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Phase Behavior in Binary

And Multicomponent Systems

At Elevated Pressures:

n-Pentane and

Methane-n-Pentane

NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards ' was established by an act of Congress March 3, 1901. Today,

in addition to serving as the Nation’s central measurement laboratory, the Bureau is a principal

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UNITED STATES DEPARTMENT OF COMMERCE

Maurice H. Stans, Secretary

NATIONAL BUREAU OF STANDARDS • Lewis M. Branscomb, Director

Phase Behavior in Binary and Multicomponent SystemsAt Elevated Pressures: n-Pentane and Methane-n -Pentane

Virginia M. Berry and B. H. Sage

Chemical Engineering Laboratory

California Institute of Technology

Pasadena, California 91109

NSRDS-NBS 32

Nat. Stand. Ref. Data Ser., Nat Bur. Stand. (U.S.), 32, 73 pages (June 1970)

CODEN: NSRDA

Issued June 1970

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C. 20402 (Order by SD Catalog No. C 13.48:32), Price 70 cent9

NATIONAL BUREAU Of STANDARDS

JUL 2 3 1970

no. /fln

/ 70Cop

.

© 1970 by the Secretary of Commerce on behalf of the United States Government.

Library of Congress Catalog Card Number: 78-603442

Foreword

The National Standard Reference Data System provides effective access to the quantitative

data of physical science, critically evaluated and compiled for convenience, and readily accessible

through a variety of distribution channels. The System was established in 1963 by action of the

President’s Office of Science and Technology and the Federal Council for Science and Technology,

with responsibility to administer it assigned to the National Bureau of Standards.

The System now comprises a complex of data centers and other activities, carried on in

academic institutions and other laboratories both in and out of government. The independent

operational status of existing critical data projects is maintained and encouraged. Data centers

that are components of the NSRDS produce compilations of critically evaluated data, critical

reviews of the state of quantitative knowledge in specialized areas, and computations of useful

functions derived from standard reference data. In addition, the centers and projects establish

criteria for evaluation and compilation of data and make recommendations on needed improvements

in experimental techniques. They are normally closely associated with active research in the

relevant field.

The technical scope of the NSRDS is indicated by the principal categories of data compilation

projects now active or being planned: nuclear properties, atomic and molecular properties, solid

state properties, thermodynamic and transport properties, chemical kinetics, and colloid and

surface properties.

The NSRDS receives advice and planning assistance from the National Research Council of

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international collaboration. Advisory Panels, each concerned with a single technical area, meet

regularly to examine major portions of the program, assign relative priorities, and identify specific

key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor

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existing data resources as a basis for recommending one or more data compilation activities. This

assembly of advisory services contributes greatly to the guidance of NSRDS activities.

The NSRDS-NBS series of publications is intended primarily to include evaluated reference

data and critical reviews of long-term interest to the scientific and technical community.

Lewis M. Branscomb, Director

ill

Preface

In 1966 support was received from the Office of Standard Reference Data of the National

Bureau of Standards for a program of data review undertaken in the Chemical Engineering Labora-

tory of the California Institute of Technology. Emphasis was directed to the volumetric and phase

behavior of the coexisting phases of pure paraffin hydrocarbons and their binary mixtures. Aneffort was made to provide conservative estimates of the accuracy in contradistinction to the

precision of the tabulations presented. As a result of the withdrawal of B. H. Sage from active

research on July 1, 1969, the program has been limited to work completed at that time. The current

presentation covers a review of the methods employed, the volumetric and phase behavior of

n-pentane, and the volumetric and phase behavior in the methane-n-pentane system.

A number of the members of the staff of the Chemical Engineering Laboratory contributed

to the work and among these should be mentioned Donna Johnson, who aided in the tabulation of

the results and the preparation of the manuscript, and June Gray, who assisted the authors in the

preparation of the numerous diagrams associated with this activity.

