 ( 8 x 4) cation-anion pairs,
in other words, using experimental data for 16 RTILs the authors were able to develop predictive
equations f or 32 R TILs. A ll of t he c alculated c ation-specific a nd a nion-specific equation
coefficients pertain to 298.15 K. Room temperature ionic liquids are used as stationary phases in
gas-liquid chromatographic separations. The new generation room temperature ionic liquids are
stable at h igh t emperatures, and in many practical gas chromatographic separations with RTIL
stationary phases the column is maintained at a temperature of 100 oC or higher. T here is need
to develop a computational methodology that can be used to extrapolate predicted a solute’s log
K value at 298 K on a given RTIL to the much higher temperatures that are commonly employed
in gas chromatographic separations and chemical analysis.
16
Abraham, Ibrahim and others have used Eqs. 2.1 and 2.2 to correlate the partitioning of
organic solutes and drugs into body tissues and fluids, both from the gas phase and from blood.
Tissues and f luids that were s tudied i nclude blood,35 brain,36,37 liver,38 lung,39 fat,36 muscle,40
skin.41 Published correlations described the experimental partition coefficient data to within a
standard d eviation of approximately 0.3 l og uni ts, which i s qui te good for biological systems.
Experimental biological data generally have larger experimental uncertainties/errors, due in part
to differences in metabolic rate, gender, age and other genetic differences. Even though one may
be correlating partition coefficient blood-to-muscle partition coefficient data for a single animal
species, s uch as rats, ea ch individual rat does h ave a unique ge netic m akeup. The a uthors’
studies were directed mainly on human and rat tissues. For blood, the authors were able to find
sufficient experimental gas-to-blood partition coefficient data to develop a correlation for human
blood and a second correlation for rat blood. T he derived equation coefficients for the human
blood and rat blood correlations were nearly identical. As part of the human and rat blood study,
the authors calculated the difference log Khuman blood – log Krat b lood for 86 compounds for which
both l og K human b lood and l og K rat b lood data w ere av ailable. T he calculated av erage ab solute
difference of 0.124 l og uni ts be tween l og K human b lood and l og K rat b lood was co mparable i n
magnitude to the inter-laboratory variation of log K human b lood for 2 -propanone (SD = 0.34) , for
chloroform (SD = 0.09) and for trichloroethene (SD = 0.06). Based largely on this comparison,
the authors combined the all log Khuman b lood and log Krat b lood values into a s ingle database, and
developed one correlation equation capable of describing the combined data sets. Sprunger et
al.32 later r evisited t he assumption t hat hum an a nd r at d ata c ould be c ombined i nto a s ingle
correlation m odel, a nd i ntroduced a nimal s pecies i ndicator va riables into t he predictive
expression that allowed for species differences in log K values for each given solute.
17
The basic Abraham model has also been used to correlate b iological properties that are
directly r elated t o s olute pa rtitioning. O ne s uch a pplication concerns the t oxicity of or ganic
compounds to aquatic organisms. Aquatic organisms are exposed to toxicants dissolved in lakes,
rivers, and na tural w aterways. Once th e to xicant ma kes its w ay in to th e o rganism, it c an
partition i nto t he c ells a nd di srupt t he c ell f unction. T he or ganism t hen di es ( or experiences
decreased mobility) as a direct result of the toxicant’s presence in the cell. This particular mode
of toxic action is referred to as narcosis (both nonpolar and polar narcosis). Hoover et al .,42-45
Abraham and coworkers46,47 and Poole et al.48,49 have developed Abraham model correlations for
describing t he nons pecific t oxicity of or ganic c ompounds t o s everal s pecies of f ish ( guppy,
fathead minnow, Golden orfe, bluegill, goldfish, and high-eyes Medaka), water f leas (Daphnia
magna, Ceriodaphnia dubia, and Daphnia pulex), pr otozoas ( Tetrahymena pyriformis,
Spirostomum ambiguum, Entosiphon sulcantum, Uronema parduczi and Chilomonas
paramecium), b acterium (Pseudomonas putida) and t adpoles (Rana temporaria, Rana pipiens,
Rana japonica, Xenopus laevis and Rana brevipoda porosa). The aquatic toxicity correlations
will be discussed at greater length in a later chapter.
The aforementioned studies represent just a few of the many published papers that have
used t he A braham general s olvation m odel to mathematically d escribe p roperties o f ch emical,
biological, and pharmaceutical importance. T he advantage of using a s ingle mathematical form
and a s ingle set of common solute descriptors is that one can compare equation coefficients to
determine which p rocesses ar e chemically s imilar. Once a given p rocess h as b een f ully
characterized, that is once the equation coefficients have been calculated, one can use the derived
mathematical correlation to make predictions for all other solutes with known solute descriptors.
18
CHAPTER 3
STATISTICAL ANALYSIS
3.1. Multiple Linear Regression Analysis
Abraham’s general s olvation m odel pr ovides a us eful a pproach f or t he pr ediction of
many partitioning processes in chemical and biochemical systems. The method relies on linear
free energy relationships, and the predicted values of the Abraham model are obtained through
multiple linear regression.
Regression models are among the most useful and most used statistical method because
they allow relatively simple analyses of complicated situations. Multiple linear regressions give
the relationship between two or more independent variables and a dependent variable by fitting a
linear e quation t o t he obs erved da ta. S PSS software50 is u sed to p erform a ll r egression
calculations i n my publications ( see C hapters 4 -6). T he de scriptive s tatistics f ound f rom t he
regression that a re r eported a re s tandard d eviation, t he coefficient of de termination, t he F isher
statistic, average error, and absolute average error.
3.1.1. Standard Deviation
Standard deviation (SD) is a s tatistical measure of the spread or uncertainty around the
mean. It is defined by the equation:
SD =yi − y ∑( )2
n − p −1( ) (3.1)
19
Where, yi is each individual da ta point, y is t he m ean o f t he dataset, n is the number of da ta
points, and p is the number of independent variables.
If many data points are clustered tightly around the mean, then the standard deviation is
small. However, if data points are scattered widely around the mean, then the standard deviation
is l arge. A useful property o f s tandard deviation i s t hat, unl ike va riance, i t i s expressed in t he
same units as the data.
3.1.2. Correlation Coefficient and the Coefficient of Determination
The linear co rrelation c oefficient measures t he strength an d t he d irection o f a l inear
relationship between two variables and can be determined by the mathematical formula:
r = i∑ (yi − y)(yi − y)[ ]
(yi − y)2
i∑ (yi − y)2
i∑
(3.2)
where y is the mean observed value, and yi represents the predicted values. The value of r is such
that -1 < r < +1. The + an d – signs are used for positive linear correlations and negative linear
correlations, respectively. If the predicted and observed values have a strong linear correlation r
is close to 1, however if there is no linear correlation or a weak linear correlation r is close to 0.
The value of the correlation coefficient can be strongly influenced by one outlying point.
The coefficient of determination (R2) is found by squaring the correlation coefficient and is
used as a more precise way to interpret the correlation coefficient. It is useful because it gives the
proportion of the variance in one variable that is “explained” by the other variable. It represents
20
the percent of the data that is the closest to the line of best fit.51 The coefficient of determination
is such that 0 < R2 < 1, and the stronger the correlation (R is closer to 1) the more variance can
be explained (see Figure 3.1).
Figure 3.1. Interpretation of the correlation coefficient and the coefficient of determination.
3.1.3. Average Error and Absolute Average Error
The av erage error ( AE) an d t he av erage absolute er ror (AAE) are r eported i n my
publications when comparing the variance between the t raining-set and t he t est-set regressions
(see Chapters 4-6). The average error can be less than, equal to, or greater than 0. In this way it
measures a ccuracy or goodness of fit a nd i ndicates w hether t he r egression e quation i s
systematically over or u nder predicting the dependent va riable. T he smaller t he average er ror
(i.e. closer to 0), the more unbiased the regression equation. A verage error is calculated using
the equation:
(3.3)
AE =y^
i− yi
∑
n
21
where, iy^
is the predicted value, and iy is the observed value.
The average absolute error (AAE) is an important descriptive statistic in that it is also a
measure of bias and is the average absolute deviation of the observed values from the predicted
values. It is defined as
(3.4)
where, iy^
is the predicted value, and iy is the observed value.
3.1.4. Fischer Statistic
The F-statistic is used to test the s tatistical s ignificance of the regression.52 Hence, the
larger the F value is above the critical value, the better the regression. As can be seen from the
equation below the F-statistic increases as the number of data points increase and the coefficient
of determination increases.
F =R2 n − v −1( )
1− R2( )v (3.5)
In the above equation R2 is the coefficient of determination, n is the number of data points, and v
represents the degrees of freedom. T he degrees of freedom can be determined by subtracting one
from the number of va riables i n t he r egression equation.11 The formula compares t he amount of
variablity between datasets to the amount of variability within datasets.
AAE =y^
i− yi∑
n
22
3.2. Validation Statistics
3.2.1. Test and Training Sets
In order to evaluate the predictive ability and test the generality of the Abraham model
the original dataset of solutes can be randomly split into training and test sets and the regression
repeated (see Chapters 4-6). In this validation method the property being measured is predicted
for the solutes in the training set and a new regression equation is obtained. The new regression
equation and the test set’s solutes are then used to determine standard deviation, average error,
and a verage absolute e rror. P roviding t hat t he t est a nd t raining s ets are not bi ased, good
agreement to experimental values indicates that the model is l ikely to be general and has good
predictive ability. This method is an ideal way to test predictive ability of a model, but requires a
large dataset.
3.2.2. The Bootstrap Method
Multiple linear regression is based on m ajor assumptions from which my data came, such
as l inearity a nd nor mality of t he p redicted m inus obs erved va lues (i.e., residuals) a bout t he
population. The F-test is robust with regard to v iolations o f normality, h owever it is always a
good idea to inspect the distributions of the major variables of interest by producing histograms
of the residuals, probability plots, or to perform a bootstrap analysis of the data.
The bootstrap method is a general approach to statistical modeling based upon building a
sampling distribution for a statistic by resampling many times from the dataset. For example, for
a set of n solutes, n samplings with replacement of the dataset are made up to 1000 times and the
regression is repeated with each sampling. In this method, some solutes will be randomly left
out of the analysis, and other solutes will be included two or more times. The multiple bootstrap
23
analyses o f t hese r epeated s amplings can t hen b e av eraged t ogether an d co mpared t o t he f ull
dataset. These repeated samplings can give a sense of the bias in a statistic, e.g. R-squared. It is a
useful pr ocedure f or h andling da ta w hen I am not w illing t o m ake a ssumptions a bout t he
parameters of the populations from which I sampled. T he most that i s assumed in a bootstrap
analysis i s t hat t he d ata I have i s a r easonable r epresentation of t he pop ulation f rom w hich i t
came.53
It is also useful as a validation statistic to use in place of test and training sets (see Chapter
5). While in many situations a simple random split into training and test sets might be adequate,
there a re a num ber of problems w ith t he pr ocedure i ncluding c hance splits, i nefficiency o f
estimates among different possible splits, and decreased power.54
Bootstrap procedures in Chapter 5 of this dissertation were performed using the statistical
program R with the simpleboot package installed.55
24
CHAPTER 4
CORRELATION OF MINIMUM INHIBITORY CONCENTRATIONS TOWARD ORAL
BACTERIAL GROWTH BASED ON THE ABRAHAM MODEL
4.1. Introduction
Dental and oral diseases are among the most prevalent afflictions of mankind. The human
oral cavity contains more than 500 ba cterial strains that interact with each other, and with their
host tissue. Such interactions result in microbial biofilm formation, such as subgingival plaque,
dental plaque, and tongue surface debris, which lead to periodontal diseases, dental caries, and
oral malador, etc.
Quantitative s tructure–activity r elationships ha ve be en reported for ba cterial growth
inhibition b y or ganic compounds. P ublished s tudies ha ve f or t he m ost pa rt pe rtained t o
environmental ba cteria. A not able e xception i s t he t wo s tudies of Shapiro a nd G uggenheim56,
which e xamined growth inhibition of Porphyromonas gingivalis, Selenomonas artemidis, a nd
Streptococcus sorbrinius by phenolic compounds. The authors choose phenolic compounds for
study due to the fact that phenolic disinfectants have been widely used in medicine and dentistry
dating ba ck t o a ncient E gyptian t imes. Listed below i s t he be st c orrelation obt ained f or e ach
bacterium from the authors’ first paper.
S. sobrinus
-log MIC (mM) = -1.497 + 0.661 1χv - 0.165 S(O) (4.1)
(N = 111, SD = 0.334, R2adj = 0.877, F = 431.04)
25
S. artemidis
-log MIC (mM) = -2.335 + 0.609 1χv - 0.285 5χv (4.2)
(N = 110, SD = 0.361, R2adj = 0.708, F = 133.44)
P. gingivalis
-log MIC (mM) = -1.321 + 0.670 1χv + 2.999 ∆6χ - 0.172 T(C) (4.3)
N = 124, SD = 0.395, R2adj = 0.850, F = 223
where N denotes the number of data points, R2adj is the squared adjusted correlation coefficient,
SD refers to the regression standard deviation, and F is the Fisher F-statistic. In Eqs. 4.1-4.3 the
independent pr operty i s t he ne gative l ogarithm of th e m inimum inhibitory millimo lar
concentrations, -log M IC. T he bol d te rms in th e c orrelations p ertain to t he va rious m olecular
connectivity descriptors, which are defined in greater detail elsewhere56.
In the second paper of the series, the authors57 considered the classical Hansch approach
using the water to octanol partition coefficient as one of the independent variables, along with
TLSER and WHIM descriptors. The statistics for the second series of correlations were similar
to those in the first paper, with the standard deviations generally ranging from 0.30 t o 0.50 l og
units. T he s tatistics of t he d esired correlations a re good; how ever, t he us e of di fferent
indices/descriptors i n e ach de rived e quation doe s not pe rmit a m eaningful c omparison t o be
made between the different bacterial strains, or between the bacterial strains and other biological
systems.
The aim of the present work was to construct a Linear Free Energy Relation (LFER) for
the -log MIC data for the above-mentioned bacterial strains based on the Abraham model, and to
26
compare e ach de rived c orrelation t o pr evious LFERs t hat ha ve be en o btained f or w ater t o
organic s olvent p artitions, a nd f or t he t oxicities of o rganic compounds t o di fferent a quatic
organisms. A ll c orrelations w ill b e b ased on a common s et of de scriptors. A c omparison of
coefficients i n t he de rived LFERs will i ndicate how near one s ystem i s t o another i n t erms of
chemical interactions, and hence, whether one system can be used as a model for another.
4.2. Methods
Our method of correlation is based on the general LFER1,2,44,46
SP = c + e·E + s·S + a·A + b·B + v·V (4.4)
where SP is the dependent variable such as the logarithm of the water to organic solvent partition
coefficient o r, as in th e p resent c ase, th e n egative lo garithm o f th e min imum in hibitory
millimolar c oncentration of t he o rganic c ompounds t oward b acterial growth. T he i ndependent
variables, o r d escriptors, ar e s olute p roperties as f ollows: E and S r efer t o t he excess m olar
refraction a nd di polarity/polarizability of t he s olute, r espectively, A a nd B de note t he ove rall
solute h ydrogen-bond a cidity and ba sicity, a nd V i s t he M cGowan vol ume of t he s olute. T he
remaining qua ntities ( c, e , s , a , b, a nd v ) r epresent pr ocess or equation co efficients. T he
numerical values of the equation coefficients will be different for each oral bacterium. Molecular
descriptors for all of the compounds considered in the present study are tabulated in Table S4.1
(Supplemental Material). The numerical values i n Table S 4.1 cam e from our solute descriptor
database, which now contains va lues for more t han 3500 di fferent or ganic and or ganometallic
compounds. F or c ompounds not i n our da tabase, t he de scriptor va lues w ere obt ained f rom
experimental s olute p roperties, s upplemented b y calculations of de scriptors us ing a l iterature
procedure58 and commercial software59 , as described in detail by Abraham et al.2
27
4.3. Results and Discussion
The P. gingivalis is the largest of the three databases, and contains minimum inhibitory
concentrations f or 134 organic c ompounds. T he e xperimental da ta a re t abulated a s -log M IC
(mM) in Table 4.1.
Table 4.1. Experimental minimal inhibitory concentrations of organic compounds, -log MIC (millimolar) to Porphyromonas gingivalis, Streptococcus sobrinus and Selenomonas artemidis oral bacteria.
-log MIC (mM) Solute P. gingivalis Str. sobrinus S. artemidis Phenol -1.45 -1.55 -1.33 2-Methylphenol -1.18 -1.33 -0.89 3-Methylphenol -1.27 -1.17 -0.89 4-Methylphenol -1.27 -1.33 -0.87 2-Ethylphenol -0.61 -0.87 -0.52 3-Ethylphenol -0.69 -0.87 -0.55 4-Ethylphenol -0.64 -0.85 -0.48 2-Propylphenol -0.34 -0.73 -0.17 3-Propylphenol -0.29 -0.71 -0.34 4-Propylphenol -0.30 -0.57 -0.17 2-Allylphenol -0.44 -0.81 -0.86 2-Isopropylphenol -0.34 -0.59 -0.30 3-Isopropylphenol -0.44 -0.79 -0.30 4-Isopropylphenol -0.47 -0.69 -0.30 2-Butylphenol -0.05 -0.30 -0.02 3-Butylphenol -0.12 -0.49 -0.03 4-Butylphenol -0.05 -0.12 0.33 2-Isobutylphenol 0.33 -0.19 0.21 3-Isobutylphenol 0.31 -0.12 0.06 4-Isobutylphenol 0.35 -0.12 0.28 (±)-2-sec-Butylphenol -0.12 -0.52 -0.26 (±)-3-sec-Butylphenol -0.25 -0.58 -0.19 (±)-4-sec-Butylphenol -0.12 -0.43 -0.12 2-tert-Butylphenol 0.28 -0.12 0.33 3-tert-Butylphenol -0.34 -0.74 -0.12 4-tert-Butylphenol -0.39 -0.60 -0.30 2-Pentylphenol 0.75 0.36 0.59 *Not included in the regression analysis. (table continues)
28
Table 4.1 (continued). -log MIC (mM) Solute P. gingivalis Str. sobrinus S. artemidis 4-Pentylphenol 0.85 0.52 0.80 4-tert-Pentylphenol 0.52 0.26 0.46 2-Hexylphenol 0.89 0.62 0.75 4-Heptylphenol 1.52 1.22 1.40 4-Octylphenol 1.00 1.00 0.620* 4-tert-Octylphenyl 1.52 1.00 0.89 2-Cyclohexylphenol 0.77 0.55 0.68 3-Cyclohexylphenol 0.82 0.52 0.57 4-Cyclohexylphenol 0.82 0.55 0.62 2-Cyclohexylmethylphenol 1.16 0.85 0.85 3-Cyclohexylmethylphenol 1.10 0.85 0.82 4-Cyclohexylmethylphenol 1.40 0.92 0.92 4-(1-Adamantyl)phenol 1.89 1.66 NA 2,4-Dimethylphenol -0.58 -0.91 -0.52 2,6-Dimethylphenol -0.78 -1.28 -0.76 3,5-Dimethylphenol -0.58 -1.02 -0.58 2-tert-Butyl-4-methylphenol 0.54 -0.08 0.42 2-tert-Butyl-6-methylphenol -0.48 -0.67 -0.51 2,6-Diisopropylphenol -0.27 -0.69 -0.32 Thymol -0.19 -0.43 -0.12 Carvarol -0.34 -0.67 -0.19 2,4-Di-tert-butylphenol 0.68 0.40 -0.111* 2,6-Di-tert-butylphenol -0.250* NA NA 3,5-Di-tert-butylphenol 0.96 0.68 0.46 2-tert-Butyl-4-cyclohexylphenol 1.96 1.85 NA 2-tert-Octyl-4-cyclohexylphenol 2.22 1.89 NA 2-Cyclohexyl-4-tert-octylphenol 2.22 2.30 -0.238* 2-tert-Butyl-5-cyclohexylphenol 2.00 1.77 0.658* 2-tert-Octyl-5-cyclohexylphenol 2.52 1.80 NA 2-(1-Adamantyl)-4-methylphenol 2.10 1.85 0.96 α-Tetralol -0.13 -0.31 0.222* β-Tetralol -0.13 -0.31 0.056* 2-Phenylphenol 0.35 -0.14 0.33 4-Phenylphenol 0.66 NA 0.60 2-tert-Butyl-5-phenylphenol 2.05 1.75 0.99 *Not included in the regression analysis. (table continues)
29
Table 4.1 (continued). -log MIC (mM) Solute P. gingivalis Str. sobrinus S. artemidis 2-Benzylphenol 0.66 0.31 0.66 4-Benzylphenol -0.04 -0.21 0.04 α-Naphthol -0.07 -0.32 0.26 β-Naphthol -0.14 -0.36 -0.07 2-Methoxyphenol -1.38 -1.63 -1.27 3-Methoxyphenol -1.27 -1.43 -1.27 4-Methoxyphenol -1.33 -1.54 -1.27 Eugenol -0.35 -1.09 -0.35 2-Ethoxyphenol -1.08 -1.34 -1.16 3-Ethoxyphenol -0.43 -0.78 -0.50 4-Ethoxyphenol -0.83 -1.23 -0.83 4-Propoxyphenol -0.34 -0.93 -0.42 2-Isopropoxyphenol -1.24 -1.42 -1.12 3-Butoxyphenol 0.00 -0.26 0.11 4-Butoxyphenol -0.35 -0.41 -0.21 4-Pentoxyphenol 0.59 -0.05 0.50 4-Hexyloxyphenol 0.77 0.54 0.62 4-Heptyloxyphenol 1.00 0.85 0.68 2-Cyclohexylmethoxyphenol 0.59 -0.41 -0.11 3-Cyclohexylmethoxyphenol 0.82 0.64 0.72 4-Cyclohexylmethoxyphenol 0.89 0.72 0.62 4-Phenoxyphenol 0.64 0.15 0.42 2-Benzyloxyphenol 0.10 -0.22 0.00 3-Benzyloxyphenol 0.47 NA 0.43 4-Benzyloxyphenol 0.46 0.00 0.34 2-Acetylphenol -1.57 NA -1.57 3-Acetylphenol -1.23 -1.50 -1.17 4-Acetylphenol -1.23 -1.43 -1.23 2-Propionylphenol -0.65 NA -0.67 4-Propionylphenol -0.58 NA -0.60 2-Benzoylphenol -0.427* NA -0.53 3-Benzoylphenol 0.00 -0.31 0.00 4-Benzoylphenol 0.00 -0.31 0.00 2-Fluorophenol -1.38 -1.55 -1.32 3-Fluorophenol -1.25 -1.25 -0.92 *Not included in the regression analysis. (table continues)
30
Table 4.1 (continued). -log MIC (mM) Solute P. gingivalis Str. sobrinus S. artemidis 4-Fluorophenol -1.25 -1.25 -1.17 2-Bromophenol -0.70 -1.06 -0.63 3-Bromophenol -0.36 -0.52 -0.19 4-Bromophenol -0.36 -0.52 -0.24 2,6-Difluorophenol -1.31 -1.49 -1.25 2,6-Dichlorophenol -0.39 -0.67 -0.39 2,6-Dibromophenol -0.27 -0.58 -0.16 2-Cyanophenol -0.92 -1.23 -0.79 3-Cyanophenol -0.92 -1.23 -0.79 4-Cyaophenol -0.81 -1.29 -0.60 2-Hydroxyacetanilide -0.64 -0.90 -0.76 3-Hydroxyacetanilide -1.42 NA -1.46 4-Hydroxyacetanilide -1.52 NA -1.57 3-Nitro-2-methylphenol -0.38 -0.12 -0.04 3-Nitro-4-methylphenol -0.29 -0.59 -0.18 6-Nitro-3-methylphenol -0.51 NA -0.57 4-Nitro-3-methylphenol 0.658* -0.42 0.41 2’-Nitro-4-hydroxybiphenyl 0.54 0.03 0.43 4’-Nitro-4-hydroxybiphenyl 0.77 NA 0.72 5-Hydroxyindole -0.68 -0.90 -0.68 6-Hydroxyquinoline -0.59 -0.72 -0.68 8-Hydroxyjulolidine -0.09 NA NA (+)-Totarol 2.52 2.16 NA (+)-Ferruginol 2.16 1.96 NA Triclosan 2.16 1.39 2.00 Indole -0.80 -1.23 -0.66 Quinoline -0.67 -0.94 -0.75 2-Nitrotoluene -1.29 NA -1.29 3-Nitrotoluene -1.47 NA -1.47 2-Nitrobiphenyl -1.069* NA -1.127* 3-Nitrobiphenyl -1.002* NA -1.002* 4-Nitrobiphenyl 0.30 NA NA 4-Propylanisole -1.346* NA -1.387* (2S,5R)-(-)menthone -1.51 NA -1.48 (1S,2R,5S)-(+)-menthol -1.329* -1.533* -1.37 *Not included in the regression analysis. (table continues)
31
Table 4.1 (continued). -log MIC (mM) Solute P. gingivalis Str. sobrinus S. artemidis (1R,2S,5R)-(-)-menthol -1.329* -1.505* -1.37 (1S,2R,5R)-(+)-isomenthol -0.92 NA -0.78
*Not included in the regression analysis.
The initial a nalysis in dicated that 2,6 -di-tert-butylphenol, 2 -benzoylphenol, 4 -nitro-3-
methylphenol, 2 -nitrophenyl, 3 -nitrobiphenyl, 4 -propylanisole, (1S,2R,5S)-(+)-menthol, a nd
(1R,2S,5R)-(-)-menthol are outliers. I note t hat t he e xperimental va lue f or 4 -nitro-3-
methylphenol (-log MIC = 0.658) is out of line with the values for the other three nitrocresols (-
log M IC = -0.380 f or 3 -nitro-2-methylphenol; -log M IC = -0.292 for 3 -nitro-4-methylphenol;
and -log MIC = -0.513 for 6-nitro-3-methylphenol), suggesting that the value may be in error or
that perhaps steric recognition plays an important role in the growth inhibition for this particular
compound. Examination of t he num erical va lues i n Table 4.1 further r eveals that th e
experimental da ta f or bot h 2 -nitrobiphenyl and 3 -nitrobiphenyl di ffers from t he va lue f or 4 -
nitrobiphenyl by more t han 1 l og uni t. T he s light s tructural di fferences between t he t hree
nitrobiphenyl i somers s hould not lead t o s uch a l arge d ifference i n t he o bserved m inimum
inhibitory concentration. The e ight compounds were r emoved from the da tabase, and the f inal
regression analysis was performed to yield
-log MIC = -3.320 + 1.111E - 0.605S + 0.727A - 1.904B + 2.423V (4.5)
N = 126, s = 0.313, R2 = 0.906, R2adj = 0.902, F = 232.3.
Minitab s oftware60 was u sed f or al l r egression a nalyses. The s tatistics ar e q uite g ood
32
given the nature of the experimental data. Generally, biological data have greater experimental
uncertainties associated with the reported values than do chemical properties such as the water to
octanol pa rtition c oefficient or s aturation s olubility. A graphical co mparison o f t he cal culated
values based on Eq. 4.5 versus the experimental -log MIC values is given in Table 4.1.
Figure 4.1. A pl ot o f cal culated values b ased o n Eq. 4.5 versus observed values for Porphyromonas gingivalis.
The 126 compounds w ere di vided i nto a t raining s et a nd t est s et b y or dering t he
compounds i n t erms o f increasing v alue o f -log M IC. E very s econd compound w as removed
from th e lis t to form t he t est s et. T he r emaining 63 c ompounds that w ere l eft s erved as t he
training set. This procedure ensures that the training and test sets cover the same range of values.
Analysis of the experimental data in the training set gave
-log MIC = -3.343 + 1.099E - 0.678S + 0.862A - 1.547B + 2.337V (4.6)
N = 63, s = 0.309, R2 = 0.912, R2adj = 0.905, F = 118.5.
33
The coefficients in Eq. 4.6 are close to those in Eq. 4.5 suggesting that the training set is
representative of the total set. The training set was then used to predict -log MIC values for the
remaining 63 values in the test set, to assess the correlation’s predictive ability. For the predicted
and ex perimental v alues, I find t hat s = 0.328, Average A bsolute E rror ( AAE) = 0.261, a nd
Average Error (AE) = 0.01. There is therefore virtually no bi as in the predictions using Eq. 4.5
with AE equal to 0.01 log units.
The S. artemidis dataset is the second largest of the three oral bacterial strains considered
in the dissertation research. It contains -log M IC values for 125 c ompounds. Initial analysis of
the e xperimental da ta showed t hat ni ne c ompounds w ere out liers. These c ompounds a re
indicated in Table 4.1 by an asterisk “*”. In the case of both 2-cyclohexyl-4-tert-octylphenol and
2-tert-butyl-5-cyclohexylphenol, I believe that the observed minimum inhibitory concentrations
are much larger than what would be expected based on t he compound’s molecular s ize. While
one does not expect that the minimum inhibitory concentration of a given compound would be
the same for al l three bacterial s trains, i t seems highly unlikely that the difference would be as
large as two log units, as is the case with 2-cyclohexyl-4-tert-butylphenol (-log MIC = -0.238 for
S. artemidis vs. -log MIC = 2.222 f or P. gingivalis and -log MIC = 2.301 for S. sobrinus). The
nine c ompounds w ere eliminated f rom t he da taset, a nd t he f inal r egression a nalysis w as
performed to yield
-log MIC = -3.008 + 0.982E – 0.496S + 0.972A - 2.643B + 2.312V (4.7)
N = 116, s = 0.268, R2 = 0.871, R2adj = 0.866, F = 149.1.
The c orrelation f or S. artemidis is n ot quite a s g ood a s t he one obt ained f or P. gingivalis;
34
however, it has a much lower standard deviation and much higher squared correlation coefficient
than t he publ ished c orrelation of S hapiro a nd G uggenheim56 based on m olecular c onnectivity
indices (see Eq. 4.2). Figure 4.2 compares the experimental -log MIC data to calculated values
based on Eq. 4.7.
Figure 4.2. A plot of calculated values based on Eq. 4.7 versus observed values for Selenomonas artemidis.
As be fore, the S. artemidis database was di vided i nto a 58 c ompound t raining s et a nd a 58
compound test set based on -log MIC numerical values. Analyses of the experimental data in the
training set gave
-log MIC = -2.791 + 1.124E - 0.659S + 0.680A - 2.655B + 2.315V (4.8)
with N = 58, s = 0.250, R2 = 0.892, R2adj = 0.882, and F = 86.18.
Eq. 4.8 was then used to predict -log MIC values for the remaining 58 compounds in the test set.
35
For the predicted and experimental values, I find that s = 0.311, AAE = 0.242, and AE =
-0.056. There is therefore virtually no bias in the predictions using Eq. 4.7 with AE equal to
-0.056 log units.
Experimental growth data for S. sobrinus were analyzed in similar fashion. Compounds
that were identified as outliers in the preliminary regression analysis have been denoted b y an
asterisk in Table 4.1. Regression analysis yielded the following correlation:
-log MIC = -3.465 + 0.855E - 0.465S + 0.735A - 1.671B + 2.330V (4.9)
with N = 112, sd = 0.309, R2 = 0.902, R2adj = 0.898, and F = 195.8.
Again, t he s tatistics a re qui te good. Eq. 4.9 provides a reasonably accurate m athematical
description of the experimental data as shown in Figure 4.3.
Figure 4.3. A plot of calculated values based on Eq. 4.9 versus observed values for Streptococcus sobrinus.
36
The compounds were further divided into a training and test set. Experimental data in the
training set gave
-log MIC = -3.432 + 0.982E - 0.717S + 0.879A - 1.587B + 2.320V (4.10)
where N = 56, sd = 0.329, R2 = 0.894, R2adj = 0.883, and F = 84.02.
The full equation and the training equation are reasonably similar. The test statistics show that
the predictive ability is 0.241 (AE) or 0.298 (sd), and the latter is almost exactly the same as the
standard deviation for the full equation (sd = 0.309) or the training set (sd = 0.329).
There is little difference between the three equations, Eqs. 4.5, 4.7, and 4.9, although the
b-coefficient for S. artemidis, Eq. 4.7, is rather more negative than the b-coefficient in Eqs. 4.5
and 4.9. I can conclude that the factors that influence the three inhibitory concentrations toward
oral bacterial growth are qualitatively and semi-quantitatively the same. The two main factors are
solute hydrogen bond basicity that increases the minimum inhibitory concentration (decreases -
log MIC) and solute volume that decreases the minimum inhibitory concentration (increases -log
MIC). Other factors play a part but are not so important. One of the aims of the present work was
to compare the equations (Eqs. 4.5, 4.7, and 4.9) I have obtained for inhibitory concentrations
toward or al ba cterial growth, w ith e quations f or t oxicity t oward va rious or ganisms, a nd
equations for various water-to-solvent partition coefficients that might be used as model systems.
This can only be achieved if the same general equation is used for all correlations; in the present
case this is Eq. 4.4.
In Table 3 are listed the coefficients in Eq. 4.4 for a large number of water to wet solvent
partition systems No. 1 – 19, and for some partitions from water to “dry” organic solvents44 for
37
aqueous toxicity toward a number of fish species44 No. 25 – 30 and for aqueous toxicity toward
protozoa45 No. 31 and 36 the water flea45 No. 32 – 35 , the bacterium Pseudomonas putida45 No.
37 and toward Uronema parduczi61 No. 38, Chilomonas paramecium61 No. 39, and Entosiphon
sulcan61 No. 40. T he c oefficients obt ained i n t his w ork a re l isted a s P. gingivalis No. 41, S.
artemidis No. 42, and S. sobrinus No. 43. Inspection of Table 4.2 shows that in all 43 cases, the
two m ain f actors a re s olute h ydrogen bond ba sicity a nd s olute vol ume. H owever, i t i s ve ry
difficult t o r each a ny d efinite c onclusions b y s uch a n i nspection. A very us eful m ethod o f
comparing coefficients is that of Principal Component Analysis, PCA. The five coefficients e, s,
a, b, a nd v, a re t ransformed i nto f ive p rincipal c omponents t hat r etain a ll t he or iginal
information, but which are all mutually orthogonal. The first two principal components PC1 and
PC2 account for 84% of the total information in the present case, and so a plot of the scores of
PC2 against the scores of PC1 for all the 43 cases will give a visual indication of how close are
the coefficients in the various equations. A score plot is shown as Figure 4.4, where the points
(corresponding to the equations) are separately indicated as No. 1-19 for the water to wet solvent
equations, No. 20-24 for the water to dry solvent equations, No. 25-40 for the toxicity equations,
and No. 41-43 for the three equations Eqs. 4.5, 4.7, and 4.9.
38
Figure 4.4. A plot of the scores of PC2 against the scores of PC1 for the principal component analysis: ■ water to wet solvent partitions No 1-19; □ water to dry solvent partitions No 20-24; ∆ aqueous toxicity No 25-40; ▲ equations found in this work No 41-43.
Table 4.2. Comparison of coefficients in Eq. 4.4 for water to solvent partitions, and for aqueous toxicity towards various organisms.
System a No e s a b v Octanol 1 0.56 -1.05 0.03 -3.46 3.81 Isobutanol 2 0.51 -0.69 0.02 -2.26 2.78 Pentanol 3 0.58 -0.79 0.02 -2.84 3.25 Oleyl alcohol 4 -0.27 -0.53 -0.04 -4.04 4.20 Dichloromethane 5 0.00 0.02 -3.24 -4.14 4.26 Trichloromethane 6 0.16 -0.39 -3.19 -3.44 4.19 Tetrachloromethane 7 0.57 -1.25 -3.56 -4.59 4.59 Diethyl ether 8 0.56 -1.02 -0.23 -4.55 4.08 Dibutyl ether 9 0.68 -1.51 -0.81 -5.25 4.82 NPOE b 10 0.60 -0.46 -2.25 -3.88 3.57 Ethyl acetate 11 1.16 -1.40 -0.05 -3.76 3.73 PGDP c 12 0.50 -0.83 -1.02 -4.64 4.03 Olive oil 13 0.57 -0.80 -1.42 -4.98 4.21 aWater to solvent partition systems No 1-24, aqueous toxicity towards various organisms No 25-40, and toxicity equations found in this work No 41-43. bNPOE is o-nitrophenyl octyl ether. cPGDP is propylene glycol dipelarginate.43 (table continues)
39
Table 4.2 (continued). System a No e s a b v Benzene 14 0.46 -0.59 -3.10 -4.63 4.49 Nitrobenzene 15 0.58 0.00 -2.36 -4.42 4.26 Hexane 16 0.58 -1.72 -3.60 -4.76 4.34 Hexadecane 17 0.67 -1.62 -3.59 -4.87 4.43 Cyclohexane 18 0.78 -1.68 -3.74 -4.93 4.58 Carbon disulfide 19 0.69 -0.94 -3.60 -5.82 4.92 Ethylene glycol, dry 20 0.70 -0.67 0.73 -2.40 2.67 Isopropanol, dry 21 0.32 -1.02 0.45 -3.82 4.07 Ethanol, dry 22 0.41 -0.96 0.19 -3.65 3.93 DMF, dry 23 0.32 0.46 1.15 -4.84 3.76 DMSO, dry 24 0.23 0.88 1.31 -4.60 3.40 Fathead minnow 25 0.42 -0.18 0.42 -3.57 3.38 Guppy 26 0.78 -0.23 0.34 -3.05 3.25 Bluegill 27 0.58 -0.13 1.24 -3.92 3.31 Golden orfe 28 0.93 0.38 0.95 -2.39 3.24 Medaka (48 hr) 29 1.10 -0.41 0.81 -2.31 2.79 Medaka (96 hr) 30 1.05 0.27 0.93 -2.18 3.16 Tetrahymena pyriformis 31 0.45 -0.06 0.34 -2.67 2.94 Daphnia magna (24 hr) 32 0.35 0.17 0.42 -3.94 3.52 Daphnia magna (48 hr) 33 0.53 -0.03 0.22 -3.70 3.59 Ceriodaphnia dubia 34 0.37 -0.04 -0.44 -3.28 2.76 Daphnia pulex 35 0.39 0.30 0.66 -3.59 3.57 Spirostomum ambiguum 36 0.11 0.29 0.69 -3.30 3.14 Psedomonas putida 37 0.96 0.09 -0.08 -2.09 2.95 Uronema parduczi 38 1.43 0.43 0.94 -1.03 2.60 Chilomonas param. 39 1.13 0.16 0.44 -1.83 2.45 Entosiphon sulcan. 40 0.89 0.36 1.11 -2.50 2.85 Porphyromonas gingivalis 41 1.11 -0.61 0.73 -1.90 2.42 Selenomonas artemidis 42 0.98 -0.50 0.97 -2.64 2.31 Streptococcus sobrinus 43 0.86 -0.47 0.74 -1.67 2.33 aWater to solvent partition systems No 1-24, aqueous toxicity towards various organisms No 25-40, and toxicity equations found in this work No 41-43. bNPOE is o-nitrophenyl octyl ether. cPGDP is propylene glycol dipelarginate.43
It is immediately clear from Figure 4.4 that nearly all of the water to wet solvent systems
are far away from all the biological systems, in terms of chemistry, except for the water to wet
isobutanol a nd w ater t o wet pe ntanol s ystems. It i s no c oincidence t hat in t hese s ystems t he
40
solvent i ncludes a l arge p ercentage o f w ater, b ecause t his influences t he co efficients
considerably. However, some of the water to dry solvent systems are chemically quite close to
the bi ological s ystems, e specially w ater t o dr y e thylene g lycol ( No. 20) but a lso dr y
dimethylformamide ( DMF, N o. 23 ) a nd d ry di methylsulfoxide ( DMSO, N o. 24) . T hese t hree
systems all h ave p ositive a -coeffficients, ju st lik e th e b iological s ystems. T he th ree s ystems
considered in this work are themselves close to only some of the other biological systems shown
in Table 4.2, namely No. 28 – 30, and 37 – 40. Since the main terms in all equations are the b.B
and v.V t erms, f urther i nformation m ight b e obt ained f rom a pl ot o f b -coefficients against v -
coefficients, a s s hown i n Figure 4.5. N ow it i s v ery clear th at th e e quations f or i nhibitory
concentrations toward oral bacterial growth are characterized by more positive b-coefficients and
more negative v coefficients. S ince the water to solvent equations are l argely characterized b y
more negative b-coefficients and more positive v-coefficients, few of them are suitable models
for inhibitory concentrations toward oral bacterial growth. The latter systems behave as though
the s olute i s t ransferred f rom a n a queous environment t o a n e nvironment t hat i s e ven m ore
water-like than water saturated isobutanol. The latter contains no less than 0.46 mol fraction of
water. I conclude that no water to wet solvent system I have examined will be a suitable model
for i nhibitory concentrations t oward or al b acterial gr owth. T his i ncludes t he w ater t o o ctanol
system, widely used as a model for biological systems. As can be seen from Figures 4.4 and 4.5,
the coefficients for the water to 1-octanol system, No. 1, are quite far away from the coefficients
in the equations for inhibitory concentrations toward oral bacterial growth.
41
Figure 4.5. A plot of b-coefficients against v-coefficients for the systems in Table 3: ■ water to wet solvent partitions No. 1-19; □ water to dry solvent partitions No. 20-24; ∆ aqueous toxicity No. 25-40; ▲ equations found in this work No. 41-43.
Figure 4.5 shows a lso t hat t he poi nts f or dr y e thylene glycol ( No. 20) , as w ell a s w et
isobutanol (No. 2) and wet pentanol (No. 3) lie well within the range of those for the biological
systems. This, together with the fact that Figure 4.5 can accommodate the partition systems and
the b iological s ystems all o n mo re o r le ss th e s ame lin e, s uggests th at the ma in me chanistic
feature of the biological systems is simple transfer from one phase to another, as is the case for
the w ater t o w et s olvents a nd w ater t o dr y s olvents. T he t hree s ystems I have s tudied i n t he
present work behave as though t ransfer was taking place from an aqueous environment to one
that is c haracterized b y high d ipolarity/polarizability ( positive s -coefficient), s trong h ydrogen
bond ba sicity ( large a coefficient), m oderate h ydrogen bond a cidity ( negative but not ve ry
negative b -coefficient), an d m oderate hydrophobicity (positive but not ve ry pos itive v
coefficient). Again, the fact that the equations for minimum inhibitory concentration of organic
42
compounds f or growth i nhibition toward P. gingivalis, S. artemidis, a nd S. sorbrinius can b e
analyzed in the same way as equations for partition of organic compounds from water to wet and
dry s olvents, s uggests t hat t he f actors i nfluencing m inimum i nhibitory c oncentration a re
qualitatively the same as those that influence partition. In other words, the minimum inhibitory
concentrations lead to equations that are of the same qualitative form, and are semi-quantitatively
similar, to equations for passive partition of compounds from water to organic solvents.
Comparison of equation coefficients through PCA can also provide valuable information
that can be used in experimental design. S uppose that one wished to assess the toxicity that a
series of halogenated hydrocarbons had towards aquatic organisms. It would be quite expensive
and time-consuming to measure the toxicity that each halogenated hydrocarbon had towards each
fish s pecies, each t ype of w ater f lea, ea ch p rotozoa, an d ea ch b acterium. A m ore r ational
experimental design would be to cover the entire PCA space and study only a limited number of
the closely clustered aquatic organisms. F or example, in Figure 4.4 fathead minnow (No. 20)
and bluegill (No. 22) are chemically s imilar. O ne should be able to get a very good idea of a
compound’s toxicity towards bluegill through experimental measurements on fathead minnows.
43
CHAPTER 5
ENTHALPY OF SOLVATION CORRELATIONS FOR GASEOUS SOLUTES DISSOLVED
IN WATER AND VARIOUS ORGANIC SOLVENTS
5.1. Introduction
Accurate p rediction o f s olution-phase p roperties i s i mportant i n m any industrial
applications, r anging f rom t he de sign of c hemical s eparation pr ocesses, t o t he selection of
reaction media for opt imizing product yields, to the synthesis of potential new drug molecules
that r equire d elivery t o a s pecific b ody organ o r t arget s ite. The t hermodynamic pr operties of
molecules i n v arious ch emical an d b iological p rocesses a re greatly i nfluenced b y m olecular
interactions between the molecule and its solubilizing media. S uch in teractions may be either
non-specific o r s pecific i n n ature. N on-specific i nteractions ar e d escribed b y a random
distribution of molecules throughout the entire solution. Specific interactions, on the other hand,
are generally much stronger and often result in a specific geometric orientation of one molecule
with respect to an adjacent molecule. E ven in systems known to contain specific interactions,
the need to properly account for non-specific interactions has been long recognized.
The partition coefficient is the ratio of the concentration of a chemical species adsorbed
or di ssolved by one phase to the concentration o f the species in the other phase. Historically,
many of t he ve ry e arly s tudies de termining p artition c oefficients f ocused on m easuring and
developing predictive correlations for the 1-octanol and water system. This system is thought to
mimic s everal imp ortant b iological p rocesses. The a ir-to-water an d ai r-to-octanol pa rtition
coefficients, Kw and KOTOH, as well as their temperature dependence, are used in predicting the
fate a nd t ransport of vo latile or ganic c ompounds ( VOCs) i n t he e nvironment. O f pa rticular
interest are the processes involving the partition of VOCs from the gas phase into natural water
44
systems and water droplets, and into systems containing natural organic matter. Measured air-to-
octanol partition c oefficient da ta ha ve be en us ed w ith s uccess t o de scribe t he pa rtitioning
behavior of organic compounds between the gas phase and soils,62,63 plants,64-68 aerosols,69-72 and
human f aeces.73 Temperature d ependence o f K w and K OTOH is n eeded t o p redict t he e ffect o f
ambient temperature changes on environmental phase distribution, to explain the accumulation
of VOCs in remote mountainous regions and cold arctic climates, and to describe the release of
organic contaminants f rom me lting ic e a nd s now. A s additional e xperimental d ata b ecame
available, researchers expanded their studies to include more organic solvents.
During the last ten years Acree et al. have reported partition coefficient correlations (both
water-to o rganic s olvent a nd gas-to-organic s olvent) f or m ore t han fifty common or ganic
solvents. As part of my dissertation research I developed mathematical correlation equations for
predicting the enthalpies of solvation of gaseous solutes in water and in several organic solvents
based on t he A braham s olvation pa rameter m odel. The or ganic s olvents s tudied w ere carbon
tetrachloride, t oluene, d imethyl s ulfoxide, pr opylene c arbonate, di butyl e ther, e thyl a cetate,
chloroform, 1,2-dichloroethane, benzene, several alkane solvents (hexane, heptanes, hexadecane,
cyclohexane), a lcohol solvents ( methanol, e thanol, 1-butanol, 1 -octanol a nd tert-butanol),
“generic” linear a lkanes, N ,N-dimethylformamide, acet one, an d ac etonitrile. E ach derived
correlation was based on experimental data for a minimum of 100 organic and inorganic solutes.
Published c orrelations have f or t he m ost p art pe rtained t o 298.15 K. H owever, m anufacturing
and biological processes are not restricted to 298.15 K, and there is a growing need to estimate
partitioning properties of organic solvents at other temperatures.
45
From a thermodynamic s tandpoint, t he gas-to-condensed phase p artition coefficient, K,
and water-to-organic solvent partition coefficient, P, can be estimated by
log10 K(at T ) − log10 K(at 298.15 K) = −∆HSolv2.303R(1/T −1/298.15) (5.1)
and
log10 P(at T) − log10 P(at 298.15 K) = −∆Htrans2.303R(1/T − 1/298.15) (5.2)
at ot her t emperatures from m easured pa rtition c oefficient da ta at 298.15 K a nd t he s olute’s
enthalpy of solvation, ∆HSolv, or enthalpy of transfer, ∆Htrans, between the two condensed phases.
The enthalpy of transfer needed in Eq. 5.2 is defined as
∆Htrans = ∆HSolv,Org − ∆HSolv,W (5.3)
the difference is the enthalpy of solvation of the solute in the specified organic solvent minus its
enthalpy of solvation in water. All of the above equations assume zero heat capacity changes.
5.2. Experimental Methods
An ex tensive s earch w as co nducted o f t he ch emical l iterature i n o rder t o co mpile
experimental enthalpy o f s olvation da ta. A l arge num ber of pa pers also r eported e xperimental
partial molar enthalpies of solution of liquid and crystalline organic compounds. The latter data
was d etermined b y ei ther d irect c alorimetric m ethods o r cal culated b ased o n t he t emperature
dependence of measured infinite dilution activity coefficient data, and the published values were
converted to gas-to-organic solvent enthalpies of transfer as follows
46
Liquid solutes: ∆HSolv = ∆HSoln − ∆HVap,298K (5.4)
Crystalline solutes: ∆HSolv = ∆HSoln − ∆HSub,298K (5.5)
by s ubtracting t he s olute’s s tandard m olar e nthalpy of v aporization,74 ∆HVap,298K, or s tandard
molar e nthalpy o f s ublimation,75 ∆HSub,298K, a t 298.15 K . F or pur poses of my studies I
considered enthalpies of solvation, ∆HSolv, and what will be called “inner energies”, ∆USolv, to be
equivalent. G oss76 discusses t he d ifference b etween t he ∆HSolv and ∆USolv in te rms o f th e
concentration units used in expressing the gas-phase concentrations of the Henry’s law constant.
At 298.15 K the difference between the quantities amounts to about 2.5 kJ·mol−1 that is less than
the ex perimental u ncertainty associated w ith m any o f t he o bserved v alues.76 Given t he s light
numerical di fference be tween t he t wo va lues un der nor mal e nvironmental c onditions, I have
combined both sets of numerical values into a single database, as has been done in the past by
research groups that have developed predictive methods for enthalpies of solvation. Most of my
tabulated values are enthalpies of solvation; however, there may be a few “inner energies” listed
in the Supplemental Tables that were mislabeled as enthalpies in the original data source.
Based o n an i nitial as sessment o f t he av ailable ex perimental d ata, I eliminated f rom
consideration a ll e xperimental d ata th at p ertained to te mperatures o utside o f th e te mperature
range of 283 to 318 K. Enthalpies of solvation are temperature dependent, and I did not want to
introduce large errors in the database by including experimental data far removed from 298 K. A
recent p aper77 addressed th e mis interpretations t hat can r esult w henever t he t emperature
dependence i s not t aken i nto a ccount. A lso e xcluded w ere va lues ba sed on s olubility
measurements where the equilibrium solid phase might be a solvated form of the solid solute.
47
For s everal s olutes t here w ere m ultiple, i ndependently d etermined v alues. In s uch c ases, I
selected d irect cal orimetric d ata o ver i ndirect v alues b ased o n t he t emperature d ependence o f
measured solubilities or infinite dilution activity coefficients. Using the forementioned criteria,
experimental molar enthalpies of solvation were selected for regression analysis.
For the analysis of the data, I use the two linear free energy equations of Abraham et al.
1,2 In Eq. 5.7, the descriptor V is the McGowan volume
SP = c + e·E + s·S + a·A + b·B + l·L (5.6)
SP = c + e·E + s·S + a·A + b·B + v·V. (5.7)
Most published studies using t he A braham m odel have dealt w ith p artition p rocesses
related to the Gibbs energy of transfer, where the dependent solute property, SP, would be either
the logarithm of the gas-to-liquid (Eq. 5.6) or the logarithm of the water-to-organic solvent (Eq.
5.7) partition coefficient. The basic model can be used to correlate enthalpies of solvation and
enthalpies of solute transfer from one condensed phase to a second condensed phase. Regression
equations us ing E q. 5.6 solving f or ∆H solv correspond t o t he t emperature d erivative of t he
respective g as-to-liquid p artition c oefficient c orrelation, i.e., ΔHSolv = R∂lnK/∂(1/T). F rom a
thermodynamic s tandpoint, the temperature derivative o f the logarithm of the water-to-organic
solvent partition coefficient would be related to enthalpy of t ransfer f rom water to the organic
solvent, i.e., ΔHSolv = R∂lnP/∂(1/T). ∆ HSolv correlations ba sed on E q. 5.7, w hich us es t he
McGowan volume, V-descriptor, which is more readily available than the L-descriptor. The V-
descriptor is easily calculable from the individual atomic sizes and numbers of bonds in the.78
Molecular de scriptors f or a ll of t he c ompounds c onsidered a re a lso t abulated. T he
48
tabulated values came from our solute descriptor database, which now contains values for more
than 4,000 di fferent or ganic a nd or ganometallic c ompounds. T he de scriptors w ere obt ained
exactly as described before, using various types of experimental data, including water to solvent
partitions, gas to solvent partitions, and solubility and chromatographic data.2 Solute descriptors
used ar e all b ased o n experimental d ata. T here i s al so co mmercial s oftware79 and s everal
published e stimation s chemes58,80-82 available f or cal culating the num erical va lues o f s olute
descriptors from molecular structural information if one is unable to find the necessary partition,
solubility and/or chromatographic data.
5.3. Results and Discussion
5.3.1. 1-Octanol and Water*
Results and Discussion
From th e p ublished c hemical lite rature, I assembled i n T able S 5.1 ( Supplementary
Material) en thalpy of s olvation da ta f or 372 s olutes di ssolved i n w ater a t 298 K with da ta
covering a reasonable wide range of compound type and descriptor values. Preliminary analysis
of th is e xperimental d ata yielded s everal o utliers, which i ncluded t he c ompounds 4 -
chlorophenol, N -methylpyrrolidine, te trachloroethylene, a nd 1 -octylamine. In t he cas e o f 1 -
octylamine, t he publ ished e xperimental va lue w as -52.3 kJ /mol. T he r eported va lue doe s not
follow the observed trend of alkylamines, which become more exothermic with increasing alkyl
chain l ength. For example, t he enthalpy of solvation f or t he a lkylamines – methylamine
(∆Hsolv,w = -45.3 kJ/mol), ethylamine ((∆H solv,w
= -53.7 kJ/mol), 1-propylamine ((∆Hsolv,w = -56.0
kJ/mol), 1-butylamine (∆Hsolv,w = -59.0 kJ/mol), 1-pentylamine (∆H solv,w
= -62.1 kJ/mol), and 1- * Reproduced in part with permission from C. Mintz, M. Clark, W. E. Acree, Jr., and M. H. Abraham, J. Chem. Inf. Model. 47 (1), 115 (2007). Copyright 200 American Chemical Society.
49
hexylamine (∆H solv,w = -65.9 kJ /mol).71 A s imilar s ituation was f ound w ith 4 -chlorophenol i n
which t he reported v alue (∆H solv,w = -35.9 kJ /mol)57 was f ar out o f l ine w ith t he va lue f or 3 -
chlorophenol (∆Hsolv,w = -50.3 kJ/mol). O nce the four outliers were removed from the data set,
the final regression analysis using SPSS statistical software30 yielded
∆HSolv,w (kJ/mol) = -13.310(0.457) + 9.910(0.814)E + 2.836(0.807)S -
32.010(1.102)A -41.816(0.781)B - 6.354(0.200)L (5.8)
(N = 368, SD = 3.68, R2 = 0.964, R2adj = 0.964, F = 1950.5).
Here an d el sewhere, N co rresponds t o t he num ber of s olutes, R de notes t he c orrelation
coefficient, S D i s t he s tandard de viation, a nd F corresponds t o t he F isher F statistic. A fter
adding the additional compound erythritol a new regression equation was produced.
∆HSolv,w (kJ/mol) = -6.952(0.651) + 1.415(0.770)E - 2.859(0.855)S -
34.086(1.225)A - 42.686(0.850)B - 22.720(0.800)V (5.9)
(N = 369, SD = 4.04, R2 = 0.959, R2adj = 0.958, F = 1688.2).
I did not include erythritol in Eq. 5.8 regression analysis because its L descriptor was unknown.
However, I wanted t o i nclude i t i n de veloping a r egression e quation be cause i t ha s a l arge
negative enthalpy o f solvation, and i t he lps to demonstrate the range of data that our model i s
able t o ac curately predict. T he d ata s et u sed i n this r egression a nalysis spans a r ange of 150
kJ/mol. Both Eqs. 5.8 and 5.9 are statistically very good, with standard deviations of 3.7 kJ/mol
and 4. 0 kJ/mol, respectively. From a t hermodynamic s tandpoint, Eq. 5.8 is s lightly b etter
50
statistically, however, Eq. 5.9 is useful when the L descriptor is unknown. The V descriptor can
be c alculated f rom t he i ndividual a tomic s izes a nd num bers of bonds i n t he m olecule.83 See
Figure 5.1 and Figure 5.2 for a plot of the calculated values of ∆ HSolv,w based on Eqs. 5.8 and 5.9
against t he obs erved va lues. It i s i nteresting t o note t hat t he r are gases, i norganic gases, a nd
polyaromatic h ydrocarbons al l f it Eqs. 5.8 and 5.9, but t hey do not f it t he corresponding
equations in the gas-to-water partition coefficient.84
Figure 5.1. Plot of the calculated values of ∆HSolv,W on Eq. 5.8 against the observed values.
51
Figure 5.2. Plot of the calculated values of ∆HSolv,W on Eq. 5.9 against the observed values.
In or der t o a ccess t he predictive a bility o f Eq. 5.8 the 368 c ompounds w ere di vided i nto a
training s et a nd te st s et b y allowing S PSS to s oftware50 to r andomly select ha lf of t he
experimental data points. T he selected compounds served as the training set and the remaining
compounds became the test set. Regression analysis of the training set experimental values gave
the equation
∆HSolv,W (kJ/mol) = -13.572(0.635) + 9.211(1.174)E + 1.748(1.003)S -
31.460(1.561)A -41.665(1.103)B - 6.008(0.280)L (5.10)
(N = 184, SD = 3.58, R2 = 0.967, R2adj = 0.966, and F = 1029.4).
The equation coefficients of the training set are very similar to the coefficients for the full data
set showing that the training data set is a representative sample of the total data set. The training
set equation was then used to predict ∆HSolv,W values for the 184 compounds in the test set. For
the pr edicted a nd e xperimental v alues, I find t hat S D = 3.83, a verage a bsolute e rror ( AAE) =
3.19, and average error (AE) = -0.16. There is therefore very little bias in the predictions using
52
Eq. 5.8 with AE equal to -0.16 kJ/mol. The test and training set analyses were performed three
times. This is the first time that any predictive assessment of an equation for ∆HSolv,W has been
made.
My literature s earch for 1 -octanol f ound 138 enthalpies of s olvation va lues (see T able
S5.2 in Supplemental Materials). Applying the general solvation equations to these values using
Minitab software yields
∆HSolv,OTOH = -6.49(0.57) - 1.04(1.13)E + 5.89(1.39)S - 53.99(2.39)A -
8.99(1.36)B - 9.18(0.18)L (5.11)
(N = 138, SD = 2.66, R2 =0.988, F = 2242.0)
∆HSolv,OTOH = 1.57(1.19) - 13.34(1.75)E +0.32(2.37)S - 58.76(4.10)A -
7.63(2.33)B - 34.05(1.20)V (5.12)
(N = 138, SD = 4.53, R2 = 0.966, F = 752.0).
Equation 5.11 covers a r ange of va lues s panning 97 kJ /mol a nd i s r ecommended f or t he
prediction of ∆HSolv,OTOH over Eq. 5.12. The standard deviation of Eq. 5.11 is better and its gas-
to-solvent p artition c oefficients r epresent the r are gases, i norganic g ases, p olyaromatic
hydrocarbons, the polychorobiphenyls, and the polychloronaphthalenes. The descriptors for all
of the polychlorobiphenyls85 and a ll the polychloronaphthalenes86 were already known making
the prediction of ∆HSolv,OTOH trivial for these environmental pollutants.
To test the predictive ability of Eq. 5.11, I split the data set into a training and test set just
as I did for the water data set. The regression analysis of the 69 training set values resulted in the
equation
53
∆HSolv,OTOH = -6.48(0.83) - 1.24(1.54)E + 7.35(1.95)S - 54.81(3.11)A -
8.42(1.81)B - 9.38(0.24)L (5.13)
(N = 69, SD = 2.60, R2 = 0.989, F = 1180.1).
There is very little difference between the equation coefficients for the full dataset (Eq. 5.11) and
the tr aining d ata s et correlations ( Eq. 5.13) in dicating th at th e tr aining s et c overs a s imilar
chemical s pace t o t hat of t he t otal s et. T he t raining s et e quation w as t hen us ed t o pr edict
∆HSolv,OTOH for the remaining 69 compounds in the test set. For the predicted and experimental
values, I find that AE = 0.08, AAE = 2.07, SD = 2.79,and RMSE = 2.77 kJ/mol. There is almost
no bias in the predictions, and these statistics confirm that the full equation can be used to predict
further values of ∆HSolv,OTOH to within a SD of about 2.8 kJ/mol.
5.3.2. Carbon Tetrachloride and Toluene
Results and Discussion
I have as sembled i n Table S 5.3 (Supplemental M aterials) values of ∆HSolv,CT for 1 77
gaseous solutes dissolved in carbon tetrachloride covering a reasonably wide range of compound
type and d escriptor v alues. P reliminary analysis o f t he ex perimental data yielded a co rrelation
equation,
∆HSolv,CT (kJ/mol) = −6.402(0.377) + 3.583(0.708)E − 4.803(0.750)S −
0.877(1.078)A − 7.015(0.741)B − 8.898(0.130)L (5.14)
(N = 177, SD = 2.066, R2 = 0.984, R2adj = 0.984, F = 2141.4)
that had a relatively small numerical value for the A-coefficient. The A-coefficient was set equal
54
to zero for the Abraham model, and the final regression analyses were performed to give,
∆HSolv,CT (kJ/mol) = −6.441(0.374) + 3.517(0.703)E − 4.824(0.749)S −
7.045(0.740)B − 8.886(0.129)L (5.15)
(N = 177, SD = 2.070, R2 = 0.984, R2adj = 0.984, F = 2681.8)
∆HSolv,CT (kJ/mol) = 3.281(0.671) − 6.024(0.893)E − 14.130(1.078)S −
3.383(1.563)A − 4.729(1.049)B − 34.154(0.698)V (5.16)
(N = 177, SD = 2.84, R2 = 0.970, R2adj = 0.969, F = 1133.6).
There was very little decrease in descriptive ability resulting from setting the a-coefficient equal
to zero. The standard deviation increased very slightly from SD = 2.066 (Eq. 5.14) to 2.070 (Eq.
5.15). I did c onsider t he pos sibility of s etting t he b-coefficient e qual t o z ero; how ever, t his
caused the standard deviation to increase significantly to SD = 2.55.
55
Figure 5.3. A plot of the calculated values of ∆HSolv,CT in Eq. 5.15 against the observed values
All regression analyses were performed using SPSS statistical software. Both Eqs. 5.15
and 5.16 are s tatistically v ery good w ith s tandard d eviations of 2. 070 a nd 2.84 kJ/mol,
respectively, for a data set that covers a range o f 105 kJ/mol. See Figure 5.3 for a plot of the
calculated values of ∆HSolv,CT based on E q. 5.15 against the observed values. Equation 5.15 is
slightly th e b etter equation s tatistically, and f rom a th ermodynamic s tandpoint Eq. 5.15 is th e
enthalpic t emperature d erivative o f t he A braham m odel’s g as-to c ondensed pha se t ransfer
equation. Eq. 5.16 might be more useful in some predictive applications, in instances where the
L-descriptor i s not know n. Eq. 5.16 uses t he McGowan volume, V-descriptor, which i s easily
calculable from t he i ndividual a tomic s izes a nd num bers of bonds i n t he m olecule83. N o
noticeable pattern w as observed r egarding t he m odel’s ab ility t o describe m ore accu rately any
particular class of compound. The l argest deviation be tween the observed and ba ck-calculated
values for Eq. 5.15 is for 1-nitronaphthalene (∆HSolv,CT = −64.4 kJ·mol−1 (obs.) versus ∆HSolv,CT
= −73 .2 kJ·mol−1 (calc.)), followed by diiodomethane (∆HSolv,CT = −41 .9 kJ ·mol−1 (obs.) versus
56
∆HSolv,CT = −33 .4 kJ ·mol−1 (calc.)), 1 5-crown-5 ( ∆HSolv,CT = −83 .4 k J·mol−1 (obs.) ve rsus
∆HSolv,CT = −76 .9 kJ ·mol−1 (calc.)), a nd 2,2,4, 4-tetramethyl-3-pentanone ( ∆HSolv,CT = −44 .9
kJ·mol−1 (obs.) versus ∆HSolv,CT = −54.3 kJ·mol−1 (calc.)).