IV

Contents

Page

Foreword Ill

Preface IV

List of figures VList of tables VNomenclature and conversion factors., VII, VIII

1. Introduction 1

1.1. Measures of uncertainty 1

1.2. Residual methods 2

1.3. Dimensions and units 3

2. The n-pentane system 13

3. The methane-n-pentane system 22

4. References 66

List of Figures

Figure page

1.1. Variation in dew point volume of propane with temperature 4

1.2. Residual dew point volume of propane 5

1.3. Vapor pressure of propane 6

1.4. Vapor pressure-temperature diagram 7

2.1. Residual vapor pressure of re-pentane 15

2.2. Bubble point volume of n-pentane 16

2.3. Residual volume at dew point for re-pentane 17

3.1. Pressure-temperature diagram for methane-n-pentane system 24

3.2. Effect of pressure upon equilibrium ratio for methane-n-pentane system 25

3.3. Pressure-composition diagram for methane-n-pentane system 26

3.4. Pressure-temperature diagram for methane-n-pentane system, engineering units 27

3.5. Effect of pressure upon equilibirum ratio for methane-n-pentane system, engineering units 28

3.6. Pressure-composition diagram for methane-n-pentane system, engineering units 29

List of Tables

Table

1.1. Experimental values of dew point volume for propane

1.2. Residual specific volume of dew point gas for propane

1.3. Deviations of several sets of experimental data for specific volume of dew point gas for propane

1.4. Experimental values of vapor pressure for propane

1.5. Deviations in experimental values of vapor pressure for propane

2.1. Critical properties of n-pentane

2.2. Properties of the coexisting phases for re-pentane

2.3. Agreement of interpolated and experimental data for re-pentane

2.4. Critical properties of the n-pentane system, engineering units

2.5. Properties of the coexisting phases for re-pentane, engineering units

2.6. Agreement of interpolated and experimental data for re-pentane, engineering units

2.7. Accuracy of experimental background for re-pentane

2.8. Reviews of properties of the paraffin hydrocarbons

3.1. Properties of the coexisting phases in the methane-re-pentane system

3.2. Agreement of interpolated and experimental data for the methane-re-pentane system

3.3. Unique states for the methane-re-pentane system

3.4. Properties of the coexisting phases in the methane-n-pentane system, engineering units

3.5. Unique states for the methane-n-pentane system, engineering units

3.6. Agreement of interpolated and experimental data for the methane-re-pentane system, engineering units

3.7. Accuracy of experimental background for the methane-n-pentane system

Page

8

9

10

11

12

17

18

19

19

20

21

21

22

30

46

46

47

65

65

6t>

V

,

CO,

C«

Nomenclature

B, C, D Coefficients

Variable

Molal equilibrium ratio, K— y\x

Number of points

Pressure, atm or psia

Residual pressure, atm or psia

Average deviation defined by

2 (Cm-Cm )IN1

Absolute deviation defined by

^ (GeXp— Gsm )IN

1

Absolute temperature, K or °RTemperature, °C or °F

Specific volume, liters/kg or ft 3/lb

Molal volume, liters/kg-mol or ft3/lb-mol

V Residual volume, liters/kg

X Mole fraction liquid

y. Mole fraction gas

a Degrees of freedomcr Standard error of estimate

{ X (^exp— Csm )

2

1

/(/v-

Subscripts

exp Experimentalgr Graphical

k Component k

j Component jr Referencesm Smooth or predicted

Constants and Conversion Factors

Molecular Weight3

Methane 16.04303

Propane 44.09721n-Pentane 72.15139

Physical Constants 15

Force

1 pound (lb) avoirdupois

Length1 U.S. inch (in)

Volume1 liter (1)

Acceleration Due to Gravity— Standard

gc

Pressure1 standard atmosphere (atm)

Temperature1 degree centigrade (° C)

TICTo F

= 453.59237 grams (g)

= 2.54 centimeters (cm)

= 1000 cm 3

= 980.665 cm/sec2

= 32.1740 ft/sec 2

= 1,013,250 dyne/cm2 = 101,325 N/m 2

= 1.8 degrees Fahrenheit (°F)= 273.16 degrees Kelvin (°K)= 459.688 degrees Rankine (° R)

a Based on a Report of the International Commission on Atomic Weights, J. Am Chem. Soc. 84, 4175-97 (1962).b Wilhoit, Randolph C. and Hathaway, Wayne, Tables of Conversion Factors Based on Accepted Constants as of 1965. Am Petroleum Inst., Project 44, Chemical Thermodynamic

Properties Center, Texas A & M Univ., College Station, Texas, Nov. 1965.