The enthalpy of solution for solutes dissolved in carbon tetrachloride has been considered
in s everal e arlier publ ications. Carbon t etrachloride, as w ell as cyclohexane t etrachloride, h as
been used as an inert solvent in the “pure base” model of Arnett et al.87,88 and in the “E and C”
model of Drago et al.89,90 for obtaining enthalpies of complex formation. Neither approach was
capable of pr edicting enthalpies of s olvation i n c arbon t etrachloride. S olomonov a nd
coworkers91 proposed a simple method for extracting specific solute–solvent i nteractions f rom
measured enthalpies of s olvation. T he m ethod a ssumed t hat t he di fference b etween t he
nonspecific i nteraction contribution i n t he s olvation e nthalpy f or t he s olute di ssolved i n t he
desired s olvent a nd di ssolved i n c arbon t etrachloride w as pr oportional t o t he di fference i n t he
nonspecific i nteractional s olvation e nthalpic c ontribution of t he solute i n s olvents c arbon
tetrachloride a nd c yclohexane. W hile t he a uthors di d e xamine s everal pos sible r elationships
between the calculated proportionality constant and different solvent properties, there was never
a mathematical expression given that allowed outright predictions of the enthalpies of solvation
(or solution) of solutes in carbon tetrachloride. To my knowledge, Eqs. 5.15 and 5.16 are the first
expressions t hat a llow s uch pr edictions. In o rder t o a ssess t he p redictive ability o f Eq. 5.15, I
divided the 177 da ta points into a t raining set and a t est set by a llowing the SPSS software to
randomly select h alf o f t he ex perimental d ata points. T he s elected d ata p oints b ecame t he
training set and the compounds that were left served as the test set. Analysis of the experimental
data in the training set gave
∆HSolv,CT (kJ/mol)= − 6.808(0.500) + 3.795(0.948)E − 5.109(1.037)S −
57
5.248(1.082)B − 8.900(0.159)L (5.17)
(with N = 89, SD = 2.04, R2 = 0.986, R2adj = 0.985 and F = 1452.5).
Again, t he A-coefficient w as s et eq ual t o zero. T here i s v ery l ittle difference i n t he
equation co efficients for t he f ull d ataset an d t raining d ataset correlations. T he t raining s et
equation was then used to predict ∆HSolv,CT values for the 88 c ompounds in the test set. For the
predicted and experimental values, I find that SD = 2.23, AAE (average absolute error) = 1.52,
and AE (average error) = − 0 .1810. There is therefore very little bias in the predictions using Eq.
5.17 with AE equal to − 0.1810 kJ/mol.
Figure 5.4. A plot of the calculated values of ∆HSolv,Tol in Eq. 5.18 against the observed values
In Table S5.4 (Supplemental Material) are collected values of the enthalpies of solvation
of 108 g aseous s olutes i n t oluene, w hich i s an a romatic h ydrocarbon s olvent. R egression
analyses of the experimental ∆HSolv,Tol data in accordance with the Abraham model yielded
∆HSolv,Tol = −5.291(0.425) + 3.511(1.169)E − 12.943(1.170)S − 6.317(1.685)A −
58
4.434(1.008)B − 8.382(0.156)L (5.18)
(N = 108, SD = 2.19, R2 = 0.987, R2adj = 0.986, F = 1558.7)
∆HSolv,Tol = 4.199(0.756) − 7.143(1.534)E − 20.440(1.629)S − 10.006(2.353)A −
3.439(1.407)B − 32.235(0.843)V (5.19)
(N = 108, SD = 3.03, R2 = 0.975, R2adj = 0.974, F = 804.7).
Both E qs. 5.18 a nd 5.19 are s tatistically very good w ith s tandard de viations of 2.19 and 3.03
kJ/mol for a data set that covers a range of 116 kJ/mol. Figure 5.4 compares the calculated values
of ∆HSolv,Tol based on E q. 5.18 against the observed values. I did consider setting the A- and/or
B-coefficients in Eq. 5.18 equal to zero; however, this led to a much poorer correlation (SD =
2.33 with A = 0; SD = 2.39 with B = 0; SD = 2.61 w ith both A = 0 a nd B = 0). No noticeable
pattern w as obs erved regarding t he m odel’s a bility t o d escribe m ore a ccurately an y p articular
class of compound. The largest deviation between the observed and back-calculated values for
Eq. 5.18 is fo r 18-crown-6 (∆HSolv,Tol = −106 .0 kJ /mol (obs.) ve rsus ∆HSolv,Tol = −97 .1 kJ /mol
(calc.)), f ollowed b y 2, 2,4,4-tetramethyl-3-pentanone ( ∆HSolv,Tol = −43 .0 kJ /mol (obs.) ve rsus
∆HSolv,Tol = −51.1 kJ/mol (calc.)) and 1-nitronaphthalene (∆HSolv,Tol = −69.5 kJ/mol (obs.) versus
∆HSolv,Tol = −62 .4 kJ /mol (calc.)). 1 -Nitronaphthalene a nd 2,2,4,4 -tetramethyl-3-pentanone
exhibited the larger of the deviations noted for the carbon tetrachloride correlation. Two possible
explanations for the large deviations for 1-nitronaphthalene and 2,2,4,4-tetramethyl-3-pentanone
would be e rrors i n t he e nthalpy of s ublimation a nd e nthalpy of va porization da ta us ed i n
calculating the enthalpies of solvation from the measured enthalpies of solution, or perhaps the
solute descriptors need to be recalculated. To my knowledge there has been no previous attempt
59
to correlate ∆HSolv,Tol data.
In order to assess the predictive ability of Eq. 5.18, I divided the 108 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental data points. The s elected data points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,Tol = −5.107(0.525) + 0.226(1.583)E − 11.339(1.510)S − 2.250(2.385)A
− 6.984(1.324)B − 8.272(0.186)L (5.20)
with N = 54, SD = 2.00, R2 = 0.991, R2adj = 0.990 and F = 1085.4. There is very little difference
in the equation coefficients for the full dataset and training dataset correlations. The training set
equation was then used to predict ∆HSolv,Tol values for the 54 compounds in the test set. For the
predicted and experimental values, I find that SD = 2.66, AAE (average absolute error) = 1.919,
and AE (average error) = 0.478. T here is therefore very l ittle bias in the predictions using Eq.
5.20 with A E e qual t o 0.478 kJ /mol. A n unc ertainty/error of ± 2 kJ /mol in t he e nthalpy of
solvation results in an error of s lightly less than 0.04 log uni ts in extrapolating a log10K value
measured at 298.15 to 313.15 K. This level of error will be sufficient for most practical chemical
and e ngineering a pplications. T he c orrelations pr esented i n t his s tudy further doc ument t he
applicability of t he A braham s olvation pa rameter m odel t o di fferent s olute t ransfer pr operties.
Past s tudies have shown that the basic model describes a wide range of equilibrium properties
that are governed by the Gibbs energy for solute transfer between two condensed phases. In the
present s tudy I find t hat t he m odel a lso pr ovides a n a ccurate m athematical de scription of t he
enthalpic c ontributions t o t he G ibbs e nergy, a nd b y i nference, one can assume t hat t he m odel
60
describes t he e ntropic c ontributions a s w ell. T he de rived c orrelations for t he enthalpies of
solvation pr ovide one a dditional m ethod f or c alculating a num erical va lue of t he Abraham L-
descriptor in the absence of accurate gas chromatographic retention data.
5.3.3. DMSO and Propylene Carbonate
Results and Discussion
Assembled i n T able S 5.5 (Supplemental M aterial) are values o f ∆HSolv,DMSO for 150
gaseous solutes di ssolved in dimethyl sulfoxide (DMSO) covering a r easonably w ide r ange o f
compound type and descriptor values.
Analysis of the experimental data yielded the following correlation equations:
∆HSolv,DMSO (kJ/mol) = −2.546(0.703) − 0.329(0.952)E − 18.448(1.139)S
−47.419(1.653)A − 5.861(1.004)B − 6.380(0.197)L (5.21)
(with N = 150, SD = 2.80, R2 = 0.967, R2adj = 0.966, F = 850.6)
∆HSolv,DMSO (kJ/mol) = 2.184(0.845) − 7.233(0.951)E − 24.071(1.175)S −
50.992(1.744)A − 5.182(1.051)B − 22.301(0.723)V (5.22)
(with N = 150, SD = 2.92, R2 = 0.965, R2adj = 0.963, F = 779.8).
All regression analyses were performed using SPSS statistical software. Both Eqs. 5.21 and 5.22
are s tatistically very good with s tandard deviations of 2.80 a nd 2.92 kJ/mol for a da ta set that
covers a range of 91.76 kJ /mol. See Figure 5.5 for a plot of the calculated values of ∆HSolv,DMSO
based on E q. 5.21 against t he obs erved v alues. E q. 5.21 is s lightly the b etter eq uation
statistically, a nd f rom a th ermodynamic s tandpoint E q. 5.21 is th e enthalpic te mperature
61
derivative of the Abraham model’s gas-to-condensed phase transfer equation. Eq. 5.22 might be
more useful i n some pr edictive applications i n i nstances where t he L-descriptor i s not known.
Eq. 5.22 uses the McGowan volume, V descriptor, which is easily calculable from the individual
atomic sizes and numbers of bonds in the molecule.83 To my knowledge, Eqs. 5.21 and 5.22 are
the f irst expressions t hat a llow one t o pr edict t he e nthalpy of s olvation of gaseous s olutes i n
DMSO.
Figure 5.5. A plot of the calculated values of ∆HSolv,DMSO on Eq. 5.21 against the observed values.
Each o f t he eq uation c oefficients i n t he A braham m odel en codes ch emical i nformation. F or
example t he l arge a-coefficient in E q. 5.21 indicates th at DMSO exhibits s trong h ydrogen-
bonding ba sicity c haracter, w hich is c onsistent w ith the mo lecule’s mo lecular s tructure,
CH3S(O)CH3. T he t wo lone e lectron pa irs on t he ox ygen a tom s erve as a cceptor s ites f or
hydrogen-bond formation. The small, nonzero b-coefficient suggests a very weak hydrogen-bond
acidity c haracter. W hile di methyl s ulfoxide i s not nor mally c onsidered to pos sess a ny a cidic
62
hydrogen(s), s everal pu blished s tudies ha ve m entioned t he pos sibility t hat one o f t he C –H
hydrogens m ay e ngage in h ydrogen bondi ng. F ujimoto et al .92 rationalized t he pr oton N MR
spectra of s olutions of di methyl s ulfoxide, 2 -propanol a nd/or a cetone w ith t etrasulfonated
derivatives of calix[4]resorcarene dissolved in D2O in terms of well-defined complexes resulting
from C H–π interactions b etween t he el ectron r ich b enzene r ings o n t he cal ix[4]resorcarene
derivatives and the polarized C–H bonds on the three guest molecules.
The authors presented a very compelling argument for why CH– π interactions should be
regarded as C–H· · ·π hydrogen bonding. Leggett93 had earlier estimated acidity parameters for
solvents l ike di methyl s ulfoxide, pr opylene c arbonate, N,N-dimethylformamide a nd
butyrolactone t hat w ere believed t o not pos sess hydrogen donor ability. At t his t ime I do not
place too much significance on the nonzero b-coefficient in Eq. 5.21 as it possible to still obtain
a very good correlation:
∆HSolv,DMSO (kJ/mol)= −2.767(0.778) + 2.477(0.911)E − 22.053(1.062)S −
50.701(1.724)A − 6.563(0.216)L (5.23)
(N = 150, SD = 3.11, R2 = 0.969, R2adj = 0.967, F = 539.1)
by setting the b-coefficient equal to zero. The s tandard deviation increased s lightly f rom SD =
2.80 ( Eq. 5.21) t o S D = 3.11 (Eq. 5.23). G iven t he l ikely experimental u ncertainty i n t he
measured enthalpy of solvation data there is virtually no difference in the two correlations.
In order to assess the predictive ability of Eq. 5.21, the 150 data points were divided into
a t raining s et an d a t est s et b y allowing t he S PSS s oftware t o randomly s elect h alf o f t he
experimental da ta points. The selected da ta points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
63
∆HSolv,DMSO (kJ/mol) = −4.505(0.928) + 1.003(1.406)E − 21.371(1.565)S
−47.478(2.190)A − 1.793(1.492)B − 5.816(0.272)L (5.24)
(with N = 75, SD = 2.49 ,R2 = 0.969, R2adj = 0.967, F = 434.3).
There is very little difference in the equation coefficients for the full dataset and training dataset
correlations, thus showing that the t raining set of compounds i s a representative sample of the
total da ta set. The t raining set equation was then used to predict ∆HSolv,DMSO values for the 75
compounds in the test set. For the predicted and experimental values, I find that SD = 3.57, AAE
(average absolute error) = 2.288, and AE (average error) = −0.797. There is therefore very little
bias in the predictions using Eq. 5.24 with AE equal to −0.797 kJ/mol.
In Table S5.6 (Supplemental Material) are collected values of the enthalpies of solvation
of 107 gaseous solutes in propylene carbonate. Regression analyses of the experimental ∆HSolv,PC
data in accordance with the Abraham model yielded:
∆HSolv,PC (kJ/mol) = −4.377(0.791) + 0.478(1.510)E − 13.370(1.526)S −
17.898(2.185)A − 12.596(1.362)B − 6.685(0.299)L (5.25)
(N = 107, SD = 2.61 ,R2 = 0.967, R2adj = 0.965, F = 584.5)
∆HSolv,PC (kJ/mol) = 1.409(0.987)−7.886(1.336)E − 18.776(1.535)S −
20.632(2.205)A − 11.636(1.413)B − 24.199(1.056)V (5.26)
(N = 107, S.D. = 2.55, R2 = 0.964, R2adj = 0.962, F = 564.9) .
Both E qs. 5.25 and 5.26 are s tatistically very good w ith s tandard de viations of 2.61 and 2.55
64
kJ/mol for a data set that covers a range of 103.13 kJ /mol. Figure 5.6 compares the calculated
values of ∆HSolv,PC based on E q. 5.25 against t he observed values. I did not f ind any previous
attempt to correlate ∆HSolv,PC data in my search of the published chemical literature.
Figure 5.6. A plot of the calculated values of ∆HSolv,PC on Eq. 5.25 against the observed values.
I assessed the predictive ability of Eq. 5.25 by dividing the 107 data points into a training
set and a test set as before. Analysis of the experimental data in the training set gave
∆HSolv,PC (kJ/mol) = −1.618(0.924) + 2.630(1.953)E − 17.421(1.873)S −
21.095(2.464)A − 10.426(1.606)B − 7.420(0.373)L (5.27)
with N = 54, SD = 2.03, R2 = 0.985, R2adj = 0.983 and F = 629.8. There is very little difference in
the equation coefficients for the full dataset and training dataset correlations.
The training set equation was then used to predict ∆HSolv,PC values for the 53 compounds
in th e te st s et. For th e p redicted and ex perimental v alues, I find t hat S D = 3.50 k J/mol, A AE
(average absolute error) = 3.46, and AE (average error) = 0.793. There is therefore very little bias
65
in t he pr edictions us ing Eq. 5.27 with A E equal to 0.793 kJ /mol. A n unc ertainty/error of ± 2
kJ/mol i n t he e nthalpy of s olvation r esults i n a n e rror of s lightly l ess t han 0.04 l og uni ts i n
extrapolating a log K value measured at 298.15–313.15 K. This level of error will be sufficient
for most practical chemical and engineering applications. The correlations presented in this study
further document the applicability of the Abraham solvation parameter model to different solute
transfer pr operties. P ast s tudies ha ve s hown t hat the b asic m odel d escribes a w ide r ange of
equilibrium pr operties that ar e governed b y t he Gibbs en ergy for s olute t ransfer b etween two
condensed phases or between a gas and condensed phase.
In t his study, it is f ound that t he m odel al so p rovides an a ccurate m athematical
description of the enthalpic contributions to the Gibbs energy, and by inference, one can assume
that the model describes the entropic contributions as well.
5.3.4. Dibutyl Ether and Ethyl Acetate
Results and Discussion
I have assembled i n Table S5.7 (Supplemental M aterial) values of ∆ HSolv,BE for 68 gaseous
solutes di ssolved in di butyl e ther c overing a r easonably w ide r ange of c ompound t ype a nd
descriptor values. Preliminary analysis of the experimental data yielded a correlation equation
∆HSolv,BE = −7.205(0.787) + 6.190(1.386)E − 7.583(1.179)S − 36.482(1.595)A +
4.093(1.108)B − 9.263(0.198)L (5.28)
(N= 68, SD = 1.564, R2 = 0.976, R2adj = 0.974 F = 495.9)
66
that had relatively small numerical value for the b-coefficient. The coefficient for the B solute
descriptor was set equal to zero as would be expected for the transfer of a gaseous solute into an
ether solvent having no a cidic H-bond character, and the final regression analyses performed to
give
∆HSolv,BE (kJ/mol) = − 6.366(0.826) + 3.943(1.365)E − 5.105(1.062)S −
33.970(1.581)A − 9.325(0.217)L (5.29)
(N= 68, SD = 1.882, R2 = 0.970,R2adj = 0.968, F = 513.5)
∆HSolv,BE (kJ/mol) = 0.324(1.199) − 6.480(1.748)E − 14.644(1.534)S −
37.094(2.047)A + 4.354(1.418)B − 32.989(0.913)V (5.30)
(N= 68, SD = 2.003, R2 = 0.960, R2adj = 0.957, F = 298.0).
There was very little decrease in descriptive ability resulting from setting the coefficient equal to
zero. The s tandard deviation increased very s lightly from SD = 1.564 ( Eq. 5.28) to 1.882 ( Eq.
5.29), w hich is l ess th an th e e stimated uncertainty associated w ith t he experimental d ata. T he
intercorrelation matrices, in R2, between the descriptors used in Eqs. 5.29 and 5.30 are given in
Table 5.1 and Table 5.2, r espectively. Inter-correlations be tween m ost of t he de scriptors a re
negligible, and even the largest inter-correlation between E and S, 0.466 (Eq. 5.29) and 0.546
(Eq. 5.30), is not too significant. The inter-correlation between the E and S solute descriptors has
been n oted i n e arlier p apers.37,42,44,94. A ll r egression an alyses w ere p erformed u sing S PSS
statistical software.50
67
Table 5.1. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.29
E S A L
E 1.000
S 0.466 1.000
A 0.091 0.007 1.000
L 0.054 0.018 0.110 1.000
Table 5.2. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.30
E S A B V
E 1.000
S 0.546 1.000
A 0.148 0.113 1.000
B 0.213 0.303 0.181 1.000
V 0.000 0.035 0.075 0.006 1.000
Both Eqs. 5.29 and 5.30 are statistically very good with standard deviations of 1.882 and
2.003 kJ/mol for a data set that covers a range of about 53 kJ/mol. See Figure 5.7 for a plot of the
calculated values of ∆HSolv,BE based on Eq. 5.29 against the observed values. Eq. 5.29 is slightly
the better equation statistically, and from a thermodynamic standpoint Eq. 5.29 is the enthalpic
temperature derivative o f t he Abraham m odel’s gas-to-condensed phase transfer equation. The
Abraham solute descriptors are taken to be independent of temperature.95,96.
68
Figure 5.7. A plot of the calculated values of ∆HSolv,BE based on Eq. 5.29 against the observed values.
Equation 5.30 might be more useful in some predictive applications in instances where
the L-descriptor i s not known. Equation 5.30 uses the McGowan volume, V-descriptor, that is
easily calculable from the individual atomic sizes and numbers of bonds in the molecule.83
I am aware of one group method and an earlier application of the Abraham model for estimating
enthalpies of solvation in dibutyl ether. Bernazzani et al .97 predicted the ∆HSolv,BE values of 59
compounds i n di butyl ether t o w ithin a s tandard de viation of 1.59 kJ /mol us ing 22 s tructural
fragment v alues d educed b y a multiple least-squares regression an alysis o f t he en tire d ata s et.
The authors’ second method, in which the CH2 group value was preassigned an average of the
increments of t he e nthalpies of s olvation i n ho mologous s eries of a lkanes, e thers, 1 -alkanols,
ketones, amines and chloroalkanes, gave a slightly larger deviation of 3.78 kJ /mol. The method
of Eq. 5.29 is quite comparable and predicts the enthalpies of solvation in dibutyl ether to within
a s tandard d eviation of 1.882 kJ /mol. B ernazzani et al .98 described t he ∆HSolv,BE values of 28
compounds in dibutyl ether using the Abraham equation and molecular descriptors. The authors
69
obtained a standard deviation of 0.97 kJ/mol for their correlation equation for the 28 compounds
that spanned at most a range of 50 kJ/mol. The enthalpy of solvation database for dibutyl ether
contains only 68 solutes. It would be difficult to obtain a good training set correlation by using
only half of the experimental values. To assess the predictive ability of Eq. 5.29, the parent data
points were divided into three subsets (A, B, and C) as follows: the 1st, 4th, 7th, etc. data points
comprise the first subset (A); the 2nd, 5th, 8th, etc. data points comprise the second subset (B);
and t he 3r d, 6t h, 9t h, etc. da ta poi nts c omprise the t hird s ubset ( C). T hree t raining s ets w ere
prepared as combinations of two subsets (A and B), (A and C), and (B and C). For each training
set, a correlation was derived:
Training Set (A and B)
∆HSolv,BE (kJ/mol) = −6.270(0.780) + 4.044(1.351)E − 4.377(1.044)S −
34.356(1.525)A − 9.414(0.201)L (5.31)
(N= 46, SD = 1.394, R2 = 0.984, R2adj = 0.983, F = 633.3)
Training Set (A and C)
∆HSolv,BE (kJ/mol) = −6.374(1.094) + 4.079(1.761)E − 5.982(1.418)S −
33.789(1.982)A − 9.275(0.310)L (5.32)
(N= 45, SD = 1.748, R2 = 0.966, R2adj = 0.963, F = 286.4)
Training Set (B and C)
∆HSolv,BE (kJ/mol) = −6.571(1.290) + 3.729(1.952)E − 5.201(1.488)S −
33.328(2.562)A − 9.241(0.315)L (5.33)
(N= 45, SD = 1.975, R2 = 0.956, R2adj = 0.952, F = 218.5).
70
Each validation computation gave a training set correlation equation having coefficients
not t oo di fferent from t hat obt ained f rom t he p arent 68 compound da tabase. T he t raining s et
equations were then used to predict ∆HSolv,BE values for the compounds in the respective test sets
(A, B, and C). Computations on t he three test sets yielded: s tandard deviations of SD = 1.680
(Test set C), SD = 1.734 (Test set B) and S.D. = 1.155 (Test set A); Average Absolute Errors of
AAE = 1.618 (Test set C), AAE = 1.323 (Test set B) and AAE = 0.706 (Test set A); and Average
Errors of AE = −0.302 (Test set C), AE = 0.462 (Test set B) and AE = −0.108 (Test set A). There
is therefore very little bias in the predictions based on Eqs. 5.31 – 5.33.
In Table S5.8 (Supplemental M aterial) are co llected v alues o f t he m olar en thalpies o f
solvation of 79 c ompounds i n e thyl a cetate. R egression a nalysis of t he e xperimental ∆HSolv,EA
data in accordance with the Abraham model yielded
∆HSolv,EA (kJ/mol) = −7.063(0.705) + 4.671(0.963)E − 15.141(1.084)S −
28.763(1.423)A − 7.691(0.169)L (5.34)
(N= 79, SD = 2.156, R2 = 0.977, R2adj = 0.976, F = 797.7)
∆HSolv,EA (kJ/mol) = 0.679(0.909) − 4.403(1.146)E − 20.424(1.504)S −
32.125(1.543)A − 1.299(1.256)B − 28.598(0.670)V (5.35)
(N = 79, SD = 2.279, R2 = 0.975, R2adj = 0.973, F = 561.3).
Again, the b·B term is eliminated from Eq. 5.34 because ethyl acetate has no acidic hydrogen-
bonding capability. The b·B term was retained in Eqs. 5.30 and 5.35 as there i s no theoretical
reason that I know of for setting the term equal to zero. There is little intercorrelation between
the descriptors in Eqs. 5.34 and 5.35; the maximum intercorrelation is R2 = 0.524 (Eq. 5.34) and
71
R2 = 0.664 (Eq. 5.35) between E and S.
In t he or iginal A braham m odel f or g as-to-condensed pha se t ransfer t he e quation
coefficients encode chemical i nformation about t he condensed solubilizing solvent media.99,100
For the water-to-organic solvent transfer expression the coefficients represent differences in the
properties of t he or ganic s olvent r elative t o t hose of w ater. W hile I have us ed t he A braham
expression f or w ater-to-organic s olvent t ransfer to c orrelate e nthalpies o f s olvation f or s olutes
dissolved in dibutyl e ther (Eq. 5.30) and i n et hyl acet ate (Eq. 5.35) I realize t hat t he equation
coefficients have lost their original significance. Eqs. 5.30 and 5.35 are not the 1/T derivative of
the A braham m odel w ater-to-organic s olvent l og P correlation. B oth E qs. 5.34 and 5.35 are
statistically ve ry good with s tandard de viations of 2.1 56 a nd 2.279 kJ /mol f or a da ta s et t hat
covers a range of about 76 kJ/mol. Figure 5.8 compares the calculated values of ∆HSolv,EA based
on E q. 5.34 against t he observed va lues. I know of no previous at tempt to co rrelate ∆HSolv,EA
data.
Figure 5.8. A plot of the calculated values of ∆HSolv,EA based on Eq. 5.34 against the observed values.
To a ssess t he pr edictive a bility of E q. 5.34, t he 79 da ta poi nts w ere di vided i nto t hree
subsets (A, B, C) as before: the 1st, 4th, 7th, etc. data points comprise the first subset (A); the
2nd, 5th, 8th, e tc. da ta points comprise t he second subset (B); and. the 3r d, 6th, 9th, e tc. da ta
points comprise the third subset (C).
72
Three training sets were prepared as combinations of two subsets (A and B), (A and C),
and (B and C). For each training set, a correlation was derived:
Training Set (A and B)
∆HSolv,EA (kJ/mol) = −7.893(0.747) + 5.262(1.233)E − 15.641(1.240)S −
26.597(1.567)A − 7.481(0.188)L (5.36)
(N= 53, SD = 1.914, R2 = 0.980, R2adj = 0.979, F = 596.5)
Training Set (A and C)
∆HSolv,EA = −5.967(1.013) + 5.638(1.196)E − 16.147(1.431)S − 31.228(1.842)A −
7.919(0.227)L (5.37)
(N= 53, SD = 2.211, R2 = 0.974, R2adj = 0.972, F = 445.5)
Training Set (B and C)
∆HSolv,EA (kJ/mol) = −6.945(0.858) + 3.826(1.154)E −14.322(1.330)S −
28.692(1.812)A − 7.714(0.207)L (5.38)
(N= 52, SD = 2.201, R2 = 0.980, R2adj = 0.978, F = 574.0)
Each validation computation gave a training set correlation equation having coefficients not too
different from that obtained from the parent 79 compound database. The training set equations
were then used to predict ∆HSolv,EA values for the compounds in the respective test sets (A, B and
C). Computations on the three test sets yielded: standard deviations of S.D. = 2.757 (Test set C),
S.D. = 2.309 ( Test s et B) a nd S .D. = 2.121 ( Test s et A ); A verage A bsolute E rrors of A AE =
73
2.189 (Test set C), AAE = 1.508 (Test set B) and AAE = 1.623 (Test set A); and Average Errors
of AE = − 0.360 (Test set C), AE = 0.445 (Test set B) and AE = − 0.427 (Test set A). There is
therefore very little bias in the predictions based on Eqs. 5.36 – 5.38.
More t han 40 di fferent water-to-organic s olvent, g as-to-organic s olvent, g as-to-humic
acid and/or gas-to-folvic acid partition systems have been reported in the published chemical and
environmental l iterature ba sed on t he A braham m odel a s m odified by G oss.101-105 While I
personally prefer to use the Abraham model for the reasons discussed previously106; however, I
do r ecognize t hat t he Goss m odification i s now be ing u sed to correlate experimental p artition
coefficient and sorption data (See Eq. 5.39)
∆HSolv(kJ/mol) = c + s·S + a·A + b·B + l·L + v·V (5.39)
where the lower case letters c, s, a, b, l and v r epresent the properties of the solvent. The latter
model us es the f ive A braham solute d escriptors S, A, B, V and L. T he A braham E solute
descriptor i n equations are replaced b y the M cGowan vol ume ( Abraham V solute de scriptor),
which is easily calculable from the individual atomic sizes and number of bonds in the molecule.
In the Abraham model, the V descriptor generally appears in the expression for solute t ransfer
between two condensed phases
SP = c + e·E + s·S + a·A + b·B + v·V (5.40)
where SP is some property of a series of solutes in a fixed phase. Equation 5.40 has been used on
few o ccasions t o describe gas-to-condensed phase t ransfer processes in p redictive applications
where the L-descriptors were not known.
Past computations106,107 have shown that there is very little difference in the descriptive
74
ability of t he A braham model a nd G oss m odified A braham m odel w hen a pplied t o pa rtition
coefficient data. The descriptive abilities of the two models have not been compared using other
solute pr operties. T he s ingle comparison involving ∆HSolv,W data us ed di fferent m ethodologies
and datasets.
Goss76 proposed an indirect method for estimating ∆HSolv,W on the basis of the Eq. 5.39.
The au thor u sed t he experimental gas-to-water p artition c oefficients a t 2 98 K reported b y
Abraham et al.84, along with the enthalpies of solvation compiled by Kühne et al.108 in order to
calculate the gas-to-water partition coefficients at several temperatures between 273 and 318 K.
A separate log Kw (where Kw is the gas-to-water partition coefficient) was developed for each
temperature s tudied ba sed on Eq. 5.39. The de rived l og Kw correlations w ere t hen u sed t o
generate p redicted l og Kw values at each t emperature, w hich w ere t hen plotted ve rsus 1/ T.
Enthalpies of solvation were back-calculated from the slopes of the resulting log Kw versus 1/T
curves for each of the 217 compounds studied. No statistical information was given in the paper
comparing the back-calculated and observed ∆HSolv,W values; however, the graphical comparison
the author presented showed deviations as large as 10–15 kJ/mol for many of the 217 compounds
studied. The ∆HSolv,W equation (Eq. 5.8) derived by Mintz et al .100 in Section 5.2.1 provided a
more ac curate p rediction o f ∆HSolv,W than di d t he i ndirect m ethod of G oss. T he e xperimental
∆HSolv,W database used in generating the equation derived by Mintz et al.100 was not the same as
the da tabase used b y Goss. Mintz et al .100 constructed their ∆HSolv,W database f rom publ ished
experimental d ata in t he t emperature r ange of 2 83–318 K . E xperimental da ta out side of t his
temperature w ere e xcluded f rom c onsideration. E nthalpies of s olvation a re t emperature
dependent a nd t he a uthors di d not w ant t o i ntroduce l arge e rrors i n t he da tabase b y i ncluding
experimental data far removed from 298 K. The Kühne et al.108 database used by Goss covered a
75
temperature range of from 0 to 100 ◦C. An assessment of the descriptive ability of the Abraham
model versus the Goss modified Abraham model needs to be performed using identical ∆HSolv,W
databases. As pa rt of t he c urrent s tudy m athematical c orrelations w ere de veloped f or bot h
dibutyl ether
∆HSolv,BE (kJ/mol) = − 4.350(1.111) − 8.983(1.551)S − 35.970(1.604)A +
3.530(1.095)B − 5.997(0.798)L − 11.730(2.913)V (5.41)
(N= 68, SD = 1.602, R2 = 0.974, R2adj = 0.972, F = 472.9)
and ethyl acetate
∆HSolv,EA (kJ/mol) = − 3.476(1.087) − 16.482(1.660)S − 30.388(1.399)A −
1.551(1.082)B − 4.330(0.732)L − 12.601(2.786)V (5.42)
(N = 79, SD = 2.055, R2 = 0.979, R2adj = 0.978, F = 694.0)
based on t he Goss modified Abraham model. Both equations provide very good descriptions of
the observed enthalpy o f solvation data, and are comparable in descriptive ability to Eqs. 5.29
and 5.34 based on the Abraham model. The slightly lower standard deviations for Eqs. 5.41 and
5.42 were likely t he r esult of t he one a dditional c urve-fit co efficient. The F-test t akes i nto
account the number of descriptors and hence the F-statistics for Eqs. 5.41 and 5.42 (472.9 and
694.0) are not quite as good as those for Eqs. 5.29 and 5.34 (513.5 and 797.7). The b·B term was
retained in Eqs. 5.41 and 5.42 as there is no theoretical reason that I know of for setting the term
equal t o z ero. W hen t he A braham m odel w as d eveloped each of the five t erms r epresented a
76
different type of molecular interaction as discussed above. The existing numerical values of the
Abraham solute d escriptors w ere determined ba sed on t he de fined five-term s eparation of
molecular in teractions. Goss e liminated the e· E term t hat i nvolved s olute–solvent i nteractions
arising through the presence of pol arizable e lectrons i n t he solute i n favor of adding a s econd
cavity effect. The l·L and v·V terms are both cavity “size” terms measuring the endoergic effect
of disrupting s olvent–solvent in teractions. S olute v olume/size is well c orrelated w ith mo lar
refraction and with polarizability, and the v·V and l ·L terms will also include exoergic solute–
solvent effects that arise through solute polarizability. There is no guarantee though that once the
e·E term is removed that all of its mathematical contribution will end up in the v·V and l·L terms.
Some of the r emoved polarizable effect may be mathematically distributed to the a ·A and b·B
terms. This is not expected to be a problem h ere as both t he a- and b-coefficients o f t he four
alkane solvents (hexane, heptane, hexadecane and cyclohexane) and two aromatic hydrocarbon
solvents (benzene and toluene) have fairly small numerical values. The correlation matrix, in R2,
between t he de scriptors us ed in E qs. 5.41 and 5.42 are g iven i n Table 5.3 and Table 5.4,
respectively. Examination of the numerical entries in Table 5.3 and Table 5.4 reveals that in the
Goss m odified ve rsion of t he A braham m odel t he solute descriptors ar e m ore highly i nter-
correlated, with R2 values as large as R2 = 0.937 (Eq. 5.41) and R2 = 0.953 (Eq. 5.42) between
the L and V solute descriptors. High inter-correlations were also noted between the L and S (V
and S) solute descriptors.
Table 5.3. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.41
S A B L V
S 1.000
A 0.106 1.000
77
B 0.256 0.156 1.000
L 0.716 0.113 0.157 1.000
V 0.740 0.158 0.133 0.937 1.000
Table 5.4. Inter-correlation matrix, in R2, for solute descriptors in Eq. 5.42
S A B L V
S 1.000
A 0.001 1.000
B 0.317 0.008 1.000
L 0.776 0.021 0.166 1.000
V 0.757 0.049 0.157 0.953 1.000
As not ed b y t wo of t he reviewers at th e time th is particular s tudy was s ubmitted f or
publication, i nter-correlations of t his magnitude be tween s olute de scriptors a re hi ghly
undesirable i n the development of QSPR correlations. If i nter-correlated s olute parameters a re
used, there could be many different sets of solvent parameters that fit the experimental data. If
this w ere t o ha ppen, then t he n umerical v alues o f s olvent p arameters obtained from in ter-
correlation lose their physical meaning. This is one of the reasons that the Abraham model uses
only L or V (and not both) in a derived correlation equation. While the Goss modified form of
the Abraham model has been used to mathematically correlate water-to-organic solvent, gas-to-
humic aci d and/or ga s-to-folvic a cid p artition s ystems n o o ne h as cr itically evaluated t he
equation co efficients t o determine i f t he cal culated values ar e r easonable g iven t he t ypes o f
molecular interactions that are believed to be present in the various partition systems studied by
78
the Goss modified Abraham model. Such a determination will require Goss modified Abraham
model e quation coefficients f or s everal t ypes o f p rocess, an d for a s everal d ifferent organic
solvents. Equation coefficients and the associated statistical information are given in Table 5.5
for t he G oss m odified Abraham model f or or ganic a nd gaseous s olutes di ssolved i n he xane,
heptane, he xadecane, cyclohexane, be nzene, t oluene, c arbon tetrachloride, c hloroform, 1,2 -
dichloroethane, methanol, ethanol, 1-butanol, 1-octanol, propylene carbonate, dimethyl sulfoxide
and w ater. T he ∆HSolv databases us ed i n d eriving t he correlations a re given i n earlier
publications12,94,99,100,109-111. Examination of the numerical entries reveals that the Goss modified
version of the Abraham model correlated the ∆HSolv data to within an overall average standard
deviation of 2.29 kJ /mol for water and the 17 or ganic solvents studied. The standard deviations
are comparable to those noted previously for the Abraham model correlations that were derived
from t he s ame ∆HSolv data sets. I defer di scussion of t he num erical va lues of t he e quation
coefficients until such time that ∆HSolv correlations become available for more of the other polar
organic solvents such as N,N-dimethylformamide and acetonitrile.
79
Table 5.5. Equation coefficients for ∆HSolv correlations based on the Goss modified Abraham model.
Solvent c s A b l v N SD R2
Hexane −3.164(0.680) −2.191(1.039) 0.755(1.270) 0.692(0.749) −6.746(0.425) −10.808(1.751) 118 1.663 0.989
Heptane −3.783(0.697) −2.312(1.037) −1.224(1.508) 1.179(0.840) −6.341(0.437) −11.276(1.780) 134 1.687 0.987
Hexadecane −2.968(0.710) −3.204(1.049) −1.505(1.126) 2.579(0.834) −6.786(0.467) −10.856(1.908) 102 1.601 0.988
Cyclohexane −5.059(0.538) 0.974(0.830) −0.510(0.939) −2.007(0.690) −7.631(0.352) −5.284(1.386) 201 1.828 0.985
Benzene −2.880(0.740) −11.713(1.206) −8.224(1.721) −5.085(0.898) −6.880(0.498) −5.892(1.963) 174 2.212 0.985
Toluene −3.660(0.923) −12.984(1.411) −6.298(1.769) −5.119(0.968) −6.877(0.612) −5.623(2.524) 108 2.229 0.986
Carbon tetrachloride -3.714(0.708) −6.522(0.985) −1.553(1.093) −6.982(0.730) −6.451(0.408) −9.325(1.763) 177 2.054 0.984
Chloroform −2.043(0.990) −17.802(1.516) −4.536(1.734) −17.429(0.956) −1.996(0.685) −23.780(2.594) 100 2.108 0.982
1,2-Dichloroethane −0.163(1.018) −19.040(1.488) −9.828(1.944) −8.196(1.035) −4.556(0.628) −12.097(2.400) 88 1.844 0.979
Methanol −7.172(0.806) −2.449(1.214) −37.225(1.199) −14.370(0.867) −8.646(0.522) 3.292(2.040) 188 2.739 0.982
Ethanol −6.300(1.080) −1.327(1.490) −11.042(1.236) −48.528(1.755) −8.113(0.600) −0.517(2.554) 111 2.531 0.982
1-Butanol −5.557(1.068) −2.183(1.712) −52.603(2.039) −3.689(1.180) −7.091(0.716) −6.087(2.919) 103 2.274 0.986
1-Octanol −6.672(0.741) 6.044(1.104) −53.656(2.373) −9.190(1.120) −9.663(0.336) 1.566(1.397) 138 2.591 0.989
Propylene carbonate −2.267(1.252) −16.484(1.830) −20.377(2.216) −10.693(1.316) −4.823(0.811) −7.524(3.250) 107 2.543 0.964
Dimethyl sulfoxide −2.390(0.958) −19.041(1.510) −47.799(1.781) −5.521(1.000) −6.189(0.706) −0.746(2.609) 150 2.791 0.968
Water −8.414(1.007) 0.732(1.285) −33.558(1.470) −43.462(0.958) −1.403(0.579) −17.313(2.466) 368 4.739 0.941
80
5.3.5. Chloroform and 1,2 Dichloroethane
Results and Discussion
I have assembled i n Table S 5.9 (Supplemental M aterial) values of ∆HSolv,CFM for 100
gaseous solutes dissolved in chloroform covering a reasonably wide range of compound type and
descriptor values. Analysis of the experimental data yielded the following correlation equations
∆HSolv,CFM (kJ/mol) = − 6.516(0.701) + 8.628(0.936)E − 13.956(1.160)S
−2.712(1.666)A − 17.334(0.958)B − 8.739(0.158)L (5.43)
(N = 100, S.D. = 2.10, R2 = 0.982, R2adj = 0.981, F = 1049.5)
∆HSolv,CFM (kJ/mol) = − 0.425(0.829) − 0.844(0.916)E − 20.735(1.251)S
−5.817(1.753)A − 16.434(1.003)B − 31.039(0.587)V (5.44)
(N = 100, SD = 2.19, R2 = 0.981, R2adj = 0.980, F = 964.5).
All regression analyses were performed using SPSS statistical software. Both Eqs. 5.43
and 5.44 are statistically very good with standard deviations of 2.10 and 2.19 k J/mol for a data
set t hat covers a r ange o f 106.89 kJ /mol. See Figure 5.9 for a p lot o f t he cal culated values o f
∆HSolv,CFM based on E q. 5.43 against t he obs erved va lues. E quation 5.44 is s lightly th e b etter
equation statistically, and from a thermodynamic standpoint Eq. 5.43 is the enthalpic temperature
derivative o f t he A braham m odel’s gas-to-condensed p hase t ransfer e quation. E quation 5.44
might be more useful in some predictive applications in instances where the L-descriptor is not
known. Equation 5.44 uses the McGowan volume, V-descriptor, that is easily calculable from the
individual a tomic s izes and numbers of bonds in the molecule78. To my knowledge, Eqs. 5.43
81
and 5.44 represent the f irst e xpressions t hat a llow one t o pr edict t he e nthalpy of s olvation of
gaseous solutes in chloroform.
Figure 5.9. A plot of the calculated values of ∆HSolv,CFM on Eq. 5.43 against the observed values.
In order to assess the predictive ability of Eq. 5.43, I divided the 100 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental data points. The selected da ta points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,CFM (kJ/mol) = −6.291(0.775) + 7.456(1.008)E − 13.902(1.237)S −
4.694(2.179)A − 15.674(1.082)B − 8.734(0.168)L (5.45)
(N = 50, SD = 1.66, R2 = 0.988, R2adj = 0.987, F = 746.1).
The t raining s et e quation, E q. 5.45, w as then us ed t o pr edict ∆HSolv,CFM for t he 50
compounds i n t he t est s et. C omparison of t he p redicted a nd obs erved va lues gave S D = 2.24,
average absolute error (AAE) = 1.60 and an average error (AE) = −0.3705. There is therefore
82
very little b ias in th e p redictions using E q. 5.45 with A E e qual to −0.3705 kJ/mol. I a m not
aware of any attempts to correlate ∆HSolv,CFM data.
In Table S 5.10 (Supplemental M aterial) are collected v alues o f t he en thalpies o f
solvation of 88 gaseous solutes in 1,2-dichloroethane. Regression analyses of the experimental
∆HSolv,DCE data in accordance with the Abraham model yielded
∆HSolv,DCE (kJ/mol) = −2.345 (0.672) + 5.555(0.861)E − 18.328(1.122)S −
9.599(1.794)A − 7.101(1.013)B − 8.045(0.144)L (5.46)
(N = 88, SD = 1.72, R2 = 0.982, R2adj = 0.980, F = 875.3)
∆HSolv,DCE (kJ/mol) = 3.623(1.002) − 3.208(1.050)E − 24.665(1.520)S −
11.165(2.348)A − 6.589(1.322)B − 28.520(0.671)V (5.47)
(N = 88, SD = 2.24, R2 = 0.969, R2adj = 0.967, F = 509.1).
Both Eqs. 5.46 and 5.47 are statistically very good with standard deviations of 1.72 a nd
2.24 kJ/mol for a data set that covers a range of 71.7 kJ/mol. Figure 5.10 compares the calculated
values of ∆HSolv,DCE based on Eq. 5.46 against the observed values. To my knowledge there has
been no previous attempt to correlate ∆HSolv,DCE data.
83
Figure 5.10. A plot of the calculated values of ∆HSolv,DCE on Eq. 5.46 against the observed values.
In order to assess the predictive ability of Eq. 5.46 the 88 data points were divided into a
training s et a nd a te st set b y allowing t he S PSS s oftware t o r andomly s elect ha lf o f t he
experimental d ata p oints. T he s elected d ata p oints b ecame t he t raining s et an d t he r emaining
compounds that were left served as the test set. Analysis of the experimental data in the training
set gave
∆HSolv,DCE (kJ/mol) = −2.972(0.943) + 4.717(1.443)E − 17.267(1.804)S −
5.233(2.530)A − 8.317(1.984)B − 7.886(0.181)L (5.48)
(N = 44, SD = 1.48, R2 = 0.983, R2adj = 0.980, F = 432.7).
The t raining s et e quation, E q. 5.48, w as t hen us ed t o pr edict ∆HSolv,DCE for t he 44
compounds i n t he t est s et. C omparison of t he p redicted a nd obs erved va lues gave S D = 2.07,
average absolute error (AAE) = 1 .54 and an average er ror (AE) = −0.0764. There is therefore
very l ittle bi as i n t he predictions us ing E q. 5.48 with A E e qual t o −0.0764 kJ/mol. An
84
uncertainty/error of ±2 kJ/mol in the enthalpy of solvation results in an error of slightly less than
0.04 log units in extrapolating a log K value measured at 298.15-313.15 K. This level of error
will b e s ufficient f or mo st p ractical ch emical an d en gineering ap plications. To my knowledge
there has been no previous attempt to correlate ∆HSolv,DCE data to date.
As not ed pr eviously, correlations f or pr edicting e nthalpies of s olvation i n t he va rious
organic solvents can be combined with the ∆HSolv,W equation (Eq. 5.8) derived by Mintz et al.100
in S ection 5.2.1 to g ive enthalpies of s olute t ransfer f rom w ater t o t he given or ganic s olvent.
Enthalpies of solute t ransfer are particularly useful in that knowledge of ∆Htrans enables one to
predict h ow water-to-organic s olvent pa rtition c oefficients va ry with t emperature. T here i s
considerable pu blished partition c oefficient da ta f or s olutes di stributed be tween water a nd
chloroform,6,112 and be tween w ater and 1,2 -dichloroethane.112-114 Solutes s tudied i nclude
nonionic molecules as well as ionizable drugs. Most of the published data pertain to 298 K, and
the c orrelations p resented in th e p resent s tudy w ill a llow o ne to e stimate lo g P values at
temperatures not too far removed from 298 K.
5.3.6. Benzene and Alkane Solvents
Results and Discussion
Tabulated in Table S5.11 (Supplemental Material) are values of ∆HSolv,Hp for 134 gaseous
solutes dissolved in heptane covering a reasonably wide range of compound type and descriptor
values. P reliminary analysis o f t he experimental d ata yielded a co rrelation eq uation t hat h ad
relatively s mall n umerical va lues f or t he s -, a -, a nd b -coefficients, a s one w ould e xpect f or a
saturated hydrocarbon. Heptane possesses no acidic or basic hydrogen-bonding character, nor is
a s aturated h ydrocarbon e xpected t o exhibit m uch i n t he way o f di polarity/polarizability t ype
85
molecular i nteractions. T he s -, a -, a nd b -coefficients w ere s et eq ual t o z ero f or the general
Abraham e quation f or processes i nvolving gas-to-condensed pha se t ransfer (Eq. 5.6) of t he
Abraham model, and the final regression analyses performed to give
∆HSolv,Hp (kJ/mol) = -7.018(0.344) + 4.036(0.647) E - 9.209(0.109) L (5.49)
(N = 134, SD = 1.85, R2 = 0.984, R2adj = 0.984, F = 4106.4)
∆HSolv,Hp (kJ/mol) = 3.368(0.604) - 8.941(1.146)E - 7.065(1.260)S -
2.836(1.730)A + 0.657(1.052)B - 35.595(0.568)V (5.50)
(N = 134, SD = 2.32, R2 = 0.975, R2adj = 0.974, F = 1002.8).
There was very little decrease in descriptive ability resulting from setting the s-, a-, and
b-coefficients equal to zero. The standard deviation increased very s lightly f rom SD = 1.81 to
1.85, when the three coefficients were set to zero. All the regression analyses were performed
using th e S PSS s tatistical software. B oth Eqs. 5.49 a nd 5.50 are statistically v ery g ood with
standard deviations of 1.85 and 2.32 kJ /mol for a data set that covers a range of 89 kJ /mol. See
Figure 5.11 for a plot of the calculated values of ∆HSolv,Hp based on Eq. 5.49 against the observed
values. Equation 5.49 is s lightly th e b etter e quation statistically, a nd from a th ermodynamic
standpoint Eq. 5.49 is t he en thalpic t emperature d erivative o f t he A braham model’s ga s-to-
condensed pha se t ransfer e quation. Equation 5.50 might be m ore us eful i n s ome pr edictive
applications in i nstances w here t he L-descriptor i s not know n. Eq. 5. 50 uses t he M cGowan
volume, V-descriptor, which is easily calculable from the individual atomic sizes and numbers of
86
bonds in the molecule.115 To the best of my knowledge, there has been no previous attempt to
correlate ∆HSolv,Hp data.
Figure 5.11. A plot of the calculated values of ∆HSolv,Hp in Eq. 5.49 against the observed values.
In order to assess the predictive ability of Eq. 5.49, I divided the 134 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental data points. The s elected data points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,Hp (kJ/mol) = -7.014(0.582) + 3.932(1.077)E - 9.270(0.191)L (5.51)
(N = 67, SD = 2.05, R2 = 0.977, R2adj = 0.976, F = 1345.5).
Again, the s-, a-, and b-coefficients were set equal to zero. There is very little difference in the
equation coefficients between the full dataset and training dataset correlations. The training set
was then used to predict ∆H Solv,Hp values for the 67 compounds in the test set. For the predicted
and ex perimental v alues, I find t hat S D = 1.61, A verage A bsolute E rror ( AAE) = 1.308, a nd
87
Average Error (AE) = 0.409. There is therefore very little bias in the predictions using Eq. 5.49
with AE equal to 0.409 kJ /mol. An uncertainty/error of ±2 kJ /mol in the enthalpy of solvation
results in an error of slightly less than 0.04 log units in extrapolating a log L value measured at
298.15 – 313.15 K. This level of error will be sufficient for most practical applications.
In Table S5.12 (Supplemental Material) are collected values of the enthalpies of solvation
in hexadecane for 102 compounds. Application of the general Abraham equations leads to Eqs.
5.52 and 5.53, respectively.
∆HSolv,Hxd (kJ/mol) = -6.097(0.377) + 2.305(0.680)E - 9.364(0.133)L (5.52)
(N = 102, SD = 1.84, R2 = 0.985, R2adj = 0.984, F = 3194.7)
∆HSolv,Hxd (kJ/mol) = 4.696(0.619) - 9.621(1.131)E - 7.902(1.224)S -
2.933(1.536)A + 1.102(1.189)B - 36.610(0.674)V (5.53)
(N = 102, SD = 2.16, R2 = 0.979, R2adj = 0.978, F = 890.6)
Although bot h E qs. 5.52 a nd 5.53 are s tatistically r easonable, E q. 5.52 is s lightly b etter
statistically th an E q. 5.53, a nd i t is E q. 5.52 that I would r ecommend for a ny pr edictions of
values of ∆HSolv,Hxd if the L-descriptors are known.
In order to assess the predictive ability of Eq. 5.52, I divided the 102 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental da ta points. The selected da ta points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
88
∆HSolv,Hxd (kJ/mol) = -5.847(0.636) + 1.869(1.044)E - 9.384(0.224)L (5.54)
(N = 51, SD = 1.95, R2 = 0.979, R2adj = 0.978, F = 1132.1)
There is very little difference in the equation coefficients for the full dataset and training
dataset co rrelations. T he t raining s et w as t hen u sed t o p redict ∆H Solv,Hxd values f or t he 51
compounds in the test set. For the predicted and experimental values, I find that SD = 1.75, AAE
= 1.186, a nd AE = -0.119. There i s t herefore v ery l ittle bi as i n t he predictions us ing Eq. 5.52
with AE equal to -0.119 kJ/mol. This seems to be the first time that any predictive assessment
of a n e quation f or ∆H Solv,Hxd has b een m ade. A braham an d co workers116 previously co rrelated
enthalpies of t ransfer f rom w ater-to-hexadecane us ing a n earlier ve rsion of t he A braham
solvation parameter model; however, the authors did not correlate the enthalpies of solvation.
Cyclohexane is the last saturated hydrocarbon solvent that is considered in this section. In
Table S5.13 (Supplemental Material) are collected values of the enthalpies of solvation of 201
gaseous s olutes i n cyclohexane. R egression analyses o f t he experimental ∆H Solv,Cy data i n
accordance with the Abraham model yielded
∆HSolv,Cy (kJ/mol) = -6.507(0.250) + 3.375(0.352)E - 9.078(0.079)L (5.55)
(N = 201, SD = 1.66, R2 = 0.988, R2adj = 0.988, F = 8045.5)
∆HSolv,Cy (kJ/mol) = 3.046(0.540) - 8.735(0.804)E - 6.353(1.016)S -
1.264(2.015)A - 2.449(1.156)B - 33.550(0.486)V (5.56)
(N = 201, SD = 2.63, R2 = 0.969, R2adj = 0.969, F = 1238.3).
89
One additional solute, 2,2-dimethylhexane, was used in developing Eq. 5.56. I could not include
2,2-dimethylhexane in the Eq. 5.55 regression a nalyses because i ts L-descriptor i s not known.
Both E qs. 5.55 a nd 5.56 are s tatistically very good w ith s tandard de viations of 1.66 and 2.63
kJ/mol for a data set that covers a range of 88 kJ/mol. See Figure 5.12 for a plot of the calculated
values of ∆H Solv,Cy based on E q. 5.55 against t he obs erved va lues. E quation 5.55 is a slightly
better equation s tatistically, and it is E q. 5.55 that I would r ecommend f or a ny predictions o f
values of ∆HSolv,Hxd, if the L-descriptors are known.
Figure 5.12. A plot of the calculated values of ∆HSolv,Cy in Eq. 5.55 against the observed values.
The e nthalpy of s olution f or s olutes di ssolved i n c yclohexane has be en c onsidered i n
several earlier publications. C yclohexane, as well as carbon tetrachloride, has been used as the
inert solvent in the “pure base” model of Arnett et al.87,88 and in the “E and C” model of Drago
and coworkers89,90 for obtaining enthalpies of complex formation. Neither approach was capable
of pr edicting e nthalpies of s olvation in c yclohexane. Solomonov et al .91 proposed a s imple
90
method for extracting specific solute–solvent interactions from measured enthalpies of solvation.
The method assumed that the difference between the nonspecific interaction contribution in the
solvation enthalpy for the solute dissolved in the desired solvent and dissolved in cyclohexane
was pr oportional t o t he di fference i n t he nonspecific i nteractional s olvation e nthalpic
contribution of t he s olute i n s olvents c arbon t etrachloride a nd c yclohexane. W hile t he a uthors
examined s everal pos sible r elationships be tween t he c alculated pr oportionality c onstant a nd
different s olvent p roperties, t here w as n ever a m athematical expression g iven t hat allowed
outright predictions of the enthalpies of solvation (or solution) of solutes in cyclohexane. To the
best of my knowledge, Eqs. 5.55 and 5.56 are the first expressions that allow such predictions.
In order to assess the predictive ability of Eq. 5.55, I divided the 201 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental da ta points. The selected da ta points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,Cy (kJ/mol) = -6.144(0.376) + 3.560(0.537)E - 9.162(0.120)L (5.57)
(N = 101, SD = 1.76, R2 = 0.987, R2adj = 0.987, F = 3757.0).
There is very little difference in the equation coefficients for the full dataset and training dataset
correlations. The training set was then used to predict ∆H Solv,Cy values for the 100 compounds in
the test set. For the predicted and experimental values, I find that SD = 1.56, A AE = 1.12, a nd
AE = -0.308. There is therefore very little bias in the predictions using Eq. 5.55 with AE equal to
-0.308 kJ/mol.
The correlations that have been derived thus far pertain to gaseous solutes in anhydrous
91
heptane, a nhydrous he xadecane, a nd a nhydrous c yclohexane. In t he c ase of c yclohexane, i t i s
possible t o en large t he d atabase s lightly b y including d ata d etermined f rom tw o-phase
partitioning ex periments. W ater an d c yclohexane ar e n early co mpletely i mmiscible w ith each
other, a nd t o a f irst a pproximation one w ould not e xpect t he s mall a mount of w ater i n t he
cyclohexane rich phase (cyclohexane saturated with water) of a partitioning experiment to have
an appreciable effect on ∆H Solv,Cy. Giraldo and Moreno117 reported calorimetrically determined
enthalpies of t ransfer of a liphatic l inear a nd br anched a lcohols f rom a ctual pa rtitioning
experiments. Dearden and Bresnen118 published enthalpy data of 45 simple aromatic compounds
(substituted phe nols, s ubstituted be nzoic a cids, a nd s ubstituted a cetanilides) f rom w ater t o
cyclohexane. T he l atter d ata w ere calculated f rom t he t emperature de pendence of t he
cyclohexane–water partition coefficients measured a t 293.15 t o 318.15 K. I have assembled in
Table 5.6 the necessary information for calculating the enthalpy of solvation in water, ∆H Solv,Cy,
from measured ∆Htrans and ∆HSolv,W values. The partitioning data allows one to add an additional
nine s olutes t o our c yclohexane da tabase. The ∆H Solv,W values w ere t aken f rom an e arlier
compilation.100 I was not able t o i nclude a ll o f t he publ ished p artitioning da ta be cause t he
∆HSolv,Cy computation requires knowledge of the solute’s enthalpy of solvation in water (see Eq.
5.3). T he required ∆H Solv,W values a re s imply n ot a vailable f or ma ny o f the a romatic s olutes
studied b y D earden and Bresnen. The ∆H Solv,Cy values were c ombined an d r egression analyses
yielded the following correlations:
∆HSolv,Cy (kJ/mol) = -6.599(0.274) + 3.307(0.383)E - 9.060(0. 088)L (5.58)
(N = 215, SD = 1.86, R2 = 0.984, R2adj = 0.984, F = 6638.6)
92
∆HSolv,Cy (kJ/mol) = 3.131(0.544) – 8.503(0.801)E – 6.829(0.955)S –
4.246(1.323)A – 1.831(1.056) B – 33.608(0.489)V (5.59)
(N = 215, SD = 2.69, R2 = 0.967, R2adj = 0.966, F = 1226.4).
Table 5.6. Enthalpies of solvation of gaseous solutes in cyclohexane, ∆HSolv,Cy (kJ/mol) calculated from published water-to-cyclohexane enthalpy of transfer data.
Solute ∆Htrans ∆HSolv,W ∆HSolv,Cy Reference
Ethanol 34.64 -50.60 -15.96 [117]
1-Propanol 33.04 -59.90 -26.86 [117]
2-Propanol 33.00 -58.20 -25.20 [117]
1-Butanol 31.42 -61.90 -30.48 [117]
2-Butanol 32.52 -62.72 -30.20 [117]
2-Methyl-1-propanol 31.10 -60.20 -29.10 [117]
1-Pentanol 29.11 -61.90 -32.79 [117]
Phenol 15.30 -57.70 -42.40 [118]
3-Chlorophenol 10.20 -50.30 -40.20 [118]
2-Methylphenol 15.60 -64.80 -49.20 [118]
3-Methylphenol 19.20 -58.70 -39.50 [118]
4-Methylphenol 15.30 -61.30 -46.00 [118]
2-Nitrophenol 5.70 -49.80 -44.10 [118]
3-Nitrophenol 11.50 -67.70 -56.70 [118]
The number of data points is slightly larger than the number solutes because ethanol, 1-
propanol, 2 -propanol, 1 -butanol, a nd 1 -pentanol a re i ncluded t wice, onc e f or t ransfer i nto
93
anhydrous cyclohexane and once for transfer into the water-saturated cyclohexane solvent. Again
the s tatistics f or bot h c orrelations a re qui te good. T he c orrelations f or t he dr y anhydrous
cyclohexane are slightly better than the correlations obtained by combining the dry and wet data
sets. This is to be expected as the presence of water in cyclohexane may have some affect on the
enthalpies of solvation of t he more acidic phenolic solutes. Moreover, t here i s l ikely a greater
experimental u ncertainty associated w ith the ∆H Solv,Cy values de rived f rom t he pa rtitioning
measurements. T he l atter ∆H Solv,Cy values ha ve unc ertainties i n bot h t he m easured ∆H trans and
∆HSolv,W values used in their calculation.
In Table S5.14 (Supplemental Material) are collected values of the enthalpies of solvation
of 174 gaseous solutes in benzene, which is an aromatic hydrocarbon solvent. Unlike saturated
hydrocarbons, b enzene does ha ve a pol arizable π-electron s ystem, an d as a r esult, t here i s a
greater oppor tunity f or slightly s tronger m olecular in teractions w ith p olar s olute mo lecules.
Regression analyses of the experimental ∆H Solv,Ben data in accordance with the Abraham model
yielded
∆HSolv,Ben (kJ/mol) = -4.637(0.335) + 4.446(0.783)E - 12.599(0.851)S -
9.775(1.393) A - 4.023(0.828)B - 8.488(0.106)L (5.60)
(N = 174, SD = 2.08, R2 = 0.987, R2adj = 0.986, F = 2470.9)
∆HSolv,Ben (kJ/mol) = 4.391( 0.621) - 5.422(1.099)E - 21.268(1.280)S -
11.797(2.043)A - 3.118(1.220) B - 31.674(0.586)V (5.61)
(N = 174, SD = 3.05, R2 = 0.971, R2adj = 0.970, F = 1135.7)
94
Both E qs. 5.60 a nd 5.61 are s tatistically very good w ith s tandard de viations of 2.08 and 3.05
kJ/mol for a da ta set that covers a range of 111 kJ /mol. I did consider setting the a- and/or b-
coefficients in the Eq. 5.60 equal to zero; however, this led to a m uch poorer correlation (SD =
2.37 with a = 0; SD = 2.23 with b = 0; and SD = 2.57 with both a = 0 and b = 0). To the best of
my knowledge there has been no previous attempt to correlate ∆HSolv,Ben data.
In order to assess the predictive ability of Eq. 5.60, the 174 data points were divided into
a t raining s et an d a t est s et b y allowing t he S PSS s oftware t o randomly s elect h alf o f t he
experimental data points. The s elected data points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,Ben (kJ/mol) = -4.142(0.370) + 6.236(0.966)E - 13.339(0.982)S - 8.944(1.592)A -
5.430(0.935)B - 8.583(0.124)L (5.62)
(N = 87, SD = 1.70, R2 = 0.992, R2adj = 0.991, F = 1947.4).
There is very little difference in the equation coefficients for the full dataset and training dataset
correlations. The training set was then used to predict ∆H Solv,Ben values for the 87 compounds in
the test set. For the predicted and experimental values, I find that SD = 2.63, AAE = 1.662, and
AE = -0.110. There is therefore very little bias in the predictions using Eq. 5.60 with AE equal to
-0.110 kJ/mol.
As an informational note, Herbst et al.119 reported a value of ∆HSoln = -0.50 kJ/mol for the
enthalpy of solution of buckminsterfullerene, C 60, in benzene. The enthalpy of solution can be
combined w ith publ ished e nthalpy o f s ublimation da ta, ∆H Sub,298 K = 1 99 k J/mol75, t o gi ve a
value of ∆H Solv,Ben = -199.5 kJ /mol. I elected not t o i nclude buc kminsterfullerene i n t he
95
regression analysis because it is much larger than all other solutes considered, and its calculated
descriptors ( E = 1.873, S = 1.477, A = 0.000, B = 0.540, L = 19.84, a nd V = 3.906) 120 were
calculated b ased on an estimated a queous m olar s olubility. E ven s o, E q. 5.60 can be us ed t o
make a n out right p rediction f or t he enthalpy of solvation of buc kminsterfullerene i n be nzene.
The predicted value of ∆HSolv,Ben = -185.38 kJ/mol, obtained by substituting the solute descriptors
directly into Eq. 5.60, i s in reasonably good agreement with the experimental value, given the
fact that the molecule’s L-solute descriptor f alls considerably outside of t he r ange o f L-values
used in deriving the enthalpy of solvation correlation.
The derived correlations, when combined with the correlation equations for enthalpies of
solvation in water (Eqs. 5.8 and 5.9), can be used to estimate the enthalpies of transfer of solutes
from water t o t he r espective organic solvent. Enthalpies of t ransfer a re needed to describe t he
temperature d ependence o f t he w ater-to-organic s olvent partition c oefficients. In pa rtitioning
processes, t he s olute i s distributed b etween t he water (saturated w ith t he o rganic s olvent) and
organic s olvent ( saturated w ith w ater). T he e nthalpies of t ransfer b ased on Eq. 5.3 and t he
derived ∆HSolv correlations pertain to the neat solvents. The mutual miscibility of water and the
organic s olvent mig ht affect th e s olute’s e nthalpy o f s olution in th e e quilibrated immis cible
phases d uring a p ractical ex traction p rocess. T here h ave b een v ery f ew cal orimetric s tudies
performed und er a ctual pa rtitioning c onditions. G iraldo a nd M oreno117 reported e nthalpies f or
direct transfer of several aliphatic linear and branched alcohols between water and cyclohexane.
The measured transfer enthalpies (
∆Htransdirect ) are given in column 2 of Table 5.7, a long with the
∆Htransindirect values cal culated from th e e xperimental e nthalpies o f s olution of t he a lcohol solutes
that were used in deriving Eqs. 5.8 and 5.55.
96
Table 5.7. Comparison of direct vs. indirect enthalpies of transfer for alcohol solutes between water and cyclohexane.