VII

Conversion Factors 3

Length

Units cm m in ft

1 cm 1 0.01 0.3937008 0.03280401 m 100 1 39.37008 3.2808401 in 2.540000 0.02540000 1 0.083333331 ft 30.48000 0.3048000 12.0000 1

Area

Units cm 2 m2 in 2ft

2

1 cm21 io-4 0.1550003 1.076391 x 10-3

1 m 2 104 1 1550.0003 10.76391

1 in2 6.451600 6.451600 X 10-41 6.944444 X IO*3

1 ft 2 929.0304 0.09290304 144.0000 1

Volume

Units cm 3 in3 ft 3 liter

1 cm 3 1 0.06102374 3.531467 x 10-5 1.000 x io-3

1 in3 16.38706 1 5.787037 x 10~4 1.638661 X 10-2

1 ft3 28316.85 1728.000 1 28.316851 liter 1000.000 61.02375 0.0351467 1

Weight

Units g lb

1 g 1 2.204623 X IO-3

1 lb 453.5924 1

Specific Weight

Units g/cm 3 g/ml lb/ft 3

1 g/cm31 1 62.42795

1 g/ml 1 1 62.427951 lb/ft 3 0.01601847 0.01601847 1

Pressure

Units atm kg/cm 2 lb/in 2 Newton/m2

1 atm 1 1.033227 14.69595 1.013250 X 105

1 kg/cm 2 0.9678411 1 14.22334 9806.6501 lb/in2 0.06804596 0.07030696 1 6894.757

Newtons/

m

2 9.869233 X 10-6 1.019716 X 10-5 14.50377 X 10-51

a See footnote b on page VII.

VIII

Phase Behavior in Binary and Multicomponent SystemsAt Elevated Pressures: n-Pentane and Methane-n-Pentane

Virginia M. Berry and B. H. Sage

This paper, which is concerned with the critical evaluation of data on the phase behavior of binary

systems, consists of three parts. In the first part the rationale of the evaluation process used is dis-

cussed, in the second the behavior of n-pentane, and in the third the behavior of the system methane-n-pentane.

The properties of n-pentane considered are the critical constants and the vapor pressures anddensities of the saturated coexistent phases as functions of temperature. For the methane-n-pentanesystem the compositions and densities of the coexisting phases are given as functions of temperatureand total pressure. Data for the unique states of the two-component system are also presented.

Discussions are given of the reliability of the selected values and of the differences between the

selected values and various measured values.

Key words: Evaluated data; liquid-vapor equilibria; methane-n-pentane system; n-pentane;

thermodynamics.

1. Introduction

The critical review of experimental data in the

field of volumetric and phase behavior of pure

substances and mixtures involves, at best, certain

elements of judgment, particularly in regard to the

actual in contradistinction to the stated uncer-

tainties of measurement. Probably historical evi-

dence is the best evidence of the difference be-

tween the stated and actual uncertainties associated

with experimental observations. Often precision is

confused with accuracy even though the author

has made a conscientious effort to appraise the

uncertainties in each of the primary experimental

variables involved. In this critical review and com-pilation, an effort was made to apply realistic andconservative uncertainties to the tabulated values

which, to many readers, may seem unusually large

when the claims of the investigators are considered.

In the authors’ experience, the accepted intensive

properties of materials continue to change with the

passage of time by amounts which are many times

the original estimated uncertainties involved in the

experimental work. An example of such a situation

is the thermodynamic properties of water. Accuratevalues of the thermodynamic properties of waterin both the liquid and gas phase are of importancein the design of large steam turbines. Yet, within

the last 10 years, differences in the properties of

water employed in this country and in Russia re-

sulted in significant differences in the prediction

of the efficiency of large steam turbines manu-factured in the two countries. Even with unusualinternational cooperation in this matter [l] 1 in-

dividual nations still prepare their own tabulations

1 Figures in brackets indicate the literature references at the end of this paper.

of the thermodynamic properties of water whichdiffer somewhat in detail.

On the basis of such experience it is hoped that

the reader will understand the conservatism

employed in assigning rather large measures of

uncertainty to the individual experimental data as

compared to that which has often been suggested

by the original experimental investigator. In addi-

tion, the uncertainties assigned to the recorded

values have been set forth on what is hoped to bea realistic basis. It will remain for investigators

of the future to ascertain whether the somewhatsubjective assignment of uncertainty in connection

with the recorded values has been correct.

1.1. Measures of Uncertainty

In the following section a short discussion of the

measures of uncertainty employed is presented.No attempt has been made to justify the choice of

such measures but only to indicate in a specific

manner what was involved. The use of an exampleis perhaps the best method to illustrate the fashion

in which the several measures of uncertainty canbe applied. In figure 1.1 2 is portrayed the variation

in the specific volume with temperature of the dewpoint gas for propane. In addition, the various ex-

perimental values upon which the critically chosenfine was evaluated have been presented. There is

set forth in table 1.1 the several results obtained bydifferent experimental methods. The points shownin figure 1.1 are presented in the table together with

2 Figures and tables will be found at the end of the section to which they pertain.

372-701 0 - 70 -2

1

an estimate of the measure of uncertainty of eachset of experimental data.

In the example, presented in table 1.1, it has beenassumed that all of the uncertainty is in the specific

volume and none in the temperature. The curvewas established by direct graphical inspection of

the data coupled with the application of “least

squares” methods of analysis to a particular

polynomial which will be presented later in the

discussion.

The greatest weight was given to the experimentaldata which was assigned the smallest uncertainty

in table 1.1. Usually there is not as much experi-

mental data as is indicated in figure 1.1 and the

choice of the smooth functional relation becomes,in part, a matter of judgment. The average deviationwith regard and without regard to sign was estab-

lished by use of the following expressions:

s = f(G-Gsm )IN, (1.1)

variable undergoes marked change from a low tem-

perature to temperatures approaching that of the

critical state. In some circumstances it is desirable

to treat only portions of the range of the independentvariables as an independent statistical population.

This is particularly true when the data from different

investigators do not extend over the entire range of

the independent variable as is the case in figure 1.1.

In many ways it would be advantageous to consider

the normal distance of the curve from the experi-

mental points in question. However, this introduces

significant complexities in the evaluation of eachmeasure of uncertainty and for that reason has not

been adopted in the current tabulations.

1.2. Residual Methods

In many situations the combination of analytical

and graphical techniques is useful. For example,it is possible to approximate the smooth curveshown in figure 1.1 by a polynomial of the following

form:

s'=2\G-Gm \IN. (1.2)

1

For the most part, the value of the average deviation

with regard to sign should be small and deviate

from zero primarily as a result of intentional bias

in locating the critically chosen value in order to

favor the more accurate data. This is illustrated bythe values of the average deviation with regard to

sign of the points shown in figure 1.1 which havebeen tabulated in table 1.1 for each of the several

investigators.

As a second measure of uncertainty, the average

deviation without regard to sign was established

from eq (1.2) and is one useful measure of the

variability of the data from the smooth curve shown.The results of applying eq (1.2) to the experimental

information presented in figure 1.1 are also recorded

in a portion of table 1.1. The average difference be-

tween deviations with regard to and without

regard to sign is evident.

For many purposes, the standard error of estimate

is a useful means of indicating the difference be-

tween a chosen continuous function such as the

curve in figure 1.1 and the experimental points

involved. This quantity may be defined by eq (1.3):

a 2<c-csmvi- l

(N-a)}1'2 (1.3)

The quantity a represents the degrees of freedomassociated with the system. In the case of a puresubstance it is one since the temperature fully

establishes all of the intensive properties of the twocoexisting phases. The values of the standard error

of estimate as established from eq (1.3) for eachof the experimental investigations are recordedin a portion of table 1.1.