Alcohol solute
∆Htransdirect a
∆Htransindirect b
∆Htransc
Methanol 27.67±2.01 35.1 24.77
Ethanol 34.64±0.11 33.1 33.08
1-Propanol 33.04±0.89 36.5 34.62
2-Propanol 33.00±2.29 37.4 34.46
1-Butanol 31.42±0.78 34.2 36.65
2-Butanol 32.52±0.73
2-Methyl-1-propanol 31.10±0.24 35.46
1-Pentanol 29.11±0.17 30.1 37.04
1-Hexanol 25.56±0.57 31.0
1-Octanol -10.58±0.60
2-Octanol -9.36±0.86 a Experimental values (in kJ/mol) are from Giraldo and Moreno.68 b Values are calculated based on Eq. 5.3 and the enthalpy of solvation data used in deriving the cyclohexane and water ∆HSolv correlations. Calculated values are expressed in units of kJ/mol. c Experimental values (in kJ/mol) are from Torres72 as reported in Giraldo and Moreno.68
I have also included the prior literature values of Torres121 that Giraldo and Moreno cited in their
study. The authors expressed concern about the anomalous transfer enthalpies of both 1-octanol
and 2 -octanol, a nd m entioned that th eir experimental r esults ma y b e in e rror d ue to th e s low
dissolution of the two larger alcohols into water. The indirectly calculated enthalpies of transfer
are in reasonably good agreement with the measured values of Giraldo and Moreno. While the
number of values compared was not large, the comparison does suggest that indirect enthalpies
of transfer c an b e u sed t o es timate p artition co efficients at other t emperatures. An
97
uncertainty/error of ±2 kJ/mol in the enthalpy of transfer results in an error of slightly less than
0.04 log units in extrapolating a log P value measured at 298.15 – 313.15 K. This level of error
will be sufficient for most of the practical applications. The experimental ∆H Solv,Hp, ∆H Solv,Hxd,
∆HSolv,Cy, a nd ∆H Solv,Benz values ar e l isted in T ables S 5.11 – S5.14 ( Supplemental M aterials),
respectively.
5.3.7. Alcohol Solvents
Results and Discussion
Assembled i n T able S 5.15 (Supplementary M aterial) are values of ∆ Hsolv,MeOH for 1 88
gaseous solutes dissolved in methanol covering a reasonably wide range of compound type and
descriptor values. Analysis of the experimental data yielded the following correlation equations:
ΔHSolv,MeOH (kJ/mole) = - 6.366(0.454) – 2.506(0.898)E – 1.807(0.907)S –
37.692(1.163)A – 15.466(0.904)B – 7.674(0.140)L (5.63)
(N = 188, SD = 2.749, R2 = 0.982, R2adj = 0.982, F = 2039.7)
ΔHSolv,MeOH (kJ/mole) = 1.636(0.737) – 11.797(1.103)E – 9.336(1.161)S –
41.378(1.504)A – 15.984(1.165)B – 27.891(0.668)V (5.64)
(N = 188, SD = 3.549, R2 = 0.971, R2adj = 0.970, F = 1211.9)
All regression analyses were performed using SPSS statistical software50. The correlation
matrix, in R2, between the descriptors for Eqs. 5.63 and 5.64 are given in Table 5.8 and Table
5.9, respectively. Inter-correlations between most of the descriptors is negligible, and even the
98
largest in ter-correlation be tween E a nd S , 0.534 ( Eq. 5.63) a nd 0.584 ( Eq. 5.64), i s no t t oo
significant. The inter-correlation between the E and S solute descriptors has been noted in earlier
papers.37,42,44,94
Table 5.8. Inter-correlation matrix, in R2, for solute descriptors for Eq. 5.63.
E S A B L
E 1.000
S 0.534 1.000
A 0.000 0.065 1.000
B 0.208 0.349 0.002 1.000
L 0.122 0.003 0.008 0.024 1.000
Table 5.9. Inter-correlation matrix, in R2, for solute descriptors for Eq. 5.64.
E S A B V
E 1.000
S 0.584 1.000
A 0.000 0.049 1.000
B 0.212 0.375 0.004 1.000
V 0.029 0.008 0.024 0.021 1.000
Both Eqs. 5.63 and 5.64 are statistically very good with SDs of 2.749 a nd 3.549 kJ/mol
for a data set that covers a range of about 105 kJ/mol. See Figure 5.13 for a plot of the calculated
values of ∆H solv.MeOH based on Eq. 5.63 against the observed values. Eq. 5.63 is a slightly better
equation statistically, and from a thermodynamic standpoint Eq. 5.63 is the enthalpic temperature
99
derivative o f t he A braham m odel's gas-to-condensed pha se t ransfer e quation. Equation 5.64
might be more useful in some predictive applications in instances where the L-descriptor is not
known.
Figure 5.13. A plot of the calculated values of ΔH Solv,MeOH on Eq. 5.63 against the observed values.
In order to assess the predictive ability of Eq. 5.63, I divided the 188 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental da ta points. The selected da ta points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
ΔHSolv,MeOH (kJ/mole) = -6.880(0.721) – 2.431(1.351)E – 1.768(1.216)S –
38.875(1.858)A – 16.053(1.218) B – 7.512(0.236) L (5.65)
(N = 94, SD = 2.565, R2 = 0.980, R2adj = 0.979, F = 888.5).
100
The training set equation (Eq. 5.65) was then used to predict ∆Hsolv,MeOH for the 94 compounds in
the t est s et. C omparison of t he pr edicted a nd obs erved va lues gave SD = 2.565, A verage
Absolute Error (AAE) = 2.016, and an Average Error (AE) = 0.297. There is therefore very little
bias i n t he pr edictions using Eq. 5.65 with A E e qual t o 0.297 kJ/mol. T o t he be st of my
knowledge, only the COSMO-RS method of Klamt and coworkers (e.g., see Klamt )122 allows
one to predict the enthalpy of solvation of gaseous solutes in methanol.
Collected values of the enthalpies of solvation of 111 gaseous solutes in ethanol are listed
in Table S 5.16 (Supplementary Material). Regression analyses o f t he experimental ∆H solv, E tOH
data in accordance with the Abraham model yielded
ΔHSolv,EtOH (kJ/mole) = -6.558(0.472) - 48.600(1.699)A – 11.899(1.045)B –
8.298(0.153)L (5.66)
(N = 111, SD = 2.558, R2 = 0.981, R2adj = 0.981, F = 1865.3)
ΔHSolv,EtOH (kJ/mole) = 4.411(0.817) – 11.175(1.388)E – 9.123(1.540)S –
52.352(2.425)A – 12.074(1.714)B – 32.384(0.934)V (5.67)
(N = 111, SD = 3.017, R2 = 0.970, R2adj = 0.969, F = 589.7)
The e·E and s ·S te rms w ere eliminated f rom Eq. 5.66 because t he s tandard e rrors i n t he
coefficients were larger than the coefficients themselves. Both Eqs. 5.66 and 5.67 are statistically
very good with SDs of 2.558 and 3.017 kJ/mol for a d ata set th at covers a r ange of about 89
kJ/mol . Figure 5.14 compares the calculated values of ∆H solv,EtOH based on Eq. 5.66 against the
observed values.
101
Figure 5.14. A plot of the calculated values of ∆Hsolv,EtOH based on Eq. 5.66 against the observed values.
In order to assess the predictive ability of Eq. 5.66, I divided the 111 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental d ata p oints. T he s elected d ata p oints b ecame t he t raining s et an d the r emaining
compounds that were left served as the test set. Analysis of the experimental data in the training
set gave
ΔHSolv,EtOH (kJ/mole) = -6.086(0.583) – 48.481(2.083)A – 10.213(1.320)B –
8.447(0.173)L (5.68)
(N = 56, SD = 2.155, R2 = 0.988, R2adj = 0.987, F = 1350.2)
The t raining s et e quation ( Eq. 5.68) w as t hen used t o pr edict ∆Hsolv,EtOH for t he 55
compounds in the test set. Comparison of the predicted and observed values gave SD = 2.995,
102
AAE=2.337, and an AE = 0.232. T here is therefore very little bias in the predictions using Eq.
5.68 with AE equal to 0.232 kJ/mol. To the best of my knowledge, there has been no previous
attempt t o co rrelate ∆HSolv,EtOH data. Search of t he chemical l iterature al so found ex perimental
enthalpy of s olvation d ata f or 103 s olutes di ssolved i n 1 -butanol ( see T able S 5.17 of t he
Supplementary Material f or v alues o f ∆HSolv,BtOH). Regression analyses of t he e xperimental
∆Hsolv,BtOH data in accordance with the Abraham model yielded
ΔHSolv,BtOH (kJ/mole) = -7.629(0.421) – 50.806(1.945)A – 4.261(0.841)B –
8.507(0.140)L (5.69)
(N = 103, SD = 2.365, R2 = 0.984, R2adj = 0.984, F = 2059.8)
ΔHSolv,BtOH (kJ/mole) = 3.210(0.742) – 8.481(1.487)E – 11.902(1.201)S –
60.017(2.930)A – 33.882(0.819)V (5.70)
(N = 103, SD = 3.012, R2 = 0.972, R2adj = 0.971, F = 760.0).
The e·E and s·S terms were eliminated from Eq. 5.69 because the standard errors in the
coefficients were larger than the coefficients themselves. The b·B term was similarly eliminated
from Eq. 5.70 because of a l arge s tandard error. Both Eqs. 5.69 and 5.70 are s tatistically very
good with SDs of 2.365 and 3.012 kJ/mol for a d ata set that covers a range of about 88 kJ/mol.
Figure 5.15 compares the calculated values of ∆Hsolv.BtOH based on Eq. 5.69 against the observed
values.
103
Figure 5.15. A plot of the calculated values of ΔHSolv,BtOH on Eq. 5.69 against the observed values.
In order to assess the predictive ability o f Eq. 5.69, 103 data experimental values were
divided into a training set and a test set by allowing the SPSS software to randomly select half of
the experimental data points. The selected data points became the training set and the remaining
compounds that were left served as the test set. Analysis of the experimental data in the training
set gave
ΔHSolv,BtOH (kJ/mole) = -7.738(0.680) – 50.705(2.783)A – 7.173(1.564)B –
8.067(0.283)L (5.71)
(N = 52, SD = 2.639, R2 = 0.979, R2adj = 0.978, F = 756.7).
The training set equation (Eq. 5.71) was then used to predict ∆Hsolv,EtOH for the 51 compounds in
the test set. Comparison of the predicted and observed values gave SD = 2.441, AAE = 1.897,
104
and an AE = -0.606. There is therefore very little bias in the predictions using Eq. 5.71 with AE
equal to -0.606 kJ/mol.
The 1 -butanol d ata s et h as th e s mallest number of e xperimental da ta poi nts. I also
employed the bootstrap method53,55 as part of the validation process. The model was fit to 100
bootstrapped samples, and the results from the bootstrapped samples applied to the original data
to determine fit. Averaging over these repeated occasions can give one a sense of the optimism,
or b ias, in a s tatistic, e.g., R2 For m ore regarding t he p rocedure s ee E fron a nd T ibshirani,53
Davidson a nd H inckley,123 or H arrell.54 There w as f ound to b e lit tle o ptimism in R2 and
coefficients with a co rrected R2 of 0.98059. I am not aware of any previous attempt to correlate
∆Hsolv,BtOH data.
I have elected t o c orrelate t he e nthalpies of s olvation of i norganic gases a nd or ganic
solutes in methanol, ethanol, and 1-butanol using the Abraham solvation parameter model. Each
term i n t he b asic m odel r epresents a t ype o f s olute-solvent i nteraction. F or e xample, A i s t he
solute's h ydrogen-bond a cidity a nd the a-coefficient i s t he complementary s olvent h ydrogen-
bond basicity. The a·A term in the general Abraham equations (Eqs 5.6 a nd 5.7) describes the
enthalpic contribution that the solute (acid)-solvent (base) interaction has in regards to the gas-
to-condensed pha se t ransfer p rocess. E xamination of t he equation c oefficients and t heir
associated SDs for the three alcohol solvents reveals that the last three terms are more important
than the others, particularly in the case of dissolved acidic and/or basic solute molecules. Both
hydrogen bondi ng t erms (a·A a nd b·B) a re i mportant, as w ould b e ex pected i n t he cas e o f an
alcoholic solvent. Numerical values of a and b coefficients for the general Abraham equation for
gas-to-condensed pha se t ransfer ( Eq. 5.6 ) form of t he A braham m odel do f ollow t rends i n
regards t o a lcohol s ize. In t he c ase of t he a-coefficient, t he n umerical v alues b ecome m ore
105
negative with increasing alcohol size, without exception, from -37.7 for methanol to -48.60 for
ethanol to -50.8 for 1-butanol to -54.0 for 1-octanol. The numerical values of the b coefficient
become less negative with increasing alkyl chain length on the whole; however, the numerical
value of 1 -butanol s eems a bi t out of l ine compared to t he other t hree a lcohols. The V and L
solute descriptors were set up as measures of the endoergic effect of disrupting solvent-solvent
bonds t o c reate a s olvent c avity i n w hich t he solute r esides. S olute v olume i s a lways w ell
correlated w ith pol arizability, how ever, and t he v·V a nd l·L terms w ill in clude n ot o nly a n
endoergic cav ity effect but a lso e xoergic s olute-solvent e ffects th at a rise th rough s olute
polarizability. T he v·V a nd l·L terms m ake t he l argest c ontribution. G aseous s olutes a re qui te
energetic, and upon dissolution into a condensed phase, the solute releases enthalpy as it returns
to a more confined, less energetic state.
5.3.8. Linear Alkanes
Introduction
This s tudy c oncerns t he de velopment of a ∆H Solv correlation f or h exane as w ell as an
expression for a generic linear alkane solvent that could be used to predict enthalpies of solvation
in the linear alkane solvents from pentane through hexadecane. Among the remaining 11 l inear
alkane solvents, except for heptane and hexadecane for which ∆HSolv correlations were recently
published,12 there w ere n ot s ufficient ex perimental d ata i n any given a lkane s olvent f or us t o
develop a solvent-specific correlation. There were sufficient experimental ∆HSolv data, however,
for us to examine the possibility of a single, generic equation for all liquid linear alkane solvents.
The entire set of ∆HSolv data is tabulated in Table S5.18 (Supplemental Material) according to the
alkane solvent, along with the literature references.
106
Results and Discussion
I have tabulated in T able S5.18 (Supplemental M aterial) values of ∆HSolv,Hx for 118
gaseous s olutes di ssolved i n he xane c overing a reasonably w ide r ange of c ompound t ype a nd
descriptor v alues. P reliminary analysis o f t he ex perimental d ata yielded a co rrelation eq uation
that had relatively small numerical values for the s-, a-, and b-coefficients, as one would expect
for a saturated h ydrocarbon. Hexane possesses no acidic or basic h ydrogen-bonding character,
nor is a s aturated hydrocarbon expected to exhibit much in the way of dipolarity/polarizability
type m olecular i nteractions. T he s -, a -, and b -coefficients were s et equal t o 0 f or t he general
Abraham g as-to-condensed pha se e quation ( Eq. 5.6 ) and a f inal r egression a nalysis w as
performed to give
∆HSolv,Hx (kJ/mol) = -6.458(0.327) + 3.610(0.565)E - 9.399(0.113)L (5.72)
(N = 118, SD = 1.819, R2 = 0.987, R2adj = 0.986, F = 4269.3)
and
∆HSolv,Hx (kJ/mol) = 4.894(0.580) - 8.916(1.014)E - 8.463(1.163)S -
1.168(1.762)A + 0.773(1.090)B - 36.769(0.620)V (5.73)
(N = 118, SD = 2.306, R2 = 0.979, R2adj = 0.978, F = 1025.9).
There was very little decrease in the descriptive ability resulting from setting the s-, a-,
and b -coefficients e qual t o 0. T he s tandard de viation increased s lightly f rom S D = 1.794 t o
1.819, w hen t he t hree coefficients were s et e qual t o 0. A ll o f t he r egressions w ere pe rformed
107
using the SPSS s tatistical software. Eq. 5.72 is s lightly the b etter equation s tatistically, with a
standard deviation of 1.810 compared to a standard deviation of 2.306 kJ /mol for Eq. 5.73. It is
Eq. 5.72 that I would recommend for any predictions of values of ∆HSolv,Hx, if the L-descriptors
are known. See Figure 5.16 for a plot of the calculated values of ∆HSolv,Hx values based on Eq.
5.72 against the observed values for a dataset that spans a range of 89 kJ/mol.
Figure 5.16. A plot of the calculated values of ΔHSolv,Hx from Eq. 5.72 against the observed values.
In order to assess the predictive ability of Eq. 5.72, I divided the 118 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f the
experimental data points. The s elected data points became the t raining set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
∆HSolv,Hx (kJ/mol) = -6.285(0.487) + 4.017(0.884)E - 9.437(0.153)L (5.74)
(N = 59, SD = 1.966, R2 = 0.987, R2adj = 0.986, F = 2109.0).
108
Again, t he s -, a -, and b -coefficients were s et equal t o 0 . The t raining s et equation, Eq.
5.74, was then used to predict ∆HSolvHx for the 59 compounds in the test set. Comparison of the
predicted and observed values gave SD = 1.667, average absolute error (AAE) = 1.147 and an
average error (AE) = -0.350. There is therefore very little bias in the predictions using Eq. 5.74
with AE equal to -0.350 kJ/ mol. An uncertainty/error of ±2kJ/mol in the enthalpy of solvation
results in an error of slightly less than 0.04 log units in extrapolating a log K value measured at
298.15-313.15 K . T his l evel of e rror will be s ufficient f or most o f t he p ractical ch emical an d
engineering applications. There has been no previous at tempt to correlate ∆HSolv,Hx data to the
best of my knowledge.
During my search o f t he l iterature, I found ∆HSolv data for solutes di ssolved in s everal
other l inear alkane solvents. The correlation equations for gaseous solutes in both heptane and
hexadecane were recently reported. For the remaining nine linear alkane solvents, I did not feel
that th e c hemical d iversity o f th e d issolved s olutes a nd th e range o f d escriptors co vered i n a
given solvent was sufficient for us to develop a meaningful correlation a t this time. There is a
need for being able to predict ∆HSolv in other linear alkane solvents, and one way to address this
need would be to explore the possibility of developing a single, generic linear alkane correlation
that would be applicable to the linear alkanes from pentane to hexadecane. The similarity in the
equation coefficients for the ∆HSolv,Hx (Eq. 5.72), ∆HSolv,Hp (Eq. 5.49), and ∆HSolv,Hxd (Eq. 5.52)
solvent specific correlations suggest that this may, indeed, be possible.
The ex perimental ∆HSolv,Hx, ∆HSolv,Hp, a nd ∆HSolv,Hxd values were an alyzed as a s ingle
dataset. I used the descriptors in the Abraham gas-to-condensed phase equation (Eq. 5.6) plus
the i ndicator va riables IHx and I Hxd; I Hx takes t he va lue 1.0 f or t he e nthalpy o f s olvation da ta
109
pertaining to hexane and 0.0 f or heptane and hexadecane solvent values. The indicator variable
IHxd is used in similar fashion to identify the experimental data for the hexadecane solvent. The
resulting equation is
∆HSolv (kJ/mol) = -6.697(0.250) + 3.957(0.502)E - 0.676(0.533)S +
0.680(0.734)A + 1.358(0.487)B - 9.394(0.071)L - 0.044(0.231)IHx -
0.001(0.241)IHxd (5.75)
(N = 362, SD = 1.81, R2 = 0.986, R2adj = 0.985, F = 3439.4).
The s -, a -, a nd b -coefficients w ere again s et e qual t o 0 as be fore. T he ve ry small
coefficients for both the IHx and IHxd indicator descriptors suggest that the ∆HSolv,Hx, ∆HSolvHp, and
∆HSolv,Hxd values can be combined into a s ingle dataset. There is a very little difference between
the equation coefficients of Eq. 5.75 and the three solvent-specific correlations for Eq. 5.72 and
for ∆HSolv,Hx (Eq. 5.49), ∆HSolvHp (Eq. 5.52).
Finally, I performed a regression analysis on all of the 521 experimental ∆HSolv values in
Table S5.18 (Supplemental Material) to give the following generic linear alkane correlation.
∆HSolv,Alk (kJ/mol) = -6.708(0.144) + 2.999(0.285)E - 9.279(0.049)L (5.76)
(N = 521, SD = 1.82, R2 = 0.988, R2adj = 0.988, F = 21622.6).
Equation 5.76 is statistically very good, and the number of experimental data points for a s ingle
solvent r anges f rom 1 ∆HSolv value for t ridecane to 141 ∆HSolv values f or h eptane. S everal
additional ∆HSolv,Hp values for heptane were found as the result of an expanded literature search.
Figure 5.17 depicts a plot of the experimental ∆HSolv,Alk data versus the calculated values based
110
on E q. 5.76. T he g eneric l inear al kane co rrelation p redicts that t he e nthalpy of s olvation of a
given solute will be the same in all linear alkane solvents from pentane through hexadecane. The
experimental ∆HSolv data in T able S5.18 (Supplemental M aterial) support t his pr ediction. In
addition, D uce et al .124 recently r eported t he enthalpies of s olvation of pe rfluorohexane in
pentane, h exane, he ptane, a nd oc tane. I have not i ncluded t hese v alues i n T able S 5.18
(Supplemental Material) because solute descriptors are not known for perfluorohexane; however,
the experimental values do show that the enthalpy of solvation of perfluorohexane is essentially
the same in the four alkane solvents: ∆HSolv = -19.55 kJ/mol in pentane, ∆HSolv = -19.04 kJ/mol
in heptane, and ∆HSolv = -19.54 kJ/mol in octane, in accordance with the expectations based on
Eq. 5.76.
Figure 5.17. A plot of the calculated values of ∆HSolv,Alk from Eq. 5.76 against the observed values.
As a p art of our data analyses, I estimated how much predictive ability was likely to be
lost as a result o f u sing t he generic l inear alkane correlation r ather t han a n alkane-specific
correlation t o pr edict e nthalpies of s olvation in the di fferent l inear a lkane s olvents. A braham
111
model c orrelations ha ve be en de veloped f or he xane, he ptane, a nd h exadecane. T he results of
these computations are summarized in Table 5.10.
Table 5.10. Summarized comparison of the descriptive ability of the solvent-specific Abraham model correlations for enthalpies of solvation in hexane, heptane, and hexadecane vs. the generic alkane correlation equation.
Alkane solvent Standard deviation (SD)a
Solvent specific Generic alkane
Hexane 1.82 1.85
Heptane 1.85 1.86
Hexadecane 1.84 1.90
a
SD = (∆HSolvCalc∑ − ∆HSolv
Exp )2 /N − 3)
Examination of the numerical entries reveals that there is only a very s light loss in the
predictive ability when one uses Eq. 5.76 to predict the enthalpies of gaseous solutes in hexane,
heptane, and hexadecane. S imilar results would be expected for the other nine a lkane solvents
considered i n t he pr esent s tudy. The generic l inear a lkane s olvent correlation t hat ha s be en
developed for ∆HSolv more than doubles the number of organic solvents for which I could make
enthalpy of solvation predictions.
It is therefore suggested that predictions of enthalpies of solvation of gaseous solutes in
the solvents hexane, heptane, and hexadecane (Eqs. 5.72, 5.49, 5.52, respectively) be made using
the al kane-specific correlations, and for enthalpies of solvation of gaseous solutes i n t he other
linear alkanes from pentane through hexadecane predictions be made using the generic Eq. 5.76.
112
5.3.9. N,N-Dimethylformamide and tert-Butanol
Results and Discussion
I have assembled in Table S5.19 values of ΔHSolv,DMF for 159 gaseous solutes dissolved in
N,N-dimethylformamide c overing a r easonably wide r ange of c ompound t ype a nd de scriptor
values. Preliminary analysis of the experimental data yielded a correlation equation
ΔHSolv,DMF (kJ/mole) = -4.329(0.711) – 0.052(1.1.090)E – 15.122(1.236)S –
42.212(1.466)A – 8.253(1.244)B – 7.118(0.192)L (5.77)
(with N = 159, SD = 3.084, R2 = 0.977, R2adj = 0.977 F = 1329.1),
that had relatively small numerical value for the e -coefficient. T he e·E term was eliminated,
and the final regression analyses performed to give
ΔHSolv,DMF (kJ/mole) = - 4.324(0.700) – 15.168(0.762) S – 42.211(1.461) A –
8.223(1.609) B –7.121(0.181) L (5.78)
(with N = 159, SD = 3.084, R2 = 0.977, R2adj = 0.977, F = 1672.2)
ΔHSolv,DMF (kJ/mole) = 2.301(0.907) – 7.377(1.095) E - 23.129(1.302) S -
45.258(1.557)A – 6.463(1.309) B - 25.733(0.731) V (5.79)
(with N = 159, SD = 3.239, R2 = 0.975, R2adj = 0.974, F = 1202.6) .
There was no decrease in descriptive ability resulting from setting the coefficient equal to
zero, SD = 3.084 f or both Eqs. 5.77 and 5.78. The intercorrelation matrices, in R2, between the
descriptors us ed i n Eqs. 5.78 and 5.79 are given i n Table 5.11 and Table 5.12, respectively.
113
Inter-correlations between most of the descriptors are negligible. The largest inter-correlation of
0.736 i s be tween E and S in Eq. 5.79 . T he inter-correlation be tween t he E and S solute
descriptors h as b een n oted i n ear lier p apers.37,42,44,94 All r egression an alyses w ere performed
using SPSS statistical software.50
Table 5.11. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.78.
S A B L
S 1.000
A 0.138 1.000
B 0.151 0.002 1.000
L 0.306 0.034 0.024 1.000
Table 5.12. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.79.
E S A B V
E 1.000
S 0.736 1.000
A 0.002 0.042 1.000
B 0.277 0.375 0.001 1.000
V 0.023 0.011 0.050 0.006 1.000
Both Eqs. 5.78 and 5.79 are statistically very good with standard deviations of 3.084 and
3.239 kJ/mole for a data set that covers a range of about 108 kJ/mole. See Figure 5.18 for a plot
of the calculated values of ΔHSolv,DMF based on Eq. 5.78 against the observed values. Eq. 5.78 is
slightly th e b etter equation s tatistically, and f rom a th ermodynamic s tandpoint Eq. 5.78 is th e
114
enthalpic t emperature d erivative o f t he A braham m odel’s gas-to-condensed p hase t ransfer
equation. Eq. 5.79 might be more useful in some predictive applications in instances where the
L-descriptor is not known. Eq. 5.79 uses the McGowan volume, V-descriptor, which is easily
calculable from the individual atomic sizes and numbers of bonds in the molecule.83
Figure 5.18. A plot of the calculated values of ∆HSolv,DMF based on Eq. 5.78 against the observed values
In order to assess the predictive ability of Eq. 5.78, I divided the 159 da ta points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental data points. T he selected data points became the training set and the compounds
that were left served as the test set. Analysis of the experimental data in the training set gave
ΔHSolv,DMF (kJ/mole) = - 5.235(0.911) – 14.966(0.855) S – 43.585(1.805) A –
4.677(1.610) B - 7.081(0.207) L (5.80)
(with N = 80, SD = 2.586, R2 = 0.983, R2adj = 0.982, F = 1103.6).
115
The training set equation was then used to predict ΔHSolv,DMF values for the 79 compounds in the
test set. C omparison of the predicted and observed values gave SD = 3.772, A verage Absolute
Error (AAE) = 2.319 and an Average Error (AE) = -0.364 kJ/mole. There is therefore very little
bias in the predictions using Eq. 5.80 with AE equal to -0.364 kJ/mole. I am not aware of any
previous attempt to correlate ΔHSolv,DMF data.
In Table S5.20 (Supplemental M aterial) are compiled values of t he e nthalpies of
solvation of 84 or ganic s olutes a nd gases i n tert-butanol. R egression a nalyses of t he
experimental ΔHSolv,t-BTOH data in accordance with the Abraham model yielded:
ΔHSolv,t-BTOH (kJ/mole) = - 3.179(1.032) + 4.379(1.292) E + 2.563(1.468) S –
57.447(1.750) A - 12.008(1.478) B - 8.881(0.258) L (5.81)
(with N = 84, SD = 2.484, R2 = 0.977, R2adj = 0.976, F = 677.2)
ΔHSolv,t-BTOH (kJ/mole) = 3.637(1.514) – 6.914(1.548) E - 3.098(1.856) S -
60.220(2.165) A - 14.133(1.846) B - 30.934(1.140) V (5.82)
(with N = 84, SD = 3.088, R2 = 0.965, R2adj = 0.963, F = 432.8).
Both Eqs. 5.81 and 5.82 are statistically very good with standard deviations of 2.484 a nd 3.088
kJ/mole for a d ata s et t hat covers a r ange o f about 71 kJ/mole. T here i s l ittle i ntercorrelation
between the descriptors in Eqs. 5.81 and 5.82; the maximum intercorrelation is R2 = 0.446 (Eq.
5.81) and R2 = 0.436 (Eq. 5.82) between E and S. Figure 5.19 compares the calculated values of
ΔHSolv,EA based on Eq. 5.81 against the observed values.
116
Figure 5.19. A plot of the calculated values of ∆HSolv,t-BTOH based on Eq. 5.81 against the observed values
The enthalpy of solvation database for tert-butanol contains only 84 solutes. It would be
difficult to obtain a good training set correlation by using only half of the experimental values.
To assess the predictive ability of Eq. 5.81 the parent data points were divided into three subsets
(A, B, C) as follows: the 1st, 4th, 7th, etc. data points comprise the first subset (A); the 2nd, 5th, 8th,
etc. data points comprise the second subset (B); and the 3rd, 6th, 9th, etc. data points comprise the
third subset (C). Three training sets were prepared as combinations of two subsets (A and B), (A
and C), and (B and C). For each training set, a correlation was derived:
Training Set (A and B)
ΔHSolv,t-BTOH (kJ/mole) = -2.573(1.333) + 3.879(1.648) E + 2.879(1.887) S -
56.003(2.721) A – 13.712(1.814) B - 8.947(0.348) L (5.83)
(with N = 56, SD = 2.476, R2 = 0.973, R2adj = 0.971, F = 363.8)
117
Training Set (A and C)
ΔHSolv,t-BTOH (kJ/mole) = -4.211(1.029) + 5.354(1.384) E + 1.275(1.643) S -
58.962(1.697) A – 8.885(1.988) B - 8.768(0.262) L (5.84)
(with N = 56, SD = 2.046, R2 = 0.985, R2adj = 0.984, F = 656.8)
Training Set (B and C)
ΔHSolv,t-BTOH (kJ/mole) = -2.838(1.471) + 4.439(1.804) E + 2.711(1.897) S -
57.282(2.304) A – 12.076(1.833) B - 8.938(0.347) L (5.85)
(with N = 56, SD = 2.803, R2 = 0.975, R2adj = 0.973, F = 393.6).
Each validation computation gave a training set correlation equation having coefficients not too
different from that obtained from the parent 84 c ompound database. T he training set equations
were then used to predict ΔHSolv,t-BTOH values for the compounds in the respective test sets (A, B,
and C ). T he s tatistical i nformation f or th e th ree te st s et p redictions a re s ummarized in Table
5.13. For the three test sets the average values of SD = 2.548, AAE = 1.763, and AE = -0.096. I
conclude that there is very little bias in the predictions based on Eqs. 5.83 – 5.85, and that Eq.
5.81 can be used to predict further values with an SD of about 2.55 kJ/mol.
Table 5.13. Summary of test set computations for tert-butanol
Training Set
Test Set Predictions (kJ/mol)
SD AAE AE A + B C 2.618 1.832 0.216 A + C B 3.398 2.226 0.186 B + C A 1.629 1.230 -0.691
118
Goss proposed101-105 a modified version of the Abraham model
SP = c + s · S + a · A + b · B + l · L + v · V (5.86)
that can also be used to describe transfer properties of a series of solutes between phases. More
than 40 different water-to-organic solvent, gas-to-organic solvent, gas-to-humic acid, and gas-to-
folvic a cid pa rtition s ystems ha ve be en r eported i n t he pub lished c hemical a nd e nvironmental
literature based on the Abraham model as modified by Goss.101-105 In the forementioned studies,
the solute property, SP, was the logarithm of the respective water-to-organic partition coefficient,
logarithm o f th e gas-to-organic s olvent p artition c oefficient, or l ogarithm of t he gas-to-humic
acid ( or f olvic a cid) pa rtition c oefficient. As part of t he p resent s tudy I also an alyzed t he
ΔHSolv,DMF and ΔHSolv,t-BTOH data in accordance with the Goss modified version of the Abraham
model
ΔHSolv,DMF (kJ/mole) = -3.279(1.113) – 17.088(1.765) S – 42.624(1.499) A –
7.427(1.255) B – 6.234(0.757) L – 3.468(2.877) V (5.87)
(with N = 159, SD = 3.070, R2 = 0.978, R2adj = 0.977, F = 1342.0)
ΔHSolv,t-BTOH (kJ/mole) = -1.430(1.383) + 2.394(1.787) S – 57.896(1.833) A -
13.375(1.413) B – 6.665(0.829) L – 7.672(3.052) V (5.88)
(with N = 84, SD = 2.559, R2 = 0.976, R2adj = 0.975, F = 637.3).
119
Both equations provide very good descriptions of the observed enthalpy of solvation data (see
Figure 5.20 for a plot of ΔHSolv,DMF based on Eq. 5.87 versus ex perimental v alues), and ar e
comparable in descriptive ability to Eqs. 5.78 and 5.81 based on the Abraham model.
Figure 5.20. A plot of the calculated values of ∆HSolv,DMF based on Eq. 5.87 against the observed values
The Abraham model and Goss modified version of the Abraham model both provide very
good mathematical descriptions of published enthalpy of solvation data for organic solutes and
gases di ssolved i n bot h N ,N-dimethylformamide a nd tert-butanol. O ne c an us e c orrelations
based on e ither m odel to pr edict of ΔHSolv values f or additional s olutes. F rom a p ersonal
standpoint the Abraham model is preferred because there is very little inter-correlation between
the five descriptors used in the two Abraham LFERs. There is however considerable correlation
between t he L and V solute de scriptors (see Table 5.14 and Table 5.15 for i nter-correlation
matrices).
120
Table 5.14. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.87
Table 5.15. Inter-correlation Matrix, in R2, for Solute Descriptors in Eq. 5.88
S A B L V
S 1.000
A 0.004 1.000
B 0.160 0.196 1.000
L 0.582 0.054 0.069 1.000
V 0.604 0.038 0.042 0.904 1.000
Moreover, predictions using the Goss form of the Abraham model require that the L descriptor
be know n. F or hi ghly nonvolatile s olutes, and f or c arboxylic a cids, t he e xperimental
determination of t he L descriptor is q uite d ifficult a nd e stimation methods are not always
reliable. The Abraham model allows one to estimate ΔHSolv values using the E, S, A, B, and V
solute descriptors (see Eqs. 5.79 and 5.82) which are more easily determined.
S A B L V
S 1.000
A 0.003 1.000
B 0.381 0.024 1.000
L 0.870 0.032 0.294 1.000
V 0.814 0.052 0.277 0.943 1.000
121
5.3.10. Acetonitrile and Acetone
Results and Discussion
Listed in Table S5.21 (Supplemental Material) are experimental values of ΔHSolv,ACN for
74 or ganic v apors and gases di ssolved i n a cetonitrile c overing a r easonably wide r ange o f
compound type and descriptor va lue. A nalysis of the experimental da ta yielded the following
two Abraham model correlation equations:
ΔHSolv,ACN (kJ/mole) = -4.148(0.657) + 3.304(1.215) E – 18.430(1.239) S –
26.104(1.385) A – 7.535(1.050) B – 6.727(0.254) L (5.89)
(with N = 74, SD = 2.171, R2 = 0.985, F = 900.39)
ΔHSolv,ACN (kJ/mole) = 2.650(1.109) – 3.000(1.410) E – 25.559(1.644) S –
30.397(1.801) A – 6.741(1.363) B – 24.961(1.247) V (5.90)
(with N = 74, SD = 2.781, R2 = 0.976, F = 543.5).
All regression analyses were performed using SPSS statistical software. Both Eqs. 5.89 and 5.90
provide a good s tatistical f it of the observed data with s tandard deviations of 2.171 and 2.781
kJ/mole for a da ta set that covers a r ange of 89.73 kJ /mole. S ee Figure 5.23 for a plot of the
calculated values ΔHSolv,ACN based on Eq. 5.89 against the observed values. Eq. 5.89 is slightly
the better equation statistically, and from a thermodynamic standpoint Eq. 5.89 is the enthalpic
derivative of the Abraham model’s gas-to-condensed phase transfer equation. Eq. 5.90 might be
more useful i n some pr edictive applications i n i nstances where t he L-descriptor i s not known.
Eq. 5.90 uses the McGowan volume, V-descriptor, which is easily calculable from the individual
122
atomic sizes and numbers of bonds in the molecule. T o my knowledge, Eqs. 5.89 and 5.90 are
the f irst expressions t hat a llow one t o pr edict t he e nthalpy of s olvation of gaseous s olutes i n
acetonitrile.
Figure 5.21. A plot of the calculated values of ΔHSolv,ACN (kJ/mole) based on Eq. 5.89 against the observed values.
In order to assess the predictive ability of Eq. 5.89, I divided the 74 data points into a
training s et a nd a te st set b y allowing th e S PSS s oftware to r andomly s elect h alf o f th e
experimental points. T he selected data points became the t raining set and the compounds that
were left served as the test set. Analysis of the experimental data in the training set gave
ΔHSolv,ACN (kJ/mole) = -4.608(1.105) + 2.996(1.906) E – 18.110(2.039) S –
25.396(2.296) A– 7.161(1.683) B – 6.715(0.393) L (5.91)
(with N = 37, SD = 2.237, R2 = 0.981, F = 325.5)
There is v ery little d ifference in th e e quation coefficients for th e f ull d ataset a nd th e tr aining
dataset correlations, thus showing that the training set of compounds is a representative sample
123
of the total data set. The training set equation was then used to predict ΔHSolv,ACN values for the
37 c ompounds i n the t est s et. F or t he pr edicted a nd e xperimental va lues, I find S D = 2.144,
AAE ( average a bsolute e rror) = 1.665 and A E ( average error) = 0.4 04 kJ /mole. T here i s
therefore very little bias in using Eq. 5.91 with AE equal to 0.404 kJ/mole. The training set and
test s et a nalyses were performed tw o mo re time s w ith s imilar r esults. T raining and t est
validations were also performed for Eq. 5.91. To conserve journal space, I give only the test set
results. T he de rived t raining s et correlation for E q. 5.91 predicted t he 3 7 experimental
ΔHSolv,ACN values in the test set to within a SD = 3.223, AAE = 2.416 and AE = 0.640. Again,
there is very little bias in the predictions using Eq. 5.91 with AE equal to 0.640 k J/mole. This
level of pr edictive e rror w ill be sufficient f or mo st p ractical c hemical a nd e ngineering
applications.
In Table S5.22 (Supplemental Material) are collected values of the enthalpies of solvation
of 81 gaseous solutes in acetone. Regression analyses of the experimental ΔHSolv,ACE data i n
accordance with the Abraham model yielded:
ΔHSolv,ACE (kJ/mole) = -4.811(0.568) + 4.397(1.295) E – 17.017(1.406) S –
36.105(1.748) A – 4.581(1.184) B – 7.326(0.226) L (5.92)
(with N = 81, SD = 2.645, R2 = 0.986, F = 1073.3)
ΔHSolv,ACE (kJ/mole) = 3.411(1.028) – 3.436(1.697) E – 25.312(1.969) S –
39.209(2.486) A – 4.076(1.679) B – 27.314(1.228) V (5.93)
(with N = 81, SD = 3.719, R2 = 0.973, F = 535.4).
124
There is little intercorrelation between the descriptors in Eqs. 5.92 and 5.93. The maximum inter-
correlation is R2 = 0.41 3 ( Eq. 5.92) an d R2 = 0.594 ( Eq. 5.93) b etween t he E and S solute
descriptors. Both Eqs. 5.92 and 5.93 are statistically very good with standard deviations of 2.715
and 3.719 kJ /mole f or a da taset t hat c overs a r ange of 117.31 kJ/mole. B oth e quations were
validated through t raining and test set analyses. Figure 5.24 compares the calculated values o f
HSolv,ACE based on E q. 5.92 against t he obs erved da ta. T o my knowledge t here has b een n o
previous attempt to correlate enthalpies of solvation for gaseous solutes in acetone.
Figure 5.22. A plot of the calculated values of ΔHSolv,ACE (kJ/mole) based on Eq. 5.92 against the observed values.
As part of the current study mathematical correlations were also developed equations for
acetonitrile
ΔHSolv,ACN (kJ/mole) = -2.794(1.255) - 18.737(1.657) S – 26.884(1.555) A –
8.128(1.039) B– 5.007(0.750) L – 5.818(3.170) V (5.94)
(with N = 74, SD = 2.232, R2 = 0.984, R2adj = 0.983, F = 851.5)
125
and for acetone
ΔHSolv,ACE (kJ/mole) = -3.778(1.212) – 15.512(1.885) S – 36.989(1.894) A –
6.272(1.182) B – 6.184(0.782) L – 3.403(3.243) V (5.95)
(with N = 81, SD =2.820, R2 = 0.984, R2adj = 0.983, F = 942.1)
based on the Goss Modified Abraham model.
There is considerable inter-correlation between the L and V solute descriptors, R2 = 0.919
(Eq. 5.94) and R2 = 0.925 (Eq. 5.95). Strong inter-correlations between the L and V descriptors
gave r ise t o t he l arge s tandard errors t hat are n oted i n t he v -coefficients. T he v ·V term w as
eliminated from the model, and the experimental enthalpy of solvation data was re-analyzed to
give
ΔHSolv,ACN(kJ/mole) = −4.784(0.642) − 16.289(1.000)S − 25.706(1.440)A −
8.961(0.951)B − 6.326(0.216)L (5.96)
(with N = 74, SD = 2.286, R2 = 0.984, R2adj = 0.983, F = 1028.3)
and
ΔHSolv,ACE(kJ/mole) = −4.879(0.605) − 13.943(1.148)S − 36.520(1.861)A−
6.860(1.041)B − 6.973(0.214)L (5.97)
(with N = 81, S.D.= 2.841, R2 = 0.984, R2adj = 0.983, F = 1175.8)
126
to predict the ΔHSolv for additional solutes dissolved in acetonitrile and in acetone. The calculated
ΔHSolv values can be used in conjunction with our existing correlation equations for predicting
gas-to-acetonitrile an d gas-to-acetone p artition coefficients. Published A braham m odel
correlation e xpressions pertain t o 298.15 K . T he c orrelations pr esented he re a llow one to
extrapolate predicted log K values to slightly higher and lower temperatures.
127
CHAPTER 6
CHARACTERIZATION OF THE PARTITIONING OF GASEOUS SOLUTES INTO HUMIC
ACID WITH THE ABRAHAM MODEL AND TEMPERATURE-INDEPENDENT
EQUATION COEFFICIENTS
6.1. Introduction
While I w as able to find sufficient experimental ΔHSolv data f or de riving pr edictive
expressions f or w ater and f or 21 organic s olvents ( see C hapter 5 ), one needs to de velop a n
alternative strategy that can be used in instances where there are too few measured ΔHSolv values
to obt ain a m eaningful c orrelation. In t his s tudy, t he i dea of i ncorporating a t emperature
dependence di rectly i nto t he e quation c oefficients i s e xplored. T he a pplicability o f t his ne w
form of the basic Abraham model will be assessed using published gas-to-humic acid partition
coefficient data Niederer et al.125 determined the Leonardite humic acid/air partition coefficients
of 188 nonpol ar a nd pol ar or ganic c ompounds at t emperatures be tween 5 a nd 75 ºC us ing a
dynamic f low-through t echnique. F or f our of the e ight t emperatures s tudied, t he a uthors103
tabulated the equation coefficients with a modified version of the Abraham model. At 288.15 K
and 98 % relative humidity, the derived correlation was103
Log KLHA (L/kgHA) = - 0.65(0.15) + 1.14(0.17) S + 3.62(0.13) A + 1.88(0.15)
+ 0.81(0.07) L + 0.08(0.27) V (6.1)
(with N = 158, R2 = 0.96, rmse = 0.32).
Thirty of t he c ompounds were excluded f rom t he r egression an alyses b ecause t he s olute
descriptors were not available. The statistics of Eq. 6.1, both in terms of the squared correlation
128
coefficient and root mean square e rror ( rmse), a re qui te good g iven the n ature of t he property
measured an d t hat t he ex perimental l og K LHA data s panned m ore t han a 7 l og uni t r ange.
Generally, b iological data have greater ex perimental uncertainties associated w ith t he r eported
values than do chemical p roperties such as the octanol/water partition coefficient o r saturation
solubilities. T he estimated uncertainty in the log KLHA values is believed to be about 0.17 log
units ba sed on t he a uthors’ obs ervation t hat di fferences be tween s eparately pr epared c olumns
and c olumn pa ckings t ypically a mounted to a n average s tandard d eviation of 0.17 l og uni ts.
Equation coefficients for the other three temperatures (298.15 K, 308.15 K, and 318.15 K) each
had a d ifferent s et o f numerical va lues, a nd while t he a uthors di d not pr ovide t he s tatistical
information of each correlation, I speculate that the statistics were comparable to those given for
Eq. 6.8.
The proposed m ethod of a nalyzing t he e xperimental l og K LHA data d iffers fro m o f
Niederer et al.103 in that the general Abraham equation for gas-to-condensed phase transfer (Eq.
2.2) has be en m odified so t hat ex perimental d ata m easured at d ifferent t emperatures can b e
included into a single correlation expression. T he proposed modification contains temperature-
independent e quation c oefficients. If s uccessful, t he m odification w ill a llow one t o de rive
Abraham correlations for many more processes than is possible with the existing computational
methodology that requires all regressed data be at the same temperature.
6.2. Experimental Methods
Past studies have shown that the basic Abraham model can describe both Gibbs energies3-
8,20,27,29,35,36,38,41,126,127
ΔGSolv = - 2.303 RT log K = cg + eg·E + sg·S + ag·A + bg·B + lg·L (6.2)
129
and enthalpies of solute transfer from the gas phase to a condensed phase12,99,100,109,111
ΔHSolv = ch + eh·E + sh·S + ah·A + bh·B + lh·L (6.3)
using a common set of five solute descriptors. T he subscripts “g” and “h” have been added to
the equation coefficients t o i ndicate t he numerical values ar e specific for t he r espective Gibbs
energy of s olvation a nd e nthalpy of s olvation i nto t he g iven s olvent. G iven t he doc umented
success of Eqs. 6.2 and 6.3 it would not be unreasonable to assume that the basic model would
be capable of describing the gas-to-liquid entropy of transfer, ΔSSolv,
ΔSSolv = cs + es·E + ss·S + as·A + bs·B + ls·L (6.4)
where the “s” subscript indicates the entropic component of the transfer process. Substituting the
individual Abraham correlations for ΔHSolv and ΔSSolv into ΔGSolv = ΔHSolv - T ΔSSolv yields
ΔGsolv = - 2.303 RT log K = ch + eh ·E + sh ·S + ah ·A + bh ·B + lh ·L - T (cs
+ es ·E + ss ·S + as ·A + bs ·B + ls ·L) (6.5)
and
LRT
lR
lBRT
bR
bART
aR
a
SRT
sR
sERT
eR
eRT
cR
cK
hshshs
hshshs
)303.2303.2
()303.2303.2
()303.2303.2
(
)303.2303.2
()303.2303.2
(303.2303.2
log
−+−+−
+−+−+−=
(6.6)
a r elatively simple m athematical expression. Over a s mall t emperature i nterval o ne w ould
expect bot h t he enthalpy and entropy o f s olvation t o be i ndependent of t emperature. If t his
assumption hol ds, t he t welve e quation c oefficients i n Eq. 6.6 are t emperature-independent
numerical values. Eq. 6.6 suggests a method for combining log K values measured at different
temperatures into a single correlation.
130
The N iederer et al .125 database o f experimental Leonardite h umic a cid/air p artition
coefficients contains numerical values for 188 nonpolar and polar organic compounds measured
at t emperatures b etween 5 a nd 75 ºC . For each s olute t he authors measured t he pa rtition
coefficient a t t hree o r f our di fferent t emperatures. N o compound w as s tudied a t all e ight
temperatures; however, the authors did give a value of KLHA for every compound at 288.15 K .
Thirty-six of the authors’ tabulated K LHA values at 288.15 K were ex trapolated from measured
values o btained at h igher t emperatures. V ery f ew m easurements w ere p erformed at t he t hree
higher temperatures (328.15, 338.15 a nd 348.15 K). I have converted the experimental humic
acid/gas partition coefficient data of Niederer et al .125 into log KHLA values, and have listed the
664 num erical va lues i n Table S 6.1 ( Supplementary M aterial) by t emperature. T he 36
extrapolated data points are given in bold font type.
Molecular descriptors for all of the compounds considered in the present study are also
tabulated i n Table S6.1 (Supplemental Materials). T he numerical va lues i n Table S6.1 came
from our s olute de scriptor da tabase, w hich no w contains va lues f or m ore t han 4,000 di fferent
organic a nd or ganometallic c ompounds. T he de scriptors w ere obt ained e xactly as de scribed
before, us ing v arious t ypes of e xperimental da ta, i ncluding w ater t o s olvent pa rtitions, g as t o
solvent partitions, solubility and chromatographic data2. S olute descriptors used in the present
study ar e al l b ased o n experimental d ata. T here i s al so co mmercial s oftware128 and s everal
published e stimation s chemes58,80,81,129 available f or cal culating t he n umerical v alues o f s olute
descriptors from molecular structural information if one is unable to find the necessary partition,
solubility and/or chromatographic data.
131
6.3. Results and Discussion
There is sufficient experimental log KLHA data at 278.15 K, 288.15 K, 298.15 K, 308.15
K and 318.15 K to develop a separate Abraham model correlation for each temperature. T hese
temperature-specific correlations provide a benchmark to use in assessing how much predictive
accuracy i s l ost w henever l og K LHA measured a t d ifferent temperatures ar e co mbined into a
single correlation. T he log KLHA values at 288.15 K in Table S6.1 were analyzed according to
the gas-to-condensed phase linear free energy relationship of the Abraham model to give
Log KLHA (L/kgHA) = - 0.766(0.112) – 0.177(0.106) E + 1.363(0.122) S +
3.659(0.124) A + 1.848(0.148) B + 0.808(0.025) L (6.7)
(with N = 162, R2 = 0.956, R2adj = 0.955, SD = 0.326, F = 684.44)
The regression analysis was performed using SPSS statistical software.50 Figure 6.1 compares
the observed log KLHA data at 288.15 K to calculated values based on Eq. 6.7. The statistics of
Eq. 6.7 are qui te g ood, a nd ar e co mparable t o t hose o f Eq. 6.1 published pr eviously. T his
observation i s i n a ccord w ith t he e arlier f indings of Flanagan et al .106 who c oncluded, a fter
comparing t he pr edictions of w ater-to-organic s olvent a nd g as-to-organic s olvent pa rtition
coefficients from Eqs. 2.1 and 2.2 of the Abraham model and the predictions from the modified
version of t he A braham m odel upon w hich Eq. 6.1 is ba sed, t hat the t wo m odels w ere
comparable in terms of their descriptive abilities.
132
Figure 6.1. A plot of the calculated values log KLHA on Eq. 6.7 against the observed values.
From a p ersonal s tandpoint, I prefer t he or iginal A braham m odel, Eqs. 2.1 a nd 2.2,
because it is easier for us to estimate E than it is for us to experimentally measure the solute’s
Ostwald coefficient in hexadecane. For liquid solutes, the excess molar refraction descriptor, E,
is obtained from the liquid refractive index. In the case of solid solutes, one either estimates a
hypothetical liquid r efractive i ndex us ing o ne o f s everal available m odels, o r can calculate E
directly through addition of fragments or substructures. I have had much less experience using
estimation s chemes f or L, a nd ha ve not h ad t he oppor tunity t o pr operly a ssess how good t he
methods are for multi-functional organic solutes. D espite my personal preferences I recognize
that Eq. 6.1 may h ave advances o ver Eq. 6.7 in c ertain a pplications. G oss101 noted t hat t he
generalized of Eq. 6.1 gave better results for predicting the gas-to-organic solvent and water-to-
organic solvent p artition coefficients of hi ghly f luorinated compounds. Superiority w as l ikely
due to the extreme E values (-0.5 to –1.5) that highly fluorinated compounds possess. The large
negative E values fall well out side of t he calibration c ompounds i n deriving my existing
correlations. However, I have recently shown130 that E values for highly fluorinated compounds
133
can be estimated quite easily well, and so there is now little reason to avoid Eq. 2.2 when dealing
with f luorinated c ompounds. For t he pr esent s tudy none of t he a fore-mentioned a dvantages
come i nto pl ay. T here a re onl y t wo hi ghly f luorinated c ompounds, 2,2,2 -trifluoroethanol a nd
1,1,1,3,3,3-hexafluoropropan-2-ol, in the data set and the L descriptors of all of the compounds
are kno wn. T he r eal a dvantage i n us ing Eq. 2.2 t o de scribe t he gas-to-humic a cid p artition
coefficient d ata i s t hat I can u se p rincipal co mponent an alysis ( PCA) t o co mpare t he d erived
KLHA correlation t o t he other gas-to-organic s olvent pa rtition e quations that I have d eveloped
previously. T he PCA that shortly follows compares the similarity of properties of the hydrated
humic acid phase to the properties of the different organic solvents studied previously.
In order to assess the predictive ability of Eq. 6.7, I divided the 162 data points into a
training set and a test set by allowing the SPSS software to randomly select half of experimental
values. The selected data points became the training set and the compounds that were left served
as the test set. Analysis of the 288 K experimental data in the training set gave
Log KLHA (L/kgHA) = - 0.718(0.168) – 0.220(0.152) E + 1.472(0.170) S +
3.563(0.190) A + 1.663(0.211) B + 0.805(0.036) L (6.8)
(with N = 81, R2 = 0.953, R2adj = 0.950, SD = 0.332, F = 302.69).
There is very little difference in the equation coefficients for the full dataset and training dataset
correlations. T he t raining set correlation was t hen used to pr edict l og KLHA values for t he 81
compounds in the test set. F or the predicted and experimental va lues, I find that SD = 0.328,
AAE (average absolute error) = 0.255 a nd the AE (average error) = -0.027. T here is therefore
very little bias in the predictions using Eq. 6.8 with AE equal to -0.027.
134
The ex perimental g as-to-humic a cid pa rtition c oefficient da ta a t 278.15 K , 298.15 K ,
308.15 K, and 318.15 K were analyzed in similar fashion. C oefficients for all five correlations
are tabulated in Table 6.1 along with the associated statistical information, where the values in
parenthesis indicate the standard errors in the coefficients. There were insufficient experimental
data to perform regression analyses at the three higher temperatures. Numerical values of all six
equation coefficients do change with temperature. In general the values decrease with increasing
temperature; however, there are a f ew exceptions as noted in Table 6.1. I did perform a quick
calculation with the coefficients to determine whether o r not the p roduct of temperature times
equation c oefficient(s) was c onstant ov er t his t emperature a s would be t he c ase i f t he Gibbs
energy of solvation was independent of temperature. My calculations did not find this to be the
case.
135
Table 6.1. Equation Coefficients for the Abraham Model Correlations for Describing the Gas-to-Humic Acid Partition Coefficient Data at Different Temperatures
c e s a b l N R2 R2adj SD F
Temperature = 278.15 K
-0.925 -0.329 1.419 4.114 2.061 0.902 102 0.886 0.88 0.335 146.156
(0.203) (0.174) (0.206) (0.259) (0.217) (0.041)
Temperature = 288.15 K
-0.766 -0.177 1.363 3.659 1.848 0.808 162 0.956 0.955 0.326 684.442
(0.112) (0.106) (0.122) (0.124) (0.148) (0.025)
Temperature = 298.15
-0.755 -0.257 1.397 3.319 1.712 0.768 118 0.907 0.903 0.313 217.772
(0.171) (0.135) (0.165) (0.169) (0.178) (0.034)
Temperature = 308.15 K
-0.551 -0.106 1.217 3.184 1.693 0.657 125 0.919 0.916 0.332 270.638
(0.156) (0.120) (0.139) (0.150) (0.168) (0.032)
Temperature = 318.15 K
-0.475 -0.09 1.251 2.944 1.572 0.587 107 0.916 0.912 0.323 219.743
(0.169) (0.124) (0.141) (0.142) (0.175) (0.034)
136
There a re 664 e xperimental l og K LHA values i n Table S 6.1 de termined at 8 d ifferent
temperatures. T he en tire s et o f n umerical v alues w ere an alyzed co llectively b y regression
analysis to yield the following correlation
logKLHA (L /kgL HA ) = cs −ch
T+ (es −
eh
T)E + (ss −
sh
T)S + (as −
ah
T)A + (bs −
bh
T)B + (ls −
lh
T)L (6.9)
(with N = 664, R2 = 0.930, R2adj = 0.929, SD = 0.327, F = 788.575) .
The c alculated eq uation co efficients are l isted i n Table 6.2. E xamination of t he num erical
entries in Table 6.2 reveals that the coefficients do have a fairly large uncertainty, which I think
may be due to either the quality of the experimental data used in the regression analysis or the
coefficients may have a slight temperature dependence that was not incorporated into the model.
I also note that the extraction of the separate enthalpic and entropic contributions to the transfer
process is further complicated because these two effects tend to compensate each other. A large
exothermic e nthalpic s olute-solvent i nteraction of ten r esults i n “ molecular or dering” and
decreased system entropy. T he net effect is a r educed Gibbs energy of transfer, which one can
model fairly accurately. However, to back out the much larger individual enthalpic and entropic
effects is not an easy task, particularly in the case of biological data that typically has a sizeable
experimental uncertainty in the measured values.
137
Table 6.2. Temperature-Independent Equation Coefficients for Eq. 6.9 of the Abraham Model for Correlating the Gas-to-Humic Acid Partition Coefficients
Coefficient Numerical Value Coefficient Numerical Value Coefficient Numerical Value
Entire Database of 664 Observed Values Training Set (Method A)a Training Set (Method B)b
cs 1.589(1.019) cs 1.627(1.608) cs 1.491(1.587)
ch 676.4(304.0) ch 702.29(482.00) ch 649.62(473.063)
es 1.145(0.887) es 1.355(1.308) es 0.200(1.334)
eh 394.5(268.7) eh 440.17(395.82) eh 114.34(404.25)
ss 0.419(1.060) ss -0.363(1.691) ss 0.982(1.568)
sh -268.3(320.4) sh -478.96(508.58) sh -103.61(475.50)
as -5.120(1.060) as -3.729(1.680) as -4.710(1.623)
ah -2541.4(322.5) ah -2127.54(506.91) ah -2414.53(494.76)
bs -0.264(1.349) bs 0.889(2.000) bs 0.281(2.048)
bh -613.7(404.9) bh -309.75(600.05) bh -459.13(616.23)
ls -1.449(0.219) ls -1.521(0.349) ls -1.499(0.332)
lh -651.4(65.63) lh -676.19(104.43) lh -666.65(99.65) a Method A: N = 332, R2 = 0.925, R2
adj = 0.922, SD = 0.334, F = 356.946.
b Method B: N = 333, R2 = 0.930, R2adj = 0.928, SD = 0.324, F = 388.151.
138
The intended application of Eq. 6.9 is to a llow one to estimate gas-to-condensed phase
partition co efficients as a f unction o f t emperature w henever t here i s i nsufficient ex perimental
data to develop a predictive expression for the desired temperature. I will continue to develop
temperature-specific c orrelations a nd e nthalpy of s olvation c orrelations w henever t here i s
sufficient experimental data to d o s o. In in stances o f limited experimental d ata a t a common
temperature, Eq. 6.9 can b e u sed t o de velop a s trictly predictive expression b y c ombining
experimental data measured at different temperatures. Given the intended application, Eq. 6.9 is
statistically very good and describes an experimental database that covers a 7.5 log unit range to
within a s tandard de viation of 0.327 l og uni ts ( see Figure 6.2 for a graphical c omparison of
observed log KLHA data versus calculated values based on Eq. 6.9). S tandard deviations for the
temperature-specific equations (see Table 6.1) were also in the 0.32 log unit range.
Figure 6.2. A plot of the calculated values log KLHA on Eq. 6.9 against the observed values.
139
As part of my data analyses I estimated how much predictive ability was likely to be lost
as a r esult of using Eq. 6.9 and the coefficients in Table 6.2 to predict log K LHA values rather
than us ing t he t emperature-specific c orrelations t hat w ere de veloped f or 278.15 K, 288.15 K ,
298.15 K , 308.15 K a nd 318.15 K . T o ha ve a common ba sis f or c omparison, t he di fference
between observed and calculated values based on Eq. 6.9 were expressed as
6)log(log 2
−−
=N
KKSD obscalc (6.10)
for each of the f ive temperatures that I had a t emperature-specific Abraham model correlation.
The r esults of my computations a re s ummarized i n Table 6.3. For the f ive t emperatures
considered, the standard deviations of Eq. 6.9 and the temperature-specific correlations differ by
approximately 0.01 log units. There is no loss in predictive ability due to my proposed method
of combining experimental data measured at different temperatures into a single correlation.
Table 6.3. Summarized Comparison of the Descriptive Ability of Eq. 6.9 Versus the Temperature-Specific Abraham Model Correlation Equations
Standard Deviation (SD)a Temperature Equation 6.9 Temperature-Specific Equations 278.15 K 0.347 0.335 288.15 K 0.334 0.326 298.15 K 0.325 0.313 308.15 K 0.341 0.332 318.15 K 0.332 0.323
140
The advantage that Eq. 6.9 has over the temperature-specific Abraham model correlation
is that one is able to utilize more of the available experimental data. For example, let’s assume
that o ne w as ab le t o f ind l og K LHA data f or 20 compounds a t 278.15 K , l og K LHA data f or a
different set of 20 compounds at 298.15 K and log KLHA data for a third set of 20 compounds at
328.15 K . T here w ould be i nsufficient e xperimental da ta t o de velop a n A braham m odel
correlation. G enerally one ne eds a m inimum of 30 t o 40 d ata poi nts ( preferably more) t o
develop a meaningful correlation equation, and the compounds need to span as wide of a range
of solute descriptors as possible. B y combining the 60 l og K LHA values into a s ingle database
one could develop a predictive expression based on Eq. 6.9. T he calculated coefficients would
likely have a fairly large standard deviation; however, the regression equation would allow one
to estimate log KLHA values for additional compounds. Such predictions would otherwise not be
possible w ith my existing r egression m odel t hat requires all ex perimental d ata b e at t he s ame
temperature.
To f urther as sess t he p redictive ab ility o f Eq. 6.7 I divided t he 664 da ta poi nts i nto a
training set and a test set by allowing the SPSS software to randomly select half of experimental
values. T wo r andom s election pr ocedures w ere e mployed: M ethod A i nvolved ha ving S PSS
select 332 data points from the entire database; Method B involved dividing the large database
into temperature subsets and letting SPSS select ha lf of the data points f rom each of the e ight
individual temperature subsets. The latter method insured that there was equal representation of
data points by temperature in the training set and test set. The selected data points became the
training set and the compounds that were left served as the test set. Analysis of the experimental
data in the training set gave the equation coefficients that are lis ted in the last two columns of
numerical entries in Table 6.2. T he s tatistical i nformation for e ach tr aining s et correlation is
141
listed in the Table 6.2 footnote. Each training set correlation had a squared correlation of R2 >
0.925 and a standard deviation of SD < 0.334. The training set correlations were then used to
predict the log KLHA values in the respective test sets. For the predicted and experimental values,
I find that SD = 0.330 for Method A and SD = 0.328 for Method B, AAE = 0.260 for Method A
and AAE = 0.253 for Method B, and the AE = -0.042 for Method A and AE = -0.046 for Method
B. There is therefore very little bias in the predictions using two training set equations with AE
equal to –0.042 (Method A) and –0.046 (Method B).
At the suggestion of a reviewer several of the terms in Eq. 6.9 were successively zeroed
out to d etermine i f a b etter m athematical co rrelation co uld b e o btained. It w as found t hat t he
following ten-parameter equation
LogKLHA =1.693(0.833) −708.088(247.738)
T+ 1.389(0.633) −
468.365(191.788)T
E
+394.699(18.176)
TS + −5.074(1.052) +
2528.05(320.15)T
A +
534.19(21.981)T
B
+ −1.456(0.217) +653.881(64.916)
T
L
(6.11)
(with N = 664, R2 = 0.930, R2adj = 0.929, SD = 0.327, F = 966.52)
also provided a very good mathematical description of the 664 experimental gas-to-humic acid
partition coefficients. T he standard deviation and squared correlation coefficient is comparable
to th at o f Eq. 6.9 , a nd t he t en-parameter equation doe s ha ve s maller s tandard e rrors for t he
derived equation coefficients. Substitution of T = 288.15 K into Eq. 6.11 yielded
log KLHA(L/kgHA) = -0.764 – 0.236E + 1.369S + 3.699A + 1.854B + 0.813L (6.12)
142
which is in good agreement with the temperature-specific correlation determined using only the
288.15 K partition coefficient data. Equation 6.11 was validated by dividing the 664 data points
into a training set and a test set.
As pointed out above, the coefficients e to l in Eq. 2.2 reflect the properties of the solvent
phase in terms of solute– solvent phase interactions. Since exactly the same form of Eq. 2.2 has
been used to correlate gas to solvent partition coefficients for a wide variety of solvents, one is
now in a position to compare the properties of humic acid with those of solvents that have been
previously characterized. V alues o f t he co efficients i n E q. 2 .2 for a n umber o f g as-to-solvent
partitions are given in Table 6.4; these include two room temperature ionic l iquids.131 It is not
easy to compare coefficients in such a table, but a useful visual method is through PCA. The five
columns of coefficients are transformed into five orthogonal columns or PCs. The advantage of
this procedure is that the first two PCs contain, in the present case, 79% of the total information.
Hence, a p lot o f t he s cores o f P C2 ag ainst P C1 w ill g ive a r easonable t wo-dimensional
visualization of t he f ive-dimensional s pace of t he e t o l coefficients. S uch a pl ot i s s hown i n
Figure 6.3; the point for water is so far away from the other points and has been left off the plot.
143
Figure 6.3. A plot of the scores of PC2 against the scores of PC1; points numbered as in Table 6.4. The point for water, no. 25, is off-scale as shown by the arrow.
In the PCA plot, the nearer the points, the closer are the coefficients and hence the closer
are the solvents chemically, i.e. in terms of solute – solvent interactions. It can be seen that the
points for humic acid at various temperatures (Nos. 1 – 5) are closer to solvents that are generally
“polar” than to “nonpolar” solvents, with solvents methanol (No. 6), wet octanol (No. 11), and
N-methylformamide ( No. 1 2) b eing especially close. T hese are al l s olvents t hat ar e d ipolar,
strong hydrogen bond ba ses and, for methanol and wet octanol, strong hydrogen bond a cids. In
the P CA pl ot, poi nts f or s olvents t hat are di polar, s trong h ydrogen b ond acids and s trong
hydrogen bond b ases t end t o l ie t owards t he t op r ight ha nd corner, a nd poi nts f or nonpol ar
solvents such as hexadecane (No. 21) and cyclohexane (No. 22) lie towards the bottom left hand
corner. Over the wide range of solvents listed in Table 6.4, humic acid can be considered to be in
the class of highly dipolar and strong hydrogenbond solvent phases.
144
Table 6.4. Coefficients in Eq. 2.2 for Gas-to-Solvent Phase Partitions
Phase N e s a b l
Humic acid, 278 1 - 0.329 1.419 4.114 2.061 0.902
Humic acid, 288 2 - 0.177 1.363 3.659 1.848 0.808
Humic acid, 298 3 -0.257 1.397 3.319 1.712 0.768
Humic acid, 308 4 -0.106 1.217 3.184 1.693 0.657
Humic acid, 318 5 -0.090 1.251 2.944 1.572 0.587
Methanol 6 -0.215 1.173 3.701 1.432 0.769
Ethanol 7 -0.206 0.789 3.635 1.311 0.853
1-Butanol 8 - 0.276 0.539 3.781 0.995 0.934
1-Octanol 9 - 0.203 0.560 2.560 0.702 0.939
Ethylene glycol 10 0.217 1.427 4.474 2.687 0.568
1-Octanol (wet) 11 0.002 0.709 3.519 1.429 0.858
N-methylformamide 12 - 0.259 2.003 4.559 0.430 0.706
Ethyl acetate 13 - 0.335 1.251 2.949 0.000 0.917
Acetone 14 -0.277 1.522 3.258 0.000 0.863
aAn ionic liquid, see Abraham and Acree.131
(table continues)
145
Table 6.4 (continued).
Phase N e s a b l
Ether 15 -0.169 0.873 3.402 0.000 0.882
Acetonitrile 16 - 0.595 2.461 2.085 0.418 0.738
Chloroform 17 - 0.467 1.203 0.138 1.432 0.994
Chlorobenzene 18 - 0.053 1.254 0.364 0.000 1.041
Nitrobenzene 19 0.121 1.682 1.247 0.370 0.915
Toluene 20 - 0.222 0.938 0.467 0.099 1.012
Hexadecane 21 0.000 0.000 0.000 0.000 1.000
Cyclohexane 22 - 0.110 0.000 0.000 0.000 1.013
[MEIM]+ [Tf 2N]- a 23 0.150 2.280 2.170 1.040 0.629
[M2EIM]+[Tf 2N]- a 24 0.210 2.350 2.080 0.900 0.655
Water 25 0.822 2.743 3.904 4.814 . 0.213
aAn ionic liquid, see Abraham and Acree.131
146
CHAPTER 7
SUMMARY
The Abraham general solvation model is a linear free energy relationship that can be used
to understand the types and relative strengths of chemical interactions controlling gas-to liquid or
solvent-to-liquid pa rtitioning, a nd c an a lso be u sed t o pr edict p artitioning p rocesses. In t his
dissertation, s everal a pplications of t he Abraham ge neral s olvation m odel are presented t o
illustrate the usefulness of using the model to describe partitioning processes in various chemical
and biological systems.
The s tudy pr esented i n Chapter 4 , s pecifically lo oks at u sing th e mo del to p redict
Minimum Inhibitory Concentrations of organic compounds for growth inhibition towards three
bacteria Porphyromonas gingivalis, Selenomonas artemidis, a nd Streptococcus sobrinus. T he
derived mathematical co rrelations describe the observed publ ished inhibitory data to within an
overall average s tandard de viation of a pproximately 0.30 l og uni ts. A principal c omponent
analysis, shows that the derived equations for the three growth inhibitions are close to each other,
are near to some, but not to all, equations for aqueous toxicity toward various organisms, and are
quite far from most equations for water to solvent partition. F urther analysis suggests that the
three g rowth inhibition s ystems behave as t hough a solute i s t ransferred f rom w ater t o an
environment that is still quite water-like.
In Chapter 5, I e xpanded t he us e of t he A braham m odel t o t emperature c onsiderations
other than 298.15 K through several studies predicting enthalpies of solvation of gaseous solutes.
Mathematical co rrelations are derived f or t he enthalpies of s olvation of ga seous s olutes of
various c ompounds di ssolved i n w ater, 1 -octanol, h exane, h eptane, h exadecane, c yclohexane,
benzene, t oluene, c arbon t etrachloride, c hloroform, m ethanol, ethanol, 1 -butanol, pr opylene
147
carbonate, dimethyl sulfoxide, 1,2-dichloroethane, N,N-dimethylformamide, tert-butanol, dibutyl
ether,ethyl acetate, acetonitrile, and acetone.
In chapter 5 I am able to find sufficient experimental ∆Hsolv data for deriving predictive
expressions for water and for the 21 organic solvents, however, there is still a need to develop an
alternative strategy that can be used in instances where there are too few measured ∆Hsolv values
to obt ain a m eaning f ull c orrelation. In C hapter 6, t he i dea of i ncorporating t emperature
dependence directly into the equation coefficients is explored. The Abraham model is modified
so t hat ex perimental d ata m easured at d ifferent t emperatures c an be i ncluded i nto a s ingle
correlation e xpression, a nd t he a pplicability of t his ne w f orm of t he ba sic A braham m odel is
assessed us ing publ ished e xperimental g as-to-humic a cid pa rtition coefficient da ta. T he
successful modification of the equation now gives the ability to derive Abraham correlations for
many mo re pr ocesses t han w as pr eviously a vailable w ith t he e xisting c omputational
methodology that required all regressed data to be at the same temperature.
149
CHAPTER 4
Table S4.1. Molecular solute descriptors of organic compounds considered in the Minimum Inhibitory Concentration study.
Solute E S A B V
Phenol 0.81 0.89 0.60 0.30 0.78
2-Methylphenol 0.84 0.86 0.52 0.30 0.92
3-Methylphenol 0.82 0.88 0.57 0.34 0.92
4-Methylphenol 0.82 0.87 0.57 0.31 0.92
2-Ethylphenol 0.83 0.84 0.52 0.37 1.06
3-Ethylphenol 0.83 0.84 0.52 0.37 1.06
4-Ethylphenol 0.80 0.90 0.55 0.36 1.06
2-Propylphenol 0.82 0.86 0.52 0.37 1.20
3-Propylphenol 0.79 0.90 0.55 0.37 1.20
4-Propylphenol 0.79 0.88 0.55 0.37 1.20
2-Allylphenol 0.92 0.92 0.52 0.41 1.16
2-Isopropylphenol 0.84 0.88 0.52 0.38 1.20
3-Isopropylphenol 0.81 0.92 0.55 0.38 1.20
4-Isopropylphenol 0.79 0.89 0.55 0.38 1.20
2-Butylphenol 0.81 0.84 0.52 0.37 1.34
3-Butylphenol 0.80 0.91 0.55 0.37 1.34
4-Butylphenol 0.80 0.88 0.55 0.37 1.34
2-Isobutylphenol 0.82 0.88 0.52 0.38 1.34
3-Isobutylphenol 0.80 0.87 0.52 0.38 1.34
4-Isobutylphenol 0.80 0.87 0.52 0.38 1.34
150
Solute E S A B V
(±)-2-sec-Butylphenol 0.82 0.91 0.52 0.41 1.34
(±)-3-sec-Butylphenol 0.80 0.90 0.55 0.40 1.34
(±)-4-sec-Butylphenol 0.80 0.89 0.55 0.41 1.34
2-tert-Butylphenol 0.82 0.92 0.52 0.40 1.34
3-tert-Butylphenol 0.80 0.91 0.55 0.42 1.34
4-tert-Butylphenol 0.81 0.89 0.56 0.39 1.34
2-Pentylphenol 0.81 0.86 0.52 0.35 1.48
3-Pentylphenol 0.80 0.86 0.55 0.35 1.48
4-Pentylphenol 0.79 0.88 0.55 0.36 1.48
4-tert-Pentylphenol 0.81 0.89 0.56 0.41 1.48
2-Hexylphenol 0.80 0.86 0.52 0.35 1.62
4-Heptylphenol 0.79 0.88 0.55 0.35 1.76
4-Octylphenol 0.77 0.88 0.55 0.36 1.90
4-tert-Octylphenyl 0.79 0.91 0.55 0.41 1.90
2-Cyclohexylphenol 1.07 1.00 0.52 0.44 1.51
3-Cyclohexylphenol 1.07 0.98 0.55 0.39 1.51
4-Cyclohexylphenol 1.07 0.98 0.55 0.39 1.51
2-Cyclohexylmethylphenol 1.14 0.99 0.52 0.40 1.65
3-Cyclohexylmethylphenol 1.14 0.99 0.52 0.40 1.65
4-Cyclohexylmethylphenol 1.14 0.99 0.52 0.40 1.65
4-(1-Adamantyl)phenol 1.46 1.56 0.52 0.44 1.86
2,4-Dimethylphenol 0.84 0.80 0.53 0.39 1.06
2,6-Dimethylphenol 0.86 0.79 0.39 0.39 1.06
3,5-Dimethylphenol 0.82 0.84 0.57 0.36 1.06
151
Solute E S A B V
2-tert-Butyl-4-methylphenol 0.82 0.91 0.49 0.42 1.48
2-tert-Butyl-6-methylphenol 0.83 0.88 0.37 0.56 1.48
2,6-Diisopropylphenol 0.82 0.88 0.32 0.51 1.62
Thymol 0.82 0.79 0.52 0.44 1.34
Carvarol 0.82 0.81 0.54 0.36 1.34
2,4-Di-tert-butylphenol 0.83 0.92 0.44 0.50 1.90
2,6-Di-tert-butylphenol 0.84 0.90 0.23 0.54 1.90
3,5-Di-tert-butylphenol 0.81 0.93 0.51 0.50 1.90
2-tert-Butyl-4-cyclohexylphenol 1.02 0.93 0.41 0.55 2.08
2-tert-Octyl-4-cyclohexylphenol 1.00 0.94 0.41 0.55 2.64
2-Cyclohexyl-4-tert-octylphenol 1.00 0.94 0.41 0.55 2.64
2-tert-Butyl-5-cyclohexylphenol 1.02 0.93 0.41 0.55 2.08
2-tert-Octyl-5-cyclohexylphenol 1.00 0.94 0.41 0.55 2.64
2-(1-Adamantyl)-4-methylphenol 1.47 1.58 0.52 0.46 2.00
α-Tetralol 1.04 0.90 0.34 0.68 1.23
β-Tetralol 1.04 0.90 0.34 0.75 1.23
2-Phenylphenol 1.55 1.40 0.56 0.49 1.38
4-Phenylphenol 1.56 1.41 0.59 0.45 1.38
2-tert-Butyl-5-phenylphenol 1.42 1.43 0.55 0.55 1.95
2-Benzylphenol 1.44 1.38 0.52 0.50 1.52
152
Solute E S A B V
4-Benzylphenol 1.44 1.38 0.55 0.50 1.52
α-Naphthol 1.52 1.05 0.60 0.37 1.14
β-Naphthol 1.52 1.08 0.61 0.40 1.14
2-Methoxyphenol 0.84 0.91 0.22 0.52 0.98
3-Methoxyphenol 0.88 1.17 0.59 0.38 0.98
4-Methoxyphenol 0.90 1.17 0.57 0.48 0.98
Eugenol 0.95 0.99 0.22 0.51 1.35
2-Ethoxyphenol 0.81 0.90 0.20 0.58 1.12
3-Ethoxyphenol 0.85 1.16 0.56 0.45 1.12
4-Ethoxyphenol 0.87 1.17 0.57 0.52 1.12
4-Propoxyphenol 0.84 1.17 0.57 0.52 1.26
2-Isopropoxyphenol 0.80 0.90 0.20 0.67 1.26
3-Butoxyphenol 0.81 1.17 0.54 0.47 1.40
4-Butoxyphenol 0.84 1.16 0.57 0.52 1.40
4-Pentoxyphenol 0.85 1.14 0.57 0.49 1.44
4-Hexyloxyphenol 0.85 1.12 0.57 0.46 1.68
4-Heptyloxyphenol 0.84 1.12 0.57 0.46 1.82
2-Cyclohexylmethoxyphenol 1.00 1.08 0.30 0.60 1.71
3-Cyclohexylmethoxyphenol 1.00 1.27 0.55 0.47 1.71
4-Cyclohexylmethoxyphenol 1.00 1.27 0.57 0.47 1.71
4-Phenoxyphenol 1.41 1.36 0.57 0.47 1.44
2-Benzyloxyphenol 1.39 1.20 0.20 0.74 1.58
3-Benzyloxyphenol 1.41 1.41 0.55 0.61 1.58
4-Benzyloxyphenol 1.41 1.41 0.57 0.61 1.58
153
Solute E S A B V
2-Acetylphenol 0.95 1.14 0.00 0.42 1.07
3-Acetylphenol 0.98 1.35 0.72 0.55 1.07
4-Acetylphenol 1.01 1.15 0.76 0.54 1.07
2-Propionylphenol 0.94 1.18 0.00 0.42 1.21
4-Propionylphenol 1.00 1.30 0.77 0.55 1.21
2-Benzoylphenol 1.65 1.49 0.00 0.55 1.54
3-Benzoylphenol 1.65 1.68 0.70 0.65 1.54
4-Benzoylphenol 1.65 1.68 0.70 0.65 1.54
2-Fluorophenol 0.66 0.69 0.61 0.28 0.79
3-Fluorophenol 0.67 0.98 0.68 0.17 0.79
4-Fluorophenol 0.67 0.97 0.63 0.23 0.79
2-Bromophenol 1.04 0.90 0.35 0.31 0.95
3-Bromophenol 1.06 1.15 0.70 0.16 0.95
4-Bromophenol 1.08 1.17 0.67 0.20 0.95
2,6-Difluorophenol 0.59 0.69 0.63 0.23 0.81
2,6-Dichlorophenol 0.90 0.90 0.38 0.24 1.02
2,6-Dibromophenol 1.27 0.93 0.47 0.22 1.13
2-Cyanophenol 0.92 1.33 0.78 0.34 0.93
3-Cyanophenol 0.93 1.55 0.84 0.25 0.93
4-Cyanophenol 0.94 1.63 0.80 0.29 0.93
2-Hydroxyacetanilide 1.05 1.56 1.09 0.79 1.17
3-Hydroxyacetanilide 1.05 1.70 1.09 0.78 1.17
4-Hydroxyacetanilide 1.06 1.63 1.04 0.86 1.17
3-Nitro-2-methylphenol 1.08 1.52 0.75 0.26 1.09
154
Solute E S A B V
3-Nitro-4-methylphenol 1.07 1.57 0.77 0.25 1.09
6-Nitro-3-methylphenol 1.03 1.05 0.05 0.41 1.09
4-Nitro-3-methylphenol 1.10 1.65 0.83 0.25 1.09
2’-Nitro-4-hydroxybiphenyl 1.74 1.86 0.57 0.53 1.56
4’-Nitro-4-hydroxybiphenyl 1.75 1.84 0.57 0.54 1.56
5-Hydroxyindole 1.45 1.32 0.60 0.60 1.01
6-Hydroxyquinoline 1.62 1.25 0.60 0.61 1.10
8-Hydroxyjulolidine 1.48 1.28 0.52 0.75 1.50
(+)-Totarol 1.16 1.10 0.50 0.48 2.53
(+)-Ferruginol 1.16 1.15 0.40 0.47 2.53
Triclosan 1.85 1.70 0.40 0.31 1.81
Indole 1.20 1.12 0.44 0.22 0.95
Quinoline 1.27 0.97 0.00 0.54 1.04
2-Nitrotoluene 0.87 1.11 0.00 0.27 1.03
3-Nitrotoluene 0.87 1.10 0.00 0.25 1.03
2-Nitrobiphenyl 1.63 1.51 0.00 0.39 1.50
3-Nitrobiphenyl 1.66 1.48 0.00 0.38 1.50
4-Nitrobiphenyl 1.66 1.49 0.00 0.39 1.50
4-Propylanisole 0.73 0.80 0.00 0.33 1.34
(2S,5R)-(-)menthone 0.32 0.61 0.00 0.62 1.43
(1S,2R,5S)-(+)-menthol 0.40 0.50 0.23 0.58 1.47
(1R,2S,5R)-(-)-menthol 0.40 0.50 0.23 0.58 1.47
(1S,2R,5R)-(+)-isomenthol 0.40 0.50 0.23 0.58 1.47
155
CHAPTER 5
Table S5.1. Values of the gas to water solvation enthalpy in kJ/mol at 298K for 370 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Chlorine gas 0.36 0.32 0.10 0.00 1.19 0.34 -23.40 1
Hydrogen sulfide 0.35 0.31 0.10 0.07 0.72 0.27 -18.00 1
Hydrogen selenide 0.50 0.30 0.03 0.09 1.06 0.32 -15.70 1
Chlorine dioxide 0.10 0.46 0.00 0.30 0.55 0.33 -27.80 1
Sulphur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -20.70 2
Ammonia 0.14 0.39 0.16 0.56 0.32 0.30 -35.40 1
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -12.00 2
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -17.90 2
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -20.40 2
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -24.80 2
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -21.70 2
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -28.30 3
2,2-Dimethylpropane 0.00 0.00 0.00 0.00 1.82 0.81 -23.40 2
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -31.90 2
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -30.50 2
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 0.95 -36.80 2
2,3-Dimethylbutane 0.00 0.00 0.00 0.00 2.50 0.95 -32.40 2
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -34.00 3
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -36.00 3
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -31.00 2
2,3,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.48 1.24 -38.50 2
156
Solute E S A B L V Exp Ref
Cyclopropane 0.41 0.23 0.00 0.00 1.31 0.42 -15.40 2
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.71 -30.33 3
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -30.00 2
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -38.30 2
trans-1,2-Dimethylcyclohexane 0.23 0.20 0.00 0.00 3.73 1.13 -36.10 2
Ethylcyclohexane 0.26 0.10 0.00 0.00 3.88 1.13 -36.80 2
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -39.00 2
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -13.70 2
Propene 0.10 0.08 0.00 0.07 0.95 0.49 -21.60 3
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -24.10 3
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -30.40 2
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -39.20 1
2-Methylpropene 0.12 0.08 0.00 0.08 1.58 0.63 -22.70 2
2-Methyl-2-butene 0.06 0.06 0.00 0.05 1.93 0.77 -26.61 4
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -31.40 2
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -27.30 2
Cyclooctene 0.46 0.24 0.00 0.10 4.12 1.08 -45.50 2
Propyne 0.18 0.25 0.12 0.10 1.03 0.45 -15.60 2
1-Butyne 0.18 0.25 0.12 0.10 1.03 0.59 -13.50 2
Fluoromethane 0.07 0.35 0.00 0.09 0.06 0.27 -16.10 2
Difluoromethane -0.32 0.49 0.06 0.05 0.04 0.30 -17.20 2
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 0.32 -13.50 2
157
Solute E S A B L V Exp Ref
1,1-Difluoroethane -0.25 0.47 0.04 0.07 0.57 0.43 -20.70 2
Trifluoromethane -0.43 0.18 0.11 0.03 -0.27 0.30 -22.60 2
1,1,1,2-Tetrafluoroethane -0.39 0.16 0.16 0.05 0.40 0.46 -22.20 2
Pentafluoroethane -0.51 -0.02 0.11 0.06 0.10 0.48 -21.50 2
1,1,1,2,3,3,3-Heptafluoropropane -0.69 0.05 0.06 0.03 0.65 0.66 -24.80 2
Chloromethane 0.25 0.43 0.00 0.08 1.16 0.37 -20.20 2
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -30.30 2
Trichloromethane 0.43 0.49 0.15 0.02 2.48 0.62 -33.50 2
Tetrachloromethane 0.46 0.38 0.00 0.00 2.82 0.74 -30.50 5
Chloroethane 0.23 0.40 0.00 0.10 1.68 0.51 -22.00 2
1,1-Dichloroethane 0.32 0.49 0.10 0.10 2.32 0.64 -30.30 2
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -27.90 2
1,1,1-Trichloroethane 0.37 0.41 0.00 0.09 2.73 0.76 -28.70 2
1,1,2-Trichloroethane 0.50 0.68 0.13 0.13 3.29 0.76 -32.50 2
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -34.80 2
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 0.88 -36.20 2
1-Chloropropane 0.22 0.40 0.00 0.10 2.20 0.65 -27.00 2
1,2-Dichloropropane 0.37 0.63 0.00 0.17 2.84 0.78 -31.10 2
1,3-Dichloropropane 0.41 0.74 0.00 0.17 3.10 0.78 -29.70 2
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.80 -28.20 2
2-Chlorobutane 0.19 0.35 0.00 0.12 2.54 0.80 -34.60 2
1-Chloropentane 0.21 0.38 0.00 0.09 3.22 0.94 -34.10 2
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 1.08 -34.50 2
158
Solute E S A B L V Exp Ref
Tetrafluoroethene -0.31 -0.10 0.00 0.00 -0.05 0.42 -15.10 2
Hexafluoropropene -0.50 -0.10 0.00 0.10 0.34 0.60 -17.40 2
1,1-Dichloroethylene 0.36 0.34 0.00 0.05 2.11 0.59 -28.50 2
cis-1,2-Dichloroethylene 0.44 0.61 0.11 0.05 2.44 0.59 -26.90 6
trans-1,2-Dichloroethylene 0.43 0.41 0.09 0.05 2.28 0.59 -29.30 6
Trichloroethylene 0.52 0.37 0.08 0.03 3.00 0.72 -32.20 2
Tetrachloroethylene 0.64 0.44 0.00 0.00 3.58 0.84 -41.50* 1
Bromomethane 0.40 0.43 0.00 0.10 1.63 0.42 -23.80 2
Dibromomethane 0.71 0.69 0.11 0.07 2.89 0.60 -33.00 2
Tribromomethane 0.97 0.68 0.15 0.06 3.78 0.78 -35.80 1
Bromoethane 0.37 0.40 0.00 0.12 2.12 0.57 -29.50 2
2-Methyl-2-bromopropane 0.31 0.29 0.00 0.07 2.61 0.85 -25.40 3
Iodomethane 0.68 0.43 0.00 0.12 2.11 0.51 -28.20 2
Diiodomethane 1.20 0.69 0.05 0.17 3.86 0.77 -41.60 1
Iodoethane 0.64 0.40 0.00 0.15 2.57 0.65 -31.70 2
1-Iodopropane 0.63 0.40 0.00 0.14 3.13 0.79 -35.30 2
2-Iodopropane 0.62 0.35 0.00 0.17 2.90 0.79 -36.60 2
Fluorochloromethane 0.04 0.61 0.07 0.04 0.98 0.39 -21.70 1
Difluorochloromethane 0.00 0.25 0.20 0.00 0.69 0.41 -22.80 2
Bromodichloromethane 0.59 0.69 0.10 0.04 2.89 0.67 -28.90 2
Chlorodibromomethane 0.78 0.68 0.12 0.10 3.30 0.72 -33.30 1
Fluorotrichloromethane 0.21 0.24 0.00 0.07 1.95 0.63 -19.80 1
159
Solute E S A B L V Exp Ref
Difluorodichloromethane 0.04 0.13 0.00 0.00 1.12 0.53 -26.00 1
1,1,2-Trichlorotrifluoroethane 0.01 0.13 0.00 0.00 2.21 0.81 -28.80 2
1,2-Dichlorotetrafluoroethane -0.19 0.05 0.00 0.00 1.43 0.71 -20.20 2
Dimethylether 0.00 0.27 0.00 0.41 1.29 0.45 -34.00 7
Diethylether 0.04 0.25 0.00 0.45 2.02 0.73 -45.30 2
Di-n-propylether 0.01 0.25 0.00 0.45 2.95 1.01 -49.90 7
Di-isopropylether -0.06 0.16 0.00 0.58 2.53 1.01 -51.70 7
Dibutylether 0.00 0.25 0.00 0.45 3.92 1.30 -55.80 2
Methylpropylether 0.06 0.25 0.00 0.45 2.09 0.73 -38.00 7
Ethylbutylether 0.01 0.25 0.00 0.45 2.99 1.02 -48.40 7
Methyltert-butylether 0.02 0.21 0.00 0.59 2.38 0.87 -48.70 7
Ethyltert-butylether -0.02 0.16 0.00 0.60 2.72 1.01 -53.40 7
Methyltert-pentylether 0.05 0.21 0.00 0.60 2.92 1.01 -52.50 7
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -47.30 7
2,5-Dimethyltetrahydrofuran 0.20 0.38 0.00 0.58 2.98 0.90 -56.30 8
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -51.40 8
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -48.90 8
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -48.40 2
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -59.30 8
1,2-Diethoxyethane 0.01 0.73 0.00 0.79 3.31 1.07 -71.90 8
1-Methoxy-2-ethoxyethane 0.06 0.70 0.00 0.74 2.98 0.93 -66.10 7
160
Solute E S A B L V Exp Ref
1-Methoxy-2-propoxyethane 0.01 0.73 0.00 0.79 3.31 1.07 -69.10 7
1,2-Dipropoxyethane 0.00 0.64 0.00 0.78 4.39 1.35 -76.80 7
3,6,9-Trioxoundecane 0.04 0.87 0.00 1.20 4.82 1.41 -96.20 7
2,5,8,11-Tetraoxododecane 0.00 0.98 0.00 1.44 5.16 1.47 -102.40 7
2,5,8,11,14-Pentaoxopentadecane -0.02 1.11 0.00 1.79 6.50 1.81 -125.80 7
Methoxyflurane 0.11 0.67 0.07 0.14 2.86 0.87 -30.40 2
Isoflurane -0.24 0.50 0.10 0.10 1.90 0.80 -35.30 2
Propanone 0.18 0.70 0.04 0.49 1.70 0.55 -39.70 2
Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -41.90 2
Pentan-2-one 0.14 0.68 0.00 0.51 2.76 0.83 -45.31 9
Pentan-3-one 0.15 0.66 0.00 0.51 2.81 0.83 -49.45 10
Hexan-2-one 0.14 0.68 0.00 0.51 3.29 0.97 -48.90 2
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 0.97 -44.60 2
Methylisopropylketone 0.13 0.65 0.00 0.51 2.69 0.83 -57.60 2
3,3-Dimethyl-2-butanone 0.11 0.62 0.00 0.51 2.93 0.97 -47.50 11
Diisopropylketone 0.07 0.60 0.00 0.51 3.40 1.11 -54.00 11
Heptan-2-one 0.12 0.68 0.00 0.51 3.76 1.11 -54.90 2
Heptan-4-one 0.11 0.66 0.00 0.51 3.71 1.11 -58.10 11
Octan-2-one 0.11 0.68 0.00 0.51 4.26 1.25 -58.30 2
Nonan-5-one 0.10 0.66 0.00 0.51 4.70 1.39 -62.80 2
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -44.30 2
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -49.80 2
161
Solute E S A B L V Exp Ref
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -53.30 2
Propiophenone 0.80 0.95 0.00 0.51 4.97 1.16 -61.90 2
Methylacetate 0.14 0.64 0.00 0.45 1.91 0.61 -38.10 2
Ethylacetate 0.11 0.62 0.00 0.45 2.31 0.75 -40.80 2
Propylacetate 0.09 0.60 0.00 0.45 2.82 0.89 -48.70 10
Isopropylacetate 0.06 0.57 0.00 0.47 2.55 0.89 -46.80 10
Butylacetate 0.07 0.60 0.00 0.45 3.35 1.03 -52.70 10,12
Isobutylacetate 0.05 0.57 0.00 0.47 3.16 1.03 -51.80 10
sec-Butylacetate 0.04 0.57 0.00 0.47 3.05 1.03 -47.99 12
tert-Butylacetate 0.03 0.54 0.00 0.47 2.80 1.03 -42.60 10
Pentylacetate 0.07 0.60 0.00 0.45 3.84 1.17 -55.34 10
Isopentylacetate 0.05 0.57 0.00 0.47 3.74 1.17 -53.80 10
Hexylacetate 0.06 0.60 0.00 0.45 4.35 1.31 -60.80 10
Methylformate 0.19 0.68 0.00 0.38 1.29 0.47 -32.70 10
Ethylformate 0.15 0.66 0.00 0.38 1.85 0.61 -38.10 10
Propylformate 0.13 0.63 0.00 0.38 2.43 0.75 -40.51 10
Isopropylformate 0.09 0.60 0.00 0.40 2.23 0.75 -43.00 10
Isobutylformate 0.10 0.60 0.00 0.40 2.79 0.89 -43.00 10
Pentylformate 0.10 0.63 0.00 0.38 3.49 1.03 -48.10 10
3-Methylbutylformate 0.09 0.60 0.00 0.40 3.31 1.03 -47.70 10
Methylpropanoate 0.13 0.60 0.00 0.45 2.43 0.75 -44.50 10
Ethylpropanoate 0.09 0.58 0.00 0.45 2.81 0.89 -49.50 10
Propylpropanoate 0.07 0.56 0.00 0.45 3.34 1.03 -51.20 10
Butylpropanoate 0.06 0.56 0.00 0.47 3.83 1.17 -57.80 10
162
Solute E S A B L V Exp Ref
Isobutylpropanoate 0.03 0.53 0.00 0.47 3.64 1.17 -54.70 10
Methylbutanoate 0.11 0.60 0.00 0.45 2.89 0.89 -47.50 10
Ethylbutanoate 0.07 0.58 0.00 0.45 3.27 1.03 -52.70 10
Propylbutanoate 0.05 0.56 0.00 0.45 3.78 1.17 -54.90 10
Butylbutanoate 0.04 0.56 0.00 0.45 4.28 1.31 -63.50 10
Methyl2-methylpropanoate 0.09 0.57 0.00 0.47 2.64 0.89 -46.00 10
Ethyl2-methylpropanoate 0.03 0.55 0.00 0.47 3.07 1.03 -51.30 10
Isobutyl2-methylpropanoate 0.00 0.50 0.00 0.47 3.89 1.31 -55.30 10
Methylpentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -50.40 10
Ethylpentanoate 0.05 0.58 0.00 0.45 3.77 1.17 -56.50 10
Methyl2,2-dimethylpropanoate 0.05 0.54 0.00 0.45 2.93 1.03 -46.20 10
Ethyl2,2-dimethylpropanoate -0.01 0.52 0.00 0.45 3.48 1.17 -50.30 10
Ethyl3-methylbutanoate 0.03 0.55 0.00 0.47 3.58 1.17 -56.00 10
Ethyl2-methylbutanoate 0.03 0.55 0.00 0.47 3.57 1.17 -55.40 10
Methylhexanoate 0.08 0.60 0.00 0.45 3.87 1.17 -54.70 10
Ethylhexanoate 0.04 0.58 0.00 0.45 4.25 1.31 -60.20 10
Methylbenzoate 0.73 0.85 0.00 0.46 4.70 1.07 -50.25 3
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -35.70 3
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.57 -32.50 2
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 0.71 -34.40 2
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 0.71 -34.10 2
163
Solute E S A B L V Exp Ref
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -52.00 13
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -50.60 2
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -59.90 2
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 0.59 -58.20 14
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -61.90 2
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -62.72 15
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 0.73 -60.20 8, 3
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -62.90 15
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -61.90 2
3-Methyl-1-butanol 0.19 0.39 0.37 0.48 3.01 0.87 -66.00 8
2-Pentanol 0.20 0.36 0.33 0.56 2.84 0.87 -63.30 2
3-Pentanol 0.20 0.36 0.33 0.56 2.86 0.87 -59.60 2
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 1.02 -67.40 2
Hexan-3-ol 0.20 0.36 0.33 0.56 3.44 1.02 -69.60 8
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -68.44 16
4-Methyl-2-pentanol 0.17 0.33 0.33 0.56 3.18 1.01 -69.90 2
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 1.15 -72.13 3
Heptane-2-ol 0.19 0.36 0.33 0.56 3.84 1.15 -72.60 17
Heptan-4-ol 0.18 0.36 0.33 0.56 3.85 1.15 -75.30 8
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 1.30 -74.14 3
Dodecan-1-ol 0.18 0.42 0.37 0.48 6.64 1.86 -81.90 18
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 0.76 -58.50 2
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 0.90 -70.70 19
Cycloheptanol 0.51 0.54 0.32 0.58 4.41 1.05 -74.60 3
164
Solute E S A B L V Exp Ref
Ethan-1,2-diol 0.40 0.90 0.58 0.78 2.66 0.51 -77.30 8
Propan-1,3-diol 0.40 0.91 0.77 0.85 3.26 0.65 -81.10 20
Butan-1,4-diol 0.40 0.93 0.72 0.90 3.80 0.79 -89.60 20
Glycerol 0.51 0.76 0.47 1.43 3.97 0.71 -103.50 8
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 0.65 -60.40 8
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 0.79 -66.40 8
2-Propoxyethanol 0.21 0.50 0.30 0.83 3.31 0.93 -69.60 8
2-Butoxyethanol 0.20 0.50 0.30 0.83 3.81 1.07 -73.60 8
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -28.10 2
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -32.40 2
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -39.40 2
o-Xylene 0.66 0.56 0.00 0.16 3.94 1.00 -37.70 3
m-Xylene 0.62 0.52 0.00 0.16 3.84 1.00 -38.60 2
p-Xylene 0.61 0.52 0.00 0.16 3.84 1.00 -34.80 2
Propylbenzene 0.60 0.50 0.00 0.15 4.23 1.14 -36.40 2
Isopropylbenzene 0.60 0.49 0.00 0.16 4.08 1.14 -33.70 2
1,2,3-Trimethylbenzene 0.73 0.61 0.00 0.19 4.57 1.14 -37.36 3
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 1.14 -36.60 2
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 1.14 -39.12 3
4-Isopropyltoluene 0.61 0.49 0.00 0.19 4.59 1.28 -34.60 2
Butylbenzene 0.60 0.51 0.00 0.15 4.73 1.28 -38.50 2
Pentylbenzene 0.59 0.51 0.00 0.15 5.23 1.42 -49.45 3
Hexylbenzene 0.59 0.50 0.00 0.15 5.72 1.56 -52.72 3
1,4-Diethylbenzene 0.65 0.50 0.00 0.18 4.73 1.28 -46.40 2
165
Solute E S A B L V Exp Ref
Styrene 0.85 0.65 0.00 0.16 3.86 0.96 -28.40 2
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -29.30 2
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -30.60 2
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -37.30 2
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 0.96 -35.30 2
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -28.40 2
1,2,3-Trichlorobenzene 1.03 0.86 0.00 0.00 5.42 1.08 -32.60 2
1,3,5-Trichlorobenzene 0.98 0.73 0.00 0.00 5.05 1.08 -34.20 2
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 1.21 -35.00 2
Pentachlorobenzene 1.33 0.96 0.00 0.00 6.72 1.33 -39.90 2
2-Chlorotoluene 0.76 0.65 0.00 0.07 4.17 0.98 -38.30 2
3-Chlorotoluene 0.74 0.67 0.00 0.07 4.18 0.98 -37.00 2
4-Chlorotoluene 0.71 0.74 0.00 0.05 4.21 0.98 -33.30 2
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -33.50 2
Phenylmethylether 0.71 0.75 0.00 0.29 3.89 0.92 -41.42 3
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -56.50 2
2-Ethylaniline 0.96 0.85 0.23 0.45 4.83 1.10 -59.70 2
4-Ethylaniline 0.94 0.91 0.23 0.45 4.90 1.10 -65.00 2
2,4-Dimethylaniline 0.95 0.95 0.20 0.49 4.98 1.10 -58.70 2
2,5-Dimethylaniline 0.96 0.93 0.20 0.48 4.97 1.10 -61.50 2
2,6-Dimethylaniline 0.97 0.90 0.05 0.59 5.03 1.10 -60.50 2
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -49.60 2
N,N-Diethylaniline 0.95 0.80 0.00 0.41 5.29 1.10 -45.70 2
166
Solute E S A B L V Exp Ref
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -43.80 2
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 1.03 -46.40 2
3-Nitrotoluene 0.87 1.10 0.00 0.25 5.10 1.03 -38.50 2
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -57.70 21
2-Methylphenol 0.84 0.86 0.52 0.30 4.22 0.92 -64.80 2
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -58.70 8
4-Methylphenol 0.82 0.87 0.57 0.31 4.31 0.92 -61.30 8
4-tert-Butylphenol 0.81 0.89 0.56 0.41 5.26 1.34 -63.80 8
3-Chlorophenol 0.91 1.06 0.69 0.15 4.77 0.90 -50.30 8
3-Cyanophenol 0.93 1.55 0.77 0.28 5.18 0.93 -70.70 8
4-Cyanophenol 0.93 1.55 0.77 0.28 5.18 0.93 -70.30 8
2-Nitrophenol 1.02 1.05 0.05 0.37 4.76 0.95 -49.80 2
3-Nitrophenol 1.05 1.57 0.79 0.23 5.69 0.95 -67.70 8
4-Nitrophenol 1.07 1.72 0.82 0.26 5.88 0.95 -68.60 8
Biphenyl(approx) 1.36 0.99 0.00 0.26 6.01 1.32 -47.20 2
Naphthalene(approx) 1.34 0.92 0.00 0.20 5.16 1.09 -42.80 2
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 1.23 -45.00 2
2-Methylnaphthalene 1.30 0.81 0.00 0.25 5.62 1.23 -44.90 2
Acenaphthene 1.60 1.05 0.00 0.22 6.47 1.26 -52.10 2
Fluorene 1.59 1.06 0.00 0.25 6.92 1.36 -42.70 2
Propanal 0.20 0.65 0.00 0.45 1.82 0.55 -39.40 2
Pentanal 0.16 0.65 0.00 0.45 2.77 0.83 -42.90 2
Hexanal 0.15 0.65 0.00 0.45 3.37 0.97 -55.20 2
Heptanal 0.14 0.65 0.00 0.45 3.86 1.11 -56.60 2
167
Solute E S A B L V Exp Ref
Octanal 0.16 0.65 0.00 0.45 4.38 1.25 -48.80 2
Isobutylaldehyde 0.14 0.62 0.00 0.45 2.12 0.69 -40.00 2
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -42.10 2
3-Hydroxybenzaldehyde 0.99 1.38 0.73 0.40 5.06 0.93 -70.70 8
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -34.80 22
Propionitrile 0.16 0.90 0.02 0.36 2.08 0.55 -39.52 22
Butyronitrile 0.18 0.90 0.00 0.36 2.55 0.69 -42.10 22
Pentanenitrile 0.18 0.90 0.00 0.36 3.11 0.83 -45.60 22
2-Cyanopropane 0.14 0.87 0.00 0.40 2.47 0.69 -40.00 22
1,2-Dicyanoethane 0.35 2.10 0.00 0.50 3.92 0.70 -58.20 22
1,3-Dicyanopropane 0.33 2.05 0.00 0.59 4.34 0.84 -63.50 22
1,4-Dicyanobutane 0.32 2.08 0.00 0.62 4.85 0.98 -66.60 22
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -48.50 3
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 0.50 -50.20 3
1,1,1-Trifluoropropan-2-ol 0.11 0.47 0.37 0.36 1.96 0.64 -53.50 8
2,2,3,3-Tetrafluoropropan-1-ol 0.01 0.44 0.77 0.18 1.95 0.66 -57.90 8
2,2,3,3,3-Pentafluoropropan-1-ol -0.17 0.33 0.62 0.17 1.60 0.68 -51.90 8
1,1,1,3,3,3-Hexafluoropropan-2-ol -0.24 0.55 0.77 0.10 1.39 0.70 -57.10 8
Methylamine 0.25 0.35 0.16 0.58 1.30 0.35 -45.27 3
Ethylamine 0.24 0.35 0.16 0.61 1.68 0.49 -53.68 3
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -55.98 3
168
Solute E S A B L V Exp Ref
Isopropylamine 0.18 0.32 0.16 0.61 1.91 0.63 -55.00 8
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -59.20 3
sec-Butylamine 0.17 0.32 0.16 0.63 2.41 0.77 -57.10 8
tert-Butylamine 0.12 0.29 0.16 0.71 2.49 0.77 -59.00 8
Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -62.13 3, 8
Hexylamine 0.20 0.35 0.16 0.61 3.66 1.05 -65.93 3, 8
Octylamine 0.19 0.35 0.16 0.61 4.52 1.34 **-52.3 2
Dimethylamine 0.19 0.30 0.08 0.66 1.60 0.49 -53.09 3
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -64.30 3
Dipropylamine 0.12 0.30 0.08 0.69 3.35 1.05 -65.20 2
Dibutylamine 0.11 0.30 0.08 0.69 4.35 1.34 -59.30 2
Trimethylamine 0.14 0.20 0.00 0.67 1.62 0.63 -52.71 3
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -69.70 8
1,2-Diaminoethane 0.46 0.17 0.04 1.29 1.88 0.59 -76.10 8
1,3-Diaminopropane 0.45 0.61 0.43 1.14 2.85 0.73 -85.60 8
1,4-Diaminobutane 0.43 0.62 0.42 1.14 3.37 0.87 -91.60 8
1,5-Diaminopentane 0.42 0.63 0.39 1.15 3.90 1.01 -95.10 8
Piperidine 0.42 0.46 0.10 0.69 3.30 0.80 -65.41 8
N-Methylpiperidine 0.32 0.34 0.00 0.72 3.33 0.95 -65.77 8
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -42.10 2
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -50.30 2
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 0.82 -50.30 2
4-Methylpyridine 0.63 0.82 0.00 0.54 3.64 0.82 -51.80 2
2-Ethylpyridine 0.61 0.71 0.00 0.59 3.84 0.96 -55.70 8
169
Solute E S A B L V Exp Ref
3-Ethylpyridine 0.64 0.79 0.00 0.57 4.09 0.96 -53.50 8
4-Ethylpyridine 0.63 0.80 0.00 0.57 4.12 0.96 -52.20 8
2,3-Dimethylpyridine 0.66 0.77 0.00 0.62 4.05 0.96 -57.70 8
2,4-Dimethylpyridine 0.63 0.76 0.00 0.63 4.01 0.96 -60.70 8
2,5-Dimethylpyridine 0.63 0.74 0.00 0.62 3.99 0.96 -54.90 8
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -52.30 2
3,4-Dimethylpyridine 0.68 0.85 0.00 0.62 4.32 0.96 -50.50 2
3,5-Dimethylpyridine 0.66 0.79 0.00 0.60 4.21 0.96 -51.30 2
2-Chloropyridine 0.74 1.03 0.00 0.37 3.88 0.80 -42.56 23
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -46.20 8
Quinoline 1.27 0.97 0.00 0.54 5.46 1.04 -58.20 2
Methanethiol 0.40 0.60 0.00 0.12 1.64 0.41 -25.80 3, 2
Ethanethiol 0.39 0.35 0.00 0.24 2.17 0.55 -28.30 2
1-Propanethiol 0.39 0.35 0.00 0.24 2.69 0.70 -30.20 24
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 0.84 -36.29 24
Dimethylsulfide 0.40 0.43 0.00 0.27 2.04 0.55 -31.50 24
Diethylsulfide 0.37 0.38 0.00 0.33 3.02 0.84 -40.20 24
Dipropylsulfide 0.36 0.38 0.00 0.34 4.01 1.12 -47.60 24
Thiophene 0.69 0.56 0.00 0.15 2.82 0.64 -29.90 3
Aceticacid 0.27 0.65 0.61 0.44 1.75 0.47 -52.80 1
Propanoicacid 0.23 0.65 0.61 0.44 2.28 0.61 -56.50 1
Butanoicacid 0.21 0.64 0.61 0.45 2.75 0.75 -59.50 8
2-Methoxyphenol 0.84 0.91 0.22 0.52 4.45 0.98 -62.60 2
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 -0.67 3
170
Solute E S A B L V Exp Ref
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 -3.90 3
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -12.20 3
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -15.60 3
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -19.40 3
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -24.00 3
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 -0.40 25
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -1.21 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 -1.04 25
NitrousOxide 0.07 0.35 0.00 0.10 0.16 0.28 -19.80 1
NitricOxide 0.37 0.02 0.00 0.09 -0.59 0.20 -11.90 1
CarbonMonoxide 0.00 0.00 0.00 0.04 -0.84 0.22 -11.13 3
CarbonDioxide 0.00 0.28 0.05 0.10 0.06 0.28 -17.90 2
Benzylalcohol 0.80 0.87 0.33 0.56 4.22 0.92 -66.94 3
2-Chlorobiphenyl 1.48 1.07 0.00 0.20 6.34 1.45 -42.80 2
2,3-Dichlorobiphenyl 1.63 1.20 0.00 0.18 7.17 1.57 -45.60 2
2,4-Dichlorobiphenyl 1.62 1.20 0.00 0.18 7.04 1.57 -43.00 2
2,4'-Dichlorobiphenyl 1.62 1.20 0.00 0.18 7.20 1.57 -44.20 2
2,5-Dichlorobiphenyl 1.63 1.20 0.00 0.18 7.00 1.57 -45.60 2
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -5.93 8
Isophorone 0.51 1.12 0.00 0.53 4.74 1.24 -59.10 2
Morpholine 0.43 0.79 0.06 0.91 3.29 0.72 -69.50 8
N-Methylmorpholine 0.33 0.74 0.00 0.90 3.27 0.86 -68.70 8
Propanamide 0.44 1.30 0.55 0.66 3.51 0.65 -73.40 1
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -62.90 8
171
Solute E S A B L V Exp Ref
Dimethylsulfoxide 0.52 1.72 0.00 0.97 3.46 0.61 -71.90 8
N-Methylpyrrolidine 0.30 0.98 0.00 0.40 3.13 0.80 **-63.4 8
Hexan-3-one 0.14 0.66 0.00 0.51 3.31 0.97 -46.00 2
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -65.30 2
cis1,2-Cyclohexanediol 0.60 0.86 0.50 0.86 4.20 0.96 -82.40 19
12-Crown-4 0.42 0.99 0.00 1.39 5.14 1.36 -94.65 26
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -119.28 26
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -149.51 26
Erithritol 0.62 1.60 0.48 1.39 0.91 -114.00 27
Table S5.2. Values o f t he gas t o 1 -octanol s olvation enthalpy i n kJ /mol a t 298K for 138 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Sulphurhexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -6.56 3
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -3.90 3
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -25.52 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -30.33 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -35.31 28
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.09 -34.23 29
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -40.08 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -44.89 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -49.71 28
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -59.12 28
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -78.20 28
172
Solute E S A B L V Exp Ref
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -35.50 30
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -34.33 29
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -6.25 31
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -22.40 32
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -26.56 32
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -38.14 32
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 0.32 0.92 3
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -27.86 33
Trichloromethane 0.43 0.49 0.15 0.02 2.48 0.62 -32.69 33
Tetrachloromethane 0.46 0.38 0.00 0.00 2.82 0.74 -28.76 33
1,1-Dichloroethane 0.32 0.49 0.10 0.10 2.32 0.64 -28.68 33
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -29.58 33
1,1,1-Trichloroethane 0.37 0.41 0.00 0.09 2.73 0.76 -26.45 33
1,1,2-Trichloroethane 0.50 0.68 0.13 0.13 3.29 0.76 -36.73 33
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 0.88 -42.27 33
1-Chloropropane 0.22 0.40 0.00 0.10 2.20 0.65 -26.02 29
1,2-Dichloropropane 0.37 0.63 0.00 0.17 2.84 0.78 -32.69 33
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -31.00 29
2-Chlorobutane 0.19 0.35 0.00 0.12 2.54 0.80 -28.87 29
1-Chloropentane 0.21 0.38 0.00 0.09 3.22 0.94 -35.92 29
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 1.08 -40.43 29
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -49.97 29
Dibromomethane 0.71 0.69 0.11 0.07 2.89 0.60 -38.08 33
173
Solute E S A B L V Exp Ref
Trichloroethylene 0.52 0.37 0.08 0.03 3.00 0.71 -34.43 34
Diethylether 0.04 0.25 0.00 0.45 2.02 0.73 -24.86 30
Di-n-propylether 0.01 0.25 0.00 0.45 2.95 1.01 -33.19 30
Di-isopropylether -0.06 0.16 0.00 0.58 2.53 1.01 -31.04 29
Dibutylether 0.00 0.25 0.00 0.45 3.92 1.30 -42.58 30
Methyltert-butylether 0.02 0.21 0.00 0.59 2.38 0.87 -28.03 30
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -28.32 30
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -30.66 30
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -28.73 35
Propanone 0.18 0.70 0.04 0.49 1.70 0.55 -22.37 30
Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -27.36 30
Pentan-2-one 0.14 0.68 0.00 0.51 2.76 0.83 -31.03 30
Pentan-3-one 0.15 0.66 0.00 0.51 2.81 0.83 -32.86 30
Hexan-2-one 0.14 0.68 0.00 0.51 3.29 0.97 -36.12 30
Heptan-4-one 0.11 0.66 0.00 0.51 3.71 1.11 -40.47 30
Nona-2-one 0.12 0.68 0.00 0.51 4.73 1.39 -50.29 29
Nonan-5-one 0.10 0.66 0.00 0.51 4.70 1.39 -47.19 29
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -34.34 30
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -37.27 29
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -50.23 29
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -24.62 29
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -27.78 29
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -33.00 29
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -37.13 29
174
Solute E S A B L V Exp Ref
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -41.31 29
Methyl formate 0.19 0.68 0.00 0.38 1.29 0.46 -21.40 29
Propyl formate 0.13 0.63 0.00 0.38 2.43 0.75 -30.39 29
Methyl propionate 0.13 0.60 0.00 0.45 2.43 0.75 -26.67 29
Ethyl propionate 0.09 0.58 0.00 0.45 2.81 0.89 -32.54 29
Methylbutanoate 0.11 0.60 0.00 0.45 2.94 0.89 -33.04 29
Methylpentanoate 0.11 0.60 0.00 0.45 3.44 1.03 -37.02 29
Ethylbenzoate 0.69 0.85 0.00 0.46 5.08 1.21 -54.52 29
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -37.08 29
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -41.79 29
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -46.96 29
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -51.84 30
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -49.40 30
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -46.99 30
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -56.74 29
2,2-Dimethyl-1-propanol 0.22 0.36 0.37 0.53 2.65 0.87 -53.64 29
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 1.02 -61.49 29
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 1.30 -70.98 29
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 1.58 -81.40 29
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -30.98 29
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.99 29
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -39.91 29
o-Xylene 0.66 0.56 0.00 0.16 3.94 1.00 -41.53 29
175
Solute E S A B L V Exp Ref
m-Xylene 0.62 0.52 0.00 0.16 3.84 1.00 -41.00 29
p-Xylene 0.61 0.52 0.00 0.16 3.84 1.00 -40.59 29
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 1.14 -45.88 29
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -49.30 36
1,2,3-Trichlorobenzene 1.03 0.86 0.00 0.00 5.42 1.08 -55.70 36
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 1.21 -62.30 36
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 1.21 -60.80 36
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 1.45 -75.20 36
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -51.19 29
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -47.14 29
Phenanthrene 2.06 1.29 0.00 0.29 7.63 1.45 -75.50 37
Pyrene 2.81 1.71 0.00 0.28 8.83 1.58 -76.30 37
Butyronitrile 0.18 0.90 0.00 0.36 2.55 0.69 -31.39 37
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -40.90 30
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -45.11 30
Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -50.03 30
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -42.52 30
Dipropylamine 0.12 0.30 0.08 0.69 3.35 1.05 -50.82 30
Dibutylamine 0.11 0.30 0.08 0.69 4.35 1.34 -60.07 30
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -43.58 30
Piperidine 0.42 0.46 0.10 0.69 3.30 0.80 -48.99 30
N-Methylpiperidine 0.32 0.34 0.00 0.72 3.33 0.95 -43.24 30
176
Solute E S A B L V Exp Ref
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 3.93 3
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.67 3
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -9.64 38
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -1.17 3
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 2.51 3
CarbonMonoxide 0.00 0.00 0.00 0.04 -0.84 0.22 0.21 3
CarbonDioxide 0.00 0.28 0.05 0.10 0.06 0.28 -9.13 39
3-Chlorobiphenyl 1.51 1.05 0.00 0.18 6.67 1.45 -66.44 40
2,2',4,5'-Tetrachlorobiphenyl 1.89 1.48 0.00 0.15 8.19 1.81 -76.23 40
2,2',5,6'-Tetrachlorobiphenyl 1.87 1.48 0.00 0.15 7.95 1.81 -75.92 40
2,3,3',4,4'-Pentachlorobiphenyl 2.04 1.59 0.00 0.11 9.59 1.04 -89.57 40
2,3',4,4',5-Pentachlorobiphenyl 2.06 1.59 0.00 0.11 9.40 1.04 -89.86 40
3,3',4,4',5-Pentachlorobiphenyl 2.11 1.57 0.00 0.09 9.88 1.04 -93.25 40
2,2',3,4,4',5'-Hexachlorobiphenyl 2.18 1.74 0.00 0.11 9.77 2.06 -89.90 40
2,2',4,4',5,5'-Hexachlorobiphenyl 2.18 1.74 0.00 0.11 9.59 2.06 -87.77 40
2,2',3,3',4,4',6-Heptachlorobiphenyl 2.30 1.87 0.00 0.09 10.03 2.18 -91.08 40
2,2',3,4,4',5,6-Heptachlorobiphenyl 2.30 1.87 0.00 0.09 9.97 2.18 -86.83 40
1,4-Dichloronaphthalene 1.57 1.06 0.00 0.09 6.76 1.33 -62.19 37
177
Solute E S A B L V Exp Ref
1,3,5-Trichloronaphthalene 1.69 1.12 0.00 0.00 7.59 1.45 -72.49 37
1,4,5-Trichloronaphthlalene 1.69 1.12 0.00 0.00 8.07 1.45 -74.60 37
1,2,4,5-Tetrachloronaphthalene 1.81 1.24 0.00 0.00 8.67 1.58 -81.62 37
1,2,4,8-Tetrachloronaphthalene 1.81 1.24 0.00 0.00 8.74 1.58 -80.53 37
1,2,5,8-Tetrachloronaphthalene 1.81 1.24 0.00 0.00 8.82 1.58 -80.05 37
1,4,5,8-Tetrachloronaphthalene 1.81 1.18 0.00 0.00 9.14 1.58 -80.53 37
1,2,4,5,7-Pentachloronaphthalene 1.93 1.30 0.00 0.00 9.23 1.70 -84.32 37
1,2,4,6,8-Pentachloronaphthalene 1.93 1.30 0.00 0.00 9.28 1.70 -84.57 37
1,2,3,4,6-Pentachloronaphthalene 1.93 1.36 0.00 0.00 9.20 1.70 -88.63 37
1,2,4,7,8-Pentachloronaphthalene 1.93 1.36 0.00 0.00 9.46 1.70 -85.24 37
1,2,3,5,8-Pentachloronaphthalene 1.93 1.36 0.00 0.00 9.50 1.70 -89.69 37
1,2,4,5,8-Pentachloronaphthalene 1.93 1.36 0.00 0.00 9.59 1.70 -92.12 37
1,2,3,5,7,8-Hexachloronaphthalene 2.05 1.42 0.00 0.00 10.24 1.82 -93.99 37
1,2,3,4,5,6-Hexachloronaphthalene 2.05 1.42 0.00 0.00 10.54 1.82 -89.34 37
1,2,3,4,5,8-Hexachloronaphthalene 2.05 1.42 0.00 0.00 10.66 1.82 -96.50 37
N-Methylpyrrolidine 0.30 0.50 0.00 0.71 2.81 0.80 -40.33 30
178
Solute E S A B L V Exp Ref
Pyrrolidine 0.41 0.67 0.12 0.63 2.89 0.66 -47.85 30
Table S5.3. Values of t he gas t o c arbon t etrachloride s olvation e nthalpy i n kJ/mol at 298 K for 177 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.29 -3.01 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -9.20 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -14.40 25
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -18.49 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -25.19 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -29.75 28
Heptane 0.00 0.00 0.00 0.00 3.17 0.95 -34.48 28
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -39.13 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -43.18 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -48.37 28
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -57.70 28
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -76.30 28
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -16.15 25
2-Methylbutane 0.00 0.00 0.00 0.00 2.01 0.81 -23.93 41
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -25.90 41
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 0.95 -33.89 41
2,2,4,4 -Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -36.23 41
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -28.47 42
179
Solute E S A B L V Exp Ref
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -32.34 41
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -37.91 43
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -42.95 43
Cyclodecane 0.47 0.10 0.00 0.00 5.34 1.41 -52.00 43
Methylcyclopentane 0.23 0.10 0.00 0.00 2.82 0.85 -30.95 43
Methylcyclohexane 0.24 0.10 0.00 0.00 3.32 0.99 -34.65 43
cis Decalin 0.55 0.25 0.00 0.00 5.16 1.30 -50.78 43
trans Decalin 0.47 0.23 0.00 0.00 4.98 1.30 -49.22 43
Bicyclohexyl 0.53 0.33 0.00 0.07 5.92 1.58 -57.16 43
Tetralin 0.89 0.65 0.00 0.17 5.20 1.17 -55.50 43
Adamantane 0.67 0.66 0.00 0.02 5.10 1.19 -48.40 44
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -9.58 45
1-Heptene 0.09 0.08 0.00 0.07 3.06 1.05 -35.21 46
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -39.58 41
Norbornadiene 0.50 0.32 0.00 0.11 3.11 0.79 -35.52 47
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -28.14 41
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -33.13 41
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.07 41
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -37.73 48
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -41.84 41
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -46.40 41
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -45.64 41
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -50.65 41
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -55.19 41
180
Solute E S A B L V Exp Ref
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -54.77 41
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -41.38 41
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -44.68 41
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -44.89 41
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 0.84 -39.88 41
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.87 -28.96 49
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 1.02 -36.69 50
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -46.46 51
Methyl tert-butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -28.79 41
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -37.50 52
1,2-Diethoxyethane 0.01 0.73 0.00 0.79 3.31 1.07 -45.50 52
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -37.90 52
Tetrahdropyran 0.28 0.47 0.00 0.55 3.06 0.77 -37.20 52
Butyl Methyl Ether 0.05 0.25 0.00 0.44 2.66 0.87 -34.50 52
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 0.65 -30.40 52
2,5,8,11 - Tetraoxadodecane 0.00 0.98 0.00 1.44 5.16 1.47 -71.30 52
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -34.60 42
12-Crown-4 0.42 0.99 0.00 1.39 5.14 1.36 -63.90 52
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -76.90 52
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -100.80 53
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -30.13 50
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -32.43 41
181
Solute E S A B L V Exp Ref
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -33.18 41
1-Chlorooctane 0.19 0.40 0.00 0.10 4.77 1.36 -53.59 41
cis-1,2 - Dichloroethylene 0.44 0.61 0.11 0.05 2.44 0.59 -27.61 51
trans-1,2 - Dichloroethylene 0.43 0.41 0.09 0.05 2.28 0.59 -28.03 51
Tetrachloroethylene 0.64 0.44 0.00 0.00 3.58 0.84 -39.33 51
Iodomethane 0.68 0.43 0.00 0.12 2.11 0.51 -27.12 54
1-Iodobutane 0.63 0.40 0.00 0.15 3.63 0.93 -40.39 54
2-Iodo-2-methylpropane 0.59 0.35 0.00 0.19 3.44 0.93 -35.57 54
Diiodomethane 0.71 0.69 0.11 0.07 2.89 0.77 -41.88 55
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 0.63 -10.63 45
Propanal 0.20 0.65 0.00 0.45 1.82 0.55 -28.79 56
Butanal 0.19 0.65 0.00 0.45 2.27 0.69 -32.90 56
Pentanal 0.16 0.65 0.00 0.45 2.77 0.83 -38.15 56
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -28.37 57
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.56 -32.90 58
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 0.71 -38.23 59
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 0.71 -35.84 59
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -25.36 41
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -19.80 60
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -24.28 60
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -27.90 61
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -26.40 61
182
Solute E S A B L V Exp Ref
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -34.53 49
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -37.82 62
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -42.20 61
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -52.20 63
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -30.71 62
Propyl formate 0.13 0.63 0.00 0.38 2.43 0.75 -35.14 64
Butyl formate 0.12 0.63 0.00 0.38 2.96 0.89 -39.97 65
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -30.94 66
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -34.97 41
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -44.23 64
Methyl propionate 0.13 0.60 0.00 0.45 2.43 1.03 -35.77 67
Ethyl propionate 0.09 0.58 0.00 0.45 2.81 0.89 -39.78 64
Propyl propionate 0.07 0.56 0.00 0.45 3.34 1.03 -44.45 64
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.31 41
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -38.12 41
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -41.83 41
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -46.74 41
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -63.06 41
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -54.14 41
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -77.18 41
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -50.08 41
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -45.27 41
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -46.86 41
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -48.10 41
183
Solute E S A B L V Exp Ref
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -42.97 41
1,3,5-Tribromobenzene 1.45 1.02 0.00 0.00 6.31 1.24 -60.67 51
1,3,4,5-Tetrabromobenzene 1.83 1.19 0.00 0.00 7.43 1.42 -68.20 51
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -40.33 41
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -46.15 41
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -46.70 41
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 1.21 -58.09 51
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 1.45 -71.48 51
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -34.43 41
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -48.01 41
Trifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -34.35 41
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -44.52 41
Dimethyl Sulfoxide 0.52 1.74 0.00 0.88 3.46 0.61 -44.98 41
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -50.21 41
4-Chloro-1-nitrobenzene 0.98 1.18 0.00 0.24 5.22 1.01 -56.08 41,68
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -33.21 69
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -38.99 41
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -46.47 69
N-Methylaniline 0.95 0.90 0.17 0.43 4.48 0.96 -49.59 69
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -51.99 41
N-Ethylaniline 0.95 0.85 0.17 0.43 4.81 1.10 -54.37 69
184
Solute E S A B L V Exp Ref
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -38.31 50
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -43.01 70
2,4-Dimethylpyridine 0.63 0.76 0.00 0.63 4.01 0.96 -48.88 70
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -46.68 70
2-Bromopyridine 0.92 1.21 0.00 0.36 4.39 0.85 -50.38 71
3-Bromopyridine 0.91 0.90 0.00 0.38 4.19 0.85 -51.14 71
2-Chloropyridine 0.74 1.03 0.00 0.37 3.88 0.80 -45.20 70
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -48.60 70
3-Cyanopyridine 0.75 1.26 0.00 0.62 4.16 0.83 -49.40 70
4-Cyanopyridine 0.75 1.21 0.00 0.59 4.03 0.83 -49.10 70
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -35.53 72
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -33.22 72
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -38.04 72
Tributylamine 0.05 0.15 0.00 0.79 6.05 1.90 -68.72 41
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.42 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 5.78 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 2.34 25
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 1.25 73
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -9.42 74
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 0.04 25
Carbon tetrafluoride -0.58 -0.26 0.00 0.00 -0.82 0.32 0.59 25
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -6.99 25
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.28 -1.42 75
Tetrahydrothiophene 0.62 0.66 0.00 0.26 3.66 0.73 -41.31 76
185
Solute E S A B L V Exp Ref
Dimethyl sulfide 0.40 0.43 0.00 0.27 2.04 0.55 -23.38 51
Diethyl sulfide 0.37 0.38 0.00 0.33 3.02 0.84 -38.73 76
Dibutyl sulfide 0.35 0.38 0.00 0.32 4.95 1.40 -54.72 71
N,N-Dimethylacetamide 0.36 1.33 0.00 0.78 3.72 0.79 -47.56 77
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -43.40 42
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 0.90 -46.10 78
4-Bromophenol 1.08 1.17 0.67 0.20 5.14 0.95 -59.70 78
Pentafluorophenol 0.36 0.83 0.79 0.09 3.57 0.86 -42.00 79
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -46.06 80
2-Methoxyphenol 0.84 0.91 0.22 0.52 4.45 0.97 -54.40 78,81
3-Methoxyphenol 0.88 1.17 0.59 0.38 4.80 0.97 -59.50 78, 81
4-Methoxyphenol 0.90 1.17 0.57 0.48 4.77 0.97 -57.60 78, 81
γ-Butyrolactone 0.39 1.38 0.00 0.59 3.33 0.64 -48.63 82
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -60.70 83
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -42.81 71
Phenyl methyl sulfide 1.06 0.68 0.00 0.32 4.66 1.03 -52.79 71
Acrylonitrile 0.30 0.83 0.03 0.30 2.00 0.50 -27.20 51
1,4-Difluorobenzene 0.38 0.60 0.00 0.06 2.77 0.75 -33.89 51
Benzophenone 1.45 1.50 0.00 0.50 1.48 -74.48 51
trans-Stilbene 1.45 1.05 0.00 0.34 7.52 1.56 -78.24 51
Quinoline 1.27 0.97 0.00 0.54 5.46 1.04 -55.40 84
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 1.21 -62.37 84
186
Solute E S A B L V Exp Ref
1-Nitronaphthalene 1.60 1.59 0.00 0.29 7.06 1.26 -64.39 84
Table S5.4. Values of the gas to toluene solvation enthalpy in kJ/mol at 298 K for 108 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -5.06 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -8.91 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -24.91 85
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -26.65 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -31.00 28
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -35.48 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -39.66 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -43.85 28
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -70.08 28
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -27.33 42
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -30.54 86
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -36.50 87
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -41.19 87
cis Decalin 0.55 0.25 0.00 0.00 5.16 1.30 -47.92 88
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -33.22 89
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -8.79 45
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -29.43 90
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -30.08 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.58 92
187
Solute E S A B L V Exp Ref
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -38.55 86
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -38.77 93
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -47.86 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -46.82 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -51.91 86
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -54.98 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -53.35 91
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -65.52 86
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -43.01 91
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -46.15 91
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -27.57 62
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -42.17 94
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -32.55 95
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.30 -44.81 94
Methyl tert butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -27.78 62
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.02 -35.74 96
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -33.76 42
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -38.31 73
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -35.96 73
Oxirane 0.25 0.74 0.07 0.32 1.37 0.34 -32.80 97
Tetraglyme -0.02 1.11 0.00 1.79 6.50 1.81 -79.60 98
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -79.57 99
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -53
188
Solute E S A B L V Exp Ref
106.00
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -47.61 94
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -50.38 94
γ-Butyrolactone 0.39 1.38 0.00 0.59 3.33 0.64 -53.02 82
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -28.85 100
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -33.64 100
Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -37.98 100
Octylamine 0.19 0.35 0.16 0.61 4.52 1.34 -52.83 100
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -34.60 101
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -23.20 102
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -27.90 102
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -31.20 102
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -37.10 102
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -41.90 102
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -52.76 94
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -31.96 103
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -33.68 62
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 10.13 25
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 8.24 25
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 0.96 25
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -3.72 25
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -8.28 25
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -12.68 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 5.10 25
189
Solute E S A B L V Exp Ref
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 6.19 25
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 1.88 25
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -10.54 45
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -0.59 25
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 0.32 5.98 25
Sulfur Hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -5.31 25
Chlorine gas 0.36 0.32 0.10 0.00 1.19 0.34 -23.97 104
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.60 42
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.99 95
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -42.44 105
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -46.78 95
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -46.46 106
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 0.84 -38.62 107
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -50.30 42
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -51.25 62
2,6-Dimethylphenol 0.85 0.82 0.51 0.37 4.50 1.06 -53.87 108
Ttrifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -37.20 95
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -52.54 109
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -31.20 110
Propyl formate 0.13 0.63 0.00 0.38 2.43 0.75 -36.44 111
Butyl formate 0.12 0.63 0.00 0.38 2.96 0.89 -40.63 111
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -34.88 111
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -39.28 111
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -44.23 111
190
Solute E S A B L V Exp Ref
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -35.40 111
Ethyl propanoate 0.09 0.58 0.00 0.45 2.81 0.89 -39.57 111
Propyl propanoate 0.07 0.56 0.00 0.45 3.34 1.03 -43.96 111
Cyclohexyl acetate 0.28 0.69 0.00 0.47 4.14 1.20 -52.50 112
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -58.66 113
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 0.84 -36.84 114
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -44.30 115
2-Chlorotoluene 0.76 0.65 0.00 0.07 4.17 0.98 -46.28 116
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 0.96 -48.44 117
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -41.47 118
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -34.71 89
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -48.95 51
1-Nitronaphthalene 1.34 0.94 0.00 0.22 5.80 1.26 -69.45 51
4-Chloronitrobenzene 0.98 1.18 0.00 0.24 5.22 1.01 -56.48 51,68
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -49.23 119
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -41.49 120
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -39.79 120
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -49.60 121
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -57.25 122
191
Table S5.5. Values of t he gas t o d imethyl s ulfoxide s olvation e nthalpy in kJ/mol at 298K for 150 solutes, together with the solute descriptors.
Solute E S A B L V Exp. Ref.
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -12.10 123
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -15.23 124
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -17.61 125
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -21.13 125
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -24.10 125
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -27.66 125
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -30.79 125
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -21.60 126
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -15.50 123
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -20.31 127
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -21.51 127
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -31.78 127
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -17.00 123
1-Octyne 0.16 0.22 0.09 0.10 3.52 1.15 -37.15 128
2-Octyne 0.23 0.30 0.00 0.10 3.85 1.15 -37.36 128
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -30.71 16, 129
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -34.40 130
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -37.32 130
1,3-Dimethylbenzene 0.62 0.52 0.00 0.16 3.84 1.00 -41.75 16
Propylbenzene 0.60 0.50 0.00 0.15 4.23 1.14 -39.86 130
Isopropylbenzene 0.60 0.49 0.00 0.16 4.08 1.14 -39.66 131
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -39.37 95
192
Solute E S A B L V Exp. Ref.
Butylbenzene 0.60 0.51 0.00 0.15 4.73 1.28 -42.66 130
Pentylbenzene 0.59 0.51 0.00 0.15 5.23 1.42 -45.44 130
Hexylbenzene 0.59 0.50 0.00 0.15 5.72 1.56 -48.72 130
Heptylbenzene 0.58 0.48 0.00 0.15 6.22 1.70 -52.16 130
Octylbenzene 0.58 0.48 0.00 0.15 6.71 1.84 -53.12 130
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -53.19 132
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -60.96 16
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -76.60 133
Methylamine 0.25 0.35 0.16 0.58 1.30 0.35 -26.80 133
n-Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -30.23 130
n-Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -33.59 130
n-Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -36.48 130
n-Hexylamine 0.20 0.35 0.16 0.61 3.66 1.05 -40.40 130
n-Heptylamine 0.20 0.35 0.16 0.61 4.15 1.19 -43.15 130
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -29.87 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -32.47 91
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -35.49 127
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -39.80 133
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -41.00 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -39.83 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -43.90 133
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -47.20 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -44.81 91
193
Solute E S A B L V Exp. Ref.
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -35.15 91
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 1.00 -41.84 91
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -21.59 62
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 1.01 -29.59 134
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.29 -32.01 94
Ethyl propyl ether 0.00 0.25 0.00 0.45 2.49 0.87 -25.25 134
n-Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -25.36 95
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.29 -36.38 94
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -24.23 62
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -27.34 135
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -30.16 135
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -36.63 135
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -34.73 135
1,2-Diethoxyethane 0.01 0.73 0.00 0.79 3.31 1.07 -39.15 135
Furan 0.37 0.51 0.00 0.13 1.91 0.54 -29.99 136
12-Crown-4 0.42 0.99 0.00 1.39 5.14 1.36 -65.98 26
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -78.85 26
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -103.86 137
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -37.49 94
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -34.27 138
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -36.78 139
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -32.40 131
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -27.68 54
194
Solute E S A B L V Exp. Ref.
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -39.79 94
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -22.72 54
1,1,1-Trichloroethane 0.37 0.41 0.00 0.09 2.73 0.76 -30.03 140
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -56.82 141
Dibromomethane 0.71 0.69 0.11 0.07 2.89 0.60 -39.22 142
Methyl iodide 0.68 0.43 0.00 0.12 2.11 0.51 -26.39 54
1-Iodobutane 0.63 0.40 0.00 0.15 3.63 0.93 -33.49 54
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -34.45 143
1,2-Difluorobenzene 0.39 0.63 0.00 0.06 2.84 0.75 -34.93 144
1,3-Difluorobenzene 0.37 0.58 0.00 0.06 2.78 0.75 -34.41 144
4-Fluorotoluene 0.49 0.55 0.00 0.14 3.37 0.68 -36.99 143
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -39.23 143
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -48.31 144
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 0.96 -51.20 144
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -43.90 133
4-Chlorotoluene 0.71 0.74 0.00 0.05 4.21 0.98 -43.13 143
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -42.32 143
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -48.30 124
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -33.24 145
Propanenitrile 0.16 0.90 0.02 0.36 2.08 0.55 -34.57 145
1-Butanenitrile 0.19 0.90 0.00 0.36 2.55 0.69 -36.87 145
1-Pentanenitrile 0.18 0.90 0.00 0.36 3.11 0.83 -41.04 145
1-Hexanenitrile 0.17 0.90 0.00 0.36 3.61 0.97 -43.54 145
195
Solute E S A B L V Exp. Ref.
1-Heptanenitrile 0.16 0.90 0.00 0.36 4.09 1.11 -46.30 145
1-Octanenitrile 0.16 0.90 0.00 0.36 4.59 1.25 -49.87 145
1-Nonanenitrile 0.16 0.90 0.00 0.36 4.97 1.39 -53.36 145
1-Decanenitrile 0.16 0.90 0.00 0.36 5.46 1.53 -56.98 145
1-Undecanenitrile 0.15 0.90 0.00 0.36 5.94 1.67 -59.66 145
1-Dodecanenitrile 0.15 0.90 0.00 0.36 6.46 1.81 -63.30 145
1-Tridecanenitrile 0.15 0.90 0.00 0.36 6.92 1.95 -66.13 145
1-Tetradecanitrile 0.15 0.90 0.00 0.36 7.40 2.10 -68.94 145
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -39.17 145
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -41.13 145
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -43.76 145
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -41.56 16
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -48.16 145
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -51.45 145
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -53.97 145
1-Heptanol 0.21 0.42 0.37 0.48 4.12 1.15 -58.29 145
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -60.25 94
1-Nonanol 0.19 0.42 0.37 0.48 5.12 1.44 -66.92 145
1-Decanol 0.19 0.42 0.37 0.48 5.63 1.58 -68.42 145
1-Undecanol 0.18 0.42 0.37 0.48 6.13 1.72 -70.85 145
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 0.73 -40.34 131
2-methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -44.52 62
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 0.90 -54.14 146
cis 1,2-Cyclohexanediol 0.60 0.86 0.50 0.86 4.20 0.96 -69.70 126
196
Solute E S A B L V Exp. Ref.
Ethylene glycol 0.40 0.90 0.58 0.78 2.66 0.51 -69.66 147
Propylene glycol 0.37 0.90 0.58 0.80 2.92 0.65 -66.70 147
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -74.56 62
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -66.48 148
N-Methylaniline 0.95 0.94 0.17 0.47 4.49 0.96 -57.70 149
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -49.29 150
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -34.65 151
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -38.49 151
Benzyl alcohol 0.80 0.87 0.33 0.56 4.22 0.92 -70.30 152
2-Phenylethanol 0.81 0.91 0.30 0.64 4.63 1.06 -70.47 152
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -30.38 153
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -32.80 154
tert-Butyl acetate 0.03 0.54 0.00 0.47 2.80 1.03 -33.46 154
N,N-Dimethyl formamide 0.37 1.31 0.00 0.74 3.17 0.65 -45.64 153
N,N-Dimethyl acetamide 0.36 1.33 0.00 0.78 3.72 0.79 -52.29 153
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -51.35 155
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -39.00 150
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -42.60 156
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -52.88 16
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -38.96 157
(Trifluoromethy)lbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -32.68 95
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -44.27 95
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -26.30 101
197
Solute E S A B L V Exp. Ref.
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -54.68 120
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -40.17 120
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -37.67 158
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -26.53 127
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 1.01 -27.50 127
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.01 -29.07 127
Acetaldehyde 0.21 0.67 0.00 0.45 1.23 0.41 -26.80 127
Vinyl acetate 0.22 0.64 0.00 0.43 2.15 0.70 -30.38 127
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -90.60 159
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -50.90 160
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -66.00 160
Table S5.6. Values of t he g as t o pr opylene c arbonate s olvation e nthalpy i n kJ/mol at 298K for 106 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -5.73 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -6.44 25
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -9.71 25
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -10.83 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -17.57 25
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -21.00 25
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -24.66 25
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -31.41 127
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -37.97 127
198
Solute E S A B L V Exp Ref
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -24.18 16
Methylcyclopentane 0.23 0.10 0.00 0.00 2.82 0.85 -23.14 127
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -26.22 127
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -17.60 123
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -24.81 127
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -30.56 127
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -27.01 127
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -19.30 123
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -32.50 162
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -34.51 162
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -38.46 162
Vinyl acetate 0.22 0.64 0.00 0.43 2.15 0.70 -34.28 162
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -41.22 162
tert-butyl acetate 0.03 0.54 0.00 0.47 2.80 1.03 -35.42 162
Isobutyl acetate 0.05 0.57 0.00 0.47 3.16 1.03 -36.13 162
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -45.45 162
Hexyl acetate 0.06 0.60 0.00 0.45 4.35 1.31 -47.36 162
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -35.21 162
Ethyl propanoate 0.09 0.58 0.00 0.45 2.81 0.89 -37.79 162
Propyl propanoate 0.07 0.56 0.00 0.45 3.34 1.03 -40.40 162
Butyl propanoate 0.06 0.56 0.00 0.47 3.83 1.17 -46.95 162
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -38.08 162
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 1.03 -39.85 162
Propyl butanoate 0.05 0.56 0.00 0.45 3.78 1.17 -44.43 162
199
Solute E S A B L V Exp Ref
Methyl pentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -40.89 162
Ethyl pentanoate 0.05 0.58 0.00 0.45 3.77 1.17 -43.63 162
Ethyl hexanoate 0.04 0.58 0.00 0.45 4.25 1.31 -48.30 162
Ethyl heptanoate 0.03 0.58 0.00 0.45 4.73 1.45 -47.61 162
Ethyl isobutyrate 0.03 0.55 0.00 0.47 3.07 1.03 -37.63 162
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -37.49 163
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -42.47 163
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -30.79 164
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.27 164
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.60 127
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -40.78 164
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -47.43 164
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -59.14 164
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -43.77 164
2-Methylcyclohexanone 0.37 0.83 0.00 0.56 4.05 1.00 -45.28 164
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -45.45 165
Phenetole 0.68 0.70 0.00 0.32 4.24 1.06 -47.61 165
Dimethyl sulfoxide 0.52 1.72 0.00 0.97 3.46 0.61 -51.44 166
Benzyl alcohol 0.80 0.87 0.33 0.56 4.22 0.92 -57.40 16
2-Phenylethanol 0.81 0.86 0.31 0.65 4.63 1.06 -62.37 167
3-Phenyl-1-propanol 0.82 0.94 0.31 0.65 5.31 1.20 -65.00 167
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -25.50 127
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -28.95 127
200
Solute E S A B L V Exp Ref
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -29.09 127
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 1.01 -30.73 127
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.01 -33.78 127
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -34.33 168
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -31.72 168
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -39.01 168
1,3-Dioxolane 0.30 0.51 0.00 0.62 1.83 0.54 -36.10 168
12-Crown-4 0.42 0.99 0.00 1.39 5.14 1.36 -68.73 169
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -90.00 161,26
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -108.86 170
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -31.52 16
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -33.85 16
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -36.80 16
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 0.59 -34.83 171
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -41.31 16
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -38.36 171
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -36.10 16
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -45.31 16
2-Pentanol 0.20 0.36 0.33 0.56 2.84 0.87 -39.35 172
3-Pentanol 0.20 0.36 0.33 0.56 2.86 0.87 -39.68 172
2-Methyl-1-butanol 0.22 0.39 0.37 0.48 3.01 0.87 -39.90 16
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -38.87 172
201
Solute E S A B L V Exp Ref
3-Methyl-1-butanol 0.19 0.39 0.37 0.48 3.01 0.87 -39.95 172
3-Methyl-2-butanol 0.19 0.33 0.33 0.56 2.79 0.87 -38.84 172
Ethan-1,2-diol 0.40 0.90 0.58 0.78 2.66 0.51 -54.35 173
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 0.65 -40.20 174
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 0.79 -42.42 174
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -32.30 16
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.65 16
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -39.19 16
Isopropylbenzene 0.60 0.49 0.00 0.16 4.08 1.14 -41.38 16
1,2-Dimethylbenzene 0.66 0.56 0.00 0.16 3.94 1.00 -39.90 127
1,3-Dimethylbenzene 0.62 0.52 0.00 0.16 3.84 1.00 -39.31 16
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -38.88 127
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -62.65 16
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -34.98 16
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -39.24 16
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -41.55 16
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -46.17 16
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -53.89 16
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -27.62 127
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -32.19 127
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -32.47 127
trans-1,2-Dichloroethylene 0.43 0.41 0.09 0.05 2.28 0.59 -29.00 175
Trichloroethylene 0.52 0.37 0.08 0.03 3.00 0.71 -33.78 175
202
Solute E S A B L V Exp Ref
Tetrachloroethylene 0.64 0.44 0.00 0.00 3.58 0.84 -36.51 175
Carbon Dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -15.70 176
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -38.64 157
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -31.38 176
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -52.30 160
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -61.10 160
Table S5.7. Experimental values of the gas to dibutyl ether solvation enthalpy, ΔHSolv,BE in kJ/mol, for 68 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -26.28 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -31.12 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -36.07 28
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -40.96 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -45.73 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -50.64 177
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -60.12 28
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -79.57 28
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 0.95 -29.99 178
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.10 -34.90 29
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -34.80 29
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -32.38 29
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -30.70 179
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -40.40 29
203
Solute E S A B L V Exp Ref
1-Octyne 0.16 0.22 0.09 0.10 3.52 1.15 -43.22 29
2-Octyne 0.23 0.30 0.00 0.10 3.85 1.15 -44.85 29
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.06 29
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.85 29
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -42.02 29
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -43.38 29
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -31.24 29
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -35.32 29
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -39.45 29
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 0.59 -39.64 29
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -44.94 29
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -40.65 29
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 0.73 -44.58 29
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -37.13 29
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -48.71 29
2,2-Dimethyl-1-propanol 0.22 0.36 0.37 0.53 2.65 0.87 -40.63 29
1-Heptanol 0.21 0.42 0.37 0.48 4.12 1.15 -59.02 29
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -38.79 62
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -26.69 62
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -32.32 29
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -29.00 62
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -45.00 29
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -31.03 29
204
Solute E S A B L V Exp Ref
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -26.02 29
Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -30.74 29
Pentan-2-one 0.14 0.68 0.00 0.51 2.76 0.83 -35.12 29
Pentan-3-one 0.15 0.66 0.00 0.51 2.81 0.83 -35.87 29
Hexan-2-one 0.14 0.68 0.00 0.51 3.29 0.97 -40.01 29
Heptan-2-one 0.12 0.68 0.00 0.51 3.76 1.11 -44.31 29
Heptan-4-one 0.11 0.66 0.00 0.51 3.71 1.11 -44.44 29
Octan-2-one 0.11 0.68 0.00 0.51 4.26 1.25 -49.33 29
Nonan-2-one 0.12 0.68 0.00 0.51 4.73 1.39 -53.95 29
Nonan-5-one 0.10 0.66 0.00 0.51 4.70 1.39 -51.33 29
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -44.31 29
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -38.88 29
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -41.58 29
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -28.23 29
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -32.99 29
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -30.50 72
Dibutylamine 0.11 0.30 0.08 0.69 4.35 1.34 -49.24 29
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -35.55 29
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -26.78 29
1-Chloropentane 0.21 0.38 0.00 0.09 3.22 0.94 -38.14 29
1-Bromobutane 0.36 0.40 0.00 0.12 3.11 0.85 -36.36 29
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -50.95 29
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -44.53 29
205
Solute E S A B L V Exp Ref
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -52.90 29
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 0.85 -36.66 107
1,1,2,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 0.88 -50.12 141
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -67.03 62
Ttrifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -37.45 95
Hexafluorobenzene 0.09 0.56 0.00 0.01 2.35 0.82 -33.38 180
Benzyl alcohol 0.80 0.87 0.33 0.56 4.22 0.92 -58.10 181
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -37.80 182
Table S5.8. Experimental values of the gas to ethyl acetate solvation enthalpy, ΔHSolv,EA in kJ/mol, for 79 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -21.30 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -25.69 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -29.87 28
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -33.84 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -37.61 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -41.84 28
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -48.01 183
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -50.04 28
Tridecane 0.00 0.00 0.00 0.00 6.20 1.94 -56.61 183
Pentadecane 0.00 0.00 0.00 0.00 7.21 2.22 -63.65 183
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -66.86 28
Heptadecane 0.00 0.00 0.00 0.00 8.22 2.50 -73.75 183
206
Solute E S A B L V Exp Ref
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -23.83 184
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 0.95 -24.63 184
3-Methylhexane 0.00 0.00 0.00 0.00 3.04 1.10 -29.19 184
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.10 -29.08 185
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.80 -27.36 95
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -30.79 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.27 91
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.78 186
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -41.55 186
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -45.94 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -44.39 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -49.24 186
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -54.02 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -51.71 91
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -43.26 91
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -44.02 91
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -31.80 186
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -35.38 187
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -38.81 188
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -43.39 62
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -47.45 62
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -59.67 94
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -37.14 188
207
Solute E S A B L V Exp Ref
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -41.30 62
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -25.98 62
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -40.79 94
Butyl methyl 0.05 0.25 0.00 0.44 2.66 0.87 -30.79 95
Methyl tert-butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -29.37 62
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.30 -43.35 94
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -79.32 99
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -46.65 94
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -36.90 182
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.80 -27.98 189
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -49.00 94
2-Bromo-2-methylpropane 0.31 0.29 0.00 0.07 2.61 0.85 -30.73 189
1,2-Dibromoethane 0.75 0.76 0.10 0.17 3.38 0.74 -41.31 190
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.48 187
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.49 95
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -45.31 95
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -55.89 132
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -64.40 191
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -76.60 191
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 0.50 -46.00 187
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -35.14 192
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -67.28 62
208
Solute E S A B L V Exp Ref
Trifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -37.70 95
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -56.02 95
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -47.11 95
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -29.71 176
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.20 -2.53 75
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -49.53 120
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -40.46 120
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -31.80 101
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -55.80 193
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -63.80 193
Salicylamide 1.16 1.65 0.63 0.48 5.91 1.03 -83.53 194,195
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -64.43 186
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -50.63 186
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -39.87 185
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -59.29 185
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -42.50 196
Piperidine 0.42 0.46 0.10 0.69 3.30 0.80 -39.50 196
1-Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -34.86 196
Acetic acid 0.27 0.64 0.63 0.44 1.82 0.47 -47.46 196
Formic acid 0.34 0.75 0.76 0.33 1.55 0.32 -48.55 196
Trichloroethene 0.52 0.37 0.08 0.03 3.00 0.72 -36.72 197
Tetrachloroethene 0.64 0.44 0.00 0.00 3.58 0.84 -38.05 197
209
Table S5.9. Values of the gas to chloroform solvation enthalpy, ∆H Solv,CFM, in kJ/mol at 298K for 100 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -24.21 198
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -28.25 198
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -32.95 198
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -37.57 198
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -41.95 198
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -46.12 198
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -51.27 198
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -55.83 198
Tridecane 0.00 0.00 0.00 0.00 6.20 1.94 -60.03 198
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -65.37 198
Pentadecane 0.00 0.00 0.00 0.00 7.21 2.22 -67.72 198
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -73.95 198
Heptadecane 0.00 0.00 0.00 0.00 8.22 2.50 -78.09 198
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -30.29 199
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -35.97 200
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -40.81 200
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -35.85 182
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -41.09 182
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -46.20 182
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 1.14 -50.29 182
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -57.18 201
210
Solute E S A B L V Exp Ref
Phenanthrene 2.06 1.29 0.00 0.26 7.63 1.45 -77.17 201
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -78.45 201
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -36.40 182
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 1.01 -42.20 202
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -41.28 202
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.29 -51.00 182
Dipentyl ether 0.00 0.25 0.00 0.45 4.88 1.58 -57.19 203
Ethoxypropane 0.00 0.25 0.00 0.45 2.49 0.87 -38.73 202
Ethoxybutane 0.01 0.25 0.00 0.45 2.99 1.01 -46.90 202
Methyl tert-butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -38.53 204
Furan 0.37 0.51 0.00 0.13 1.91 0.54 -29.14 205
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -42.60 182
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -43.98 206
1,3-Dioxane 0.31 0.72 0.00 0.70 2.52 0.68 -48.20 206
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -49.70 182
Digylme 0.11 0.76 0.00 1.17 3.92 1.13 -72.40 182
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -105.58 161,26
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -131.10 53
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -39.34 182
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -43.51 207
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -47.76 203
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -56.07 203
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -63.26 203
211
Solute E S A B L V Exp Ref
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -55.90 208
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -60.00 182
Dimethyl sulfoxide 0.52 1.72 0.00 0.97 3.46 0.61 -66.69 182
Ethyl formate 0.15 0.66 0.00 0.38 1.85 0.61 -35.02 209
Propyl formate 0.13 0.63 0.00 0.38 2.43 0.75 -43.97 210
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -39.68 211
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -43.84 182
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -49.37 212
Ethyl propanoate 0.09 0.58 0.00 0.45 2.81 0.89 -48.91 213
Propyl propanoate 0.07 0.56 0.00 0.45 3.34 1.03 -53.24 214
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 1.03 -52.85 215
Propyl butanoate 0.05 0.56 0.00 0.45 3.78 1.17 -56.77 216
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -46.40 182
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -56.10 182
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -58.23 182
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -48.40 182
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -36.93 182
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -37.70 182
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -28.70 182
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -32.80 182
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -35.20 61
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -35.10 182
212
Solute E S A B L V Exp Ref
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -42.00 182
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -50.40 182
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -60.00 182
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -30.32 200
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -31.31 217
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -35.06 218
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -35.65 218
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -45.63 218
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -51.00 219
2-Methoxyphenol 0.84 0.91 0.22 0.52 4.45 0.92 -61.98 219
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -50.44 219
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -41.12 69
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -46.73 69
N-Methylaniline 0.95 0.90 0.17 0.43 4.49 0.96 -56.76 69
N-Ethylaniline 0.95 0.85 0.17 0.43 4.81 1.10 -60.81 69
Diethyl sulfide 0.37 0.38 0.00 0.32 3.10 0.84 -43.50 220
Piperidine 0.42 0.46 0.10 0.69 3.30 0.80 -49.51 221
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -59.20 222
Bromoethane 0.37 0.40 0.00 0.12 2.12 0.57 -27.90 223
1,2-Diamobenzene 1.26 1.40 0.24 0.73 4.85 0.91 -61.40 224
1-Chloropentane 0.21 0.38 0.00 0.09 3.22 0.94 -40.17 225
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 1.08 -44.44 225
1-Chloroheptane 0.19 0.40 0.00 0.10 4.28 1.22 -48.99 225
213
Solute E S A B L V Exp Ref
1-Chlorooctane 0.19 0.40 0.00 0.10 4.77 1.36 -53.47 225
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -45.05 226
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -50.40 226
Methyl pentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -52.59 226
Methyl hexanoate 0.08 0.60 0.00 0.45 3.87 1.17 -57.93 226
Methyl octanoate 0.07 0.60 0.00 0.45 4.84 1.45 -67.35 226
Methyl nonanoate 0.06 0.60 0.00 0.45 5.32 1.59 -70.94 226
Methyl decanoate 0.05 0.60 0.00 0.45 5.80 1.73 -75.74 226
Table S5.10. Values of t he gas t o 1,2 -dichloroethane s olvation e nthalpy, ∆HSolv,DCE, in kJ/mol at 298K for 88 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -18.87 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -22.80 227
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -26.57 227
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -30.25 227
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -34.52 227
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -38.53 227
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -45.70 228
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -46.02 227
Tridecane 0.00 0.00 0.00 0.00 6.20 1.94 -54.15 229
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -57.35 230
Pentadecane 0.00 0.00 0.00 0.00 7.21 2.22 -61.54 231
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -61.55 227
214
Solute E S A B L V Exp Ref
Heptadecane 0.00 0.00 0.00 0.00 8.22 2.50 -71.71 232
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 0.95 -27.00 133
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -27.13 200
2,2,4,4-Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -28.70 133
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -25.60 133
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -32.89 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -36.36 91
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -46.00 133
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -47.49 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -45.98 91
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -55.10 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -53.14 91
2,2,4,4-Tetramethyl-3-pentanone
0.10 0.56 0.00 0.52 4.37 1.39 -44.30 91
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -47.15 91
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -23.83 233
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -26.85 233
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -29.75 233
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -35.74 233
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -52.13 94
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -27.10 133
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.29 -40.08 94
215
Solute E S A B L V Exp Ref
Butyl Methyl Ether 0.05 0.25 0.00 0.44 2.66 0.87 -31.50 133
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -30.80 133
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.29 -43.60 94
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -33.90 133
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -39.30 133
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -90.57 99
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -44.69 94
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -48.07 94
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -54.79 132
Methyl formate 0.19 0.68 0.00 0.38 1.29 0.46 -28.22 234
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -33.38 235
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -36.00 133
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -39.79 235
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -44.53 235
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -47.30 235
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -36.75 234
Ethyl propanoate 0.09 0.58 0.00 0.45 2.81 0.89 -37.94 235
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -40.29 234
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 1.03 -41.86 235
Methyl pentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -43.97 234
Ethyl pentanoate 0.05 0.58 0.00 0.45 3.77 1.17 -47.81 236
Ethyl hexanoate 0.04 0.58 0.00 0.45 4.25 1.31 -50.46 235
Butyl formate 0.12 0.63 0.00 0.38 2.96 0.89 -41.21 237
216
Solute E S A B L V Exp Ref
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -33.10 133
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -33.20 133
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.50 133
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -34.70 133
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -38.90 133
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -42.70 133
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -47.70 133
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -46.00 133
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -45.20 133
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -64.00 133
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -76.60 133
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.70 133
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -45.20 133
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -40.60 133
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -54.80 133
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -46.90 133
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -56.50 133
4-Methoxyphenol 0.90 1.17 0.57 0.48 4.77 0.97 -68.60 238
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -35.10 217
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -45.02 239,240
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -31.87 241
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -23.01 176
217
Solute E S A B L V Exp Ref
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -38.14 242
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 1.21 -62.25 239,240
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -34.84 223
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.56 -38.15 223
Propionitrile 0.16 0.90 0.02 0.36 2.08 0.55 -35.03 223
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -31.95 241
1,1,1-Trichloroethane 0.37 0.41 0.00 0.09 2.73 0.76 -31.28 243
trans 1,2-Dichloroethene 0.43 0.41 0.09 0.05 2.28 0.59 -28.91 244
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -47.03 244
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -50.60 133
Table S5.11. Values of the gas to heptane solvation enthalpy in kJ/mol at 298K for 134 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -3.81 45
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -11.17 45
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -26.53 91
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -31.55 91
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -36.57 91
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -41.51 91
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -46.40 91
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -51.38 91
218
Solute E S A B L V Exp Ref
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -61.17 91
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -80.92 91
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.09 -35.19 199
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -30.05 43
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 0.95 -30.43 43
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -27.85 43
2,3-Dimethylbutane 0.00 0.00 0.00 0.00 2.50 0.95 -29.30 43
2,4-Dimethylpentane 0.00 0.00 0.00 0.00 2.81 1.09 -32.92 199
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -35.06 245
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -32.29 199
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -37.81 43
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -42.66 43
Cyclodecane 0.47 0.10 0.00 0.00 5.34 1.41 -52.10 43
Methylcyclopentane 0.23 0.10 0.00 0.00 2.82 0.85 -31.39 43
Methylcyclohexane 0.24 0.10 0.00 0.00 3.32 0.99 -35.37 43
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -39.76 43
trans-1,2-Dimethylcyclohexane 0.23 0.20 0.00 0.00 3.72 1.13 -38.69 43
cis Decalin 0.55 0.25 0.00 0.00 5.16 1.30 -50.82 43
trans Decalin 0.47 0.23 0.00 0.00 4.98 1.30 -49.95 43
Bicyclohexyl 0.53 0.33 0.00 0.07 5.92 1.58 -57.84 43
Tetralin 0.89 0.65 0.00 0.17 5.20 1.17 -52.80 43
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -30.38 246
219
Solute E S A B L V Exp Ref
1-Octyne 0.16 0.22 0.09 0.10 3.52 1.15 -40.04 128
2-Octyne 0.23 0.30 0.00 0.10 3.85 1.15 -42.63 128
Propanal 0.20 0.65 0.00 0.45 1.82 0.55 -20.19 247
Butanal 0.19 0.65 0.00 0.45 2.27 0.69 -25.19 247
Pentanal 0.16 0.65 0.00 0.45 2.77 0.83 -31.15 247
Hexanal 0.15 0.65 0.00 0.45 3.37 0.97 -36.45 247
Heptanal 0.14 0.65 0.00 0.45 3.86 1.11 -41.59 247
Octanal 0.16 0.65 0.00 0.45 4.38 1.25 -45.76 247
Nonanal 0.15 0.65 0.00 0.45 4.86 1.39 -50.84 247
2-Methylpropanal 0.14 0.62 0.00 0.45 2.12 0.69 -26.30 247
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -21.59 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -26.53 91
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -41.09 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -41.51 91
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -50.12 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -50.08 91
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -42.13 91
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -37.78 91
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -38.72 248
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -44.52 249
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -53.08 113
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 0.84 -33.11 250
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -24.31 62
220
Solute E S A B L V Exp Ref
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -44.22 94
Dipentyl ether 0.00 0.25 0.00 0.45 4.88 1.58 -52.54 251
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -30.96 199
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -30.79 95
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.29 -46.11 94
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -24.81 62
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 1.01 -32.28 252
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.01 -34.61 253
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -29.32 254
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -31.59 255
2,5,8,11,14-Pentaoxopentadecane -0.02 1.11 0.00 1.79 6.50 1.81 -68.10 256
2,5,8,11-Tetraoxododecane 0.00 0.98 0.00 1.44 5.16 1.47 -54.12 257
2,5,8-Trioxanonane 0.11 0.76 0.00 1.17 3.92 1.13 -39.94 258
Diethoxymethane 0.01 0.49 0.00 0.54 2.79 0.93 -33.14 259
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -31.76 259
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 0.65 -26.06 259
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -47.86 94
Tetrachloromethane 0.46 0.38 0.00 0.00 2.82 0.74 -31.21 55
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 0.64 -27.98 233
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -50.88 94
Diiodomethane 0.71 0.69 0.11 0.07 2.89 0.77 -37.74 55
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -14.90 260
221
Solute E S A B L V Exp Ref
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -18.60 260
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -22.10 261
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -27.87 62
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -34.14 62
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -38.32 261
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -47.57 94
1-Nonanol 0.19 0.42 0.37 0.48 5.12 1.44 -53.66 262
1-Undecanol 0.18 0.42 0.37 0.48 6.13 1.72 -61.83 262
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -26.70 263
2-Methyl-1-propanol 0.22 0.39 0.37 0.48 2.41 0.73 -26.60 263
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 0.73 -22.60 263
3-Methyl-1-butanol 0.19 0.39 0.37 0.48 3.01 0.87 -35.63 264
2-Pentanol 0.20 0.36 0.33 0.56 2.84 0.87 -35.90 264
3-Methyl-2-butanol 0.19 0.33 0.33 0.56 2.79 0.87 -31.93 264
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -26.44 62
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 0.76 -37.21 265
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 0.90 -37.50 266
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 0.65 -34.22 267
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -34.45 199
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -25.14 266
Isopropylamine 0.18 0.32 0.16 0.61 1.91 0.63 -22.87 266
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -29.97 266
sec-Butylamine 0.17 0.32 0.16 0.63 2.41 0.77 -27.89 266
iso-Butylamine 0.12 0.29 0.16 0.71 2.49 0.77 -28.11 266
222
Solute E S A B L V Exp Ref
tert-Butylamine 0.12 0.29 0.16 0.71 2.49 0.77 -24.98 266
Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -34.12 266
Hexylamine 0.20 0.35 0.16 0.61 3.66 1.05 -39.47 266
Heptylamine 0.20 0.35 0.16 0.61 4.15 1.19 -44.97 266
Octylamine 0.19 0.35 0.16 0.61 4.52 1.34 -49.41 266
Nonylamine 0.19 0.35 0.16 0.61 5.10 1.48 -54.09 266
Decylamine 0.18 0.35 0.16 0.61 5.61 1.62 -58.69 266
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -39.92 62
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -30.54 95
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.94 95
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -46.23 95
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -51.82 201
Trifluorotoluene 0.23 0.48 0.00 0.10 2.89 0.91 -33.35 95
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -44.73 95
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -41.21 95
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -40.75 185
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -17.56 268
Helium 0.00 0.00 0.00 0.00 -1.74 0.06 7.72 45
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 5.56 45
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -1.22 45
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -5.51 45
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -10.08 269
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 3.78 45
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -9.66 45
223
Solute E S A B L V Exp Ref
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 0.32 -1.59 45
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -8.28 45
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -15.90 176
Difluorodichloromethane 0.04 0.13 0.00 0.00 1.12 0.53 -18.91 45
Hexafluorobenzene 0.09 0.56 0.00 0.01 2.35 0.82 -31.62 270
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 0.43 -12.84 45
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -24.40 157
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 1.23 -54.06 271
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 0.84 -33.81 114
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 1.14 -46.76 272
Table S5.12. Values of t he g as t o he xadecane s olvation e nthalpy i n kJ /mol a t 298K for 102 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.29 -3.97 3
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -11.51 3
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -15.94 3
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -20.79 3
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -25.94 3
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -31.04 3
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -36.15 3
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -41.13 3
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -81.38 3
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -18.74 3
224
Solute E S A B L V Exp Ref
2,2-Dimethylpropane 0.00 0.00 0.00 0.00 1.82 0.81 -21.14 273
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -27.66 3
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -31.50 3
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -11.17 3
Propene 0.10 0.08 0.00 0.07 0.95 0.49 -13.35 3
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -21.42 3
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -26.48 3
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -31.05 3
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -35.77 3
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -40.46 3
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -44.89 3
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -44.89 3
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -49.37 3
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -36.48 3
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -25.19 3
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 1.01 -34.15 274
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -43.42 275
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -30.53 276
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.02 -30.67 277
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.02 -34.12 278
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -28.53 3
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -30.78 279
225
Solute E S A B L V Exp Ref
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.46 -23.18 3
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -28.07 3
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -30.92 3
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -30.88 3
Tetrachloroethene 0.64 0.44 0.00 0.00 3.58 0.84 -38.41 3
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -25.36 3
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 0.71 -30.15 59
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -19.08 3
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -13.35 3
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -16.32 3
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -21.17 3
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -22.38 3
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -28.07 3
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -31.34 3
431-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -39.79 3
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 1.15 -44.43 3
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -49.07 3
1-Nonanol 0.19 0.42 0.37 0.48 5.12 1.44 -52.81 262
1-Undecanol 0.18 0.42 0.37 0.48 6.13 1.72 -61.39 262
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -23.01 3
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 0.90 -47.53 280
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -27.99 3
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -38.49 3
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 1.07 -48.37 3
226
Solute E S A B L V Exp Ref
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -30.38 3
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.90 3
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -40.12 3
Propylbenzene 0.60 0.50 0.00 0.15 4.23 1.14 -44.14 3
m-Xylene 0.62 0.52 0.00 0.16 3.84 1.00 -41.37 3
p-Xylene 0.61 0.52 0.00 0.16 3.84 1.00 -41.51 3
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -46.56 3
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -47.36 3
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -41.24 3
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -41.17 3
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -41.25 3
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -38.24 3
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -31.05 3
1,4-Difluorobenzene 0.38 0.60 0.00 0.06 2.77 0.75 -32.19 270
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -41.80 3
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -45.65 3
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -48.36 3
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -32.64 3
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -35.90 3
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 0.82 -37.49 3
4-Methylpyridine 0.63 0.82 0.00 0.54 3.64 0.82 -36.78 3
Propylamine 0.23 0.35 0.16 0.61 2.14 0.63 -23.97 3
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -29.41 3
Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -34.81 281
227
Solute E S A B L V Exp Ref
Hexylamine 0.20 0.35 0.16 0.61 3.66 1.05 -39.46 3
Heptylamine 0.20 0.35 0.16 0.61 4.15 1.19 -45.27 281
Nonylamine 0.19 0.35 0.16 0.61 5.10 1.48 -55.03 281
Decylamine 0.18 0.35 0.16 0.61 5.61 1.62 -60.02 281
tert-Butylamine 0.12 0.29 0.16 0.71 2.49 0.77 -26.15 3
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -24.60 3
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -34.14 3
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 8.24 3
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 6.78 3
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.79 3
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -5.02 3
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -10.08 3
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -14.18 3
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 4.56 25
Diiodomethane 0.71 0.69 0.11 0.07 2.89 0.77 -38.95 3
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 0.50 -20.88 3
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 0.70 -22.09 3
Benzyl alcohol 0.80 0.87 0.33 0.56 4.22 0.92 -42.38 3
Thiophene 0.69 0.56 0.00 0.15 2.82 0.64 -29.92 3
Benzyl chloride 0.82 0.82 0.00 0.33 4.38 0.98 -43.32 3
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 1.21 -61.74 282
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 1.23 -55.80 283
228
Table S5.13. Values of t he gas t o c yclohexane solvation enthalpy in kJ /mol a t 298K for 201 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -3.01 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -11.13 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -16.50 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -25.52 91
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -30.42 91
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -34.94 91
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -39.66 91
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -44.48 91
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -49.08 91
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -58.41 91
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -68.20 284
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -77.32 28
2-Methylbutane 0.00 0.00 0.00 0.00 2.01 0.81 -24.60 41
2,2-Dimethylpropane 0.00 0.00 0.00 0.00 1.82 0.81 -24.27 284
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.09 -34.27 41
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -27.16 41
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -28.91 285
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 0.95 -28.87 284
2,2-Dimethylpentane 0.00 0.00 0.00 0.00 2.80 1.09 -31.38 284
2,3-Dimethylbutane 0.00 0.00 0.00 0.00 2.50 0.95 -27.17 285
2,4-Dimethylpentane 0.00 0.00 0.00 0.00 2.81 1.09 -31.76 199
3,3-Diethylpentane 0.00 0.00 0.00 0.00 3.82 1.38 -41.76 286
229
Solute E S A B L V Exp Ref
3-Methylheptane 0.00 0.00 0.00 0.00 3.51 1.24 -37.66 284
2-Methyloctane 0.00 0.00 0.00 0.00 3.97 1.38 -43.10 284
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -34.31 284
2,2-Dimethylhexane 0.00 0.00 0.00 0.00 1.24 -35.56 284
2,2,4,4-Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -38.24 41
2,2,5,5-Tetramethylhexane 0.00 0.00 0.00 0.00 4.04 1.52 -40.17 284
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -28.54 286
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -33.05 41
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -38.50 287
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -43.47 286
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -35.40 286
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -38.03 286
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -9.03 74
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -24.31 286
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -29.39 90
1-Heptene 0.09 0.08 0.00 0.07 3.06 1.05 -34.18 286
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -38.95 286
1-Nonene 0.09 0.08 0.00 0.07 4.07 1.33 -43.72 286
1-Decene 0.09 0.08 0.00 0.07 4.55 1.47 -48.41 286
1-Dodecene 0.09 0.08 0.00 0.07 5.52 1.76 -58.24 286
1-Tridecene 0.09 0.08 0.00 0.07 6.02 1.90 -63.39 286
1-Tetradecene 0.09 0.08 0.00 0.07 6.51 2.04 -68.07 286
230
Solute E S A B L V Exp Ref
1-Pentadecene 0.08 0.08 0.00 0.07 7.01 2.18 -72.97 286
cis 2-Octene 0.14 0.08 0.00 0.07 3.68 1.19 -38.16 286
trans 2-Octene 0.12 0.08 0.00 0.07 3.60 1.19 -38.24 286
cis 4-Octene 0.13 0.08 0.00 0.07 3.61 1.19 -37.99 286
trans 4-Octene 0.14 0.08 0.00 0.07 3.59 1.19 -37.70 286
1,5-Hexadiene 0.19 0.15 0.00 0.10 2.45 0.87 -29.37 286
Cyclopentene 0.34 0.20 0.00 0.10 2.40 0.66 -27.20 286
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -33.05 286
1-Methylcyclohexene 0.39 0.20 0.00 0.10 3.48 0.94 -37.95 286
Norbornadiene 0.50 0.32 0.00 0.11 3.11 0.79 -33.56 47
1-Octyne 0.16 0.22 0.09 0.10 3.52 1.15 -38.57 128
2-Octyne 0.23 0.30 0.00 0.10 3.85 1.15 -41.59 128
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -25.25 288
Trichloromethane 0.43 0.49 0.15 0.02 2.48 0.62 -28.23 288
Tetrachloromethane 0.46 0.38 0.00 0.00 2.82 0.74 -31.80 288
1-Chloropropane 0.22 0.40 0.00 0.10 2.20 0.65 -25.42 288
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -30.62 41
1-Chlorooctane 0.19 0.40 0.00 0.10 4.77 1.36 -51.46 41
Difluorodichloromethane 0.04 0.04 0.00 0.04 1.00 0.53 -19.75 289
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 0.43 -9.29 45
Diiodomethane 1.20 0.69 0.05 0.17 3.86 0.77 -38.58 55
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -21.09 41
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -26.69 41
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -31.30 41
231
Solute E S A B L V Exp Ref
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -30.42 290
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -36.15 41
3-Hexanone 0.14 0.66 0.00 0.51 3.31 0.97 -34.52 290
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -40.67 41
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -39.62 41
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -45.00 41
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -50.01 41
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -48.89 41
2-Decanone 0.11 0.68 0.00 0.51 5.25 1.53 -52.51 290
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -56.90 290
6-Undecanone 0.08 0.66 0.00 0.51 5.68 1.67 -56.27 290
3,3-Dimethyl-2-butanone 0.11 0.62 0.00 0.51 2.93 0.97 -31.05 290
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -41.05 291
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -33.64 41
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -37.65 41
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 1.00 -42.43 290
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 0.84 -33.35 41
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -23.05 62
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 1.01 -34.11 199
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -30.34 199
Methyl tert-butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -28.44 292
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 1.01 -32.14 293
232
Solute E S A B L V Exp Ref
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -28.70 294
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -33.60 294
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -29.67 62
1,3-Dioxane 0.31 0.72 0.00 0.70 2.52 0.68 -31.26 295
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -30.98 295
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -31.79 294
2,5-Dimethyltetrahydrofuran 0.20 0.38 0.00 0.58 2.98 0.90 -33.31 294
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -16.90 288
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -17.50 296
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -22.50 296
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -27.70 296
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -20.80 296
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -31.80 296
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -36.40 61
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -46.40 61
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -25.44 62
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 0.65 -32.56 297
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 0.79 -35.88 298
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -23.94 299
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -27.86 41
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -32.20 299
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -17.93 41
Propionitrile 0.16 0.90 0.02 0.36 2.08 0.55 -23.50 300
233
Solute E S A B L V Exp Ref
Butyronitrile 0.18 0.90 0.00 0.36 2.55 0.69 -29.00 300
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -30.66 41
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.05 41
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -39.40 41
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -38.79 69
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -43.35 41
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -49.89 41
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -57.80 41
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -72.00 41
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -42.66 41
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -39.62 41
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -39.92 41
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -40.77 41
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -39.33 41
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -37.19 41
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -42.48 41
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -42.70 41
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 1.45 -64.80 41
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -30.92 41
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -44.12 41
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -43.10 41
Trifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -30.62 41
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -32.68 41
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -38.12 286
234
Solute E S A B L V Exp Ref
N-Methylaniline 0.95 0.90 0.17 0.43 4.48 0.96 -43.61 69
N-Ethylaniline 0.95 0.85 0.17 0.43 4.81 1.10 -48.43 69
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -46.39 41
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 0.84 -30.53 107
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -36.53 62
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -25.60 288
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.56 -28.40 288
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 0.71 -33.00 288
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 0.71 -30.23 59
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 10.13 25
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 6.11 25
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.92 25
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -3.56 25
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -10.00 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 5.19 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 2.13 25
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 0.84 25
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -6.66 74
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 0.25 25
Carbon tetrafluoride -0.58 -0.26 0.00 0.00 -0.82 0.32 0.50 25
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -5.77 25
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.20 -4.46 75
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -32.01 286
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -35.92 70
235
Solute E S A B L V Exp Ref
2,4-Dimethylpyridine 0.63 0.76 0.00 0.63 4.01 0.96 -39.87 70
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -39.89 70
2-Chloropyridine 0.74 1.03 0.00 0.37 3.88 0.80 -39.70 70
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -41.70 70
3-Cyanopyridine 0.75 1.26 0.00 0.62 4.16 0.83 -40.50 70
4-Cyanopyridine 0.75 1.21 0.00 0.59 4.03 0.83 -38.80 70
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 0.84 -33.32 114
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -34.10 41
Dimethyl Sulfoxide 0.52 1.74 0.00 0.88 3.46 0.61 -35.40 41
n-Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -29.51 301
n-Pentylamine 0.21 0.35 0.16 0.61 3.14 0.91 -33.95 301
n-Hexylamine 0.20 0.35 0.16 0.61 3.66 1.05 -39.57 301
Octylamine 0.19 0.35 0.16 0.61 4.52 1.34 -49.24 301
Nonylamine 0.19 0.35 0.16 0.61 5.10 1.48 -53.39 301
Decylamine 0.18 0.35 0.16 0.61 5.61 1.62 -58.15 301
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -33.80 199
Tri-n-butylamine 0.05 0.15 0.00 0.79 6.05 1.90 -67.51 41
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -52.55 302
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 0.65 -23.74 303
Propyl propionate 0.07 0.56 0.00 0.45 3.34 1.03 -38.21 304
Propionaldehyde 0.20 0.65 0.00 0.45 1.82 0.55 -21.38 305
Carbon disulfide 0.88 0.26 0.00 0.03 2.37 0.49 -26.11 305
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -27.61 305
236
Solute E S A B L V Exp Ref
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -29.50 305
Hexafluorobenzene 0.09 0.56 0.00 0.01 2.35 0.82 -27.15 305
Trichloroethene 0.52 0.37 0.08 0.03 3.00 0.71 -32.21 305
1,4-Difluorobenzene 0.38 0.60 0.00 0.06 2.77 0.75 -30.92 305
1-Iodopropane 0.63 0.40 0.00 0.15 3.13 0.79 -32.97 305
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -37.40 305
1-Decanol 0.19 0.42 0.37 0.48 5.63 1.58 -56.27 305
Phenanthrene 2.06 1.29 0.00 0.26 7.63 1.45 -68.70 305
Benzil 1.45 1.59 0.00 0.62 7.61 1.64 -65.98 305
Adamantane 0.76 0.57 0.00 0.04 4.93 1.19 -49.30 44
Iodomethane 0.68 0.43 0.00 0.12 2.11 0.51 -24.27 54
1-Iodobutane 0.63 0.40 0.00 0.15 3.63 0.93 -35.55 54
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -26.74 54
2-Iodo-2-methylpropane 0.59 0.35 0.00 0.19 3.44 0.93 -33.39 54
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -14.64 176
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -58.40 193
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -57.60 193
Table S5.14. Values of the gas to benzene solvation enthalpy in kJ/mol at 298K for 174 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -1.26 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -8.37 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -13.39 25
237
Solute E S A B L V Exp Ref
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -15.48 25
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -17.41 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -22.13 91
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -26.65 91
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -31.00 91
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -35.48 91
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -39.66 91
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -43.85 91
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -52.30 91
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -61.63 306
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -70.08 91
2-Methylbutane 0.00 0.00 0.00 0.00 2.01 0.67 -20.50 307
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.09 -30.00 185
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -22.88 286
2,2-Dimethylpentane 0.00 0.00 0.00 0.00 2.80 1.09 -26.94 286
3,3-Diethylpentane 0.00 0.00 0.00 0.00 3.82 1.09 -36.86 286
2-Methyloctane 0.00 0.00 0.00 0.00 3.97 1.38 -38.03 286
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -29.16 286
2,2,4,4-Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -32.01 286
2,2,5,5-Tetramethylhexane 0.00 0.00 0.00 0.00 4.04 1.52 -34.43 286
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -25.65 286
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -29.41 286
238
Solute E S A B L V Exp Ref
Cycloheptane 0.35 0.10 0.00 0.00 3.70 0.99 -35.34 87
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -39.68 87
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -31.30 286
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -35.27 286
cis Decalin 0.55 0.25 0.00 0.00 5.16 1.30 -46.43 88
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -9.00 45
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -18.53 308
cis 2-Butene 0.14 0.08 0.00 0.05 1.74 0.63 -20.95 308
trans 2-Butene 0.13 0.08 0.00 0.05 1.66 0.63 -19.23 308
2-Methylpropene 0.12 0.08 0.00 0.08 1.58 0.63 -19.10 308
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -22.92 286
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -27.91 286
1-Heptene 0.09 0.08 0.00 0.07 3.06 1.05 -32.47 286
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -36.69 286
1-Nonene 0.09 0.08 0.00 0.07 4.07 1.33 -41.21 286
1-Decene 0.09 0.08 0.00 0.07 4.55 1.47 -45.56 286
1-Dodecene 0.09 0.08 0.00 0.07 5.52 1.76 -54.52 286
1-Tridecene 0.09 0.08 0.00 0.07 6.02 1.90 -59.07 286
1-Tetradecene 0.09 0.08 0.00 0.07 6.51 2.04 -63.43 286
1-Pentadecene 0.08 0.08 0.00 0.07 7.01 2.18 -67.82 286
cis 2-Octene 0.14 0.08 0.00 0.07 3.68 1.19 -35.98 286
trans 2-Octene 0.12 0.08 0.00 0.07 3.60 1.19 -35.81 286
cis 4-Octene 0.13 0.08 0.00 0.07 3.61 1.19 -35.44 286
239
Solute E S A B L V Exp Ref
trans 4-Octene 0.14 0.08 0.00 0.07 3.59 1.19 -35.31 286
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -20.28 308
1,5-Hexadiene 0.19 0.15 0.00 0.10 2.45 0.87 -29.20 286
Cyclopentene 0.34 0.20 0.00 0.10 2.40 0.66 -26.27 286
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -31.51 286
1-Methylcyclohexene 0.39 0.20 0.00 0.10 3.48 0.94 -34.94 286
Norbornadiene 0.50 0.32 0.00 0.11 3.11 0.79 -33.66 47
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -30.08 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.27 91
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.61 290
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -38.58 290
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -42.17 290
3-Hexanone 0.14 0.66 0.00 0.51 3.31 0.97 -41.97 290
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -46.44 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -45.81 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -50.84 290
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -54.98 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -53.35 91
2-Decanone 0.11 0.68 0.00 0.51 5.25 1.53 -58.62 290
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -62.80 290
6-Undecanone 0.08 0.66 0.00 0.51 5.68 1.67 -61.37 290
3,3-Dimethyl-2-butanone 0.11 0.62 0.00 0.51 2.93 0.97 -37.66 290
240
Solute E S A B L V Exp Ref
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -43.01 91
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -43.72 290
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -46.16 91
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 1.00 -49.62 290
Dimethyl ether 0.00 0.27 0.00 0.41 1.29 0.45 -21.10 308
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -26.36 307
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -42.17 94
Methyl butyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -31.38 307
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.30 -44.81 94
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -28.03 307
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.02 -34.61 99
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -31.80 108
1,3-Dioxane 0.31 0.72 0.00 0.70 2.52 0.68 -39.77 295
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -39.03 295
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -34.16 309
Diglyme 0.11 0.76 0.00 1.17 3.92 1.13 -49.00 182
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -81.45 99
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -100.80 53
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -35.14 307
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -39.33 307
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -49.66 310
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -52.76 94
1-Decanol 0.19 0.42 0.37 0.48 5.63 1.58 -65.00 311
241
Solute E S A B L V Exp Ref
tert-Butanol 0.18 0.30 0.31 0.60 1.96 0.73 -34.00 312
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -33.47 307
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 0.79 -39.43 313
1,1-Difluoroethane -0.25 0.47 0.04 0.07 0.57 0.43 -18.13 308
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -47.61 94
Chloroethane 0.23 0.40 0.00 0.10 1.68 0.51 -25.62 308
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 1.08 -41.97 314
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -50.38 94
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -47.72 119
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -49.95 98
2,6-Dimethylphenol 0.85 0.82 0.51 0.37 4.50 1.06 -52.59 108
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -69.20 159
Dimethyl sulfoxide 0.52 1.72 0.00 0.97 3.46 0.61 -48.08 98
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -40.20 98
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -42.43 70
2,4-Dimethylpyridine 0.63 0.76 0.00 0.63 4.01 0.96 -47.04 70
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -45.00 70
2-Chloropyridine 0.74 1.03 0.00 0.37 3.88 0.80 -47.90 70
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -48.50 70
3-Cyanopyridine 0.75 1.26 0.00 0.62 4.16 0.83 -54.10 70
4-Cyanopyridine 0.75 1.21 0.00 0.59 4.03 0.83 -55.00 70
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -37.06 98
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.20 2.45 75
242
Solute E S A B L V Exp Ref
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 10.29 25
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 10.46 25
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 1.26 25
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -1.92 25
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -7.11 25
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -13.31 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 6.36 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 4.27 25
Carbon Monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 2.68 25
Carbon Dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -9.20 315
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 1.72 25
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 0.32 2.26 25
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -3.26 25
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -24.27 176
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.85 307
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.66 307
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -42.15 302
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -44.77 307
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -55.28 201
Phenanthrene 2.06 1.29 0.00 0.26 7.63 1.45 -74.04 201
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -63.40 191
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 0.96 -45.95 316
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -46.58 106
γ-Butyrolactone 0.39 1.38 0.00 0.59 3.33 0.64 -53.92 82
243
Solute E S A B L V Exp Ref
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -34.74 187
Difluorodichloromethane 0.04 0.04 0.00 0.04 1.00 0.53 -18.58 289
Ethyl formate 0.15 0.66 0.00 0.38 1.85 0.61 -30.38 317
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 0.84 -35.79 114
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 0.84 -38.44 107
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -52.03 318
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 0.43 -5.02 45
Diiodomethane 0.71 0.69 0.11 0.07 2.89 0.77 -45.02 55
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -52.72 307
Trifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -35.15 307
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -51.04 307
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -58.78 302
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -31.23 319
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 0.71 -43.37 59
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 0.71 -40.30 59
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -35.01 157
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.56 -38.29 320
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -35.44 302
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -40.83 302
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -43.60 302
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -48.76 302
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -50.54 185
Carbon Tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -31.88 286
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -32.27 321
244
Solute E S A B L V Exp Ref
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 0.65 -28.12 303
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -37.21 298
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -29.62 89
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -48.95 51
1-Nitronaphthalene 1.34 0.94 0.00 0.22 5.80 1.26 -68.20 51
4-Chloronitrobenzene 0.98 1.18 0.00 0.24 5.22 1.01 -55.23 51
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 1.07 -54.54 222
4-Nitrotoluene 0.87 1.11 0.00 0.28 5.15 1.01 -61.33 222
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.56 -42.10 120
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -40.02 120
Table S5.15. Values of t he gas t o methanol solvation enthalpy, ΔHSolv,MeOH, i n kJ/mole at 298 K for 188 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -3.60 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -7.95 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -13.10 25
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -16.36 25
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -18.79 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -22.38 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -26.53 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -30.75 28
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -34.89 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -38.83 28
245
Solute E S A B L V Exp Ref
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -42.80 28
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -51.09 28
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -59.50 286
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -67.99 28
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -23.26 286
3,3-Diethylpentane 0.00 0.00 0.00 0.00 3.82 1.09 -37.24 286
2-Methyloctane 0.00 0.00 0.00 0.00 3.97 1.38 -37.70 286
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -29.46 286
2,2,4,4-Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -32.30 286
2,2,5,5-Tetramethylhexane 0.00 0.00 0.00 0.00 4.04 1.52 -34.31 286
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -24.60 286
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -28.11 286
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -36.90 286
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -30.29 286
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -34.35 286
Adamantane 0.76 0.57 0.00 0.04 4.93 1.19 -42.30 322
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -19.20 123
cis 2-Butene 0.14 0.08 0.00 0.05 1.74 0.63 -20.73 323
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -23.43 286
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -27.82 286
1-Heptene 0.09 0.08 0.00 0.07 3.06 1.05 -31.84 286
246
Solute E S A B L V Exp Ref
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -35.81 286
1-Nonene 0.09 0.08 0.00 0.07 4.07 1.33 -39.96 286
1-Decene 0.09 0.08 0.00 0.07 4.55 1.47 -44.27 286
1-Dodecene 0.09 0.08 0.00 0.07 5.52 1.76 -52.59 286
1-Tridecene 0.09 0.08 0.00 0.07 6.02 1.90 -56.57 286
1-Tetradecene 0.09 0.08 0.00 0.07 6.51 2.04 -60.88 286
1-Pentadecene 0.08 0.08 0.00 0.07 7.01 2.18 -65.18 286
cis 2-Octene 0.14 0.08 0.00 0.07 3.68 1.19 -34.98 286
trans 2-Octene 0.12 0.08 0.00 0.07 3.60 1.19 -34.94 286
cis 4-Octene 0.13 0.08 0.00 0.07 3.61 1.19 -34.69 286
trans 4-Octene 0.14 0.08 0.00 0.07 3.59 1.19 -34.39 286
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -21.50 123
1,5-Hexadiene 0.19 0.15 0.00 0.10 2.45 0.87 -29.12 286
Cyclopentene 0.34 0.20 0.00 0.10 2.40 0.66 -25.44 286
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -29.54 286
1-Methylcyclohexene 0.39 0.20 0.00 0.10 3.48 0.94 -33.85 286
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -37.80 324
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -42.30 324
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -45.86 324
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -51.15 324
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -55.33 324
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 1.02 -59.52 325
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 1.30 -67.39 324
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 1.58 -76.49 326
247
Solute E S A B L V Exp Ref
Ethylene glycol 0.40 0.90 0.58 0.78 2.66 0.51 -64.93 327
1,2-Propanediol 0.37 0.90 0.58 0.80 2.92 0.65 -64.70 327
1,3-Propanediol 0.40 0.91 0.77 0.85 3.26 0.65 -71.50 328
1,4-Butanediol 0.40 0.93 0.72 0.90 3.80 0.79 -76.20 328
Glycerol 0.51 0.76 0.47 1.43 3.97 0.71 -90.10 328
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -32.37 129
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.37 102
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -39.94 329
Isopropylbenzene 0.60 0.49 0.00 0.16 4.08 1.14 -42.34 329
4-Isopropyltoluene 0.61 0.49 0.00 0.19 4.59 1.14 -46.58 329
sec-Butylbenzene 0.60 0.48 0.00 0.16 4.51 1.28 -46.74 329
tert-Butylbenzene 0.62 0.49 0.00 0.18 4.41 1.28 -44.63 329
Hexamethylbenzene 0.95 0.72 0.00 0.21 6.56 1.56 -62.25 329
Octylbenzene 0.58 0.48 0.00 0.15 6.71 1.84 -60.37 329
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 1.14 -46.45 329
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -53.79 132
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -61.85 329
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -36.10 182
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -32.98 330
Chloroethane 0.23 0.40 0.00 0.10 1.68 0.51 -23.72 323
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -27.44 331
2-Methyl-2-bromopropane 0.31 0.29 0.00 0.07 2.61 0.85 -28.80 332,333
248
Solute E S A B L V Exp Ref
2-Methyl-2-iodopropane 0.59 0.35 0.00 0.19 3.44 0.93 -32.80 334
Methyl iodide 0.68 0.43 0.00 0.12 2.02 0.51 -25.95 335
1,1-Difluoroethane -0.25 0.47 0.04 0.07 0.57 0.42 -18.97 323
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -28.79 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -32.26 91
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -35.86 290
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -36.02 290
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -40.12 290
3-Hexanone 0.14 0.66 0.00 0.51 3.31 0.97 -39.46 290
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -44.31 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -43.22 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -48.24 290
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -51.88 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -50.96 91
2-Decanone 0.11 0.68 0.00 0.51 5.25 1.53 -55.27 290
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -59.00 290
6-Undecanone 0.08 0.66 0.00 0.51 5.68 1.67 -57.44 290
4-Methyl-2-pentanone 0.11 0.65 0.00 0.51 3.09 0.97 -39.63 91
3,3-Dimethyl-2-butanone 0.11 0.62 0.00 0.51 2.93 0.97 -35.52 290
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -41.51 91
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -39.25 290
249
Solute E S A B L V Exp Ref
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -44.48 91
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 1.00 -46.65 290
Dimethyl ether 0.00 0.27 0.00 0.41 1.29 0.45 -17.70 323
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -32.89 336
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -30.63 95
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -30.75 337
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.01 -34.72 338
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -30.96 339
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -33.48 340
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -34.82 339
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -36.50 328
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -91.28 161,341
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -101.60 53
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -59.17 342
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.20 -2.64 75
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 5.86 25
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 4.81 25
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.84 25
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -4.90 25
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -9.41 38
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -15.98 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 0.50 25
250
Solute E S A B L V Exp Ref
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 0.67 25
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -10.67 45
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -0.96 25
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -29.02 343
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -31.74 188
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -28.62 319
Butyronitrile 0.18 0.90 0.00 0.36 2.55 0.69 -35.87 344
Dimethyl sulfoxide 0.52 1.74 0.00 0.88 3.46 0.61 -53.89 319
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -47.80 319
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -40.19 345
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -46.28 329
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -46.11 84
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -35.39 329
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -42.55 329
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -47.47 329
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -33.94 157
4-Nitrophenol 1.07 1.72 0.82 0.26 5.88 0.95 -91.16 346
4-Bromophenol 1.08 1.17 0.67 0.20 5.14 0.95 -82.82 346
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -66.02 346
4-Methylphenol 0.82 0.87 0.57 0.31 4.31 0.92 -66.66 346
4-tert-Butylphenol 0.81 0.89 0.56 0.41 5.26 1.34 -78.34 346
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -44.21 347
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -48.36 347
4-Methylpyridine 0.63 0.82 0.00 0.54 3.64 0.82 -50.43 348
251
Solute E S A B L V Exp Ref
4-Ethylpyridine 0.63 0.80 0.00 0.57 4.12 0.76 -50.80 349
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 0.96 -52.89 347
3,5-Dimethylpyridine 0.66 0.79 0.00 0.60 4.21 0.96 -54.77 348
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -49.60 347
4-Cyanopyridine 0.75 1.21 0.00 0.59 4.03 0.83 -52.00 347
4-Methoxypyridine 0.68 0.93 0.00 0.53 4.28 0.88 -56.57 348
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -53.93 302
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -50.84 329
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 1.07 -64.05 329
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 1.07 -70.25 329
1-Chloro-2-nitrobenzene 1.02 1.24 0.00 0.24 5.24 1.01 -61.15 329
1-Chloro-3-nitrobenzene 1.00 1.14 0.00 0.25 5.21 1.01 -57.87 329
1-Chloro-4-nitrobenzene 0.98 1.18 0.00 0.24 5.22 1.01 -57.12 329
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -48.37 329
2-Nitrophenol 1.02 1.05 0.05 0.37 4.76 0.95 -53.22 329
3-Nitrophenol 1.05 1.57 0.79 0.23 5.69 0.95 -88.06 329
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -43.26 95
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -48.70 329
3-Methylaniline 0.97 0.92 0.23 0.45 4.46 0.96 -60.94 329
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 0.99 -71.42 329
3-Nitroaniline 1.20 1.71 0.40 0.35 5.88 0.99 -78.09 329
4-Nitroaniline 1.22 1.93 0.46 0.35 6.34 0.99 -86.44 329
252
Solute E S A B L V Exp Ref
1,2-Diphenylethane 1.20 1.03 0.00 0.28 6.76 1.61 -66.71 329
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -48.52 329
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 1.21 -61.70 329
1-Nitronaphthalene 1.60 1.59 0.00 0.29 7.06 1.26 -72.90 329
1-Naphthylamine 1.67 1.20 0.20 0.57 6.49 1.19 -78.49 329
Styrene 0.85 0.65 0.00 0.16 3.86 0.96 -42.04 329
alpha-Methylstyrene 0.85 0.64 0.00 0.19 4.29 1.10 -46.47 329
trans-Stilbene 1.45 1.05 0.00 0.34 7.52 1.56 -74.91 329
Diphenyl ether 1.22 1.08 0.00 0.20 6.29 1.38 -62.34 329
Trifluorotoluene 0.23 0.48 0.00 0.10 2.89 0.91 -37.78 95
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -83.47 350
Quinoline 1.27 0.97 0.00 0.54 5.46 1.04 -60.33 84
Pyrrole 0.61 0.73 0.41 0.29 2.87 0.58 -46.48 120
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -37.32 120
Salicylamide 1.16 1.65 0.63 0.48 5.91 1.03 -78.66 194,195
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 0.50 -47.10 351
Ferrocene 1.35 0.85 0.00 0.20 5.62 1.12 -58.11 352
Benzamide 0.99 1.50 0.49 0.67 5.77 0.97 -85.05 353
Benzoic acid 0.73 0.90 0.59 0.40 4.51 0.93 -77.03 353
Picric acid 1.43 2.66 0.46 0.42 8.13 1.30 -95.57 354
Tetramethylsilicon -0.06 0.08 0.00 0.00 1.81 0.92 -20.90 332
Tetraethyltin 0.46 0.18 0.00 0.13 4.92 1.61 -42.82 355
253
Table S5.16. Values of the gas to ethanol solvation enthalpy, ΔHSolv,EtOH, i n kJ/mole at 298 K for 111 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.29 -3.85 45
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -8.79 25
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -14.06 25
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -20.56 356
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -20.09 356
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -24.97 124
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -28.83 357
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -33.46 296
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -34.35 358
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -47.32 359
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -50.59 357
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -73.59 360
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -32.28 361
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -26.52 362
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -30.24 288
Adamantane 0.76 0.57 0.00 0.04 4.93 1.19 -45.02 322
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -37.40 124
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -42.30 324
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -46.18 324
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -51.82 324
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -55.65 324
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 1.02 -60.00 363
254
Solute E S A B L V Exp Ref
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 1.30 -69.35 324
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 1.58 -78.91 364
2-Propanol 0.21 0.36 0.33 0.56 1.76 0.59 -45.46 365
Ethylene glycol 0.40 0.90 0.58 0.78 2.66 0.51 -63.36 366
1,2-Propanediol 0.37 0.90 0.58 0.80 2.92 0.65 -69.84 327
Dimethyl ether 0.00 0.27 0.00 0.41 1.29 0.45 -16.37 367
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -25.63 368
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -41.99 369
Methyl butyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -30.37 370
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -31.95 336
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -29.36 371
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.01 -34.61 339,359
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -30.44 372
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 0.77 -32.58 373
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -32.99 374
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 0.79 -34.73 375
1,2-Diethoxyethane 0.01 0.73 0.00 0.79 3.31 1.07 -41.78 89
2-Methyl-2-bromopropane 0.31 0.29 0.00 0.07 2.61 0.85 -30.06 333
2-Methyl-2-chloropropane 0.14 0.30 0.00 0.03 2.27 0.79 -27.48 334
2-Methyl-2-iodopropane 0.59 0.35 0.00 0.19 3.44 0.93 -33.61 334
Nitric oxide 0.37 0.02 0.00 0.09 -0.59 0.20 -4.52 75
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 7.23 45
255
Solute E S A B L V Exp Ref
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 3.90 45
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -0.38 45
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -9.44 38
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -11.88 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 3.72 45
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 0.46 45
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -1.21 45
Carbon Monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 0.33 45
Carbon Dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -12.80 45
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -32.01 157
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -55.34 333
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -44.00 101
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -30.39 376
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -37.85 377
alpha-Methylstyrene 0.85 0.64 0.00 0.19 4.29 1.10 -47.11 378
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -26.20 296
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -30.83 379
4-Methyl-2-pentanone 0.11 0.65 0.00 0.51 3.09 0.97 -37.76 379
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -41.00 380
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -57.25 381
Ethyl formate 0.15 0.66 0.00 0.38 1.85 0.61 -27.62 317
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -27.86 299
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -30.44 188
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -34.61 299
256
Solute E S A B L V Exp Ref
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -38.83 382
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -44.20 383
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -30.53 384
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -35.99 384
Methyl pentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -38.21 384
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -27.14 385
Butyronitrile 0.19 0.90 0.00 0.36 2.55 0.69 -33.87 386
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -33.19 387
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -36.90 182
Dimethyl sulfoxide 0.52 1.74 0.00 0.88 3.46 0.61 -49.19 388
Piperidine 0.42 0.46 0.10 0.69 3.30 0.80 -53.89 389
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -47.31 389
Benzylamine 0.83 0.88 0.10 0.72 4.39 0.96 -59.50 389
Morpholine 0.43 0.79 0.06 0.91 3.29 0.72 -52.15 389
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -43.42 389
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 0.82 -46.89 389
4-Ethylpyridine 0.63 0.80 0.00 0.57 4.12 0.96 -48.80 349
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -46.30 349
Quinoline 1.27 0.97 0.00 0.54 5.46 1.04 -60.07 389
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 0.50 -48.20 351
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -32.17 124
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.40 102
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -40.48 124
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -39.93 390
257
Solute E S A B L V Exp Ref
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -40.67 124
Ferrocene 1.35 0.85 0.00 0.20 5.62 1.12 -52.65 352
Ammonia 0.14 0.39 0.16 0.56 0.32 0.21 -26.23 391
Difluoromethane -0.32 0.49 0.06 0.05 0.04 0.28 -11.53 392
Dichlorodifluoromethane 0.04 0.04 0.00 0.04 1.00 0.53 -17.64 392
Chlorodifluoromethane 0.00 0.25 0.20 0.00 0.69 0.41 -15.82 392
Pentafluoroethane -0.51 -0.02 0.11 0.06 0.10 0.48 -16.54 392
1,1,1,2-Tetrafluoroethane -0.39 0.16 0.16 0.05 0.40 0.46 -15.14 392
1,1-Difluoroethane -0.25 0.47 0.04 0.07 0.57 0.43 -15.14 392
Chloropentafluoroethane -0.36 -0.10 0.00 0.00 0.54 0.60 -12.55 392
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -52.40 122
Imidazole 0.71 0.85 0.42 0.78 4.02 0.54 -73.48 393
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 0.65 -44.77 394
2,4,4-Trimethyl-1-pentene 0.09 0.07 0.00 0.07 3.29 1.19 -33.13 395
Benzamide 0.99 1.50 0.49 0.67 5.77 0.97 -82.75 353
Benzoic acid 0.73 0.90 0.59 0.40 4.51 0.93 -76.53 353
Tetramethylsilicon -0.06 0.08 0.00 0.00 1.81 0.92 -22.20 332
258
Table S5.17. Values o f t he gas t o 1 -butanol solvation enthalpy, ΔHSolv,BtOH, i n kJ/mole at 298 K for 103 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.29 -3.77 25
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -12.14 398
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -17.70 25
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 0.67 -17.87 399
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -25.69 124
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -30.17 124
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -34.81 124
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -39.21 357
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -42.55 89
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -48.38 400
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -54.03 401
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -56.66 89
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -67.94 400
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -76.64 400
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -33.69 361
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -30.54 25
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -31.60 400
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -32.98 402
Ethene 0.11 0.10 0.00 0.07 0.29 0.35 -10.42 398
Propene 0.10 0.08 0.00 0.07 0.95 0.49 -14.12 399
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -18.50 399
iso-Butene 0.12 0.08 0.00 0.08 1.58 0.63 -18.40 399
259
Solute E S A B L V Exp Ref
cis-2-Butene 0.14 0.08 0.00 0.05 1.74 0.63 -21.48 323
trans-2-Butene 0.13 0.08 0.00 0.05 1.66 0.63 -19.84 399
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -19.20 399
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -26.03 403
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -37.80 124
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -42.30 124
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -46.30 124
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -52.10 124
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -56.69 124
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 1.02 -60.38 124
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 1.30 -70.24 404
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 1.58 -80.45 405
Dimethyl ether 0.00 0.27 0.00 0.41 1.29 0.45 -17.80 323
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -24.01 403
Methyl butyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -30.37 72
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 1.01 -31.65 336
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -31.55 406
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -30.56 407
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -70.37 99
2,5,8,11,14-pentaoxopentadecane -0.02 1.11 0.00 1.79 6.50 1.81 -68.73 408
1-Bromobutane 0.36 0.40 0.00 0.12 3.11 0.93 -34.08 409
2-Methyl-2-bromopropane 0.31 0.29 0.00 0.07 2.61 0.93 -29.44 387
260
Solute E S A B L V Exp Ref
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -29.35 403
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -35.50 182
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -32.63 387
Chloroethane 0.23 0.40 0.00 0.10 1.68 0.51 -23.45 323
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -31.65 410
2-Chlorobutane 0.19 0.35 0.00 0.12 2.54 0.79 -29.61 410
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 1.08 -40.48 411
2-Methyl-2-chloropropane 0.14 0.30 0.00 0.03 2.27 0.79 -26.88 387
Trichloroethene 0.52 0.37 0.08 0.03 3.00 0.71 -34.05 34
2-Methyl-2-iodopropane 0.59 0.35 0.00 0.19 3.44 0.93 -32.89 334
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 5.52 398
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 6.53 398
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 -2.38 25
Krypton 0.00 0.00 0.00 0.00 -0.21 0.25 -4.89 398
Xenon 0.00 0.00 0.00 0.00 0.38 0.33 -10.49 398
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 -1.42 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 -1.63 25
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 -1.21 25
Carbon Monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 -1.42 25
Carbon Dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -11.43 398
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 0.46 -7.78 398
Carbon tetrafluoride -0.58 -0.26 0.00 0.00 -0.82 0.32 -1.71 398
261
Solute E S A B L V Exp Ref
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -55.75 333
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -45.40 72
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -29.81 412
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -35.65 413
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -25.33 403
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -26.93 403
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -53.49 414
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -25.14 415
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -28.99 416
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -33.54 417
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -37.92 418
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 1.17 -42.72 419
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -29.37 384
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -33.37 384
Methyl pentanoate 0.11 0.60 0.00 0.45 3.39 1.03 -36.99 384
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -23.71 420
Butyronitrile 0.19 0.90 0.00 0.36 2.55 0.69 -32.01 386
Dimethyl sulfoxide 0.52 1.74 0.00 0.88 3.46 0.61 -46.72 388
Butylamine 0.22 0.35 0.16 0.61 2.62 0.77 -45.80 72
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -40.40 349
4-Ethylpyridine 0.63 0.80 0.00 0.57 4.12 0.96 -50.90 349
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 0.80 -45.30 349
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -31.34 124
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -35.86 124
262
Solute E S A B L V Exp Ref
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -40.11 124
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -39.63 414
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -48.54 414
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -47.47 414
1,1-Difluoroethane -0.25 0.47 0.04 0.07 0.57 0.43 -17.25 323
Benzamide 0.99 1.50 0.49 0.67 5.77 0.97 -81.11 353
Benzoic acid 0.73 0.90 0.59 0.40 4.51 0.93 -74.65 353
Tetramethylsilicon -0.06 0.08 0.00 0.03 1.81 0.92 -23.30 332
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -43.45 396
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -47.29 421
N-Methylpyrrole 0.56 0.79 0.00 0.31 2.92 0.72 -35.61 120
beta-Pinene 0.53 0.24 0.00 0.19 4.39 1.26 -44.68 422
Table S5.18. Experimental E nthalpies of S olvation i n kJ /mole of G aseous Solutes in Linear Alkane Solvents.
Solute E S A B L Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 -26.74 217
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 -32.17 250
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 -43.96 249
Butyl acetate 0.07 0.60 0.00 0.45 3.35 -40.09 248
Butyl propanoate 0.06 0.56 0.00 0.47 3.83 -44.17 248
Propyl acetate 0.09 0.60 0.00 0.45 2.82 -34.04 423
Propyl propanoate 0.07 0.56 0.00 0.45 3.34 -38.58 423
Propyl butanoate 0.05 0.56 0.00 0.45 3.78 -41.90 423
263
Solute E S A B L Exp Ref
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 -38.29 183
Ethyl pentanoate 0.05 0.58 0.00 0.45 3.77 -43.46 183
Ethyl hexanoate 0.04 0.58 0.00 0.45 4.25 -48.71 183
Xenon 0.00 0.00 0.00 0.00 0.38 -10.95 424
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 -40.64 425
Propanenitrile 0.16 0.90 0.02 0.36 2.08 -26.10 426
Acetophenone 0.82 1.01 0.00 0.48 4.50 -44.93 427
Methyl acrylate 0.25 0.66 0.00 0.42 2.36 -29.79 428
1,1,1-Trichloroethane 0.37 0.41 0.00 0.09 2.73 -30.86 429
Hexane
Methane 0.00 0.00 0.00 0.00 -0.32 -2.25 25
Ethane 0.00 0.00 0.00 0.00 0.49 -8.33 25
Propane 0.00 0.00 0.00 0.00 1.05 -14.10 25
Butane 0.00 0.00 0.00 0.00 1.62 -20.50 25
Pentane 0.00 0.00 0.00 0.00 2.16 -26.74 25
Hexane 0.00 0.00 0.00 0.00 2.67 -31.54 25
Heptane 0.00 0.00 0.00 0.00 3.17 -36.56 25
Octane 0.00 0.00 0.00 0.00 3.68 -41.50 25
Decane 0.00 0.00 0.00 0.00 4.69 -50.84 430
Undecane 0.00 0.00 0.00 0.00 5.19 -56.22 431
Dodecane 0.00 0.00 0.00 0.00 5.70 -61.60 200
Hexadecane 0.00 0.00 0.00 0.00 7.71 -81.34 432
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 -18.87 25
264
Solute E S A B L Exp Ref
2,2-Dimethylpropane 0.00 0.00 0.00 0.00 1.82 -21.55 25
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 -27.80 433
2,4-Dimethylpentane 0.00 0.00 0.00 0.00 2.81 -32.67 434
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 -35.24 433
Cyclopentane 0.26 0.10 0.00 0.00 2.48 -28.28 200
Cyclohexane 0.31 0.10 0.00 0.00 2.96 -32.43 25
Adamantane 0.76 0.57 0.00 0.04 4.93 -48.40 44
Ethene 0.11 0.10 0.00 0.07 0.29 -7.46 45
Benzene 0.61 0.52 0.00 0.14 2.79 -30.70 414
Toluene 0.60 0.52 0.00 0.14 3.33 -34.11 223
Naphthalene 1.34 0.92 0.00 0.20 5.16 -51.20 132
Bromobenzene 0.88 0.73 0.00 0.09 4.04 -41.44 435
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 -38.02 414
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 -44.35 414
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 -51.94 436
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 -40.44 414
Methanol 0.28 0.44 0.43 0.47 0.97 -15.10 260
Ethanol 0.25 0.42 0.37 0.48 1.49 -19.30 260
1-Propanol 0.24 0.42 0.37 0.48 2.03 -22.06 437
1-Butanol 0.22 0.42 0.37 0.48 2.60 -28.57 437
1-Hexanol 0.21 0.42 0.37 0.48 3.61 -34.44 438
2-Ethyl-1-butanol 0.23 0.39 0.37 0.48 3.52 -34.43 438
2-Methyl-1-pentanol 0.21 0.39 0.37 0.48 3.53 -33.51 438
1-Nonanol 0.19 0.42 0.37 0.48 5.12 -57.67 262
265
Solute E S A B L Exp Ref
1-Undecanol 0.18 0.42 0.37 0.48 6.13 -63.33 262
1,1,1,3,3,3-hexafluoro-2-propanol -0.24 0.55 0.77 0.10 1.39 -20.03 439
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 -40.89 440
Aniline 0.96 0.96 0.26 0.41 3.93 -46.80 414
Pyridine 0.63 0.84 0.00 0.52 3.02 -32.08 70
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 -36.75 70
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.91 441
4-Methylpyridiine 0.63 0.82 0.00 0.54 3.64 -37.88 442
2,4-Dimethylpyridine 0.63 0.76 0.00 0.63 4.01 -41.53 70
2,6-Dimethylpyridine 0.61 0.70 0.00 0.63 3.76 -40.16 70
2-Chloropyridine 0.74 1.03 0.00 0.37 3.88 -39.70 70
3-Chloropyridine 0.73 0.83 0.00 0.40 3.78 -42.00 70
3-Cyanopyridine 0.75 1.26 0.00 0.62 4.16 -40.40 70
4-Cyanopyridine 0.75 1.21 0.00 0.59 4.03 -39.00 70
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 -33.24 250
Propionitrile 0.16 0.90 0.02 0.36 2.08 -24.09 443
Butyronitrile 0.19 0.90 0.00 0.36 2.55 -31.68 426
Acetone 0.18 0.70 0.04 0.49 1.70 -21.84 443
2-Butanone 0.17 0.70 0.00 0.51 2.29 -27.44 443
2-Pentanone 0.14 0.68 0.00 0.51 2.76 -32.50 444
3-Pentanone 0.15 0.66 0.00 0.51 2.81 -33.08 445
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -35.07 443
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 -31.29 446
266
Solute E S A B L Exp Ref
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 -29.18 447
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 -32.50 252
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 -34.79 448
Furan 0.37 0.51 0.00 0.13 1.91 -23.83 449
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 -28.81 450
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 -31.64 255
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 -32.55 449
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 -31.15 443
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 -23.85 303
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 -31.36 443
2,5,8-Trioxanonane 0.11 0.76 0.00 1.17 3.92 -40.30 443
2,5,8,11,14-Pentaoxapentadecane -0.02 1.11 0.00 1.79 6.50 -67.61 451
Paraldehyde 0.14 0.68 0.00 0.68 3.17 -34.66 443
Anisole 0.71 0.75 0.00 0.29 3.89 -40.75 443
Acetal -0.02 0.56 0.00 0.62 3.07 -37.51 443
Quinoline 1.27 0.97 0.00 0.54 5.46 -50.19 443
Methyl acetate 0.14 0.64 0.00 0.45 1.91 -21.40 235
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 -28.28 235
Propyl acetate 0.09 0.60 0.00 0.45 2.82 -33.45 235
Butyl acetate 0.07 0.60 0.00 0.45 3.35 -38.40 235
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 -42.50 235
Ethyl propionate 0.09 0.58 0.00 0.45 2.81 -32.52 235
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 -36.71 235
267
Solute E S A B L Exp Ref
Ethyl hexanoate 0.04 0.58 0.00 0.45 4.25 -47.24 235
Propyl propionate 0.07 0.56 0.00 0.45 3.34 -37.65 452
Helium 0.00 0.00 0.00 0.00 -1.74 8.03 25
Neon 0.00 0.00 0.00 0.00 -1.58 5.44 25
Argon 0.00 0.00 0.00 0.00 -0.69 -2.72 25
Krypton 0.00 0.00 0.00 0.00 -0.21 -4.73 25
Xenon 0.00 0.00 0.00 0.00 0.38 -10.71 25
Radon 0.00 0.00 0.00 0.00 0.88 -12.68 25
Hydrogen 0.00 0.00 0.00 0.00 -1.20 5.10 25
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.79 25
Oxygen 0.00 0.00 0.00 0.00 -0.72 -0.96 25
Nitric Oxide 0.37 0.02 0.00 0.09 -0.59 -2.23 75
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 -1.46 25
Sulfur Hexafluoride -0.60 -0.20 0.00 0.00 -0.12 -8.28 25
Triethylamine 0.10 0.15 0.00 0.79 3.04 -34.58 453
Penylamine 0.21 0.35 0.16 0.61 3.14 -35.01 454
Hexylamine 0.20 0.35 0.16 0.61 3.66 -40.61 455
Heptylamine 0.20 0.35 0.16 0.61 4.15 -45.61 456
Octylamine 0.19 0.35 0.16 0.61 4.52 -50.68 457
Decylamine 0.18 0.35 0.16 0.61 5.61 -60.18 458
Nitromethane 0.31 0.95 0.06 0.31 1.89 -22.59 320
Nitroethane 0.27 0.95 0.02 0.33 2.41 -27.61 223
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 -32.66 223
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 -31.23 59
268
Solute E S A B L Exp Ref
Diethyl sulfide 0.37 0.38 0.00 0.32 3.10 -33.64 459
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 -29.23 233
Chloroform 0.43 0.49 0.15 0.02 2.48 -29.90 460
Ethyl iodide 0.64 0.40 0.00 0.15 2.57 -28.64 223
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 -34.21 223
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 -27.07 223
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 -32.40 223
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -61.74 461
Acetophenone 0.82 1.01 0.00 0.48 4.50 -44.77 462
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 -54.11 113
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 -49.08 113
Heptane
Methane 0.00 0.00 0.00 0.00 -0.32 -3.81 341
Ethane 0.00 0.00 0.00 0.00 0.49 -11.17 341
Pentane 0.00 0.00 0.00 0.00 2.16 -26.53 341
Hexane 0.00 0.00 0.00 0.00 2.67 -31.55 341
Heptane 0.00 0.00 0.00 0.00 3.17 -36.57 341
Octane 0.00 0.00 0.00 0.00 3.68 -41.51 341
Nonane 0.00 0.00 0.00 0.00 4.18 -46.40 341
Decane 0.00 0.00 0.00 0.00 4.69 -51.38 341
Dodecane 0.00 0.00 0.00 0.00 5.70 -61.17 341
Hexadecane 0.00 0.00 0.00 0.00 7.71 -80.92 341
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 -35.19 341
269
Solute E S A B L Exp Ref
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 -30.05 341
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 -30.43 341
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 -27.85 341
2,3-Dimethylbutane 0.00 0.00 0.00 0.00 2.50 -29.30 341
2,4-Dimethylpentane 0.00 0.00 0.00 0.00 2.81 -32.92 341
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 -35.06 341
Cyclohexane 0.31 0.10 0.00 0.00 2.96 -32.29 341
Cycloheptane 0.35 0.10 0.00 0.00 3.70 -37.81 341
Cyclooctane 0.41 0.10 0.00 0.00 4.33 -42.66 341
Cyclodecane 0.47 0.10 0.00 0.00 5.34 -52.10 341
Methylcyclopentane 0.23 0.10 0.00 0.00 2.82 -31.39 341
Methylcyclohexane 0.24 0.10 0.00 0.00 3.32 -35.37 341
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 -39.76 341
trans-1,2-Dimethylcyclohexane 0.23 0.20 0.00 0.00 3.72 -38.69 341
cis Decalin 0.55 0.25 0.00 0.00 5.16 -50.82 341
trans Decalin 0.47 0.23 0.00 0.00 4.98 -49.95 341
Bicyclohexyl 0.53 0.33 0.00 0.07 5.92 -57.84 341
Tetralin 0.89 0.65 0.00 0.17 5.20 -52.80 341
1-Hexene 0.08 0.08 0.00 0.07 2.57 -30.38 341
1-Octyne 0.16 0.22 0.09 0.10 3.52 -40.04 341
2-Octyne 0.23 0.30 0.00 0.10 3.85 -42.63 341
Propanal 0.20 0.65 0.00 0.45 1.82 -20.19 341
270
Solute E S A B L Exp Ref
Butanal 0.19 0.65 0.00 0.45 2.27 -25.19 341
Pentanal 0.16 0.65 0.00 0.45 2.77 -31.15 341
Hexanal 0.15 0.65 0.00 0.45 3.37 -36.45 341
Heptanal 0.14 0.65 0.00 0.45 3.86 -41.59 341
Octanal 0.16 0.65 0.00 0.45 4.38 -45.76 341
Nonanal 0.15 0.65 0.00 0.45 4.86 -50.84 341
Isobutyraldehyde 0.14 0.62 0.00 0.45 2.12 -26.30 341
Acetone 0.18 0.70 0.04 0.49 1.70 -21.59 341
2-Butanone 0.17 0.70 0.00 0.51 2.29 -26.53 341
2-Heptanone 0.12 0.68 0.00 0.51 3.76 -41.09 341
4-Heptanone 0.11 0.66 0.00 0.51 3.71 -41.51 341
2-Nonanone 0.12 0.68 0.00 0.51 4.74 -50.12 341
5-Nonanone 0.10 0.66 0.00 0.51 4.70 -50.08 341
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 -42.13 341
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 -37.78 341
Butyl acetate 0.07 0.60 0.00 0.45 3.35 -38.72 341
Butyl propionate 0.06 0.56 0.00 0.47 3.83 -44.94 341
Butyl butanoate 0.04 0.56 0.00 0.45 4.28 -47.61 341
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 -33.11 341
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -24.31 341
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 -44.22 341
Dipentyl ether 0.00 0.25 0.00 0.45 4.88 -52.54 341
Diisopropyl Ether -0.06 0.16 0.00 0.58 2.53 -30.96 341
271
Solute E S A B L Exp Ref
n-Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 -30.79 341
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 -46.11 341
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 -24.81 341
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 -32.28 341
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 -34.61 341
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 -29.32 341
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 -31.59 341
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 -47.86 341
Tetrachloromethane 0.46 0.38 0.00 0.00 2.82 -31.21 341
1,2-Dichloroethane 0.42 0.64 0.10 0.11 2.57 -27.98 341
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 -50.88 341
Diiodomethane 0.71 0.69 0.11 0.07 2.89 -37.74 341
Methanol 0.28 0.44 0.43 0.47 0.97 -14.90 341
Ethanol 0.25 0.42 0.37 0.48 1.49 -18.60 341
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 -27.87 341
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 -34.14 341
1-Octanol 0.20 0.42 0.37 0.48 4.62 -47.57 341
1-Nonanol 0.19 0.42 0.37 0.48 5.12 -53.66 341
1-Undecanol 0.18 0.42 0.37 0.48 6.13 -61.83 341
3-Methyl-1-butanol 0.19 0.39 0.37 0.48 3.01 -35.63 341
2-Pentanol 0.20 0.36 0.33 0.56 2.84 -35.90 341
3-Methyl-2-butanol 0.19 0.33 0.33 0.56 2.79 -31.93 341
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 -26.44 341
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 -37.50 341
272
Solute E S A B L Exp Ref
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 -34.22 341
Triethylamine 0.10 0.15 0.00 0.79 3.04 -34.45 341
Propylamine 0.23 0.35 0.16 0.61 2.14 -25.14 341
Isopropylamine 0.18 0.32 0.16 0.61 1.91 -22.87 341
Butylamine 0.22 0.35 0.16 0.61 2.62 -29.97 341
sec-Butylamine 0.17 0.32 0.16 0.63 2.41 -27.89 341
iso-Butylamine 0.12 0.29 0.16 0.71 2.49 -28.11 341
tert-Butylamine 0.12 0.29 0.16 0.71 2.49 -24.98 341
Pentylamine 0.21 0.35 0.16 0.61 3.14 -34.12 341
Hexylamine 0.20 0.35 0.16 0.61 3.66 -39.47 341
Heptylamine 0.20 0.35 0.16 0.61 4.15 -44.97 341
Octylamine 0.19 0.35 0.16 0.61 4.52 -49.41 341
Nonylamine 0.19 0.35 0.16 0.61 5.10 -54.09 341
Decylamine 0.18 0.35 0.16 0.61 5.61 -58.69 341
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 -39.92 341
Benzene 0.61 0.52 0.00 0.14 2.79 -30.54 341
Toluene 0.60 0.52 0.00 0.14 3.33 -35.94 341
Mesitylene 0.65 0.52 0.00 0.19 4.34 -46.23 341
Naphthalene 1.34 0.92 0.00 0.20 5.16 -51.82 341
Trifluorotoluene 0.23 0.48 0.00 0.10 2.89 -33.35 341
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 -44.73 341
Anisole 0.71 0.75 0.00 0.29 3.89 -41.21 341
Aniline 0.96 0.96 0.26 0.41 3.93 -40.75 341
Acetonitrile 0.24 0.90 0.07 0.32 1.74 -17.56 341
273
Solute E S A B L Exp Ref
Helium 0.00 0.00 0.00 0.00 -1.74 7.72 341
Neon 0.00 0.00 0.00 0.00 -1.58 5.56 341
Argon 0.00 0.00 0.00 0.00 -0.69 -1.22 341
Krypton 0.00 0.00 0.00 0.00 -0.21 -5.51 341
Xenon 0.00 0.00 0.00 0.00 0.38 -10.08 341
Hydrogen 0.00 0.00 0.00 0.00 -1.20 3.78 341
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 -9.66 341
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 -1.59 341
Sulfur Hexafluoride -0.60 -0.20 0.00 0.00 -0.12 -8.28 341
Difluorodichloromethane 0.04 0.13 0.00 0.00 1.12 -18.91 341
Hexafluorobenzene 0.09 0.56 0.00 0.01 2.35 -31.62 341
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 -12.84 341
Nitromethane 0.31 0.95 0.06 0.31 1.89 -24.40 341
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 -54.06 341
1-Butanethiol 0.38 0.35 0.00 0.24 3.24 -33.81 341
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 -46.76 341
2,5,8,11,14-Pentaoxopentadecane -0.02 1.11 0.00 1.79 6.50 -68.10 341
2,5,8,11-Tetraoxododecane 0.00 0.98 0.00 1.44 5.16 -54.15 341
2,5,8-Trioxanonane 0.11 0.76 0.00 1.17 3.92 -39.94 341
Diethoxymethane 0.01 0.49 0.00 0.54 2.79 -33.41 341
1,2-Dimethoxyethane 0.12 0.67 0.00 0.68 2.65 -31.76 341
Dimethoxymethane 0.10 0.46 0.00 0.52 1.89 -26.06 341
274
Solute E S A B L Exp Ref
1-Propanol 0.24 0.42 0.37 0.48 2.03 -22.10 341
2-Butanol 0.22 0.36 0.33 0.56 2.34 -26.70 341
2-Methyl-1-propanol 0.22 0.39 0.37 0.48 2.41 -26.60 341
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 -22.60 341
1-Hexanol 0.21 0.42 0.37 0.48 3.61 -38.32 341
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 -15.90 341
Pentyl acetate 0.07 0.60 0.00 0.45 3.84 -44.52 341
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 -37.21 341
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 -53.08 341
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 -38.07 341
Propyl butanoate 0.05 0.56 0.00 0.45 3.78 -43.10 341
Pyridine 0.63 0.84 0.00 0.52 3.02 -31.76 463
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.77 464
4-Methylpyridiine 0.63 0.82 0.00 0.54 3.64 -37.34 465
Propane 0.00 0.00 0.00 0.00 1.05 -17.13 466
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 -52.36 436
Octane
Methane 0.00 0.00 0.00 0.00 -0.32 -4.06 45
Octane 0.00 0.00 0.00 0.00 3.68 -41.51 217
Dodecane 0.00 0.00 0.00 0.00 5.70 -61.62 467
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 -35.09 433
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -25.90 468
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -34.76 469
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 -44.37 470
275
Solute E S A B L Exp Ref
n-Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 -31.22 471
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 -28.60 468
Ethyl tert-butyl ether -0.02 0.16 0.00 0.60 2.72 -32.19 252
Tetrahydropyran 0.28 0.47 0.00 0.55 3.06 -33.31 472
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 -31.02 473
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 -31.43 255
2,5,8-Trioxanonane 0.11 0.76 0.00 1.17 3.92 -40.80 474
Methanol 0.28 0.44 0.43 0.47 0.97 -15.30 260
Ethanol 0.25 0.42 0.37 0.48 1.49 -19.50 260
1-Propanol 0.24 0.42 0.37 0.48 2.03 -25.00 475
1-Butanol 0.22 0.42 0.37 0.48 2.60 -29.90 475
1-Nonanol 0.19 0.42 0.37 0.48 5.12 -55.74 476
1-Undecanol 0.18 0.42 0.37 0.48 6.13 -64.40 476
1-Hexene 0.08 0.08 0.00 0.07 2.57 -30.36 477
Chlorotrifluoromethane -0.25 -0.05 0.00 0.00 0.21 -9.41 45
Dichlorodifluoromethane 0.04 0.13 0.00 0.00 1.12 -17.07 45
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -61.57 478
Helium 0.00 0.00 0.00 0.00 -1.74 8.06 45
Neon 0.00 0.00 0.00 0.00 -1.58 6.94 45
Argon 0.00 0.00 0.00 0.00 -0.69 -0.36 45
Krypton 0.00 0.00 0.00 0.00 -0.21 -5.00 45
Xenon 0.00 0.00 0.00 0.00 0.38 -10.16 424
Hydrogen 0.00 0.00 0.00 0.00 -1.20 4.04 45
Tetrafluoromethane -0.58 -0.26 0.00 0.00 -0.82 -0.09 45
276
Solute E S A B L Exp Ref
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 -8.34 45
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 -1.13 39
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 -8.11 39
Butyronitrile 0.19 0.90 0.00 0.36 2.55 -30.26 426
Acetophenone 0.82 1.01 0.00 0.48 4.50 -44.68 427
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 -29.14 113
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 -52.89 113
Pyridine 0.63 0.84 0.00 0.52 3.02 -31.50 479
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.61 480
4-Methylpyridiine 0.63 0.82 0.00 0.54 3.64 -37.70 481
Nonane
Nonane 0.00 0.00 0.00 0.00 4.18 -46.44 217
Cycloheptane 0.35 0.10 0.00 0.00 3.70 -37.71 482
Cyclooctane 0.41 0.10 0.00 0.00 4.33 -42.53 482
Bromobenzene 0.88 0.73 0.00 0.09 4.04 -40.82 435
Helium 0.00 0.00 0.00 0.00 -1.74 9.69 45
Neon 0.00 0.00 0.00 0.00 -1.58 6.29 45
Argon 0.00 0.00 0.00 0.00 -0.69 -1.46 45
Krypton 0.00 0.00 0.00 0.00 -0.21 -4.64 45
Xenon 0.00 0.00 0.00 0.00 0.38 -9.95 424
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 -28.61 483
Methyl nonanoate 0.06 0.60 0.00 0.45 5.32 -58.51 484
Methyl decanoate 0.05 0.60 0.00 0.45 5.81 -63.41 484
Decane
277
Solute E S A B L Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 -4.31 25
Ethane 0.00 0.00 0.00 0.00 0.49 -7.78 25
Propane 0.00 0.00 0.00 0.00 1.05 -13.72 25
Butane 0.00 0.00 0.00 0.00 1.62 -20.29 25
Hexane 0.00 0.00 0.00 0.00 2.67 -31.49 485
Decane 0.00 0.00 0.00 0.00 4.69 -51.38 217
Dodecane 0.00 0.00 0.00 0.00 5.70 -61.68 467
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 -16.65 25
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 -29.73 430
3-Methylpentane 0.00 0.00 0.00 0.00 2.58 -30.14 430
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 -27.43 430
2,3-Dimethylbutane 0.00 0.00 0.00 0.00 2.50 -28.83 430
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 -34.94 245
1-Hexene 0.08 0.08 0.00 0.07 2.57 -30.26 477
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -25.63 486
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -34.66 469
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 -44.26 487
n-Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 -31.05 471
Ethyl tert-Butyl ether -0.02 0.16 0.00 0.60 2.72 -32.22 488
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 -28.73 450
2,5,8,11-Tetraoxadodecane 0.00 0.98 0.00 1.44 5.16 -53.14 257
2,5,8,11,14-Pentaoxapentadecane -0.02 1.11 0.00 1.79 6.50 -56.58 451
278
Solute E S A B L Exp Ref
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 -33.18 250
Methanol 0.28 0.44 0.43 0.47 0.97 -15.82 437
1-Nonanol 0.19 0.42 0.37 0.48 5.12 -54.96 262
1-Undecanol 0.18 0.42 0.37 0.48 6.13 -63.87 262
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 -28.30 489
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -61.92 490
Helium 0.00 0.00 0.00 0.00 -1.74 6.86 25
Neon 0.00 0.00 0.00 0.00 -1.58 6.53 25
Argon 0.00 0.00 0.00 0.00 -0.69 -1.63 25
Krypton 0.00 0.00 0.00 0.00 -0.21 -4.87 45
Xenon 0.00 0.00 0.00 0.00 0.38 -9.84 424
Nitrogen 0.00 0.00 0.00 0.00 -0.98 -0.29 25
Carbon monoxide 0.00 0.00 0.00 0.04 -0.84 0.38 25
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 -6.92 39
Oxygen 0.00 0.00 0.00 0.00 -0.72 -0.25 25
Sulfur hexafluoride -0.60 -0.20 0.00 0.00 -0.12 -7.91 25
Acetophenone 0.82 1.01 0.00 0.48 4.50 -44.75 427
Pyridine 0.63 0.84 0.00 0.52 3.02 -31.43 491
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.43 492
4-Methylpyridiine 0.63 0.82 0.00 0.54 3.64 -37.57 493
Undecane
Undecane 0.00 0.00 0.00 0.00 5.19 -56.30 217
Xenon 0.00 0.00 0.00 0.00 0.38 -9.64 424
1-Hexanol 0.21 0.42 0.37 0.48 3.61 -37.91 261
279
Solute E S A B L Exp Ref
Dodecane
Methane 0.00 0.00 0.00 0.00 -0.32 -3.95 45
Propane 0.00 0.00 0.00 0.00 1.05 -15.28 466
Hexane 0.00 0.00 0.00 0.00 2.67 -31.43 200
Heptane 0.00 0.00 0.00 0.00 3.17 -36.49 200
Octane 0.00 0.00 0.00 0.00 3.68 -41.43 200
Decane 0.00 0.00 0.00 0.00 4.69 -51.36 467
Dodecane 0.00 0.00 0.00 0.00 5.70 -61.70 217
2,4-Dimethylpentane 0.00 0.00 0.00 0.00 2.81 -32.32 434
1-Hexene 0.08 0.08 0.00 0.07 2.57 -30.15 477
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -25.42 486
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -34.49 469
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 -44.10 487
n-Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 -31.09 471
Ethyl tert-Butyl ether -0.02 0.16 0.00 0.60 2.72 -32.02 488
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 -31.27 255
2,5,8,11-Tetraoxadodecane 0.00 0.98 0.00 1.44 5.16 -53.61 257
Methyl methacrylate 0.25 0.51 0.00 0.44 2.88 -32.80 250
1,4-Difluorobenzene 0.38 0.60 0.00 0.06 2.77 -32.48 270
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -62.37 494
Helium 0.00 0.00 0.00 0.00 -1.74 7.21 45
Neon 0.00 0.00 0.00 0.00 -1.58 6.97 45
Argon 0.00 0.00 0.00 0.00 -0.69 -0.64 45
280
Solute E S A B L Exp Ref
Krypton 0.00 0.00 0.00 0.00 -0.21 -4.25 45
Xenon 0.00 0.00 0.00 0.00 0.38 -9.53 424
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 -6.00 466
Butyronitrile 0.19 0.90 0.00 0.36 2.55 -32.86 426
1-Propanol 0.24 0.42 0.37 0.48 2.03 -22.62 261
Pyridine 0.63 0.84 0.00 0.52 3.02 -31.86 441
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.52 495
4-Methylpyridiine 0.63 0.82 0.00 0.54 3.64 -37.55 496
Tridecane
Tridecane 0.00 0.00 0.00 0.00 6.20 -66.50 217
Xenon 0.00 0.00 0.00 0.00 0.38 -9.53 424
Tetradecane
Tetradecane 0.00 0.00 0.00 0.00 6.71 -71.40 217
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -25.20 468
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -33.68 468
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 -26.52 468
1-Hexene 0.08 0.08 0.00 0.07 2.57 -30.06 477
Benzene 0.61 0.52 0.00 0.14 2.79 -30.58 200
Hexafluorobenzene 0.09 0.56 0.00 0.01 2.35 -32.33 270
3-Pentanone 0.15 0.66 0.00 0.51 2.81 -31.69 485
Helium 0.00 0.00 0.00 0.00 -1.74 5.89 45
Neon 0.00 0.00 0.00 0.00 -1.58 5.88 45
Argon 0.00 0.00 0.00 0.00 -0.69 -1.47 45
Krypton 0.00 0.00 0.00 0.00 -0.21 -5.32 45
281
Solute E S A B L Exp Ref
Xenon 0.00 0.00 0.00 0.00 0.38 -9.36 424
15-Crown-5 0.41 1.20 0.00 1.75 6.77 -75.76 161 341
Pentadecane
Pentadecane 0.00 0.00 0.00 0.00 7.21 -74.50 217
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -62.39 497
Xenon 0.00 0.00 0.00 0.00 0.38 -9.34 424
Hexadecane
Methane 0.00 0.00 0.00 0.00 -0.32 -3.97 341
Ethane 0.00 0.00 0.00 0.00 0.49 -11.51 341
Propane 0.00 0.00 0.00 0.00 1.05 -15.94 341
Butane 0.00 0.00 0.00 0.00 1.62 -20.79 341
Pentane 0.00 0.00 0.00 0.00 2.16 -25.94 341
Hexane 0.00 0.00 0.00 0.00 2.67 -31.04 341
Heptane 0.00 0.00 0.00 0.00 3.17 -36.15 341
Octane 0.00 0.00 0.00 0.00 3.68 -41.13 341
Hexadecane 0.00 0.00 0.00 0.00 7.71 -81.38 341
2-Methylpropane 0.00 0.00 0.00 0.00 1.41 -18.74 341
Cyclopentane 0.26 0.10 0.00 0.00 2.48 -27.66 341
Cyclohexane 0.31 0.10 0.00 0.00 2.96 -31.50 341
Ethene 0.11 0.10 0.00 0.07 0.29 -11.17 341
Propene 0.10 0.08 0.00 0.07 0.95 -13.35 341
Acetone 0.18 0.70 0.04 0.49 1.70 -21.42 341
2-Butanone 0.17 0.70 0.00 0.51 2.29 -26.48 341
2-Pentanone 0.14 0.68 0.00 0.51 2.76 -31.05 341
282
Solute E S A B L Exp Ref
2-Hexanone 0.14 0.68 0.00 0.51 3.29 -35.77 341
2-Heptanone 0.12 0.68 0.00 0.51 3.76 -40.46 341
4-Heptanone 0.11 0.66 0.00 0.51 3.71 -44.89 341
2-Octanone 0.11 0.68 0.00 0.51 4.26 -44.89 341
2-Nonanone 0.12 0.68 0.00 0.51 4.74 -49.37 341
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 -36.48 341
Diethyl ether 0.04 0.25 0.00 0.45 2.02 -25.19 341
Dipropyl ether 0.01 0.25 0.00 0.45 2.95 -34.15 341
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 -43.42 341
Butyl Methyl Ether 0.05 0.25 0.00 0.44 2.66 -30.53 341
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 -28.53 341
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 -30.78 341
Dichloromethane 0.39 0.57 0.10 0.05 2.02 -23.18 341
Chloroform 0.43 0.49 0.15 0.02 2.48 -28.07 341
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 -30.92 341
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 -30.88 341
Tetrachloroethene 0.64 0.44 0.00 0.00 3.58 -38.41 341
Nitromethane 0.31 0.95 0.06 0.31 1.89 -25.36 341
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 -30.15 341
Acetonitrile 0.24 0.90 0.07 0.32 1.74 -19.08 341
Methanol 0.28 0.44 0.43 0.47 0.97 -13.35 341
Ethanol 0.25 0.42 0.37 0.48 1.49 -16.32 341
1-Propanol 0.24 0.42 0.37 0.48 2.03 -21.17 341
2-Propanol 0.21 0.36 0.33 0.56 1.76 -22.38 341
283
Solute E S A B L Exp Ref
1-Butanol 0.22 0.42 0.37 0.48 2.60 -28.07 341
1-Pentanol 0.22 0.42 0.37 0.48 3.11 -31.34 341
1-Hexanol 0.21 0.42 0.37 0.48 3.61 -39.79 341
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 -44.43 341
1-Octanol 0.20 0.42 0.37 0.48 4.62 -49.07 341
1-Nonanol 0.19 0.42 0.37 0.48 5.12 -52.81 341
1-Undecanol 0.18 0.42 0.37 0.48 6.13 -61.39 341
tert-Butanol 0.18 0.30 0.31 0.60 1.96 -23.01 341
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 -47.53 341
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 -27.99 341
Butyl acetate 0.07 0.60 0.00 0.45 3.35 -38.49 341
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 -48.37 341
Benzene 0.61 0.52 0.00 0.14 2.79 -30.38 341
Toluene 0.60 0.52 0.00 0.14 3.33 -35.90 341
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 -40.12 341
Propylbenzene 0.60 0.50 0.00 0.15 4.23 -44.14 341
m-Xylene 0.62 0.52 0.00 0.16 3.84 -41.37 341
p-Xylene 0.61 0.52 0.00 0.16 3.84 -41.51 341
Mesitylene 0.65 0.52 0.00 0.19 4.34 -46.56 341
Acetophenone 0.82 1.01 0.00 0.48 4.50 -47.36 341
Anisole 0.71 0.75 0.00 0.29 3.89 -41.24 341
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 -41.17 341
Benzonitrile 0.74 1.11 0.00 0.33 4.04 -41.25 341
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 -38.24 341
284
Solute E S A B L Exp Ref
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 -31.05 341
1,4-Difluorobenzene 0.38 0.60 0.00 0.06 2.77 -32.19 341
Aniline 0.96 0.96 0.26 0.41 3.93 -41.80 341
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 -45.65 341
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 -48.36 341
Pyridine 0.63 0.84 0.00 0.52 3.02 -32.64 341
2-Methylpyridine 0.60 0.75 0.00 0.58 3.42 -35.90 341
3-Methylpyridine 0.63 0.81 0.00 0.54 3.63 -37.49 341
4-Methylpyridine 0.63 0.82 0.00 0.54 3.64 -36.78 341
Propylamine 0.23 0.35 0.16 0.61 2.14 -23.97 341
Butylamine 0.22 0.35 0.16 0.61 2.62 -29.41 341
Pentylamine 0.21 0.35 0.16 0.61 3.14 -34.81 341
Hexylamine 0.20 0.35 0.16 0.61 3.66 -39.46 341
Heptylamine 0.20 0.35 0.16 0.61 4.15 -45.27 341
Nonylamine 0.19 0.35 0.16 0.61 5.10 -55.03 341
Decylamine 0.18 0.35 0.16 0.61 5.61 -60.02 341
tert-Butylamine 0.12 0.29 0.16 0.71 2.49 -26.15 341
Diethylamine 0.15 0.30 0.08 0.69 2.40 -24.60 341
Triethylamine 0.10 0.15 0.00 0.79 3.04 -34.14 341
Helium 0.00 0.00 0.00 0.00 -1.74 8.24 341
Neon 0.00 0.00 0.00 0.00 -1.58 6.78 341
Argon 0.00 0.00 0.00 0.00 -0.69 -0.79 341
Krypton 0.00 0.00 0.00 0.00 -0.21 -5.02 341
Xenon 0.00 0.00 0.00 0.00 0.38 -10.08 341
285
Solute E S A B L Exp Ref
Radon 0.00 0.00 0.00 0.00 0.88 -14.18 341
Hydrogen 0.00 0.00 0.00 0.00 -1.20 4.56 341
Diiodomethane 0.71 0.69 0.11 0.07 2.89 -38.95 341
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 -20.88 341
1,1,1,3,3,3-Hexafluoropropan-2-ol -0.24 0.55 0.77 0.10 1.39 -22.09 341
Benzyl alcohol 0.80 0.87 0.33 0.56 4.22 -42.38 341
Thiophene 0.69 0.56 0.00 0.15 2.82 -29.92 341
Benzyl chloride 0.82 0.82 0.00 0.33 4.38 -43.32 341
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 -61.74 341
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 -55.80 341
Diisopropyl ether -0.06 0.16 0.00 0.58 2.53 -30.67 341
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 -34.12 341
2,2-Dimethylpropane 0.00 0.00 0.00 0.00 1.82 -21.14 341
Table S5.19. Experimental va lues of t he gas t o N ,N-dimethylformamide solvation enthalpy, ΔHSolv,DMF, in kJ /mole, f or 159 s olutes, t ogether with t he solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.25 -2.36 498
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -13.44 498
Butane 0.00 0.00 0.00 0.00 1.62 0.67 -16.00 123
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -19.29 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -23.05 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -27.28 28
286
Solute E S A B L V Exp Ref
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -30.96 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -34.60 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -37.86 28
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -41.94 499
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -45.43 28
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -52.68 286
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -60.25 28
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -22.22 500
2,2-Dimethylbutane 0.00 0.00 0.00 0.00 2.35 0.95 -19.25 286
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.10 -26.30 133
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -25.19 286
2-Methyloctane 0.00 0.00 0.00 0.00 3.97 1.38 -32.05 286
3,3-Diethylpentane 0.00 0.00 0.00 0.00 3.82 1.38 -31.30 286
2,2,4,4-Tetramethylpentane 0.00 0.00 0.00 0.00 3.51 1.38 -27.78 291
2,2,5,5-Tetramethylhexane 0.00 0.00 0.00 0.00 4.04 1.52 -28.83 286
Cyclopentane 0.26 0.10 0.00 0.00 2.48 0.70 -22.34 286
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -25.36 286
Cyclooctane 0.41 0.10 0.00 0.00 4.33 1.13 -34.06 286
Methylcyclohexane 0.24 0.06 0.00 0.00 3.32 0.99 -27.07 286
cis-1,2-Dimethylcyclohexane 0.28 0.24 0.00 0.00 3.85 1.13 -30.84 286
1-Butene 0.10 0.08 0.00 0.07 1.49 0.63 -18.40 123
1-Pentene 0.09 0.08 0.00 0.07 2.05 0.77 -21.34 286
287
Solute E S A B L V Exp Ref
1-Hexene 0.08 0.08 0.00 0.07 2.57 0.91 -25.52 286
1-Heptene 0.09 0.08 0.00 0.07 3.06 1.05 -29.46 286
1-Octene 0.09 0.08 0.00 0.07 3.57 1.19 -32.76 286
1-Nonene 0.09 0.08 0.00 0.07 4.07 1.33 -36.65 286
1-Decene 0.09 0.08 0.00 0.07 4.55 1.48 -40.50 291
1-Dodecene 0.09 0.08 0.00 0.07 5.52 1.76 -48.16 286
1-Tridecene 0.09 0.08 0.00 0.07 6.02 1.90 -52.01 286
1-Tetradecene 0.09 0.08 0.00 0.07 6.51 2.04 -56.11 286
1-Pentadecene 0.08 0.08 0.00 0.07 7.01 2.18 -59.79 286
cis-2-Octene 0.14 0.08 0.00 0.07 3.68 1.19 -32.05 286
trans-2-Octene 0.12 0.08 0.00 0.07 3.60 1.19 -31.92 286
cis-4-Octene 0.13 0.08 0.00 0.07 3.61 1.19 -31.46 286
trans-4-Octene 0.14 0.08 0.00 0.07 3.59 1.19 -31.21 286
Cyclopentene 0.34 0.20 0.00 0.10 2.40 0.66 -24.56 286
Cyclohexene 0.40 0.20 0.00 0.10 3.02 0.80 -28.12 286
1-Methylcyclohexene 0.39 0.20 0.00 0.10 3.48 0.99 -32.05 286
1,3-Butadiene 0.32 0.23 0.00 0.10 1.54 0.59 -20.40 123
1,5-Hexadiene 0.19 0.15 0.00 0.10 2.45 0.87 -27.91 286
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -33.68 69
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.32 69
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -40.57 329
Isopropylbenzene 0.60 0.49 0.00 0.16 4.08 1.14 -42.84 329
sec-Butylbenzene 0.60 0.48 0.00 0.16 4.51 1.28 -46.82 329
tert-Butylbenzene 0.62 0.49 0.00 0.18 4.41 1.28 -44.96 329
288
Solute E S A B L V Exp Ref
1,4-Dimethylbenzene 0.61 0.52 0.00 0.16 3.84 1.00 -40.75 69
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 1.14 -44.20 69
Hexamethylbenzene 0.95 0.72 0.00 0.21 6.56 1.56 -62.67 329
Octylbenzene 0.58 0.48 0.00 0.15 6.71 1.70 -59.20 329
4-Isopropyltoluene 0.61 0.49 0.00 0.19 4.59 1.28 -46.70 329
1,2-Diphenylethane 1.20 1.03 0.00 0.28 6.76 1.61 -69.64 329
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -64.37 329
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -56.57 329
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -79.50 133
Styrene 0.85 0.65 0.00 0.16 3.86 0.96 -44.38 329
α-Methylstyrene 0.85 0.64 0.00 0.19 4.29 1.10 -48.65 329
trans-Stilbene 1.45 1.05 0.00 0.34 7.52 1.56 -79.10 329
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -31.38 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.27 91
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.40 290
3-Pentanone 0.15 0.66 0.00 0.51 2.81 0.83 -37.61 290
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -41.30 290
3-Hexanone 0.14 0.66 0.00 0.51 3.31 0.97 -40.54 290
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -45.23 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -43.72 91
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -49.08 290
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -52.55 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -50.33 91
2-Decanone 0.11 0.68 0.00 0.51 5.25 1.53 -55.48 290
289
Solute E S A B L V Exp Ref
2-Undecanone 0.10 0.68 0.00 0.51 5.73 1.67 -58.58 290
6-Undecanone 0.08 0.66 0.00 0.51 5.68 1.67 -57.11 290
3,3-Dimethyl-2-butanone 0.11 0.62 0.00 0.51 2.93 0.97 -36.78 290
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -41.59 91
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 0.72 -42.05 290
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -43.64 91
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 1.00 -48.41 290
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -37.22 14
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -41.03 14
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 0.59 -44.10 14
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 0.59 -42.19 14
2-Methyl-1-propanol 0.22 0.39 0.37 0.48 2.41 0.73 -47.62 14
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -46.19 14
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 0.73 -43.10 14
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 0.87 -53.09 14
2-Pentanol 0.20 0.36 0.33 0.56 2.84 0.87 -48.90 501
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -47.04 14
2-Hexanol 0.19 0.36 0.33 0.56 3.34 1.01 -52.81 501
2-Heptanol 0.19 0.36 0.33 0.56 3.84 1.15 -54.69 501
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -63.72 94
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -24.90 133
Dibutyl ether 0.00 0.25 0.00 0.45 3.92 1.30 -37.57 94
290
Solute E S A B L V Exp Ref
Butyl methyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -29.00 62
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -27.80 133
Methyl heptyl ether 0.05 0.25 0.00 0.45 4.09 1.30 -40.38 94
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 0.62 -31.60 372
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -37.74 502
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -100.80 53
1-Fluorooctane -0.02 0.35 0.00 0.10 3.85 1.25 -43.76 94
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -36.90 182
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 1.36 -45.81 94
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -58.58 503
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -39.72 157
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 0.73 -36.98 302
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -42.01 302
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 0.96 -50.44 329
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 0.96 -48.50 133
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 1.42 -57.70 133
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 1.45 -64.90 133
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -44.60 302
1,3,5-Tribromobenzene 1.45 1.02 0.00 0.00 6.31 1.24 -62.30 133
1,2,3,5-Tetrabromobenzene 1.83 1.19 0.00 0.00 7.43 1.42 -71.50 133
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -47.93 302
Acetophenone 0.82 1.01 0.00 0.48 4.50 1.01 -53.98 302
291
Solute E S A B L V Exp Ref
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -55.81 302
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 1.07 -71.58 329
Ethyl benzoate 0.69 0.85 0.00 0.46 5.08 1.21 -58.39 302
1-Chloro-2-nitrobenzene 1.02 1.24 0.00 0.24 5.24 1.01 -65.75 329
1-Chloro-3-nitrobenzene 1.00 1.14 0.00 0.25 5.21 1.01 -62.89 329
1-Chloro-4-nitrobenzene 0.98 1.18 0.00 0.24 5.22 1.01 -62.15 329
3-Nitroacetophenone 1.01 1.50 0.00 0.63 5.95 1.19 -91.17 329
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -70.60 329
3-Chlorophenol 0.91 1.06 0.69 0.15 4.77 0.90 -81.27 238
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 0.90 -83.03 238
4-Bromophenol 1.08 1.17 0.67 0.20 5.14 0.95 -92.22 238
2-Methoxyphenol 0.84 0.91 0.22 0.52 4.45 0.98 -74.00 238
3-Methoxyphenol 0.88 1.17 0.59 0.38 4.80 0.98 -91.30 238
4-Methoxyphenol 0.90 1.17 0.57 0.48 4.77 0.98 -85.30 238
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -75.72 302
2-Nitrophenol 1.02 1.05 0.05 0.37 4.76 0.95 -63.26 329
3-Nitrophenol 1.05 1.57 0.79 0.23 5.69 0.95 -99.36 329
4-Nitrophenol 1.07 1.72 0.82 0.26 5.88 0.95 -102.57 329
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -47.11 329
Benzonitrile 0.74 1.11 0.00 0.33 4.04 0.87 -54.31 329
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -63.02 504
3-Methylaniline 0.97 0.92 0.23 0.45 4.46 0.96 -69.51 329
292
Solute E S A B L V Exp Ref
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 0.99 -81.89 329
3-Nitroaniline 1.20 1.71 0.40 0.35 5.88 0.99 -90.64 329
4-Nitroaniline 1.22 1.93 0.46 0.35 6.34 0.99 -101.50 329
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -52.83 329
1-Chloronaphthalene 1.42 1.00 0.00 0.14 5.86 1.21 -64.79 329
1-Nitronaphthalene 1.60 1.59 0.00 0.29 7.06 1.26 -78.78 329
1-Naphthylamine 1.67 1.20 0.20 0.57 6.49 1.19 -88.90 329
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -91.70 505
Diphenyl ether 1.22 1.08 0.00 0.20 6.29 1.38 -66.52 329
Trifluoromethylbenzene 0.23 0.48 0.00 0.10 2.89 0.91 -37.61 62
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -29.70 101
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -40.60 133
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 6.73 506
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -15.23 145
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -53.40 193
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -68.40 193
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -34.17 507
Table S5.20. Experimental values o f the gas to t ert-butanol solvation enthalpy, ΔHSolv,t-BTOH in kJ/mole, for 84 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -22.80 28
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -27.70 28
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -31.51 28
293
Solute E S A B L V Exp Ref
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -35.77 28
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -40.29 28
Decane 0.00 0.00 0.00 0.00 4.69 1.52 -44.64 28
Dodecane 0.00 0.00 0.00 0.00 5.70 1.80 -53.47 28
Tetradecane 0.00 0.00 0.00 0.00 6.71 2.08 -63.53 400
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -70.58 28
3-Ethylpentane 0.00 0.00 0.00 0.00 3.09 1.10 -30.50 185
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -30.85 361
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -28.74 62
cis 2-Butene 0.14 0.08 0.00 0.05 1.74 0.63 -18.04 323
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -38.28 185
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -44.56 185
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -26.11 185
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -30.63 62
1,2-Dimethylbenzene 0.66 0.56 0.00 0.16 3.94 1.00 -37.89 508
1,3-Dimethylbenzene 0.62 0.52 0.00 0.16 3.84 1.00 -38.80 508
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -39.04 62
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -45.31 509
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -52.26 509
Trifluorotoluene 0.23 0.48 0.00 0.10 2.89 0.91 -28.87 62
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -38.95 62
Anisole 0.71 0.75 0.00 0.29 3.89 0.92 -34.85 62
3-Methylphenol 0.82 0.88 0.57 0.34 4.31 0.92 -66.07 62
294
Solute E S A B L V Exp Ref
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -54.43 62
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -59.04 62
1-Decanol 0.19 0.42 0.37 0.48 5.63 1.58 -81.28 510
2-Methyl-2-butanol 0.19 0.30 0.31 0.60 2.63 0.87 -49.71 62
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 0.73 -46.80 511
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 0.79 -47.24 512
Ethanediol 0.40 0.90 0.58 0.78 2.66 0.51 -61.10 511
Butan-1,4-diol 0.40 0.93 0.72 0.90 3.80 0.80 -84.18 512
Glycerol 0.51 0.76 0.47 1.43 3.97 0.71 -85.80 511
Dimethyl ether 0.00 0.27 0.00 0.41 1.29 0.45 -16.61 323
Diethyl ether 0.04 0.25 0.00 0.45 2.02 0.73 -24.94 62
Methyl butyl ether 0.05 0.25 0.00 0.44 2.66 0.87 -29.50 62
Methyl tert-butyl ether 0.02 0.11 0.00 0.63 2.38 0.87 -29.41 62
2-Methyltetrahydrofuran 0.24 0.48 0.00 0.53 2.82 0.76 -32.45 513
1,3-Dioxolane 0.30 0.51 0.00 0.62 1.83 0.54 -27.37 407
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -30.42 407
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -24.23 91
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -28.20 91
2-Heptanone 0.12 0.68 0.00 0.51 3.76 1.11 -41.71 91
4-Heptanone 0.11 0.66 0.00 0.51 3.71 1.11 -40.67 91
2-Nonanone 0.12 0.68 0.00 0.51 4.74 1.39 -50.88 91
5-Nonanone 0.10 0.66 0.00 0.51 4.70 1.39 -49.66 91
295
Solute E S A B L V Exp Ref
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 0.86 -41.09 91
2,2,4,4-Tetramethyl-3-pentanone 0.10 0.56 0.00 0.52 4.37 1.39 -39.33 91
Chloroethane 0.23 0.40 0.00 0.10 1.68 0.51 -21.93 323
Propyl formate 0.13 0.63 0.00 0.38 2.43 0.75 -29.44 514
Butyl formate 0.12 0.63 0.00 0.38 2.96 0.89 -32.52 515
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 0.75 -28.31 516
Propyl acetate 0.09 0.60 0.00 0.45 2.82 0.89 -32.51 514
Butyl acetate 0.07 0.60 0.00 0.45 3.35 1.03 -37.17 515
Methyl propanoate 0.13 0.60 0.00 0.45 2.43 0.75 -28.84 517
Ethyl propanoate 0.09 0.58 0.00 0.45 2.81 0.89 -32.71 516
Propyl propanoate 0.07 0.56 0.00 0.45 3.34 1.03 -37.43 514
Butyl propanoate 0.06 0.56 0.00 0.47 3.83 1.17 -41.66 515
Methyl butanoate 0.11 0.60 0.00 0.45 2.89 0.89 -32.57 517
Ethyl butanoate 0.07 0.58 0.00 0.45 3.27 1.03 -35.00 516
Propyl butanoate 0.05 0.56 0.00 0.45 3.78 1.17 -41.13 514
Butyl butanoate 0.04 0.56 0.00 0.45 4.28 1.31 -45.23 515
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -24.93 412
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -32.71 413
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -22.00 512
1-Butanenitrile 0.18 0.90 0.00 0.36 2.55 0.69 -29.35 518
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -26.34 410
2-Chlorobutane 0.19 0.35 0.00 0.12 2.54 0.79 -25.29 410
2-Methyl-1- 0.19 0.37 0.00 0.12 2.57 0.79 -25.51 410
296
Solute E S A B L V Exp Ref
chloropropane
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -22.66 387
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -27.86 387
1-Bromobutane 0.36 0.40 0.00 0.12 3.11 0.85 -24.08 409
2-Methyl-2-bromopropane 0.31 0.29 0.00 0.07 2.61 0.85 -24.55 387
2-Methyl-2-iodopropane 0.59 0.35 0.00 0.19 3.44 0.93 -27.88 334
Tetramethylsilicon -0.06 0.08 0.00 0.03 1.81 0.92 -20.20 332
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 0.84 -32.51 509
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -35.27 509
Iodobenzene 1.19 0.82 0.00 0.12 4.50 0.97 -39.62 509
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -23.61 512
β-Pinene 0.53 0.24 0.00 0.19 4.39 1.26 -41.39 519
Methyl tert-amyl ether 0.05 0.21 0.00 0.60 2.92 1.02 -34.09 520
Adipic acid 0.35 1.21 1.13 0.76 4.47 1.10 -114.60 521
Table S5.21. Experimental v alues o f th e gas to a cetonitrile e nthalpy of solvation, ΔHSolv,CAN in kJ /mole, f or 74 s olutes, t ogether w ith t he s olute descriptors.
Solute E S A B L V Exp Ref
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -17.79 288
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -21.46 288, 357
Heptane 0.00 0.00 0.00 0.00 3.17 1.09 -24.49 288
297
Solute E S A B L V Exp Ref
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -28.21 288, 357
Undecane 0.00 0.00 0.00 0.00 5.19 1.66 -38.70 357
2-Methylpentane 0.00 0.00 0.00 0.00 2.50 0.95 -19.96 288
2,2,4-Trimethylpentane 0.00 0.00 0.00 0.00 3.11 1.24 -26.04 522
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -23.25 288
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -32.14 288
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -34.42 288
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -37.43 288
1-Butanol 0.22 0.42 0.37 0.48 2.60 0.73 -41.81 288
1-Pentanol 0.22 0.42 0.37 0.48 3.11 0.87 -45.61 324
1-Hexanol 0.21 0.42 0.37 0.48 3.61 1.02 -49.90 523
1-Heptanol 0.21 0.42 0.37 0.48 4.12 1.15 -49.08 524
1-Octanol 0.20 0.42 0.37 0.48 4.62 1.30 -55.49 324
2-Methyl-1-propanol 0.22 0.39 0.37 0.48 2.41 0.73 -40.21 420
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -40.12 525
2-Methyl-2-propanol 0.18 0.30 0.31 0.60 1.96 0.73 -37.07 525
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -31.32 129
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -55.00 504
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -38.35 288
Nitroethane 0.27 0.95 0.02 0.33 2.41 0.56 -39.60 288
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 0.71 -43.41 288
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -32.93 288
298
Solute E S A B L V Exp Ref
Propionitrile 0.16 0.90 0.02 0.36 2.08 0.55 -35.89 288
Butyronitrile 0.18 0.90 0.00 0.36 2.55 0.69 -38.33 288
1-Chloropropane 0.22 0.40 0.00 0.10 2.20 0.65 -26.02 288
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -29.99 288
Dichloromethane 0.39 0.57 0.10 0.05 2.02 0.49 -31.37 288
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -32.57 288
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -29.42 288
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -37.32 526
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -41.52 526
m-Xylene 0.62 0.52 0.00 0.16 3.84 1.00 -41.97 526
p-Xylene 0.61 0.52 0.00 0.16 3.84 1.00 -41.47 526
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.79 527
Diethylamine 0.15 0.30 0.08 0.69 2.40 0.77 -29.73 528
sec-Butylamine 0.17 0.32 0.16 0.63 2.41 0.77 -31.33 528
Methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -28.68 529
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -49.45 530
Nitric Oxide 0.37 0.02 0.00 0.09 -0.59 0.20 -1.83 75
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -83.19 26
12-Crown-4 0.42 0.99 0.00 1.39 5.14 1.36 -69.31 175
cis 1,2-Dichloroethene 0.44 0.61 0.11 0.05 2.44 0.59 -31.74 197
trans-1,2-Dichloroethene 0.43 0.41 0.09 0.05 2.28 0.59 -29.54 197
299
Solute E S A B L V Exp Ref
Trichloroethene 0.52 0.37 0.08 0.03 3.00 0.72 -32.95 197
Tetrachloroethene 0.64 0.44 0.00 0.00 3.58 0.84 -34.83 197
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -25.95 189
2-Bromo-2-methylpropane 0.31 0.29 0.00 0.07 2.61 0.61 -28.01 189
Methyl acetate 0.14 0.64 0.00 0.45 1.91 0.61 -32.86 343
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -59.41 531
Pyridine 0.63 0.84 0.00 0.52 3.02 0.68 -36.00 532
Methyl isobutyrate 0.09 0.57 0.00 0.47 2.64 0.89 -36.09 110
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 6.54 506
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 0.90 -56.70 238
3-Chlorophenol 0.91 1.06 0.69 0.15 4.77 0.90 -65.87 238
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 0.90 -67.33 238
4-Bromophenol 1.08 1.17 0.67 0.20 5.14 0.95 -76.00 238
2-Methoxyphenol 0.84 0.91 0.22 0.52 4.45 0.98 -62.10 238
3-Methoxyphenol 0.88 1.17 0.59 0.38 4.80 0.98 -78.00 238
4-Methoxyphenol 0.90 1.17 0.57 0.48 4.77 0.98 -78.50 238
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -50.70 191
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -60.20 191
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -73.70 191
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -32.89 533
Sulfur dioxide 0.37 0.66 0.28 0.10 0.78 0.35 -29.71 176
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -29.50 101
300
Solute E S A B L V Exp Ref
1-Naphthol 1.52 1.05 0.60 0.37 6.13 1.14 -77.60 159
Carbon dioxide 0.00 0.28 0.05 0.10 0.06 0.28 -13.88 145
Imidazole 0.71 0.85 0.42 0.78 4.02 0.54 -63.05 393
Diphenyl ether 1.22 1.08 0.00 0.20 6.29 1.38 -60.00 534
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -47.69 533
Table S5.22. Experimental va lues of the g as t o a cetone e nthalpy o f s olvation, ΔHSolv,ACE (kJ/mole), for 81 solutes, together with the solute descriptors.
Solute E S A B L V Exp Ref
Methane 0.00 0.00 0.00 0.00 -0.32 0.29 -2.80 45
Ethane 0.00 0.00 0.00 0.00 0.49 0.39 -8.62 45
Propane 0.00 0.00 0.00 0.00 1.05 0.53 -16.07 25
Pentane 0.00 0.00 0.00 0.00 2.16 0.81 -19.58 25
Hexane 0.00 0.00 0.00 0.00 2.67 0.95 -24.14 305
Heptane 0.00 0.00 0.00 0.00 3.17 1.10 -26.76 296
Octane 0.00 0.00 0.00 0.00 3.68 1.24 -31.76 288
Nonane 0.00 0.00 0.00 0.00 4.18 1.38 -35.70 288
Hexadecane 0.00 0.00 0.00 0.00 7.71 2.36 -63.38 535
Cyclohexane 0.31 0.10 0.00 0.00 2.96 0.85 -26.13 322
Adamantane 0.76 0.57 0.00 0.04 5.10 1.19 -40.40 322
Benzene 0.61 0.52 0.00 0.14 2.79 0.72 -31.32 129
Toluene 0.60 0.52 0.00 0.14 3.33 0.86 -36.99 222
p-Xylene 0.61 0.52 0.00 0.16 3.84 1.00 -42.00 222
Mesitylene 0.65 0.52 0.00 0.19 4.34 1.14 -44.35 222
301
Solute E S A B L V Exp Ref
Naphthalene 1.34 0.92 0.00 0.20 5.16 1.09 -54.00 191
Biphenyl 1.36 0.99 0.00 0.26 6.01 1.32 -62.30 191
Anthracene 2.29 1.34 0.00 0.28 7.57 1.45 -76.10 191
Methanol 0.28 0.44 0.43 0.47 0.97 0.31 -33.89 186
Ethanol 0.25 0.42 0.37 0.48 1.49 0.45 -37.66 296
1-Propanol 0.24 0.42 0.37 0.48 2.03 0.59 -42.84 536
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 0.73 -43.95 537
2-Butanol 0.22 0.36 0.33 0.56 2.34 0.73 -42.67 537
Ethylene glycol 0.40 0.90 0.58 0.78 2.66 0.51 -53.53 536
Glycerol 0.51 0.76 0.47 1.43 3.97 0.71 -75.38 536
15-Crown-5 0.41 1.20 0.00 1.75 6.78 1.70 -78.25 538
18-Crown-6 0.40 1.34 0.00 2.13 7.92 2.04 -93.70 53
Helium 0.00 0.00 0.00 0.00 -1.74 0.07 11.51 288
Neon 0.00 0.00 0.00 0.00 -1.58 0.09 10.08 288
Argon 0.00 0.00 0.00 0.00 -0.69 0.19 1.92 288
Radon 0.00 0.00 0.00 0.00 0.88 0.38 -10.50 357
Hydrogen 0.00 0.00 0.00 0.00 -1.20 0.11 4.52 288
Oxygen 0.00 0.00 0.00 0.00 -0.72 0.18 0.13 288
Nitrogen 0.00 0.00 0.00 0.00 -0.98 0.22 1.76 288
Carbon Monoxide 0.00 0.00 0.00 0.04 -0.84 0.22 0.25 288
2-Methyl-1-propanol 0.22 0.39 0.37 0.48 2.41 0.73 -44.24 539
Iodomethane 0.68 0.43 0.00 0.12 2.11 0.51 -26.64 54
1-Iodobutane 0.63 0.40 0.00 0.15 3.63 0.93 -36.79 54
302
Solute E S A B L V Exp Ref
2-Iodo-2-methylpropane 0.59 0.35 0.00 0.19 3.44 0.93 -32.04 54
1-Chlorobutane 0.21 0.40 0.00 0.10 2.72 0.79 -31.58 54
2-Chloro-2-methylpropane 0.14 0.30 0.00 0.03 2.27 0.79 -27.08 54
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 1.10 -51.61 222
Aniline 0.96 0.96 0.26 0.41 3.93 0.82 -58.24 222
Bromobenzene 0.88 0.73 0.00 0.09 4.04 0.89 -43.51 222
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 0.87 -49.15 222
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 0.89 -54.85 222
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 1.07 -53.70 222
4-Nitrotoluene 0.87 1.11 0.00 0.28 5.15 1.01 -62.36 222
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 1.06 -73.80 222
4-Nitroaniline 1.22 1.93 0.46 0.35 6.34 0.99 -93.13 222
Acetone 0.18 0.70 0.04 0.49 1.70 0.55 -31.90 288
2-Butanone 0.17 0.70 0.00 0.51 2.29 0.69 -34.32 288
2-Pentanone 0.14 0.68 0.00 0.51 2.76 0.83 -37.87 186
2-Hexanone 0.14 0.68 0.00 0.51 3.29 0.97 -41.55 186
2-Octanone 0.11 0.68 0.00 0.51 4.26 1.25 -48.79 186
Phenol 0.81 0.89 0.60 0.30 3.77 0.78 -66.11 186
Carbon disulfide 0.88 0.26 0.00 0.03 2.37 0.49 -24.19 288
Carbon tetrachloride 0.46 0.38 0.00 0.00 2.82 0.74 -31.95 288
303
Solute E S A B L V Exp Ref
Chloroform 0.43 0.49 0.15 0.02 2.48 0.62 -34.63 288
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 0.68 -38.18 288
1,3-Dioxane 0.31 0.72 0.00 0.70 2.52 0.68 -38.91 540
Nitromethane 0.31 0.95 0.06 0.31 1.89 0.42 -39.05 288
Triethylamine 0.10 0.15 0.00 0.79 3.04 1.05 -30.30 101
1-Bromoadamantane 1.07 0.90 0.00 0.20 6.13 1.37 -53.60 160
1-Adamantanol 0.94 0.90 0.31 0.66 5.63 1.25 -63.80 160
Ferrocene 1.35 0.85 0.00 0.20 5.62 1.12 -56.53 541
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 0.88 -53.25 141
1,3,5-Trioxane 0.23 0.93 0.00 0.51 2.24 0.60 -41.70 541
Tetramethyl tin 0.32 0.11 0.00 0.10 2.65 1.04 -25.31 25
Tetraethyl tin 0.46 0.18 0.00 0.13 4.92 1.61 -40.50 25
cis 1,2-Dichloroethene 0.44 0.61 0.11 0.05 2.44 0.59 -34.75 197
trans-1,2-Dichloroethene 0.43 0.41 0.09 0.05 2.28 0.59 -32.51 197
Trichloroethene 0.52 0.37 0.08 0.03 3.00 0.72 -35.42 197
Tetrachloroethene 0.64 0.44 0.00 0.00 3.58 0.84 -37.30 197
Adipic acid 0.35 1.21 1.13 0.76 4.47 1.10 -105.80 542
methyl tert-butyl ether 0.02 0.21 0.00 0.59 2.38 0.87 -28.05 547
Dimethyl carbonate 0.14 0.54 0.00 0.57 2.33 0.66 -37.23 543
Diethyl carbonate 0.06 0.58 0.00 0.53 3.41 0.95 -43.17 543
304
Solute E S A B L V Exp Ref
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 1.14 -46.06 544
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 1.00 -40.90 545
Acetonitrile 0.24 0.90 0.07 0.32 1.74 0.40 -33.50 546
CHAPTER 6
Table S6.1. Logarithms o f th e e xperimental gas-to-Leonardite hum ic a cid partition coefficients, log KLHA data, and numerical values of the Abraham solute descriptors used in the regression analyses.
Solute E S A B L T log KLHA
n-Octane 0.00 0.00 0.00 0.00 3.68 278.15 2.71
n-Nonane 0.00 0.00 0.00 0.00 4.18 278.15 2.21
n-Decane 0.00 0.00 0.00 0.00 4.69 278.15 3.67
n-Undecane 0.00 0.00 0.00 0.00 5.19 278.15 4.24
n-Dodecane 0.00 0.00 0.00 0.00 5.70 278.15 4.75
n-Tridecane 0.00 0.00 0.00 0.00 6.20 278.15 5.24
Cyclodecane 0.47 0.10 0.00 0.00 5.34 278.15 3.99
1-Octene 0.09 0.08 0.00 0.07 3.57 278.15 2.89
1-Nonene 0.09 0.08 0.00 0.07 4.07 278.15 3.16
1-Decene 0.09 0.08 0.00 0.07 4.55 278.15 3.56
1-Undecene 0.09 0.08 0.00 0.07 5.02 278.15 4.19
1-Dodecene 0.09 0.08 0.00 0.07 5.52 278.15 4.62
1-Tridecene 0.09 0.08 0.00 0.07 6.02 278.15 5.23
Ethanol 0.25 0.42 0.37 0.48 1.49 278.15 4.03
305
Solute E S A B L T log KLHA
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 278.15 4.16
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 278.15 4.45
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 278.15 4.77
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 278.15 5.17
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 278.15 5.65
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 278.15 3.96
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 278.15 4.16
2-Methylpropan-2-ol 0.28 0.30 0.31 0.60 1.96 278.15 3.93
3-Methylbutan-1-ol 0.19 0.39 0.37 0.48 3.01 278.15 4.63
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 278.15 4.96
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 278.15 5.40
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 278.15 4.28
Phenol 0.81 0.89 0.60 0.30 3.77 278.15 6.32
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 278.15 5.77
2-Propanone 0.18 0.70 0.04 0.49 1.70 278.15 3.27
2-Butanone 0.17 0.70 0.00 0.51 2.29 278.15 3.39
2-Pentanone 0.14 0.68 0.00 0.51 2.76 278.15 3.57
2-Hexanone 0.14 0.68 0.00 0.51 3.29 278.15 3.77
2-Heptanone 0.12 0.68 0.00 0.51 3.76 278.15 4.24
2-Octanone 0.11 0.68 0.00 0.51 4.26 278.15 4.61
2-Nonanone 0.12 0.68 0.00 0.51 4.74 278.15 5.15
2-Decanone 0.11 0.68 0.00 0.51 5.25 278.15 5.61
306
Solute E S A B L T log KLHA
3-Methylbutan-2-one 0.13 0.65 0.00 0.51 2.69 278.15 3.29
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 278.15 3.57
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 278.15 4.36
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 278.15 4.59
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 278.15 5.08
Acetophenone 0.82 1.01 0.00 0.48 4.50 278.15 5.50
Methyl acetate 0.14 0.64 0.00 0.45 1.91 278.15 2.92
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 278.15 3.13
n-Propyl acetate 0.09 0.60 0.00 0.45 2.82 278.15 3.33
n-Butyl acetate 0.07 0.60 0.00 0.45 3.35 278.15 3.64
Isobutyl acetate 0.05 0.57 0.00 0.47 3.16 278.15 3.60
n-Pentyl acetate 0.07 0.60 0.00 0.45 3.84 278.15 4.05
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 278.15 5.28
Di-n-butyl ether 0.00 0.25 0.00 0.45 3.92 278.15 3.59
Di-n-pentyl ether 0.00 0.25 0.00 0.45 4.88 278.15 4.59
Methyl tert-butyl ether (MTBE) 0.02 0.21 0.00 0.59 2.38 278.15 2.40
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 278.15 3.21
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 278.15 4.18
Methyl phenyl ether (Anisole) 0.71 0.75 0.00 0.29 3.89 278.15 4.03
Benzene 0.61 0.52 0.00 0.14 2.79 278.15 2.37
Toluene 0.60 0.52 0.00 0.14 3.33 278.15 2.57
p-Xylene 0.61 0.52 0.00 0.16 3.84 278.15 2.82
307
Solute E S A B L T log KLHA
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 278.15 2.77
n-Butylbenzene 0.60 0.51 0.00 0.15 4.73 278.15 3.77
n-Pentylbenzene 0.59 0.51 0.00 0.15 5.23 278.15 4.30
n-Hexylbenzene 0.59 0.50 0.00 0.15 5.72 278.15 4.94
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 278.15 3.49
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 278.15 3.32
Styrene 0.85 0.65 0.00 0.16 3.86 278.15 3.48
Indane 0.83 0.62 0.00 0.17 4.59 278.15 3.72
Naphthalene 1.34 0.92 0.00 0.20 5.16 278.15 5.02
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 278.15 3.23
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 278.15 4.23
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 278.15 4.03
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 278.15 5.04
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 278.15 4.76
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 278.15 5.59
1,2,3,5-Tetrachlorobenzene 1.16 0.85 0.00 0.00 5.92 278.15 5.27
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 278.15 6.20
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 278.15 2.27
4-Fluorotoluene 0.49 0.55 0.00 0.14 3.37 278.15 2.53
4-Chlorobenzotrifluoride 0.53 0.58 0.00 0.01 3.73 278.15 3.24
308
Solute E S A B L T log KLHA
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 278.15 3.17
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 278.15 3.97
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 278.15 2.67
1-Chloroheptane 0.19 0.40 0.00 0.10 4.28 278.15 3.29
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 278.15 4.08
1-Bromopentane 0.36 0.40 0.00 0.12 3.61 278.15 1.97
Butanal (Butyraldehyde) 0.19 0.65 0.00 0.45 2.27 278.15 2.69
Pentanal 0.16 0.65 0.00 0.45 2.77 278.15 3.03
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 278.15 4.99
1-Cyanopropane (Butanenitrile) 0.19 0.90 0.00 0.36 2.55 278.15 3.57
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 278.15 5.38
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 278.15 5.20
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 278.15 5.38
Benzonitrile 0.74 1.11 0.00 0.33 4.04 278.15 4.98
Acetonitrile 0.24 0.90 0.07 0.32 1.74 278.15 3.42
Nitromethane 0.31 0.95 0.06 0.31 1.89 278.15 3.46
Nitroethane 0.27 0.95 0.02 0.33 2.41 278.15 3.46
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 278.15 3.57
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 278.15 3.31
Thiophenol 1.00 0.80 0.09 0.16 4.11 278.15 4.46
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 278.15 4.37
309
Solute E S A B L T log KLHA
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 278.15 5.45
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 278.15 5.44
1,4-Dimethoxybenzene 0.81 1.00 0.00 0.50 5.04 278.15 5.59
n-Octane 0.00 0.00 0.00 0.00 3.68 288.15 2.16
n-Nonane 0.00 0.00 0.00 0.00 4.18 288.15 2.82
n-Decane 0.00 0.00 0.00 0.00 4.69 288.15 3.41
n-Undecane 0.00 0.00 0.00 0.00 5.19 288.15 3.91
n-Dodecane 0.00 0.00 0.00 0.00 5.70 288.15 4.38
n-Tridecane 0.00 0.00 0.00 0.00 6.20 288.15 4.88
n-Tetradecane 0.00 0.00 0.00 0.00 6.71 288.15 5.43
Cyclodecane 0.47 0.10 0.00 0.00 5.34 288.15 3.69
1-Octene 0.09 0.08 0.00 0.07 3.57 288.15 2.08
1-Nonene 0.09 0.08 0.00 0.07 4.07 288.15 2.69
1-Decene 0.09 0.08 0.00 0.07 4.55 288.15 3.28
1-Undecene 0.09 0.08 0.00 0.07 5.02 288.15 3.83
1-Dodecene 0.09 0.08 0.00 0.07 5.52 288.15 4.35
1-Tridecene 0.09 0.08 0.00 0.07 6.02 288.15 4.77
Ethanol 0.25 0.42 0.37 0.48 1.49 288.15 3.68
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 288.15 3.82
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 288.15 4.08
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 288.15 4.39
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 288.15 4.76
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 288.15 5.18
310
Solute E S A B L T log KLHA
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 288.15 5.63
Nonan-1-ol 0.19 0.42 0.37 0.48 5.12 288.15 6.14
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 288.15 6.43
Undecan-1-ol 0.18 0.42 0.37 0.48 6.13 288.15 6.59
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 288.15 3.56
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 288.15 3.82
2-Methylpropan-2-ol 0.28 0.30 0.31 0.60 1.96 288.15 3.60
3-Methylbutan-1-ol 0.19 0.39 0.37 0.48 3.01 288.15 4.23
2-Ethyl-1-hexanol 0.21 0.39 0.37 0.48 4.43 288.15 5.38
Benzyl alcohol 0.80 0.87 0.39 0.56 4.22 288.15 6.10
1-Naphthol 1.52 1.05 0.60 0.37 6.13 288.15 8.20
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 288.15 4.56
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 288.15 4.92
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 288.15 3.42
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 288.15 3.88
Phenol 0.81 0.89 0.60 0.30 3.77 288.15 6.00
o-Cresol (2-Methylphenol) 0.84 0.86 0.52 0.30 4.22 288.15 5.96
m-Cresol (3-Methylphenol) 0.82 0.88 0.57 0.34 4.31 288.15 6.50
p-Cresol (4-Methylphenol) 0.82 0.87 0.57 0.31 4.31 288.15 6.48
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 288.15 5.44
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 288.15 7.19
311
Solute E S A B L T log KLHA
2,3-Dichlorophenol 0.90 0.94 0.48 0.20 4.99 288.15 6.36
2,6-Dichlorophenol 0.90 0.90 0.38 0.24 5.09 288.15 5.87
2,4,5-Trichlorophenol 1.07 0.92 0.73 0.10 5.73 288.15 8.08
2,4,6-Trichlorophenol 1.01 1.01 0.82 0.08 5.66 288.15 8.20
2-Propanone 0.18 0.70 0.04 0.49 1.70 288.15 2.68
2-Butanone 0.17 0.70 0.00 0.51 2.29 288.15 2.85
2-Pentanone 0.14 0.68 0.00 0.51 2.76 288.15 3.28
2-Hexanone 0.14 0.68 0.00 0.51 3.29 288.15 3.49
2-Heptanone 0.12 0.68 0.00 0.51 3.76 288.15 3.92
2-Octanone 0.11 0.68 0.00 0.51 4.26 288.15 4.29
2-Nonanone 0.12 0.68 0.00 0.51 4.74 288.15 4.81
2-Decanone 0.11 0.68 0.00 0.51 5.25 288.15 5.27
2-Undecanone 0.10 0.68 0.00 0.51 5.73 288.15 5.67
3-Methylbutan-2-one 0.13 0.65 0.00 0.51 2.69 288.15 3.08
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 288.15 3.31
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 288.15 4.05
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 288.15 4.29
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 288.15 4.75
Acetophenone 0.82 1.01 0.00 0.48 4.50 288.15 5.22
Methyl acetate 0.14 0.64 0.00 0.45 1.91 288.15 2.50
Ethyl acetate 0.11 0.62 0.00 0.45 2.31 288.15 2.39
n-Propyl acetate 0.09 0.60 0.00 0.45 2.82 288.15 2.85
n-Butyl acetate 0.07 0.60 0.00 0.45 3.35 288.15 3.28
Isobutyl acetate 0.05 0.57 0.00 0.47 3.16 288.15 3.40
312
Solute E S A B L T log KLHA
n-Pentyl acetate 0.07 0.60 0.00 0.45 3.84 288.15 3.72
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 288.15 5.01
Benzyl acetate 0.80 1.06 0.00 0.65 5.01 288.15 5.32
2-Phenylethyl acetate 0.79 1.10 0.00 0.50 5.36 288.15 5.74
Di-n-butyl ether 0.00 0.25 0.00 0.45 3.92 288.15 3.22
Di-n-pentyl ether 0.00 0.25 0.00 0.45 4.88 288.15 4.23
Methyl tert-butyl ether (MTBE) 0.02 0.21 0.00 0.59 2.38 288.15 1.94
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 288.15 2.70
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 288.15 3.82
Benzofuran 0.89 0.83 0.00 0.15 4.36 288.15 4.09
Dibenzofuran 1.41 1.02 0.00 0.17 6.72 288.15 5.80
Methyl phenyl ether (Anisole) 0.71 0.75 0.00 0.29 3.89 288.15 3.72
Benzene 0.61 0.52 0.00 0.14 2.79 288.15 2.18
Toluene 0.60 0.52 0.00 0.14 3.33 288.15 2.29
p-Xylene 0.61 0.52 0.00 0.16 3.84 288.15 2.88
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 288.15 2.79
n-Propylbenzene 0.60 0.50 0.00 0.15 4.23 288.15 3.10
n-Butylbenzene 0.60 0.51 0.00 0.15 4.73 288.15 3.53
n-Pentylbenzene 0.59 0.51 0.00 0.15 5.23 288.15 4.03
n-Hexylbenzene 0.59 0.50 0.00 0.15 5.72 288.15 4.53
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 288.15 3.33
1,3,5- 0.65 0.52 0.00 0.19 4.34 288.15 3.05
313
Solute E S A B L T log KLHA
Trimethylbenzene
Styrene 0.85 0.65 0.00 0.16 3.86 288.15 3.34
Indane 0.83 0.62 0.00 0.17 4.59 288.15 3.49
Naphthalene 1.34 0.92 0.00 0.20 5.16 288.15 4.66
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 288.15 5.48
Acenaphthene 1.60 1.05 0.00 0.22 6.47 288.15 5.75
Anthracene 2.29 1.34 0.00 0.28 7.57 288.15 7.29
Phenanthrene 2.06 1.29 0.00 0.29 7.63 288.15 7.17
Biphenyl 1.36 0.99 0.00 0.26 6.01 288.15 5.58
p-Terphenyl 2.04 1.48 0.00 0.30 9.69 288.15 9.49
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 288.15 3.05
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 288.15 4.01
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 288.15 3.81
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 288.15 3.87
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 288.15 4.69
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 288.15 4.52
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 288.15 5.36
1,2,3,5-Tetrachlorobenzene 1.16 0.85 0.00 0.00 5.92 288.15 5.14
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 288.15 5.79
Pentachlorobenzene 1.33 0.92 0.06 0.00 6.63 288.15 6.05
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 288.15 6.50
Fluorobenzene 0.48 0.57 0.00 0.10 2.79 288.15 2.21
314
Solute E S A B L T log KLHA
Bromobenzene 0.88 0.73 0.00 0.09 4.04 288.15 3.54
Iodobenzene 1.19 0.82 0.00 0.12 4.50 288.15 4.03
4-Fluorotoluene 0.49 0.55 0.00 0.14 3.37 288.15 2.60
4-Chlorobenzotrifluoride 0.53 0.58 0.00 0.01 3.73 288.15 3.00
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 288.15 3.01
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 288.15 3.70
1-Chlorohexane 0.20 0.40 0.00 0.10 3.78 288.15 2.50
1-Chloroheptane 0.19 0.40 0.00 0.10 4.28 288.15 3.10
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 288.15 3.82
1-Bromopentane 0.36 0.40 0.00 0.12 3.61 288.15 2.32
Butanal (Butyraldehyde) 0.19 0.65 0.00 0.45 2.27 288.15 2.41
Pentanal 0.16 0.65 0.00 0.45 2.77 288.15 2.59
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 288.15 4.70
1-Cyanopropane (Butanenitrile) 0.19 0.90 0.00 0.36 2.55 288.15 3.44
Aniline 0.96 0.96 0.26 0.41 3.93 288.15 5.81
o-Toluidine (2-Methylaniline) 0.97 0.92 0.23 0.45 4.44 288.15 5.82
p-Toluidine (4-Methylaniline) 0.92 0.95 0.23 0.45 4.45 288.15 6.63
2,6-Dimethylaniline 0.97 0.90 0.05 0.59 5.03 288.15 5.76
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 288.15 5.12
4-Iodoaniline 1.53 1.28 0.32 0.40 5.70 288.15 7.10
315
Solute E S A B L T log KLHA
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 288.15 5.02
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 288.15 5.12
2-Chloronitrobenzene 1.02 1.24 0.00 0.24 5.24 288.15 5.59
Benzonitrile 0.74 1.11 0.00 0.33 4.04 288.15 4.60
Acetonitrile 0.24 0.90 0.07 0.32 1.74 288.15 3.16
Nitromethane 0.31 0.95 0.06 0.31 1.89 288.15 3.27
Nitroethane 0.27 0.95 0.02 0.33 2.41 288.15 3.29
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 288.15 3.32
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 288.15 3.02
Pyridine 0.63 0.84 0.00 0.52 3.02 288.15 3.36
2-Methylpyrazine 0.63 0.90 0.00 0.64 3.25 288.15 4.99
Methylamine 0.25 0.35 0.16 0.58 1.30 288.15 3.34
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 288.15 5.78
N,N-Dimethylacetamide 0.36 1.33 0.00 0.78 3.72 288.15 6.31
Indole (1H-Indole) 1.20 1.12 0.44 0.22 5.51 288.15 6.48
Quinoline 1.27 0.97 0.00 0.54 5.46 288.15 6.25
Propanoic acid 0.23 0.65 0.61 0.44 2.28 288.15 5.51
Butanoic acid 0.21 0.64 0.61 0.45 2.75 288.15 5.73
Pentanoic acid 0.21 0.60 0.60 0.45 3.38 288.15 6.17
3-Methylbutanoic acid 0.21 0.60 0.60 0.45 3.38 288.15 5.77
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 288.15 7.08
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 288.15 7.00
316
Solute E S A B L T log KLHA
Diethyl phthalate 0.73 1.40 0.00 0.86 6.80 288.15 7.68
Triethylphosphate 0.00 1.00 0.00 1.06 4.75 288.15 6.15
Thiophene 0.69 0.56 0.00 0.15 2.82 288.15 2.55
Dimethylsulfoxide 0.52 1.72 0.00 0.97 3.46 288.15 6.03
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 288.15 4.14
Lindane (gamma-HCH) 1.45 0.91 0.00 0.68 7.47 288.15 7.27
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 288.15 5.00
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 288.15 4.94
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 288.15 7.03
1,4-Dimethoxybenzene 0.81 1.00 0.00 0.50 5.04 288.15 5.42
3-Hydroxybenzonitrile 0.93 1.55 0.77 0.28 5.18 288.15 8.30
4-Aminobenzonitrile 1.09 1.78 0.40 0.50 5.64 288.15 8.03
n-Nonane 0.00 0.00 0.00 0.00 4.18 298.15 2.81
n-Decane 0.00 0.00 0.00 0.00 4.69 298.15 3.06
n-Undecane 0.00 0.00 0.00 0.00 5.19 298.15 3.57
n-Dodecane 0.00 0.00 0.00 0.00 5.70 298.15 4.04
n-Tridecane 0.00 0.00 0.00 0.00 6.20 298.15 4.56
n-Tetradecane 0.00 0.00 0.00 0.00 6.71 298.15 5.07
Cyclodecane 0.47 0.10 0.00 0.00 5.34 298.15 3.42
1-Nonene 0.09 0.08 0.00 0.07 4.07 298.15 2.81
1-Decene 0.09 0.08 0.00 0.07 4.55 298.15 3.02
1-Undecene 0.09 0.08 0.00 0.07 5.02 298.15 3.52
317
Solute E S A B L T log KLHA
1-Dodecene 0.09 0.08 0.00 0.07 5.52 298.15 4.05
1-Tridecene 0.09 0.08 0.00 0.07 6.02 298.15 4.49
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 298.15 3.72
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 298.15 4.04
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 298.15 4.41
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 298.15 4.75
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 298.15 5.21
Nonan-1-ol 0.19 0.42 0.37 0.48 5.12 298.15 5.60
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 298.15 3.29
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 298.15 3.42
2-Methylpropan-2-ol 0.28 0.30 0.31 0.60 1.96 298.15 3.43
3-Methylbutan-1-ol 0.19 0.39 0.37 0.48 3.01 298.15 3.89
2-Ethyl-1-hexanol 0.21 0.39 0.37 0.48 4.43 298.15 4.92
Benzyl alcohol 0.80 0.87 0.39 0.56 4.22 298.15 5.70
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 298.15 4.21
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 298.15 4.62
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 298.15 3.16
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 298.15 3.52
Phenol 0.81 0.89 0.60 0.30 3.77 298.15 5.62
o-Cresol (2-Methylphenol) 0.84 0.86 0.52 0.30 4.22 298.15 5.50
m-Cresol (3-Methylphenol) 0.82 0.88 0.57 0.34 4.31 298.15 5.84
318
Solute E S A B L T log KLHA
p-Cresol (4-Methylphenol) 0.82 0.87 0.57 0.31 4.31 298.15 5.88
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 298.15 5.13
2,3-Dichlorophenol 0.90 0.94 0.48 0.20 4.99 298.15 5.87
2,6-Dichlorophenol 0.90 0.90 0.38 0.24 5.09 298.15 5.67
2-Butanone 0.17 0.70 0.00 0.51 2.29 298.15 2.88
2-Pentanone 0.14 0.68 0.00 0.51 2.76 298.15 3.02
2-Heptanone 0.12 0.68 0.00 0.51 3.76 298.15 3.63
2-Octanone 0.11 0.68 0.00 0.51 4.26 298.15 3.97
2-Nonanone 0.12 0.68 0.00 0.51 4.74 298.15 4.40
2-Decanone 0.11 0.68 0.00 0.51 5.25 298.15 4.83
2-Undecanone 0.10 0.68 0.00 0.51 5.73 298.15 5.29
3-Methylbutan-2-one 0.13 0.65 0.00 0.51 2.69 298.15 2.91
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 298.15 3.09
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 298.15 3.80
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 298.15 4.02
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 298.15 4.46
Acetophenone 0.82 1.01 0.00 0.48 4.50 298.15 4.83
n-Propyl acetate 0.09 0.60 0.00 0.45 2.82 298.15 2.99
n-Butyl acetate 0.07 0.60 0.00 0.45 3.35 298.15 3.02
Isobutyl acetate 0.05 0.57 0.00 0.47 3.16 298.15 3.12
n-Pentyl acetate 0.07 0.60 0.00 0.45 3.84 298.15 3.46
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 298.15 4.62
Benzyl acetate 0.80 1.06 0.00 0.65 5.01 298.15 5.00
319
Solute E S A B L T log KLHA
2-Phenylethyl acetate 0.79 1.10 0.00 0.50 5.36 298.15 5.27
Di-n-butyl ether 0.00 0.25 0.00 0.45 3.92 298.15 2.95
Di-n-pentyl ether 0.00 0.25 0.00 0.45 4.88 298.15 3.86
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 298.15 3.64
Benzofuran 0.89 0.83 0.00 0.15 4.36 298.15 3.79
Dibenzofuran 1.41 1.02 0.00 0.17 6.72 298.15 5.56
Methyl phenyl ether (Anisole) 0.71 0.75 0.00 0.29 3.89 298.15 3.52
Ethylbenzene 0.61 0.51 0.00 0.15 3.78 298.15 2.58
n-Propylbenzene 0.60 0.50 0.00 0.15 4.23 298.15 2.95
n-Butylbenzene 0.60 0.51 0.00 0.15 4.73 298.15 3.22
n-Pentylbenzene 0.59 0.51 0.00 0.15 5.23 298.15 3.63
n-Hexylbenzene 0.59 0.50 0.00 0.15 5.72 298.15 4.26
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 298.15 2.83
Indane 0.83 0.62 0.00 0.17 4.59 298.15 3.24
Naphthalene 1.34 0.92 0.00 0.20 5.16 298.15 4.48
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 298.15 4.95
Acenaphthene 1.60 1.05 0.00 0.22 6.47 298.15 5.30
Biphenyl 1.36 0.99 0.00 0.26 6.01 298.15 5.18
Chlorobenzene 0.72 0.65 0.00 0.07 3.66 298.15 2.91
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 298.15 3.61
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 298.15 3.46
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 298.15 3.54
320
Solute E S A B L T log KLHA
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 298.15 4.38
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 298.15 4.24
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 298.15 4.94
1,2,3,5-Tetrachlorobenzene 1.16 0.85 0.00 0.00 5.92 298.15 4.78
1,2,4,5-Tetrachlorobenzene 1.16 0.86 0.00 0.00 5.93 298.15 5.40
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 298.15 6.21
Bromobenzene 0.88 0.73 0.00 0.09 4.04 298.15 3.27
Iodobenzene 1.19 0.82 0.00 0.12 4.50 298.15 3.72
4-Fluorotoluene 0.49 0.55 0.00 0.14 3.37 298.15 2.35
4-Chlorobenzotrifluoride 0.53 0.58 0.00 0.01 3.73 298.15 2.76
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 298.15 3.36
1-Chloroheptane 0.19 0.40 0.00 0.10 4.28 298.15 2.90
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 298.15 3.47
Butanal (Butyraldehyde) 0.19 0.65 0.00 0.45 2.27 298.15 2.27
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 298.15 4.47
1-Cyanopropane (Butanenitrile) 0.19 0.90 0.00 0.36 2.55 298.15 3.16
Aniline 0.96 0.96 0.26 0.41 3.93 298.15 5.37
o-Toluidine (2-Methylaniline) 0.97 0.92 0.23 0.45 4.44 298.15 5.45
p-Toluidine (4- 0.92 0.95 0.23 0.45 4.45 298.15 6.03
321
Solute E S A B L T log KLHA
Methylaniline)
2,6-Dimethylaniline 0.97 0.90 0.05 0.59 5.03 298.15 5.41
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 298.15 4.71
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 298.15 4.71
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 298.15 4.73
2-Chloronitrobenzene 1.02 1.24 0.00 0.24 5.24 298.15 5.38
Benzonitrile 0.74 1.11 0.00 0.33 4.04 298.15 4.41
Acetonitrile 0.24 0.90 0.07 0.32 1.74 298.15 2.99
Nitromethane 0.31 0.95 0.06 0.31 1.89 298.15 3.03
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 298.15 3.03
2-Methylpyrazine 0.63 0.90 0.00 0.64 3.25 298.15 4.74
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 298.15 5.51
N,N-Dimethylacetamide 0.36 1.33 0.00 0.78 3.72 298.15 5.98
Quinoline 1.27 0.97 0.00 0.54 5.46 298.15 5.84
Propanoic acid 0.23 0.65 0.61 0.44 2.28 298.15 5.40
Butanoic acid 0.21 0.64 0.61 0.45 2.75 298.15 5.44
Pentanoic acid 0.21 0.60 0.60 0.45 3.38 298.15 5.72
Triethylphosphate 0.00 1.00 0.00 1.06 4.75 298.15 5.97
Thiophenol 1.00 0.80 0.09 0.16 4.11 298.15 3.83
Dimethylsulfoxide 0.52 1.72 0.00 0.97 3.46 298.15 5.61
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 298.15 3.97
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 298.15 4.71
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 298.15 4.68
322
Solute E S A B L T log KLHA
1,4-Dimethoxybenzene 0.81 1.00 0.00 0.50 5.04 298.15 5.06
n-Decane 0.00 0.00 0.00 0.00 4.69 308.15 2.89
n-Undecane 0.00 0.00 0.00 0.00 5.19 308.15 3.07
n-Dodecane 0.00 0.00 0.00 0.00 5.70 308.15 3.61
n-Tridecane 0.00 0.00 0.00 0.00 6.20 308.15 4.23
n-Tetradecane 0.00 0.00 0.00 0.00 6.71 308.15 4.51
Cyclodecane 0.47 0.10 0.00 0.00 5.34 308.15 3.08
1-Decene 0.09 0.08 0.00 0.07 4.55 308.15 2.81
1-Undecene 0.09 0.08 0.00 0.07 5.02 308.15 3.24
1-Dodecene 0.09 0.08 0.00 0.07 5.52 308.15 3.62
1-Tridecene 0.09 0.08 0.00 0.07 6.02 308.15 4.06
Ethanol 0.25 0.42 0.37 0.48 1.49 308.15 3.29
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 308.15 3.36
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 308.15 3.37
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 308.15 3.67
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 308.15 3.97
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 308.15 4.35
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 308.15 4.74
Nonan-1-ol 0.19 0.42 0.37 0.48 5.12 308.15 5.16
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 308.15 5.58
Propan-2-ol 0.21 0.36 0.33 0.56 1.76 308.15 3.02
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 308.15 3.12
2-Methylpropan-2-ol 0.28 0.30 0.31 0.60 1.96 308.15 3.12
323
Solute E S A B L T log KLHA
3-Methylbutan-1-ol 0.19 0.39 0.37 0.48 3.01 308.15 3.51
2-Ethyl-1-hexanol 0.21 0.39 0.37 0.48 4.43 308.15 4.50
Benzyl alcohol 0.80 0.87 0.39 0.56 4.22 308.15 5.31
1-Naphthol 1.52 1.05 0.60 0.37 6.13 308.15 7.15
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 308.15 3.91
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 308.15 4.26
2,2,2-Trifluoroethanol 0.02 0.60 0.57 0.25 1.22 308.15 2.97
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 308.15 3.18
o-Cresol (2-Methylphenol) 0.84 0.86 0.52 0.30 4.22 308.15 5.16
m-Cresol (3-Methylphenol) 0.82 0.88 0.57 0.34 4.31 308.15 5.50
p-Cresol (4-Methylphenol) 0.82 0.87 0.57 0.31 4.31 308.15 5.53
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 308.15 4.70
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 308.15 6.20
2,3-Dichlorophenol 0.90 0.94 0.48 0.20 4.99 308.15 5.55
2,6-Dichlorophenol 0.90 0.90 0.38 0.24 5.09 308.15 5.34
2,4,5-Trichlorophenol 1.07 0.92 0.73 0.10 5.73 308.15 6.75
2-Pentanone 0.14 0.68 0.00 0.51 2.76 308.15 2.73
2-Hexanone 0.14 0.68 0.00 0.51 3.29 308.15 2.91
2-Heptanone 0.12 0.68 0.00 0.51 3.76 308.15 3.27
2-Octanone 0.11 0.68 0.00 0.51 4.26 308.15 3.59
2-Nonanone 0.12 0.68 0.00 0.51 4.74 308.15 3.98
324
Solute E S A B L T log KLHA
2-Undecanone 0.10 0.68 0.00 0.51 5.73 308.15 4.79
3-Methylbutan-2-one 0.13 0.65 0.00 0.51 2.69 308.15 2.71
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 308.15 2.82
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 308.15 3.51
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 308.15 3.72
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 308.15 4.13
Acetophenone 0.82 1.01 0.00 0.48 4.50 308.15 4.50
n-Pentyl acetate 0.07 0.60 0.00 0.45 3.84 308.15 3.03
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 308.15 4.23
Benzyl acetate 0.80 1.06 0.00 0.65 5.01 308.15 4.63
2-Phenylethyl acetate 0.79 1.10 0.00 0.50 5.36 308.15 4.86
Di-n-pentyl ether 0.00 0.25 0.00 0.45 4.88 308.15 3.52
Tetrahydrofuran 0.29 0.52 0.00 0.48 2.64 308.15 2.57
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 308.15 3.38
Benzofuran 0.89 0.83 0.00 0.15 4.36 308.15 3.49
Dibenzofuran 1.41 1.02 0.00 0.17 6.72 308.15 5.24
n-Propylbenzene 0.60 0.50 0.00 0.15 4.23 308.15 2.52
n-Butylbenzene 0.60 0.51 0.00 0.15 4.73 308.15 2.94
n-Pentylbenzene 0.59 0.51 0.00 0.15 5.23 308.15 3.33
n-Hexylbenzene 0.59 0.50 0.00 0.15 5.72 308.15 3.78
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 308.15 2.67
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 308.15 2.52
325
Solute E S A B L T log KLHA
Styrene 0.85 0.65 0.00 0.16 3.86 308.15 2.92
Indane 0.83 0.62 0.00 0.17 4.59 308.15 3.14
Naphthalene 1.34 0.92 0.00 0.20 5.16 308.15 4.12
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 308.15 4.56
Acenaphthene 1.60 1.05 0.00 0.22 6.47 308.15 5.08
Anthracene 2.29 1.34 0.00 0.28 7.57 308.15 6.28
Phenanthrene 2.06 1.29 0.00 0.29 7.63 308.15 6.23
Biphenyl 1.36 0.99 0.00 0.26 6.01 308.15 4.89
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 308.15 3.39
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 308.15 3.22
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 308.15 3.34
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 308.15 4.09
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 308.15 3.90
1,2,3,4-Tetrachlorobenzene 1.18 0.92 0.00 0.00 6.17 308.15 4.59
1,2,3,5-Tetrachlorobenzene 1.16 0.85 0.00 0.00 5.92 308.15 4.50
Pentachlorobenzene 1.33 0.92 0.06 0.00 6.63 308.15 5.15
Bromobenzene 0.88 0.73 0.00 0.09 4.04 308.15 3.07
Iodobenzene 1.19 0.82 0.00 0.12 4.50 308.15 3.33
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 308.15 2.70
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 308.15 2.99
1-Chloroheptane 0.19 0.40 0.00 0.10 4.28 308.15 2.63
326
Solute E S A B L T log KLHA
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 308.15 3.16
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 308.15 4.09
Aniline 0.96 0.96 0.26 0.41 3.93 308.15 5.05
o-Toluidine (2-Methylaniline) 0.97 0.92 0.23 0.45 4.44 308.15 5.06
p-Toluidine (4-Methylaniline) 0.92 0.95 0.23 0.45 4.45 308.15 5.63
2,6-Dimethylaniline 0.97 0.90 0.05 0.59 5.03 308.15 4.97
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 308.15 4.23
4-Iodoaniline 1.53 1.28 0.32 0.40 5.70 308.15 6.29
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 308.15 4.35
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 308.15 4.48
2-Chloronitrobenzene 1.02 1.24 0.00 0.24 5.24 308.15 5.00
Benzonitrile 0.74 1.11 0.00 0.33 4.04 308.15 4.10
Acetonitrile 0.24 0.90 0.07 0.32 1.74 308.15 2.82
Nitromethane 0.31 0.95 0.06 0.31 1.89 308.15 2.88
Nitroethane 0.27 0.95 0.02 0.33 2.41 308.15 2.81
1-Nitropropane 0.24 0.95 0.00 0.31 2.89 308.15 2.79
2-Nitropropane 0.22 0.92 0.00 0.33 2.55 308.15 2.33
2-Methylpyrazine 0.63 0.90 0.00 0.64 3.25 308.15 4.41
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 308.15 5.29
N,N-Dimethylacetamide 0.36 1.33 0.00 0.78 3.72 308.15 5.65
Indole (1H-Indole) 1.20 1.12 0.44 0.22 5.51 308.15 5.68
327
Solute E S A B L T log KLHA
Quinoline 1.27 0.97 0.00 0.54 5.46 308.15 5.57
Propanoic acid 0.23 0.65 0.61 0.44 2.28 308.15 5.09
Butanoic acid 0.21 0.64 0.61 0.45 2.75 308.15 5.21
Pentanoic acid 0.21 0.60 0.60 0.45 3.38 308.15 5.39
3-Methylbutanoic acid 0.21 0.60 0.60 0.45 3.38 308.15 5.20
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 308.15 5.97
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 308.15 6.28
Dimethyl phthalate 0.78 1.41 0.00 0.84 6.05 308.15 5.87
Triethylphosphate 0.00 1.00 0.00 1.06 4.75 308.15 5.41
Dimethylsulfoxide 0.52 1.72 0.00 0.97 3.46 308.15 5.00
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 308.15 3.74
1,2-Ethanediol 0.40 0.90 0.58 0.78 2.66 308.15 6.50
Lindane (gamma-HCH) 1.45 0.91 0.00 0.68 7.47 308.15 6.27
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 308.15 4.46
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 308.15 4.39
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 308.15 5.97
1,4-Dimethoxybenzene 0.81 1.00 0.00 0.50 5.04 308.15 4.72
4-Aminobenzonitrile 1.09 1.78 0.40 0.50 5.64 308.15 7.22
n-Undecane 0.00 0.00 0.00 0.00 5.19 318.15 2.88
n-Tridecane 0.00 0.00 0.00 0.00 6.20 318.15 3.88
n-Tetradecane 0.00 0.00 0.00 0.00 6.71 318.15 4.17
1-Decene 0.09 0.08 0.00 0.07 4.55 318.15 2.59
328
Solute E S A B L T log KLHA
1-Dodecene 0.09 0.08 0.00 0.07 5.52 318.15 3.27
1-Tridecene 0.09 0.08 0.00 0.07 6.02 318.15 3.68
Ethanol 0.25 0.42 0.37 0.48 1.49 318.15 3.05
Propan-1-ol 0.24 0.42 0.37 0.48 2.03 318.15 3.19
Butan-1-ol 0.22 0.42 0.37 0.48 2.60 318.15 3.16
Pentan-1-ol 0.22 0.42 0.37 0.48 3.11 318.15 3.40
Hexan-1-ol 0.21 0.42 0.37 0.48 3.61 318.15 3.71
Heptan-1-ol 0.21 0.42 0.37 0.48 4.12 318.15 4.12
Octan-1-ol 0.20 0.42 0.37 0.48 4.62 318.15 4.39
Nonan-1-ol 0.19 0.42 0.37 0.48 5.12 318.15 4.74
Decan-1-ol 0.19 0.42 0.37 0.48 5.63 318.15 5.10
2-Methylpropan-1-ol 0.22 0.39 0.37 0.48 2.41 318.15 2.81
3-Methylbutan-1-ol 0.19 0.39 0.37 0.48 3.01 318.15 3.19
2-Ethyl-1-hexanol 0.21 0.39 0.37 0.48 4.43 318.15 4.08
Benzyl alcohol 0.80 0.87 0.39 0.56 4.22 318.15 4.97
Cyclopentanol 0.43 0.54 0.32 0.56 3.24 318.15 3.67
Cyclohexanol 0.46 0.54 0.32 0.57 3.76 318.15 3.97
1,1,1,3,3,3-Hexafluoropropan-2-ol
-0.24 0.55 0.77 0.10 1.39 318.15 2.90
Phenol 0.81 0.89 0.60 0.30 3.77 318.15 4.85
o-Cresol (2-Methylphenol) 0.84 0.86 0.52 0.30 4.22 318.15 4.81
p-Cresol (4-Methylphenol) 0.82 0.87 0.57 0.31 4.31 318.15 5.14
329
Solute E S A B L T log KLHA
2-Chlorophenol 0.85 0.88 0.32 0.31 4.18 318.15 4.42
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 318.15 5.74
2,3-Dichlorophenol 0.90 0.94 0.48 0.20 4.99 318.15 5.32
2,6-Dichlorophenol 0.90 0.90 0.38 0.24 5.09 318.15 5.11
2,4,5-Trichlorophenol 1.07 0.92 0.73 0.10 5.73 318.15 6.06
2,4,6-Trichlorophenol 1.01 1.01 0.82 0.08 5.66 318.15 6.39
2-Pentanone 0.14 0.68 0.00 0.51 2.76 318.15 2.64
2-Heptanone 0.12 0.68 0.00 0.51 3.76 318.15 3.03
2-Octanone 0.11 0.68 0.00 0.51 4.26 318.15 3.37
2-Nonanone 0.12 0.68 0.00 0.51 4.74 318.15 3.74
2-Decanone 0.11 0.68 0.00 0.51 5.25 318.15 4.07
2-Undecanone 0.10 0.68 0.00 0.51 5.73 318.15 4.39
4-Methylpentan-2-one 0.11 0.65 0.00 0.51 3.09 318.15 2.65
Cyclopentanone 0.37 0.86 0.00 0.52 3.22 318.15 3.28
Cyclohexanone 0.40 0.86 0.00 0.56 3.79 318.15 3.45
Cycloheptanone 0.44 0.86 0.00 0.56 4.38 318.15 3.94
Acetophenone 0.82 1.01 0.00 0.48 4.50 318.15 4.19
n-Butyl acetate 0.07 0.60 0.00 0.45 3.35 318.15 2.52
Methyl benzoate 0.73 0.85 0.00 0.46 4.70 318.15 4.06
Benzyl acetate 0.80 1.06 0.00 0.65 5.01 318.15 4.40
2-Phenylethyl acetate 0.79 1.10 0.00 0.50 5.36 318.15 4.52
Di-n-butyl ether 0.00 0.25 0.00 0.45 3.92 318.15 2.42
1,4-Dioxane 0.33 0.75 0.00 0.64 2.89 318.15 3.15
Methyl phenyl ether 0.71 0.75 0.00 0.29 3.89 318.15 2.97
330
Solute E S A B L T log KLHA
(Anisole)
n-Hexylbenzene 0.59 0.50 0.00 0.15 5.72 318.15 3.43
1,2,4-Trimethylbenzene 0.68 0.56 0.00 0.19 4.44 318.15 2.50
1,3,5-Trimethylbenzene 0.65 0.52 0.00 0.19 4.34 318.15 2.38
Styrene 0.85 0.65 0.00 0.16 3.86 318.15 2.87
Indane 0.83 0.62 0.00 0.17 4.59 318.15 3.00
Naphthalene 1.34 0.92 0.00 0.20 5.16 318.15 3.75
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 318.15 4.13
Anthracene 2.29 1.34 0.00 0.28 7.57 318.15 5.97
Phenanthrene 2.06 1.29 0.00 0.29 7.63 318.15 5.82
Biphenyl 1.36 0.99 0.00 0.26 6.01 318.15 4.54
1,2-Dichlorobenzene 0.87 0.78 0.00 0.04 4.52 318.15 3.03
1,3-Dichlorobenzene 0.85 0.73 0.00 0.02 4.41 318.15 2.86
1,4-Dichlorobenzene 0.83 0.75 0.00 0.02 4.44 318.15 2.96
1,4-Dibromobenzene 1.15 0.86 0.00 0.04 5.32 318.15 3.73
1,2,4-Trichlorobenzene 0.98 0.81 0.00 0.00 5.25 318.15 3.56
Pentachlorobenzene 1.33 0.92 0.06 0.00 6.63 318.15 4.90
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 318.15 5.32
Bromobenzene 0.88 0.73 0.00 0.09 4.04 318.15 2.80
1,1,1,2-Tetrachloroethane 0.54 0.63 0.10 0.08 3.64 318.15 2.62
1,1,2,2-Tetrachloroethane 0.60 0.76 0.16 0.12 3.80 318.15 2.76
331
Solute E S A B L T log KLHA
1-Chlorooctane 0.19 0.40 0.00 0.09 4.71 318.15 3.06
Benzaldehyde 0.82 1.00 0.00 0.39 4.01 318.15 3.90
1-Cyanopropane (Butanenitrile) 0.19 0.90 0.00 0.36 2.55 318.15 2.78
Aniline 0.96 0.96 0.26 0.41 3.93 318.15 4.66
o-Toluidine (2-Methylaniline) 0.97 0.92 0.23 0.45 4.44 318.15 4.76
p-Toluidine (4-Methylaniline) 0.92 0.95 0.23 0.45 4.45 318.15 5.18
2,6-Dimethylaniline 0.97 0.90 0.05 0.59 5.03 318.15 4.66
N,N-Dimethylaniline 0.96 0.81 0.00 0.41 4.70 318.15 3.98
4-Iodoaniline 1.53 1.28 0.32 0.40 5.70 318.15 6.01
Nitrobenzene 0.87 1.11 0.00 0.28 4.56 318.15 4.13
2-Nitrotoluene 0.87 1.11 0.00 0.27 4.88 318.15 4.24
2-Chloronitrobenzene 1.02 1.24 0.00 0.24 5.24 318.15 4.62
Benzonitrile 0.74 1.11 0.00 0.33 4.04 318.15 3.93
Nitromethane 0.31 0.95 0.06 0.31 1.89 318.15 2.62
Nitroethane 0.27 0.95 0.02 0.33 2.41 318.15 2.62
2-Methylpyrazine 0.63 0.90 0.00 0.64 3.25 318.15 4.16
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 318.15 4.97
N,N-Dimethylacetamide 0.36 1.33 0.00 0.78 3.72 318.15 5.27
Indole (1H-Indole) 1.20 1.12 0.44 0.22 5.51 318.15 5.45
Quinoline 1.27 0.97 0.00 0.54 5.46 318.15 5.13
Propanoic acid 0.23 0.65 0.61 0.44 2.28 318.15 4.93
332
Solute E S A B L T log KLHA
Butanoic acid 0.21 0.64 0.61 0.45 2.75 318.15 5.02
Pentanoic acid 0.21 0.60 0.60 0.45 3.38 318.15 5.17
3-Methylbutanoic acid 0.21 0.60 0.60 0.45 3.38 318.15 4.90
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 318.15 5.49
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 318.15 5.91
Dimethyl phthalate 0.78 1.41 0.00 0.84 6.05 318.15 5.50
Triethylphosphate 0.00 1.00 0.00 1.06 4.75 318.15 5.14
Dimethylsulfoxide 0.52 1.72 0.00 0.97 3.46 318.15 4.65
2,4-Pentanedione 0.41 0.78 0.00 0.63 3.33 318.15 3.55
1,2-Ethanediol 0.40 0.90 0.58 0.78 2.66 318.15 6.03
Lindane (gamma-HCH) 1.45 0.91 0.00 0.68 7.47 318.15 5.79
2-Methoxyethanol 0.27 0.50 0.30 0.84 2.49 318.15 4.16
2-Ethoxyethanol 0.24 0.52 0.31 0.81 2.79 318.15 4.06
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 318.15 5.57
1,4-Dimethoxybenzene 0.81 1.00 0.00 0.50 5.04 318.15 4.56
3-Hydroxybenzonitrile 0.93 1.55 0.77 0.28 5.18 318.15 7.26
4-Aminobenzonitrile 1.09 1.78 0.40 0.50 5.64 318.15 6.96
Undecan-1-ol 0.18 0.42 0.37 0.48 6.13 328.15 5.00
1-Naphthol 1.52 1.05 0.60 0.37 6.13 328.15 6.24
o-Cresol (2-Methylphenol) 0.84 0.86 0.52 0.30 4.22 328.15 4.52
m-Cresol (3-Methylphenol) 0.82 0.88 0.57 0.34 4.31 328.15 4.87
333
Solute E S A B L T log KLHA
p-Cresol (4-Methylphenol) 0.82 0.87 0.57 0.31 4.31 328.15 4.85
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 328.15 5.38
2,4,5-Trichlorophenol 1.07 0.92 0.73 0.10 5.73 328.15 5.33
2,4,6-Trichlorophenol 1.01 1.01 0.82 0.08 5.66 328.15 6.08
1-Methylnaphthalene 1.34 0.94 0.00 0.22 5.80 328.15 3.84
Anthracene 2.29 1.34 0.00 0.28 7.57 328.15 5.62
Phenanthrene 2.06 1.29 0.00 0.29 7.63 328.15 5.48
Biphenyl 1.36 0.99 0.00 0.26 6.01 328.15 4.05
p-Terphenyl 2.04 1.48 0.00 0.30 9.69 328.15 7.38
Hexachlorobenzene 1.49 0.99 0.00 0.00 7.62 328.15 4.52
Aniline 0.96 0.96 0.26 0.41 3.93 328.15 4.25
4-Iodoaniline 1.53 1.28 0.32 0.40 5.70 328.15 5.59
2-Chloronitrobenzene 1.02 1.24 0.00 0.24 5.24 328.15 4.32
2-Methylpyrazine 0.63 0.90 0.00 0.64 3.25 328.15 3.99
N,N-Dimethylformamide 0.37 1.31 0.00 0.74 3.17 328.15 4.89
Indole (1H-Indole) 1.20 1.12 0.44 0.22 5.51 328.15 4.94
Quinoline 1.27 0.97 0.00 0.54 5.46 328.15 4.85
3-Methylbutanoic acid 0.21 0.60 0.60 0.45 3.38 328.15 4.80
1,2-Dinitrobenzene 1.17 1.70 0.00 0.38 5.91 328.15 5.00
1,4-Dinitrobenzene 1.13 1.63 0.00 0.46 5.80 328.15 5.64
Dimethyl phthalate 0.78 1.41 0.00 0.84 6.05 328.15 5.24
Diethyl phthalate 0.73 1.40 0.00 0.86 6.80 328.15 6.11
334
Solute E S A B L T log KLHA
1,2-Ethanediol 0.40 0.90 0.58 0.78 2.66 328.15 5.71
Lindane (gamma-HCH) 1.45 0.91 0.00 0.68 7.47 328.15 5.38
2-Nitroaniline 1.18 1.37 0.30 0.36 5.63 328.15 5.05
3-Hydroxybenzonitrile 0.93 1.55 0.77 0.28 5.18 328.15 7.02
4-Aminobenzonitrile 1.09 1.78 0.40 0.50 5.64 328.15 6.69
Undecan-1-ol 0.18 0.42 0.37 0.48 6.13 338.15 4.73
1-Naphthol 1.52 1.05 0.60 0.37 6.13 338.15 5.79
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 338.15 5.10
2,4,6-Trichlorophenol 1.01 1.01 0.82 0.08 5.66 338.15 5.38
Anthracene 2.29 1.34 0.00 0.28 7.57 338.15 5.25
Phenanthrene 2.06 1.29 0.00 0.29 7.63 338.15 5.13
p-Terphenyl 2.04 1.48 0.00 0.30 9.69 338.15 6.93
Indole (1H-Indole) 1.20 1.12 0.44 0.22 5.51 338.15 4.74
Quinoline 1.27 0.97 0.00 0.54 5.46 338.15 4.67
Diethyl phthalate 0.73 1.40 0.00 0.86 6.80 338.15 5.59
3-Hydroxybenzonitrile 0.93 1.55 0.77 0.28 5.18 338.15 6.67
4-Aminobenzonitrile 1.09 1.78 0.40 0.50 5.64 338.15 6.21
Undecan-1-ol 0.18 0.42 0.37 0.48 6.13 348.15 4.34
4-Chlorophenol 0.92 1.08 0.67 0.20 4.78 348.15 4.57
2,4,5-Trichlorophenol 1.07 0.92 0.73 0.10 5.73 348.15 4.43
Anthracene 2.29 1.34 0.00 0.28 7.57 348.15 4.85
Phenanthrene 2.06 1.29 0.00 0.29 7.63 348.15 4.80
p-Terphenyl 2.04 1.48 0.00 0.30 9.69 348.15 6.49
336
REFERENCES
1 A. V. Plyasunov and E. L. Shock, Geochim. Cosmochim. Acta 67 (24), 4981 (2003).
2 R. E. Kuhne, R.U.; Schuurman, G., Environ. Sci. Technol. 39, 6705 (2005).
3 M. H. Abraham, G. S. Whiting, R. Fuchs, and E. J. Chambers, J. Chem. Soc., Perkin Trans. 2 (2), 291 (1990).
4 E. L. Purlee, R. W. Taft, Jr., and C. A. DeFazio, J. Am. Chem. Soc. 77, 837 (1955).
5 A. Lutsyk, V. Portnanskij, S. Sujkov, and V. Tchuprina, Monatsh. Chem. 136 (7), 1183 (2005).
6 T. Shimotori and W. A. Arnold, J. Chem. Eng. Data 47 (2), 183 (2002).
7 A. V. Plyasunov, N. V. Plyasunova, and E. L. Shock, J. Chem. Eng. Data 51 (1), 276 (2006).
8 S. G. Cabani, P.; Mollica, V.; Lepori, L., J. Solution Chem. 8, 563 (1981).
9 Z. Atik, D. Gruber, M. Krummen, and J. Gmehling, J. Chem. Eng. Data 49 (5), 1429 (2004).
10 A. V. Plyasunov, N. V. Plyasunova, and E. L. Shock, J. Chem. Eng. Data 49 (5), 1152 (2004).
11 A. V. Plyasunov and E. L. Shock, J. Chem. Eng. Data 46 (5), 1016 (2001).
12 N. Segatin and C. Klofutar, Monatsh. Chem. 132 (12), 1451 (2001).
13 G. L. Bertrand, F. J. Millero, C. Wu, and L. G. Hepler, J. Phys. Chem. 70 (3), 699 (1966).
14 A. C. Rouw and G. Somsen, J. Chem. Thermodyn. 13 (1), 67 (1981).
15 Y. Koga, W. W. Y. Siu, and T. Y. H. Wong, J. Phys. Chem. 94 (19), 7700 (1990).
16 C. V. Krishnan and H. L. Friedman, J. Phys. Chem. 73 (5), 1572 (1969).
17 M. H. Abraham and E. Matteoli, J. Chem. Soc., Faraday Trans. 1 84 (6), 1985 (1988).
18 M. H. Abraham, J. Chem. Soc., Faraday Trans. 1 80 (1), 153 (1984).
19 F. S. Costa, M. E. Eusebio, J. S. Redinha, and M. L. P. Leitao, J. Chem. Thermodyn. 31 (7), 895 (1999).
20 M. Y. Nagamachi and A. Z. Francesconi, J. Chem. Thermodyn. 38 (4), 461 (2006).
21 R. C. C. Guedes, K.; Cabral, B.J.C; Canuto,S., J. Phys. Chem. 107, 4304 (2003).
337
22 A. V. Plyasunov, N. V. Plyasunova, and E. L. Shock, J. Chem. Eng. Data 51 (5), 1481 (2006).
23 E. M. Arnett and B. Chawla, J. Am. Chem. Soc. 101 (24), 7141 (1979).
24 N. V. Plyasunova, A. V. Plyasunov, and E. L. Shock, J. Chem. Eng. Data 50 (1), 246 (2005).
25 M. H. Abraham, J. Am. Chem. Soc. 104 (8), 2085 (1982).
26 M. Jozwiak, Thermochim. Acta 417 (1), 31 (2004).
27 A. J. L. Jesus, L. I. N. Tome, M. E. S. Eusebio, and J. S. Redinha, J. Phys. Chem. B 110 (18), 9280 (2006).
28 R. Fuchs, Stephenson, W.K., Can. J. Chem. 63, 349 (1985).
29 L. Bernazzani, P. Gianni, V. Mollica, and P. Pizzolla, Thermochim. Acta 418 (1-2), 109 (2004).
30 S. C. Cabani, Giovanni; Mollica, Vincenzo; Bernazzani, Luca, J. Chem. Soc., Faraday Trans. 87 (15), 2433 (1991).
31 IUPAC Solubility Data Series Vol. (IUPAC, Research Triangle, NC).
32 D. Gruber, D. Langenheim, J. Gmehling, and W. Moollan, J. Chem. Eng. Data 42 (5), 882 (1997).
33 S. R. Bhatia and S. I. Sandler, J. Chem. Eng. Data 40 (6), 1196 (1995).
34 H. Iloukhani, J. Chem. Eng. Data 42 (4), 802 (1997).
35 L. Bernazzani, G. Conti, and V. Mollica, J. Solution Chem. 31 (4), 279 (2002).
36 T. Harner and D. Mackay, Environ. Sci. Technol. 29 (6), 1599 (1995).
37 T. Harner and T. F. Bidleman, J. Chem. Eng. Data 43 (1), 40 (1998).
38 G. L. Pollack, J. F. Himm, and J. J. Enyeart, J. Chem. Phys. 81 (7), 3239 (1984).
39 R. J. Wilcock, R. Battino, W. F. Danforth, and E. Wilhelm, J. Chem. Thermodyn. 10 (9), 817 (1978).
40 T. Harner and T. F. Bidleman, J. Chem. Eng. Data 41 (4), 895 (1996).
41 B. N. Solomonov, V. B. Novikov, M. A. Varfolomeev, and N. M. Mileshko, J. Phys. Org. Chem. 18 (1), 49 (2005).
42 P. Goralski, J. Chem. Soc., Faraday Trans. 1 84 (12), 4311 (1988).
338
43 B. Marongiu, S. Porcedda, L. Lepori, and E. Matteoli, Fluid Phase Equilib. 108 (1-2), 167 (1995).
44 N. Morel-Desrosiers and J. P. Morel, J. Solution Chem. 8 (8), 579 (1979).
45 E. Wilhelm and R. Battino, Chem. Rev. 73 (1), 1 (1973).
46 M. H. Karbalai Ghassemi and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 68 (1976).
47 B. S. Bjola, M. A. Siddiqi, U. Fornefeld-Schwarz, and P. Svejda, J. Chem. Eng. Data 47 (2), 250 (2002).
48 G. C. Benson, O. Kiyohara, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 64 (1991).
49 J. N. Spencer, K. J. Modarress, W. L. Nachlis, and J. W. Hovick, J. Phys. Chem. 90 (18), 4443 (1986).
50 T. E. Burchfield, University of Missouri-Rolla, 1977.
51 B. N. Solomonov, Konovalov, A.I., Norikov, V.B., Borbachuk, V.V., Neklyudov, S.A., J. Gen. Chem. 55, 1681 (1985).
52 V. P. Barannikov, S. S. Guseinov, and A. I. V'Yugin, Zh. Fiz. Khim. 78 (1), 144 (2004).
53 V. P. Barannikov, S. S. Guseynov, and A. I. Vyugin, J. Chem. Thermodyn. 36 (4), 277 (2004).
54 M. D. Borisover, A. Stolov, F. D. Baitalov, A. I. Morozov, and B. N. Solomonov, Thermochim. Acta 285 (2), 199 (1996).
55 R. Fuchs, E. J. Chambers, and W. K. Stephenson, Can. J. Chem. 65 (11), 2624 (1987).
56 B. Marongiu, Thermochim. Acta 95 (1), 105 (1985).
57 K. N. Marsh, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 62 (1992).
58 K. N. Marsh, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 63 (1992).
59 K. N. Marsh, W. A. Allan, and A. E. Richards, J. Chem. Thermodyn. 16 (12), 1107 (1984).
60 W. C. Duer and G. L. Bertrand, J. Am. Chem. Soc. 97 (14), 3894 (1975).
61 B. N. Solomonov, V. B. Novikov, M. A. Varfolomeev, and A. E. Klimovitskii, J. Phys. Org. Chem. 18 (11), 1132 (2005).
62 W. K. Stephenson and R. Fuchs, Can. J. Chem. 63 (9), 2535 (1985).
339
63 A. Otterstedt and R. W. Missen, Trans. Faraday Soc. 58, 879 (1962).
64 G. Avedis, A. H. Roux, and J. P. E. Grolier, J. Chem. Thermodyn. 24 (12), 1233 (1992).
65 G. Avedis, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 26 (1990).
66 G. Avedis, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 27 (1990).
67 G. Avedis, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 29 (1990).
68 S. P. Verevkin and C. Schick, Fluid Phase Equilib. 211 (2), 161 (2003).
69 J. N. Spencer, J. E. Gleim, C. H. Blevins, R. C. Garrett, and F. J. Mayer, J. Phys. Chem. 83 (10), 1249 (1979).
70 I. Uruska, Koschmidder, M., J. Chem. Soc., Perkin Trans. 2, 1845 (1989).
71 E. M. Arnett, E. J. Mitchell, and T. S. S. R. Murty, J. Am. Chem. Soc. 96 (12), 3875 (1974).
72 J. N. Spencer, W. S. Wolbach, J. W. Hovick, L. Ansel, and K. J. Modarress, J. Solution Chem. 14 (11), 805 (1985).
73 R. Francesconi and F. Comelli, J. Chem. Eng. Data 37 (2), 230 (1992).
74 R. Battino and K. N. Marsh, Aust. J. Chem. 33 (9), 1997 (1980).
75 A. W. Shaw and A. J. Vosper, J. Chem. Soc., Faraday Trans. 1 73 (8), 1239 (1977).
76 A. D. Sherry and K. F. Purcell, J. Amer. Chem. Soc. 94 (6), 1848 (1972).
77 G. C. Kresheck and I. M. Klotz, Biochemistry 8 (1), 8 (1969).
78 F. T. Khafizov, Breus, V.A., Kiselev, O.E., Solomonov, B.N., Konovalov, A.I., Russ. J. Gen. Chem. 60, 627 (1980).
79 P. Goralski, U. Krzemien, and S. Taniewska-Osinska, J. Chem. Soc., Faraday Trans. 1 81 (3), 695 (1985).
80 M. H. Abraham, P. P. Duce, D. V. Prior, R. A. Schulz, J. J. Morris, and P. J. Taylor, J. Chem. Soc., Faraday Trans. 1 84 (3), 865 (1988).
81 M. A. R. Matos, M. S. Miranda, and V. M. F. Morais, J. Chem. Eng. Data 48 (3), 669 (2003).
82 B. S. Bjola, M. A. Siddiqi, and P. Svejda, J. Chem. Eng. Data 46 (5), 1167 (2001).
83 I. I. Sheikhet, V. N. Levchuk, and B. Y. Simkin, J. Mol. Liq. 40 (3), 191 (1989).
340
84 B. N. Solomonov, Borisover, M.D., Konovalov, A.I., Russ. J. Gen. Chem. 56, 1 (1986).
85 I. P. C. Li, Y.-W. Wong, S.-D. Chang, and B. C. Y. Lu, J. Chem. Eng. Data 17 (4), 492 (1972).
86 R. Francesconi and F. Comelli, Thermochim. Acta 216 (1-2), 35 (1993).
87 E. Wilhelm, A. Inglese, and J. P. E. Grolier, Thermochim. Acta 229 (1-2), 271 (1993).
88 Y. Shiohama, H. Ogawa, S. Murakami, and I. Fujihara, Fluid Phase Equilib. 32 (3), 249 (1987).
89 J. J. Christensen, Rowley, R.L., Izatt, R.M., Handbook of Heats of Mixing: Supplementary Volume. Vol. (Wiley, New York, 1988).
90 Z. Wang, G. C. Benson, and B. C. Y. Lu, Thermochim. Acta 414 (1), 31 (2004).
91 W. K. Stephenson and R. Fuchs, Can. J. Chem. 63 (2), 336 (1985).
92 K. Tamura, J. Chem. Thermodyn. 33 (10), 1345 (2001).
93 K. Tamura, S. Murakami, and R. Fujishiro, J. Chem. Thermodyn. 7 (11), 1089 (1975).
94 W. K. Stephenson and R. Fuchs, Can. J. Chem. 63 (2), 342 (1985).
95 W. K. Stephenson and R. Fuchs, Can. J. Chem. 63 (9), 2529 (1985).
96 T. M. Letcher and U. Domanska, J. Chem. Thermodyn. 29 (7), 721 (1997).
97 B. Schmitt-Diefenbach, A. Steiger, and F. Becker, Thermochim. Acta 94 (1), 85 (1985).
98 J. N. Spencer, J. E. Mihalick, T. J. Nicholson, P. A. Cortina, J. L. Rinehimer, J. E. Smith, X. Ke, Q. He, S. E. Daniels, and et al., J. Phys. Chem. 97 (40), 10509 (1993).
99 J. N. Spencer, J. E. Mihalick, I. M. Paul, W. J. Nicholson, T. J. Nicholson, X. Ke, Q. He, F. J. Carter, S. E. Daniels, and et al., J. Solution Chem. 23 (6), 721 (1994).
100 J. Fernandez, R. Garriga, I. Velasco, and S. Otin, Fluid Phase Equilib. 152 (2), 243 (1998).
101 M. H. Abraham and A. Nasehzadeh, J. Chem. Thermodyn. 13 (6), 549 (1981).
102 P. Vrbka, D. Rozbroj, and V. Dohnal, Fluid Phase Equilib. 209 (2), 265 (2003).
103 H. C. Van Ness and M. M. Abbott, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 49 (1976).
104 M. Lohse and W. D. Deckwer, J. Chem. Eng. Data 26 (2), 159 (1981).
105 R. Tanaka and G. C. Benson, J. Chem. Thermodyn. 8 (3), 259 (1976).
341
106 A. H. Roux and E. Wilhelm, Thermochim. Acta 391 (1-2), 129 (2002).
107 J. George, N. V. Sastry, and D. H. L. Prasad, Fluid Phase Equilib. 214 (1), 39 (2003).
108 P. Goralski and M. Tkaczyk, J. Chem. Soc., Faraday Trans. 1 83 (9), 3083 (1987).
109 K. N. Surendranath, A. Krishnaiah, and M. Ramakrishna, Thermochim. Acta 157 (1), 83 (1990).
110 C. Cardelli, G. Conti, and P. Gianni, J. Therm. Anal. Calorim. 61 (2), 377 (2000).
111 S. Delcros, E. Jimenez, L. Romani, A. H. Roux, J. P. E. Grolier, and H. V. Kehiaian, Fluid Phase Equilib. 111 (1), 71 (1995).
112 J. Gmehling and B. Meents, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 183 (1992).
113 J. P. E. Grolier, D. Ballet, and A. Viallard, J. Chem. Thermodyn. 6 (9), 895 (1974).
114 G. C. Allred, J. W. Beets, and W. R. Parrish, J. Chem. Eng. Data 40 (5), 1062 (1995).
115 S. Murakami and F. Kimura, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 34 (1979).
116 H. P. Dahiya, S. Dagar, and P. P. Singh, J. Chem. Eng. Data 32 (3), 342 (1987).
117 R. Tanaka and G. C. Benson, J. Chem. Eng. Data 23 (1), 75 (1978).
118 R. Tanaka and G. C. Benson, J. Chem. Eng. Data 21 (3), 320 (1976).
119 B. Marongiu, E. Pusceddu, S. Porcedda, L. Lepori, and E. Matteoli, Fluid Phase Equilib. 250 (1-2), 105 (2006).
120 J. Catalan, J. Gomez, A. Couto, and J. Laynez, J. Am. Chem. Soc. 112 (5), 1678 (1990).
121 H. Ukibe, R. Tanaka, S. Murakami, and R. Fujishiro, J. Chem. Thermodyn. 6 (2), 201 (1974).
122 W. E. J. Acree, IUPAC Solubility Data Series 59 (1995).
123 X. Hu, Y. Zhang, and Z. Huang, Wuli Huaxue Xuebao 1 (2), 130 (1985).
124 C. V. Krishnan and H. L. Friedman, J. Phys. Chem. 75 (23), 3598 (1971).
125 T. Kimura, T. Matsushita, and T. Kamiyama, J. Solution Chem. 33 (6/7), 875 (2004).
126 F. S. Costa, M. E. Eusebio, J. S. Redinha, and M. L. P. Leitao, J. Chem. Thermodyn. 32 (3), 311 (2000).
127 M. Topphoff, D. Gruber, and J. Gmehling, J. Chem. Eng. Data 44 (6), 1355 (1999).
128 J. H. Hallman, W. K. Stephenson, and R. Fuchs, Can. J. Chem. 61 (9), 2044 (1983).
342
129 N. G. Manin, S. Y. Belichenko, and V. P. Korolev, Russ. J. Gen. Chem. 73 (1), 9 (2003).
130 T. Kimura, T. Matsushita, and T. Kamiyama, Thermochim. Acta 416 (1-2), 129 (2004).
131 E. M. Arnett and D. R. McKelvey, J. Am. Chem. Soc. 88 (11), 2598 (1966).
132 D. Figeys, M. Koschmidder, and R. L. Benoit, Can. J. Chem. 70 (6), 1586 (1992).
133 B. N. Solomonov, F. T. Khafizov, and V. V. Gorbachuk, Zh. Obshch. Khim. 60 (7), 1446 (1990).
134 T. Kimura and S. Takagi, Thermochim. Acta 253, 59 (1995).
135 R. Francesconi, F. Comelli, A. Bigi, and K. Rubini, Thermochim. Acta 447 (2), 154 (2006).
136 T. Kimura and S. Takagi, Netsu Sokutei 23 (2), 53 (1996).
137 K. Ohtsu and K. Ozutsumi, J. Inclusion Phenom. Macrocyclic Chem. 45 (3-4), 217 (2003).
138 R. Philippe, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 122 (1975).
139 T. Matsui, L. G. Hepler, and D. V. Fenby, J. Phys. Chem. 77 (20), 2397 (1973).
140 R. Philippe, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 126 (1975).
141 G. Pathak, A. D. Tripathi, and S. Pradhan, Thermochim. Acta 197 (2), 329 (1992).
142 R. Philippe, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 124 (1975).
143 T. Kimura, T. Tsuda, and S. Takagi, Thermochim. Acta 267, 333 (1995).
144 T. Kimura, K. Suzuki, and S. Takagi, Fluid Phase Equilib. 136 (1-2), 269 (1997).
145 A. Gennaro, A. A. Isse, and E. Vianello, J. Electroanal. Chem. Interfacial Electrochem. 289 (1-2), 203 (1990).
146 A. A. C. C. Pais, A. Sousa, M. E. Eusebio, and J. S. Redinha, Phys. Chem. Chem. Phys. 3 (18), 4001 (2001).
147 F. Comelli, S. Ottani, R. Francesconi, and C. Castellari, J. Chem. Eng. Data 48 (4), 995 (2003).
148 D. V. Batov, O. A. Antonova, and V. P. Korolev, Russ. J. Gen. Chem. 71 (5), 689 (2001).
149 R. L. Benoit, M. J. Mackinnon, and L. Bergeron, Can. J. Chem. 59 (10), 1501 (1981).
150 R. L. Benoit and M. Frechette, Thermochim. Acta 126, 155 (1988).
151 F. Comelli, R. Francesconi, A. Bigi, and K. Rubini, J. Chem. Eng. Data 51 (2), 665 (2006).
343
152 R. Francesconi, A. Bigi, K. Rubini, and F. Comelli, J. Chem. Eng. Data 50 (6), 1932 (2005).
153 G. R. Bebahani, D. Dunnion, P. Falvey, K. Hickey, M. Meade, Y. McCarthy, M. C. R. Symons, and W. E. Waghorne, J. Solution Chem. 29 (6), 521 (2000).
154 B. G. Cox, J. Chem. Soc., Perkin Trans. 2 (5), 607 (1973).
155 M. Lahti, A. Kankaanpera, and H. Sapyska, J. Chem. Soc., Perkin Trans. 2 (7), 1081 (1990).
156 R. L. Benoit, M. Frechette, and D. Lefebvre, Can. J. Chem. 66 (5), 1159 (1988).
157 G. A. Krestov, V. P. Korolev, and D. V. Batov, Thermochim. Acta 169, 69 (1990).
158 A. Nissema, T. Kaivamo, and M. Karvo, J. Chem. Thermodyn. 15 (11), 1083 (1983).
159 V. I. Smirnov, E. V. Kastorina, G. A. Kiestov, and A. Y. Fridman, Zh. Fiz. Khim. 67 (6), 1123 (1993).
160 N. M. Nunes, Luis; Leitao, Ruben E.; Martins, Filomena, Journal of Chemical Thermodynamics 39 (8), 1201 (2007).
161 Y. Takeda, T. Watanabe, H. Yamada, and S. Katsuta, J. Mol. Liq. 108 (1-3), 151 (2003).
162 F. Comelli, R. Francesconi, and S. Ottani, J. Chem. Eng. Data 43 (3), 333 (1998).
163 R. Francesconi and F. Comelli, J. Chem. Eng. Data 40 (4), 811 (1995).
164 F. Comelli and R. Francesconi, J. Chem. Eng. Data 40 (4), 805 (1995).
165 S. Ottani, F. Comelli, and C. Castellari, J. Chem. Eng. Data 46 (1), 125 (2001).
166 F. Comelli and R. Francesconi, J. Chem. Eng. Data 50 (1), 191 (2005).
167 R. Francesconi and F. Comelli, J. Chem. Eng. Data 40 (1), 31 (1995).
168 K. Ohtsu, T. Kawashima, and K. Ozutsumi, J. Chem. Soc., Faraday Trans. 91 (24), 4375 (1995).
169 R. Francesconi and F. Comelli, J. Chem. Eng. Data 41 (6), 1397 (1996).
170 R. Francesconi and F. Comelli, Thermochim. Acta 260, 95 (1995).
171 F. Comelli, R. Francesconi, and C. Castellari, Thermochim. Acta 354 (1-2), 89 (2000).
172 F. Comelli, R. Francesconi, and C. Castellari, J. Chem. Eng. Data 44 (1), 144 (1999).
173 C. Castellari, F. Comelli, and R. Francesconi, Thermochim. Acta 413 (1-2), 249 (2004).
344
174 F. Blanchard, B. Carre, F. Bonhomme, P. Biensan, and D. Lemordant, Can. J. Chem. 81 (5), 385 (2003).
175 A. F. D. de Namor, J. C. Y. Ng, M. A. L. Tanco, and M. Salomon, J. Phys. Chem. 100 (34), 14485 (1996).
176 R. L. Benoit and E. Milanova, Can. J. Chem. 57 (11), 1319 (1979).
177 G. C. Benson, B. Luo, and B. C. Y. Lu, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 180 (1988).
178 Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Solution Chem. 32 (10), 907 (2003).
179 Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Solution Chem. 33 (2), 143 (2004).
180 R. S. Murray and M. L. Martin, J. Chem. Thermodyn. 10 (8), 711 (1978).
181 C. Castellari, J. Chem. Eng. Data 51 (2), 599 (2006).
182 V. B. Novikov, D. I. Abaidullina, N. Z. Gainutdinova, M. A. Varfalomeev, and B. N. Solomonov, Russ. J. Phys. Chem. 80 (11), 1790 (2006).
183 M. Vidal, J. Ortega, and J. Placido, J. Chem. Thermodyn. 29 (1), 47 (1997).
184 J. Ortega and F. J. Toledo-Marante, J. Chem. Thermodyn. 34 (9), 1439 (2002).
185 W. K. Stephenson and R. Fuchs, Can. J. Chem. 63 (9), 2540 (1985).
186 B. N. Solomonov, A. I. Konovalov, V. B. Novikov, V. V. Borbachuk, and S. A. Neklyudov, Russ. J. Gen. Chem. 55, 1681 (1984).
187 J. Hu, K. Tamura, and S. Murakami, Fluid Phase Equilib. 134 (1-2), 239 (1997).
188 R. Zhang, W. Yan, X. Wang, and R. Lin, Thermochim. Acta 429 (2), 155 (2005).
189 M. H. Abraham, P. L. Grellier, A. Nasehzadeh, and R.A.C.Walker, J. Chem. Soc., Perkin Trans. 2, 1717 (1988).
190 J. Ortega, A. Navas, J. Placido, and F. J. Toledo, J. Chem. Thermodyn. 38 (5), 585 (2006).
191 B. N. Solomonov and I. A. Sedov, J. Phys. Chem. B 110 (18), 9298 (2006).
192 J. S. Chickos and W. E. Acree, Jr., J. Phys. Chem. Ref. Data 31 (2), 537 (2002).
193 N. Nunes, L. Moreira, R. E. Leitao, and F. Martins, J. Chem. Thermodyn. 39 (8), 1201 (2007).
194 F. L. Nordstroem and A. C. Rasmuson, J. Chem. Eng. Data 51 (5), 1775 (2006).
345
195 M. D. M. C. Ribeiro da Silva and N. R. M. Araujo, J. Chem. Thermodyn. 39 (10), 1372 (2007).
196 R. C. Paul, S. K. Rehani, S. S. Pahil, and S. C. Ahluwalia, Indian J. Chem. 7 (7), 715 (1969).
197 M. D. Borisover, A. A. Stolov, S. V. Izosimova, F. D. Baitalov, V. A. Breus, and B. P. Solomonov, Zh. Fiz. Khim. 65 (3), 594 (1991).
198 J. Ortega and J. Placido, ELDATA Int. Electron. J. Phys.-Chem. Data 1 (1), 59 (1995).
199 T. E. Burchfield, Dissertation, University of Missouri-Rolla, 1977.
200 J. J. Christensen, R. L. Rowley, and R. M. Izatt, Handbook of Heats of Mixing: Supplementary Volume Vol. (John Wiley and Sons, Inc., New York, NY, 1988).
201 H. Ogawa, S. Murakami, T. Takigawa, and M. Ohba, Fluid Phase Equilib. 136 (1-2), 279 (1997).
202 P. G. J.L. Chevalier, J. Balade, Rend. des Seances l’Acad. des Sci., Ser. C: Sci. Chim. 266, 326 (1968).
203 Z. E. Ilic and Z. B. Maksimovic, Thermochim. Acta 53 (3), 251 (1982).
204 S. C. Sharma and J. Singh, J. Solution Chem. 24 (2), 145 (1995).
205 F. Becker and F. Hallauer, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 45 (1988).
206 A. Inglese, Thermochim. Acta 199, 173 (1992).
207 T. Ohta, Int. DATA Ser., Sel. Data Mixtures, Ser. A 26 (4), 298 (1998).
208 M. L. S. J.J. Moura Ramos, J. Reisse, Chem. Phys. Lett. 42, 373 (1976).
209 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 40 (1993).
210 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 41 (1993).
211 T. Ohta, Int. DATA Ser., Sel. Data Mixtures, Ser. A 26 (4), 286 (1998).
212 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 43 (1993).
213 J. Ortega, Int. Data Ser., Sel. Data Mix., Ser. A 44 (1993).
214 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 45 (1993).
215 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 46 (1993).
216 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 47 (1993).
346
217 J. S. Chickos and W. E. Acree, Jr., J. Phys. Chem. Ref. Data 32 (2), 519 (2003).
218 A. H. R. J. Munoz Embid, J.P.E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A 67 (1990).
219 J. N. Spencer, E. S. Holmboe, D. W. Firth, and M. R. Kirshenbaum, J. Solution Chem. 10 (10), 745 (1981).
220 D. F. Gray, N. F. Pasco, and A. G. Williamson, J. Chem. Eng. Data 33 (3), 333 (1988).
221 D. Fenclova, P. Vrbka, V. Dohnal, K. Rehak, and G. Garcia-Miaja, J. Chem. Thermodyn. 34 (3), 361 (2002).
222 B. N. A. Solomonov, I.S.; Gorbachuk, V.V.; Konovalov, A.I.; Russ, A.I. , J. Gen. Chem. 48, 2113 (1978).
223 E. R. Thomas, B. A. Newman, G. L. Nicolaides, and C. A. Eckert, J. Chem. Eng. Data 27 (3), 233 (1982).
224 V. I. Smirnov, E. V. Kastorina, G. L. Perlovich, and A. Y. Fridman, Zh. Fiz. Khim. 66 (6), 1466 (1992).
225 J. Placido, J. Ortega, and H. V. Kehiaian, ELDATA: Int. Electron. J. Phys.-Chem. Data 1 (3), 239 (1995).
226 J. Ortega and J. Placido, ELDATA: Int. Electron. J. Phys.-Chem. Data 2 (2), 85 (1996).
227 W. Riebesehl, E. Tomlinson, and P. R. Niemel, J. Solution Chem. 14 (10), 699 (1985).
228 J. Ortega and J. Placido, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 6 (1993).
229 J. Ortega and J. Placido, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 7 (1993).
230 G. Hahn and P. Svejda, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 146 (1985).
231 J. Ortega and J. Placido, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 8 (1993).
232 J. Ortega and J. Placido, Int. DATA Ser., Sel. Data Mixtures, Ser. A 21 (1), 9 (1993).
233 S. K. Chaudhari and S. S. Katti, Thermochim. Acta 158 (1), 99 (1990).
234 J. Ortega and E. Marrero, J. Chem. Thermodyn. 39 (5), 742 (2007).
235 C. Airoldi and S. Roca, J. Solution Chem. 22 (8), 707 (1993).
236 J. Ortega, E. Marrero, F. J. Toledo, and F. Espiau, J. Chem. Thermodyn. 37 (12), 1332 (2005).
237 J. Ortega, E. Marrero, and F. J. Toledo, J. Chem. Thermodyn. 38 (9), 1139 (2006).
347
238 F. T. Khafizov, V. A. Breus, O. E. Kiselev, B. N. Solomonov, and A. I. Konovalov, Zh. Obshch. Khim. 60 (4), 721 (1990).
239 R. F. F. Comelli, J. Chem. Eng. Data 40, 509 (1995).
240 R. F. F. Comelli, H.V. Kehiaian, J. Chem. Eng. Data 36 (1991).
241 C. B. J. Munoz Embid, S. Otin Int. Data Ser., Sel. Data Mix., Ser. A, 273 (1991).
242 F. Comelli and R. Francesconi, J. Chem. Eng. Data 39 (3), 560 (1994).
243 J. R. Munoz Embid, A.H.; Grolier, J.P.E., Int. Data Ser., Sel. Data Mix., Ser. A 71 (1990).
244 I. Putze, R. Garriga, P. Perez, and M. Gracia, J. Chem. Thermodyn. 27 (11), 1153 (1995).
245 D.-Y. Peng, Y. Horikawa, Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 46 (2), 237 (2001).
246 Z. B. Wang, G.C.; Lu, B.C.-Y., J. Chem. Eng. Data 46, 237 (2001).
247 M. R. D. G. Tine, G.; Kehiaian, H. V., Fluid Phase Equilib. 54, 277 (1990).
248 F. J. Toledo-Marante, J. Ortega, M. Chaar, and M. Vidal, J. Chem. Thermodyn. 32, 1013 (2000).
249 J. O. M. Chaar, F. J. Toledo-Marante, C. Gonzalez, J. Chem. Thermodyn. 33, 689 (2001).
250 N. V. Sastry, S. R. Patel, and D. H. L. Prasad, Thermochim. Acta 359 (2), 169 (2000).
251 L. Wang, G. C. Benson, and B. C.-Y. Lu, Fluid Phase Equilib. 46, 211 (1989).
252 D.-Y. Peng, Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 33 (1), 83 (2001).
253 Z. Tong, G. C. Benson, L. L. Wang, and B. C. Y. Lu, J. Chem. Eng. Data 41, 865 (1996).
254 M. Keller, S. Schnabel, and A. Heintz, Fluid Phase Equilib. 110, 231 (1995).
255 Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 46 (5), 1188 (2001).
256 T. Treszczanowicz, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 33, 379 (1988).
257 T. Treszczanowicz, L. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 189, 255 (1991).
258 F. Kimura, P. J. D’Arcy, M. E. Sugamori, and G. C. Benson, Thermochim. Acta 64, 149 (1983).
348
259 B. Marongiu, S. Dernini, L. Lepori, E. Matteoli, and H. V. Kehiaian, J. Chem. Eng. Data 33, 118 (1988).
260 P. Vrbka, B. Hauge, L. Frydendal, and V. Dohnal, J. Chem. Eng. Data 47 (6), 1521 (2002).
261 M. K. Woycicka and W. M. Recko, Bull. Acad. Pol. Sci., Ser. Sci. Chim. 20, 783 (1972).
262 C. Klofutar, S. Paljk, and U. Domanska, Thermochim. Acta 158 (2), 301 (1990).
263 M. K. Woycicka and B. Kalinowska, Bull. Acad. Pol. Sci., Ser. Sci. Chim. 25, 639 (1977).
264 J. C. Young, J. S. Binford, and S. W. Campbell, Fluid Phase Equilib. 209, 255 (2003).
265 S. E. M. Haman, M. K. Kumaran, and G. C. Benson, J. Chem. Thermodyn. 16, 1013 (1984).
266 E. L. Matteoli, L.; Spanedda, A, Fluid Phase Equilib. 212, 41 (2003).
267 D.-Y. Peng, G. C. Benson, and B. C.-Y. Lu, J. Chem. Thermodyn. 30, 1141 (1998).
268 B. Marongiu and S. Porcedda, J. Chem. Eng. Data 35, 172 (1990).
269 A. Ben-Naim and Y. Marcus, J. Chem. Phys. 80, 4438 (1984).
270 E. Wilhelm, A. Inglese, A. Lainez, A. H. Roux, and J.-P. E. Grolier, Fluid Phase Equilib. 110, 299 (1995).
271 E. Wilhelm, A. Inglese, A. H. Roux, and J.-P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 260 (1991).
272 E. Wilhelm, A. Inglese, A. H. Roux, and J.-P. E. Grolier, Fluid Phase Equilib. 4, 49 (1987).
273 T. M. Letcher, R. C. Baxter, A. Bean, and J. D. Sewry, J. Chem. Thermodyn. 20, 581 (1988).
274 G. C. Benson, L. Wang, and C.-Y. Lu, Int. Data Ser., Sel. Data Mix., Ser. A, 101 (1989).
275 G. C. Benson, B. Luo, and B. C.-Y. Lu, Int. Data Ser., Sel. Data Mix., Ser. A, 182 (1988).
276 G. C. Benson, L. Wang, and B. C.-Y. Lu, Int. Data Ser., Sel. Data Mix., Ser. A, 301 (1990).
277 S. Zhu, S. Shen, G. C. Benson, and B. C.-Y. Lu, J. Chem. Thermodyn. 26, 415 (1994).
278 S. Zhu, S. Shen, G. C. Benson, and B. C.-Y. Lu, J. Chem. Thermodyn. 26, 35 (1994).
279 Z. Wang, G. C. Benson, and B. C.-Y. Lu, J. Chem. Eng. Data 47, 1030 (2002).
280 G. Li, Y. Liu, X. Sun, and F. Xue, Thermochim. Acta 247, 283 (1994).
281 J. Fernandez, I. Velasco, and S. Otin, Thermochim. Acta 143, 333 (1989).
349
282 A. Inglese and J.-P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 292 (1987).
283 E. Wilhelm, A. Inglese, A. H. Roux, and J.-P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 264 (1991).
284 A. S. Lekomtsev and I. V. Chernyshev, Russ. J. Gen. Chem. 72, 696 (2002).
285 T. Takigawa, M. Ohba, H. Ogawa, and S. Murakami, Fluid Phase Equilib. 204, 119 (2003).
286 P. P. S. Saluja, T. M. Young, R. F. Rodewald, F. H. Fuchs, D. Kohli, and R. Fuchs, J. Am. Chem. Soc. 99 (9), 2949 (1977).
287 K. N. Marsh, Int. Data Ser., Sel. Data Mix., Ser. A, 97 (1977).
288 D. M. Trampe and C. A. Eckert, J. Chem. Eng. Data 36 (1), 112 (1991).
289 E. Wilhelm and R. Battino, J. Chem. Thermodyn. 3, 379 (1971).
290 P. P. S. Saluja, L. A. Peacock, and R. Fuchs, J. Am. Chem. Soc. 101 (8), 1958 (1979).
291 R. S. Fuchs, P.S., Can. J. Chem. 54, 3857 (1976).
292 S. Zhu, S. Shen, G. C. Benson, and B. C.-Y. Lu, Thermochim. Acta 235, 161 (1994).
293 H. Ohji, A. Oskai, K. Tamura, S. Murakami, and H. Ogawa, J. Chem. Thermodyn. 30, 761 (1998).
294 C. Lafuente, P. Cea, M. Dominguez, F. M. Royo, and J. S. Urieta, J. Solution Chem. 30, 795 (2001).
295 T. Takigawa, H. Ogawa, K. Tamura, and S. Murakami, Fluid Phase Equilib. 136, 257 (1997).
296 T. Pfeffer, B. Loewen, and S. Schulz, Fluid Phase Equilib. 106 (1-2), 139 (1995).
297 M. Nishimoto, S. Tabata, K. Tamura, and S. Murakami, Fluid Phase Equilib. 136, 235 (1997).
298 H. T. Ohji, K., J. Chem. Thermodyn. 35, 1591 (2003).
299 P. L. Huyskens and L. Vanderheyden, Fluid Phase Equilib. 49, 271 (1989).
300 B. Marongiu, B. Pittau, and S. Porcedda, Thermochim. Acta 221, 143 (1993).
301 J. Fernandez, I. Velasco, and S. Otin, Int. Data Ser., Sel. Data Mix., Ser. A 1990, 164 (1990).
302 R. Fuchs, T. M. Young, and R. F. Rodewald, J. Amer. Chem. Soc. 96 (14), 4705 (1974).
303 K. V. N. S. Reddy, Y. V. L. R. Kumar, D. H. L. Prasad, and A. Krishnaiah, J. Chem. Eng. Data 51, 326 (2006).
350
304 H. Casas, L. Segade, S. García-Garabal, M. M. Piñeiro, C. Franjo, E. Jiménez, and M. I. P. Andrade, Fluid Phase Equilib. 182, 279 (2001).
305 B. N. Solomonov, I. S. Antipin, V. B. Novikov, and A. I. Konovalov, Russ. J. Gen. Chem. 52, 2364 (1982).
306 C. Menduina and M. D. Pena, Int. Data Ser., Sel. Data Mix., Ser. A, 59 (1976).
307 R. Fuchs, L. A. Peacock, and W. K. Stephenson, Can. J. Chem. 60, 1953 (1982).
308 Y. Miyano, A. Kimura, M. Kuroda, A. Matsushita, A. Yamasaki, Y. Yamaguchi, A. Yoshizawa, and Y. Tateishi, J. Chem. Eng. Data 52 (1), 291 (2007).
309 I. Gascon, B. Giner, S. Rodriguez, C. Lafuente, and F. M. Royo, Thermochim. Acta 439, 1 (2005).
310 H. Casas, J. J. d. Llano, S. García-Garabal, L. Segade, C. Franjo, E. Jiménez, and J. L. Legido, J. Chem. Eng. Data 48, 763 (2003).
311 P. Saris, J. B. Roesenholm, E. Sjoblom, and U. Henriksson, J. Phys. Chem. 90, 660 (1986).
312 U. Bhardwaj, K. C. Singh, and S. Maken, J. Chem. Thermodyn. 30, 253 (1998).
313 D. Missopolinou, I. Tsivintzelis, and C. Panayiotou, Fluid Phase Equilib. 245, 89 (2006).
314 M. M. Mato, M. Lopez, J. L. Legido, J. Salgado, P. V. Verdes, and M. I. P. Andrade, J. Chem. Eng. Data 48, 646 (2003).
315 E. Wilhelm and R. Battino, J. Chem. Thermodyn. 3, 761 (1971).
316 M. M. Mato, J. Balseiro, J. Salgado, E. Jiménez, J. L. Legido, M. M. Piñeiro, and M. I. P. Andrade, J. Chem. Eng. Data 47, 4 (2002).
317 J. Hu, K. Tamura, and S. Murakami, Fluid Phase Equilib. 131 (1-2), 197 (1997).
318 E. Wilhelm, W. Egger, M. Vencour, A. H. Roux, M. Polednicek, and J.-P. E. Grolier, J. Chem. Thermodyn. 30, 1509 (1998).
319 B. N. Solomonov, M. A. Varfolomeev, V. B. Novikov, A. E. Klimovitskii, and D. A. Faizullin, Russ. J. Phys. Chem. 79 (7), 1029 (2005).
320 K. N. Marsh, J. Chem. Thermodyn. 17 (1), 29 (1985).
321 J. P. R.-D. Grolier, G.; Kooner, Z. S.; Smith, J. F.; Hepler, L. G., J. Solution Chem. 16, 745 (1987).
322 J. P. Morel and N. Morel-Desrosiers, J. Solution Chem. 10 (7), 451 (1981).
351
323 Y. Miyano, T. Kobashi, H. Shinjo, S. Kumada, Y. Watanabe, W. Niya, and Y. Tateishi, J. Chem. Thermodyn. 38 (6), 724 (2006).
324 I. McStravick, K. Flynn, J. Lambert, N. Teahan, and W. E. Waghorne, J. Mol. Liq. 94 (2), 145 (2001).
325 G. C. Benson, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 78 (1973).
326 G. C. Benson, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 79 (1973).
327 C. Kracht, P. Ulbig, and S. Schulz, Thermochim. Acta 337 (1-2), 209 (1999).
328 V. P. Korolev, Russ. J. Appl. Chem. 79 (11), 1779 (2006).
329 R. Fuchs and R. F. Rodewald, J. Amer. Chem. Soc. 95 (18), 5897 (1973).
330 Y. A. Sivolozhskaya, N. L. Potkina, and V. P. Korolev, Russ. J. Gen. Chem. 72 (6), 864 (2002).
331 L. M. P. C. Albuquerque, M. L. C. J. Moita, A. M. N. Simoes, and R. M. C. Goncalves, Thermochim. Acta 275 (1), 67 (1996).
332 R. M. C. Goncalves, L. M. P. C. Albuquerque, A. M. N. Simoes, and J. J. M. Ramos, Thermochim. Acta 209, 63 (1992).
333 F. Martins, N. Nunes, M. L. Moita, and R. E. Leitao, Thermochim. Acta 444 (1), 83 (2006).
334 R. M. C. A. Goncalves, L.M.P.C.; Martins, F.E.L.; Simoes, A.M.N.; Moura Ramos, J.J., J. Phys. Org. Chem. 5, 93 (1992).
335 P. Haberfield, L. Clayman, and J. S. Cooper, J. Amer. Chem. Soc. 91 (3), 787 (1969).
336 A. Pineiro, A. Olvera, G. Garcia-Miaja, and M. Costas, J. Chem. Eng. Data 46 (5), 1274 (2001).
337 S. M. Cebreiro, M. Illobre, M. M. Mato, V. V. Verdes, J. L. Legido, and M. I. Paz Andrade, J. Therm. Anal. Calorim. 70 (1), 251 (2002).
338 K. Kammerer and R. N. Lichtenthaler, Thermochim. Acta 271, 49 (1996).
339 T. M. Letcher and U. P. Govender, J. Chem. Eng. Data 40 (5), 1097 (1995).
340 K. Tamura and M. M. H. Bhuiyan, J. Chem. Thermodyn. 35 (10), 1657 (2003).
341 C. Mintz, M. Clark, W. E. Acree, Jr., and M. H. Abraham, J. Chem. Inf. Model. 47 (1), 115 (2007).
342 V. P. Korolev and N. L. Potkina, Russ. J. Gen. Chem. 73 (5), 701 (2003).
352
343 M. Meade, K. Hickey, Y. McCarthy, W. E. Waghorne, M. R. Symons, and P. P. Rastogi, J. Chem. Soc., Faraday Trans. 93 (4), 563 (1997).
344 R. Garriga, J. Ilarraza, P. Perez, and M. Gracia, J. Chem. Thermodyn. 28 (2), 233 (1996).
345 Y. X. Wang, J. P. Chao, and M. Dai, Thermochim. Acta 169, 161 (1990).
346 G. H. Parsons and C. H. Rochester, J. Chem. Soc., Faraday Trans. 1 71 (5), 1069 (1975).
347 I. Uruska and M. Koschmidder, J. Chem. Soc., Perkin Trans. 2 (11), 1845 (1989).
348 C. H. Rochester and J. A. Waters, J. Chem. Soc., Faraday Trans. 1 78 (2), 631 (1982).
349 G. G. Siegel, P. L. Huyskens, and L. Vanderheyden, Ber. Bunsen-Ges. Phys. Chem. 94 (5), 549 (1990).
350 B. N. B. Solomonov, M.D.; Konovalov, A.I. , Russ. J. Gen. Chem. 57, 368 (1987).
351 T. Minamihonoki, H. Ogawa, H. Nomura, and S. Murakami, Thermochim. Acta 459 (1-2), 80 (2007).
352 O. M. Gaisinskaya, S. M. Rubinchik, and V. A. Sokolov, Zh. Neorg. Khim. 8 (12), 2814 (1963).
353 S. Taniewska-Osinska, L. Kaminska-Bartel, H. Piekarski, and T. M. Krygowski, Can. J. Chem. 59 (5), 817 (1981).
354 L. Yang, Q. Pei, T. Zhang, J. Zhang, and Y. Cao, Thermochim. Acta 463 (1-2), 13 (2007).
355 M. H. Abraham, R. J. Irving, and G. F. Johnston, J. Chem. Soc. A (2), 199 (1970).
356 C. B. Kretschmer and R. Wiebe, J. Am. Chem. Soc. 73, 3778 (1951).
357 D. V. Batov, Russ. Chem. Bull. 53 (8), 1640 (2004).
358 P.-J. Lien, H.-m. Lin, and M.-J. Lee, J. Chem. Eng. Data 48 (2), 359 (2003).
359 Z. Tong, G. C. Benson, and B. C. Y. Lu, Thermochim. Acta 288 (1-2), 29 (1996).
360 A. H. Roux, G. Roux-Desgranges, and J. P. E. Grolier, Fluid Phase Equilib. 89 (1), 57 (1993).
361 R. H. Stokes, M. Adamson, and A. Richards, J. Chem. Thermodyn. 11 (3), 303 (1979).
362 T. M. Letcher, J. Mercer-Chalmers, and A. K. Prasad, Thermochim. Acta 188 (1), 157 (1991).
363 G. C. Benson, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 82 (1973).
353
364 G. C. Benson, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 84 (1973).
365 I. Nagata, K. Tamura, and K. Miyai, Fluid Phase Equilib. 149 (1-2), 147 (1998).
366 A. Nagashima, S. Yoshii, H. Matsuda, and K. Ochi, J. Chem. Eng. Data 49 (2), 286 (2004).
367 S.-J. Park, K.-J. Han, and J. Gmehling, J. Chem. Eng. Data 52 (1), 230 (2007).
368 M. A. Villamanan, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 126 (1984).
369 M. A. Villamanan, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 119 (1984).
370 M. A. Villamanan, A. H. Roux, and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (2), 123 (1984).
371 M. M. Mato, M. Illobre, P. V. Verdes, and M. I. Paz Andrade, J. Therm. Anal. Calorim. 84 (1), 291 (2006).
372 G. Conti, P. Gianni, and E. Matteoli, Thermochim. Acta 247 (2), 293 (1994).
373 K. Tamura and M. M. H. Bhuiyan, J. Chem. Eng. Data 50 (1), 66 (2005).
374 M. M. H. Bhuiyan and K. Tamura, Thermochim. Acta 405 (1), 137 (2003).
375 D.-Y. Peng, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 43 (5), 880 (1998).
376 E. Romano, J. L. Trenzado, E. Gonzalez, J. S. Matos, L. Segade, and E. Jimenez, Fluid Phase Equilib. 211 (2), 219 (2003).
377 R. Francesconi and F. Comelli, J. Chem. Eng. Data 42 (1), 45 (1997).
378 I. Malijevska, G. Oswald, and A. Heintz, J. Chem. Thermodyn. 28 (11), 1247 (1996).
379 J. Chao and M. Dai, Thermochim. Acta 179, 257 (1991).
380 J. J. Moura Ramos, M. L. Stien, and J. Reisse, Chem. Phys. Lett. 42 (2), 373 (1976).
381 I. Nagata and M. Sano, Thermochim. Acta 200, 475 (1992).
382 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 173 (1995).
383 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 179 (1995).
384 J. Ortega, M. Chaar, and J. Placido, ELDATA: Int. Electron. J. Phys.-Chem. Data 1 (2), 139 (1995).
354
385 G. R. Behbehani, S. Ghammamy, and W. E. Waghorne, Thermochim. Acta 448 (1), 37 (2006).
386 R. Garriga, I. Putze, P. Perez, and M. Gracia, J. Chem. Thermodyn. 27 (5), 481 (1995).
387 R. M. C. Goncalves and A. M. N. Simoes, J. Solution Chem. 16 (1), 39 (1987).
388 K. Rubini, R. Francesconi, A. Bigi, and F. Comelli, Thermochim. Acta 452 (2), 124 (2007).
389 R. Parkash, S. C. Ahluwalia, and R. C. Paul, Monatsh. Chem. 115 (2), 135 (1984).
390 R. H. Stokes and H. T. French, J. Chem. Soc., Faraday Trans. 1 76 (3), 537 (1980).
391 J. R. Morton, III, J. Chem. Eng. Data 4, 251 (1959).
392 M. Takenouchi, R. Kato, and H. Nishiumi, J. Chem. Eng. Data 46 (3), 746 (2001).
393 O. Rogne, J. Chem. Soc., Perkin Trans. 2 (13), 1760 (1973).
394 G. Conti, P. Gianni, L. Lepori, and E. Matteoli, Fluid Phase Equilib. 105 (1), 93 (1995).
395 J.-P. Pokki, K. Rehak, Y. Kim, J. Matous, and J. Aittamaa, J. Chem. Eng. Data 48 (1), 75 (2003).
396 J. Mokrzan, Acta Univ. Lodz., Folia Chim. 4, 71 (1985).
397 J. Catalan, A. Couto, J. Gomez, J. L. Saiz, and J. Laynez, J. Chem. Soc., Perkin Trans. 2 (7), 1181 (1992).
398 J. Pardo, M. C. Lopez, J. Santafe, F. M. Royo, and J. S. Urieta, Fluid Phase Equilib. 109 (1), 29 (1995).
399 Y. Miyano, J. Chem. Eng. Data 49 (5), 1285 (2004).
400 D. V. Batov, N. A. Potkina, and V. P. Korolev, Russ. J. Gen. Chem. 68 (10), 1558 (1998).
401 V. C. Rose and T. S. Storvick, J. Chem. Eng. Data 11 (2), 143 (1966).
402 R. Alonso, R. Guerrero, and J. A. Corrales, J. Chem. Thermodyn. 19 (12), 1271 (1987).
403 I. Landau, A. J. Belfer, and D. C. Locke, Ind. Eng. Chem. Res. 30 (8), 1900 (1991).
404 G. C. Benson, Int. Data Ser., Sel. Data Mix., Ser. A, 100 (1975).
405 G. C. Benson, Int. Data Ser., Sel. Data Mix., Ser. A, 101 (1975).
406 C. Valles, E. Perez, A. M. Mainar, J. Santafe, and M. Dominguez, J. Chem. Eng. Data 51 (3), 1105 (2006).
355
407 I. Gascon, H. Artigas, S. Martin, P. Cea, and C. Lafuente, J. Chem. Thermodyn. 34 (9), 1351 (2002).
408 M. E. F. De Ruiz Holgado, J. Fernandez, M. I. Paz Andrade, and E. L. Arancibia, Can. J. Chem. 80 (5), 462 (2002).
409 R. Garriga, S. Martinez, P. Perez, and M. Gracia, J. Chem. Eng. Data 47 (2), 322 (2002).
410 C. Lafuente, H. Artigas, M. C. Lopez, F. M. Royo, and J. S. Urieta, Phys. Chem. Liq. 39 (6), 665 (2001).
411 P. Santana, J. Balseiro, J. Salgado, E. Jimenez, J. L. Legido, E. Carballo, and M. I. Paz Andrade, J. Chem. Eng. Data 44 (6), 1195 (1999).
412 R. Francesconi and F. Comelli, J. Chem. Eng. Data 44 (1), 44 (1999).
413 F. Comelli, R. Francesconi, and C. Castellari, J. Chem. Eng. Data 44 (4), 739 (1999).
414 V. P. Korolev, N. L. Smirnova, and D. V. Batov, Russ. J. Appl. Chem. 79 (2), 213 (2006).
415 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 156 (1995).
416 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 162 (1995).
417 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 168 (1995).
418 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 174 (1995).
419 J. Ortega, Int. DATA Ser., Sel. Data Mixtures, Ser. A 23 (3), 180 (1995).
420 I. Nagata and K. Tamura, J. Chem. Thermodyn. 20 (9), 1101 (1988).
421 J. Mokrzan, Acta Univ. Lodz., Folia Chim. 1, 65 (1982).
422 E. Langa, A. M. Mainar, J. I. Pardo, and J. S. Urieta, J. Chem. Eng. Data 51 (2), 392 (2006).
423 J. Ortega, M. Vidal, F. J. Toledo-Marante, and J. Placido, J. Chem. Thermodyn. 31, 1025 (1999).
424 G. L. Pollack and J. F. Himm, J. Chem. Phys. 77, 3221 (1982).
425 J. Ortega and J. Placido, J. Physico-Chem.Data 1, 69 (1995).
426 I. A. McLure and A. Trejo Rodriguez, J. Chem. Thermodyn. 14 (5), 439 (1982).
427 O. Urdaneta, S. Hamam, Y. P. Handa, and G. C. Benson, J. Chem. Thermodyn. 11, 851 (1979).
428 J. Placido, J. Ortega, and F. J. Toledo, J. Chem. Thermodyn. 30, 805 (1998).
356
429 J. Gmehling, J. Chem. Eng. Data 38, 143 (1993).
430 S. E. M. Hamam and G. C. Benson, J. Chem. Eng. Data 31, 45 (1986).
431 K. N. Marsh, J. B. Ott, and A. E. Richards, J. Chem. Thermodyn. 12 (9), 897 (1980).
432 B. N. Solomonov, I. S. Antipin, V. V. Gorbachuk, and A. I. Konovalov, Dokl. Akad. Nauk SSSR 243 (6), 1499 (1978).
433 D.-Y. Peng, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 32 (4), 539 (2000).
434 S. E. M. Hamam, M. K. Kumaran, D. Zhang, and G. C. Benson, J. Chem. Eng. Data 30 (2), 222 (1985).
435 E. Wilhelm, A. Inglese, J. P. E. Grolier, and H. V. Kehiaian, Thermochim. Acta 31 (1), 85 (1979).
436 E. Wilhelm, Ber. Bunsenges. Phys. Chem. 81 (11), 1150 (1977).
437 V. Dohnal and P. Vrbka, Fluid Phase Equilib. 1331, 73 (1997).
438 M. K. Kumaran, C. J. Halpin, and G. C. Benson, J. Chem. Thermodyn. 15 (3), 249 (1983).
439 R. M. Guidry and R. S. Drago, J. Phys. Chem. 78 (4), 454 (1974).
440 I. Ferino, B. Marongiu, V. Solinas, and S. Torrazza, Thermochim. Acta 57 (2), 147 (1982).
441 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 18 (1992).
442 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 25 (1992).
443 B. N. Solomonov, M. D. Borisover, and A. I. Konovalov, Russ. J. Gen. Chem. 56, 1 (1985).
444 G. C. Benson and Y. P. Handa, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 72 (1980).
445 G. C. Benson and Y. P. Handa, Int. DATA Ser., Sel. Data Mixtures, Ser. A (1), 77 (1980).
446 G. C. Benson, Int. DATA Ser., Sel. Data Mixtures, Ser. A (4), 296 (1990).
447 M. M. Mato, S. M. Cebreiro, P. V. Verdes, J. L. Legido, and M. I. Paz Andrade, J. Therm. Anal. Calorim. 80 (2), 303 (2005).
448 C. Alonso, C. R. Chamorro, J. J. Segovia, M. C. Martin, E. A. Montero, and M. A. Villamanan, Fluid Phase Equilib. 217 (2), 145 (2004).
449 M. D. Guillen and C. Gutierrez Losa, J. Chem. Thermodyn. 10 (6), 567 (1978).
357
450 Z. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 48 (1), 190 (2003).
451 T. Treszczanowicz, G. C. Benson, and B. C. Y. Lu, J. Chem. Eng. Data 33 (3), 379 (1988).
452 H. Casas, L. Segade, C. Franjo, E. Jimenez, and M. I. Paz Andrade, J. Chem. Eng. Data 45 (3), 445 (2000).
453 M. Kwaterski, E. N. Rezanova, and R. N. Lichtenthaler, Fluid Phase Equilib. 237 (1-2), 170 (2005).
454 J. Fernandez, I. Velasco, and S. Otin, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 206 (1987).
455 J. Fernandez, I. Velasco, and S. Otin, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 207 (1987).
456 J. Fernandez, I. Velasco, and S. Otin, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 208 (1987).
457 J. Fernandez, I. Velasco, and S. Otin, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 209 (1987).
458 J. Fernandez, I. Velasco, and S. Otin, Int. DATA Ser., Sel. Data Mixtures, Ser. A (3), 211 (1987).
459 E. Sapei, A. Zaytseva, P. Uusi-Kyyny, K. I. Keskinen, and J. Aittamaa, J. Chem. Eng. Data 52 (2), 571 (2007).
460 B. R. Sharma, G. S. Pundeer, and P. P. Singh, Thermochim. Acta 11 (2), 105 (1975).
461 A. Inglese and J. P. E. Grolier, Int. DATA Ser., Sel. Data Mixtures, Ser. A (4), 299 (1987).
462 J. P. E. Grolier, O. Kiyohara, and G. C. Benson, J. Chem. Thermodyn. 9 (7), 697 (1977).
463 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 12 (1992).
464 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 19 (1992).
465 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 26 (1992).
466 W. Hayduk, E. B. Walter, and P. Simpson, J. Chem. Eng. Data 17, 59 (1972).
467 M. K. Kumaran and G. C. Benson, J. Chem. Thermodyn. 18, 993 (1986).
468 K. Fukuchi, K. Miyoshi, and Y. Arai, Fluid Phase Equilib. 136, 135 (1997).
469 L. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 20, 975 (1988).
358
470 E. Jimenez, C. Franjo, L. Segade, J. L. Legido, and M. I. Paz Andrade, Fluid Phase Equilib. 133, 179 (1997).
471 L. Wang, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 22, 173 (1990).
472 I. Castro, M. Pintos, A. Amigo, R. Bravo, and M. I. Paz Andrade, J. Chem. Thermodyn. 26, 29 (1994).
473 Z. Hamoudi, F. B. Belaribi, A. Ait-Kaci, and G. Boukais-Belaribi, Fluid Phase Equilib. 244, 62 (2006).
474 H. Nakai, H. Soejima, K. Tamura, H. Ogawa, S. Murakami, and Y. Toshiyasu, Thermochim. Acta 183, 15 (1991).
475 P. Vrbka, V. Dohnal, and W. Arlt, J. Chem. Eng. Data 49, 867 (2004).
476 U. Domanska, K. Domanski, C. Klofutar, and S. Paljk, Thermochim. Acta 164, 227 (1990).
477 Z. Wang, G. C. Benson, and B. C.-Y. Lu, J. Chem. Eng. Data 49, 311 (2004).
478 A. Inglese and J. P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 288 (1987).
479 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 13 (1992).
480 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 20 (1992).
481 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 27 (1992).
482 E. Wilhelm, A. Inglese, and J. P. E. Grolier, J. Chem. Eng. Data 28, 202 (1983).
483 J. Ortega, F. Espiau, and F. J. Toledo, J. Chem. Thermodyn. 36, 193 (2004).
484 J. Ortega, J. S. Matos, and J. A. Pena, Thermochim. Acta 160, 337 (1990).
485 M. López, M. I. P. Andrade, J. Peleteiro, J. L. Legido, L. Romaní, and E. P. Martell, Thermochim. Acta 211, 33 (1992).
486 B. Luo, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 20, 267 (1988).
487 G. C. Benson, B. Luo, and B. C. Y. Lu, Can. J. Chem. 66, 531 (1988).
488 Z. Wang, Y. Horikawa, G. C. Benson, and B. C.-Y. Lu, J. Solution Chem. 30, 401 (2001).
489 B. Luo, G. C. Benson, and B. C. Y. Lu, J. Chem. Thermodyn. 19, 785 (1987).
490 A. Inglese and J. P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 289 (1987).
491 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 14 (1992).
359
492 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 21 (1992).
493 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 28 (1992).
494 A. Inglese and J. P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 290 (1987).
495 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 22 (1992).
496 R. Kechavarz, J. P. Dubes, and H. Tachoire, Int. Data Ser., Sel. Data Mix., Ser. A, 29 (1992).
497 A. Inglese and J. P. E. Grolier, Int. Data Ser., Sel. Data Mix., Ser. A, 291 (1987).
498 W. M. S. Melzer, F.; Knapp, H.;, Fluid Phase Equilib. 49, 167 (1989).
499 V. N. Vandyshev, Zhur. Obshch. Khim. 66, 35 (1996).
500 M. R. Bendova, K.; Matous, J.;Novak, J.P., J. Chem. Eng. Data (49), 1318 (2004).
501 H. P. Iloukhani, J.B.; Saboury, A.A., J. Chem. Eng. Data 45, 1016 (2000).
502 M. Jozwiak, J. Chem. Thermodyn. 39, 433 (2007).
503 P. R. Venkatesu, R.S.; Rao, M.V.P.; Prasad H.L., J. Chem. Eng. Data 45, 515 (2000).
504 A. V. B. Kustov, A.V.; Antonova, O.A.; Korolev, B.P., Russ. J. Gen. Chem. 72, 918 (2002).
505 V. I. K. Smirnov, G.A., Zhur. Khim. Termodin. Termokhim 2, 5 (1993).
506 E. Brunner, J. Chem. Eng. Data 30, 269 (1985).
507 M. V. Kulikov, Russ. Chem. Bull. 46, 274 (1997).
508 U. S. Bhardwaj, K.C.; Maken, S., J. Chem. Thermodyn. 30, 253 (1998).
509 B. N. B. Solomonov, M.D.; Konovalov, A.I., Zhur. Obshch. Khim 57, 423 (1987).
510 V. T. P. Lam, H.D.; Murakami, S.; Benson, G.C., J. Chem. Eng. Data 18, 63 (1973).
511 D. V. K. Batov, V.P., Russian Chemical Bulletin 46 (10), 1716 (1997).
512 D. V. A. Batov, O.A.; Svishchev, A.F.; Korolev, V.P., Zhur. Obshch. Khim. 66, 1773 (1996).
513 B. A. Giner, H.; Carrion, A.; Lafuente, C.; Royo, F.M., J. Mol. Liq. 108, 303 (2003).
514 J. E. Ortega, F.; Sabater, G.; Postigo, M., J. Chem. Eng. Data 51, 730 (2006).
515 J. E. Ortega, F.; Postigo, M., J. Chem. Eng. Data 50, 444 (2005).
516 J. E. Ortega, F.; Postigo, M., J. Chem. Eng. Data 48, 916 (2003).
360
517 J. E. Ortega, F.; Postigo, M., J. Chem. Eng. Data 49, 1602 (2004).
518 R. S. Garriga, F.; Perez, P.; Gracia, M., Fluid Phase Equilib. 130, 195 (1997).
519 E. M. Langa, A.M.; Pardo, J.I.; Urieta, J.S., J. Chem. Eng. Data 52, 2182 (2007).
520 B. N. Strothmann, O.; Fischer, K.; Gmehling, J., J. Chem. Eng. Data 44, 379 (1999).
521 A. N. G. Gaivoronskii, V.A., Russ. J. Appl. Chem. 78, 404 (2005).
522 H. Kalali, F. Kohler, and P. Svejda, J. Chem. Eng. Data 36, 326 (1991).
523 A. C. Galvao and A. Z. Francesconi, Thermochim. Acta 450, 81 (2006).
524 R. F. Checoni, L. D’Agostini, and A.Z. Francesconi, J. Chem. Thermodyn. 40, 759 (2008).
525 I. Nagata and K. Tamura, J. Chem. Thermodyn. 21, 955 (1989).
526 S. D. Cave, R. D. Santis, and L. Marrelli, J. Chem. Eng. Data, 70 (1980).
527 K. Tamura, M.Watanabe, S. Tsuchiya, and T. Yamada, J. Chem. Thermodyn. 33, 95 (2001).
528 R. F. Checoni and A. Z. Francesconi, J. Therm. Anal. Calorim. 80, 295 (2005).
529 I. Nagata, K. Tamura, and F. Nischikawa, J. Chem. Thermodyn. 31, 181 (1999).
530 A. D. Tripathi, J. Chem. Eng. Data 40, 1262 (1995).
531 R. C. Guedes, K. Coutinho, B. J. C. Cabral, S. Canuto, C. F. Correia, R. M. B. d. Santos, and J. A. M. Simoes, J. Phys. Chem. 106, 9197 (2003).
532 L. Audergon, F. Emmenegger, M. Piccand, H. Piekarski, and J. Mokrzan, Polyhedron 20, 387 (2001).
533 V. B. Novikov, A.A. Stolov, V. V. Gorbatchuk, and B. N. Solomonov, J. Phys. Org. Chem. 11, 283 (1998).
534 J. Burgess and R. D. Peacock, J. Chem. Soc., Dalton Trans., 1565 (1975).
535 N. L. Potkina and V. P. Korolev, Russ. J. Gen. Chem. 71, 1682 (2001).
536 D. V. Batov, A. V. Kustov, and V. P. Korolev, Russ. J. Gen. Chem. 74, 663 (2004).
537 I. Nagata, K. Tamura, H. Kataoka, and A. Ksiazczak, J. Chem. Eng. Data 41, 593 (1996).
538 M. Jozwiak, Thermochim. Acta 417, 27 (2004).
539 I. Nagata, K. Tamura, and K. Miyai, J. Chem. Eng. Data 41, 1350 (1996).
361
540 J. Reisse, M. Claessens, O. Fabre, G. Michaux, M. L. Stien, and D. Zimmermann, Bull. Soc. Chim. Belges 92, 819 (1983).
541 M. L. Sagu, J. Swarup, K. M. Sharan, and K. K. Bhattacharyya, J. Chem. Eng. Data 28, 81 (1983).
542 A. N. Gaivoronskii and V. A. Granzhan, Russ. J. Appl. Chem. 78, 404 (2005).
543 R. Francesconi and F. Comelli, Thermochim. Acta 264, 95 (1995).
544 R. Francesconi and F. Comelli, Thermochim. Acta 216, 35 (1993).
545 F. Comelli, R. Francesconi, and C. Castellari, J. Chem. Eng. Data 38 (224-226) (1993).
546 I. Nagata, K. Tamura, and S. Tokuriki, Thermochim. Acta 47, 315 (1981).
547 I. Nagata and K. Tamura, J. Chem. Thermodyn. 29, 31 (1997).