All of these measures of uncertainty suffer fromthe fact that the magnitude of the dependent

V=AT+BT2 + CT3 + DT4= 24.967T- 0.21184T2

+ 0.60276 X 10-3P - 0.57430 X HU6!74

(1.4)

In this instance, the coefficients have been indicated

in both symbolic and numerical form. There is

shown in figure 1.2 the smooth curve of figure 1.1

and the graphical representation of eq (1.4). Upona markedly enlarged scale the difference betweenthe analytical and graphical representation has beendepicted in a portion of figure 1.2. Such a difference

is called the residual specific volume of the dewpoint which would be defined by:

V=V-Vr (1.5)

The value of the residual specific volume of the

dew-point gas may be evaluated for each of the ex-

perimental points by application of eq (1.5). Thecorresponding values of the analytical reference

values established from eq (1.4) for the temperatureof measurement as well as the values of the residual

specific volume of the dew-point gas are recordedin a part of table 1.2 for each set of experimentaldata. It is apparent from a review of table 1.2 that

the residual specific volumes do not undergo changesin order of magnitude over the entire range of

temperature.

Smooth values of the residual specific volume for

each of the experimental points also are recorded in

table 1.2. It is evident that the graphical precision

realized by use of the residual techniques is muchgreater than that feasible from direct plotting of the

data. Attempts to increase the scale of the graphical

operations invariably results in such wide spacing

of the experimental points as to render any markedimprovement in the precision of the graphical

operation difficult.

In table 1.3 are shown the values obtained for

the average deviation with regard to sign, the

2

average deviation without regard to sign, and the

standard error of estimate as determined from large

plots, one such as is shown in figure 1.1 and a similar

sized plot involving the residual data shown in figure

1.2. It is believed that the comparison presented in

table 1.3 shows what can be gained by the use of

residual methods.Such approaches are also useful in connection

with the smoothing of vapor pressure data. Undersuch circumstances a form of the Antoine equation

[2] may be used as the reference expression for

vapor pressure. The reference vapor pressure maybe approximated by:

logioPr^+y (1.6)

Using propane as an example, the coefficients of

eq (1.6) become:

logic Pr= 4.294323 -990

'p--- (1.7)

There is shown in table 1.4 experimental values of

the vapor pressure of propane based upon the meas-urements of several investigators. The corre-

sponding reference vapor pressure calculated from

eq (1.7) is included along with the residual vaporpressure defined by eq (1.8):

P=P-PT (1.8)

In figure 1.3 is depicted the vapor pressure as a

function of temperature for propane with the ex-

perimental data of table 1.4 included. In the lowerpart of this figure is shown the residual vapor pres-

sure with the same experimental data. The shapeof the residual vapor pressure curve is typical for

most paraffin hydrocarbons when a form of the

Antoine equation is employed as a reference. Theprecision with which the measures of uncertainty

can be established has been increased manyfoldby the use of the residual vapor pressure shown in

the lower part of figure 1.3. The results of the

evaluation by analytic methods of the average devia-

tion with regard to sign, the average deviation

without regard to sign, and the standard error of

estimate are recorded in table 1.5 for each set of

experimental data.

Such residual techniques as have been described

were employed in this review and tabulation when-ever feasible. A certain amount of ingenuity is

required to utilize the most efficacious form of the

analytical expression to approximate the experi-

mental behavior. The use of residual methods pre-

vents a tendency to expand the scale of both the

independent and dependent variable in an attemptto increase the precision of the direct interpolative

process. Often such attempts yield unsatisfactory

results because of the wide spacing of the experi-

mental data. This is illustrated in figure 1.4 wherethe vapor pressure data for propane have beenexpanded on a large scale plot involving only a

portion of the temperature range. Physical separa-

tion of points on the diagram indicates the

uncertainties that are introduced in arriving at the

most probable curve to draw through the data.

1.3. Dimensions and Units 3

The greater part of the scientific literature is

expressed in the mass-length-time system of dimen-sions. This system of dimensions will be usedthroughout this compilation in the primary tabula-

tions. However, in the interest of utility, pressures

will be expressed in atmospheres. A conversionfactor is available to permit the establishment of

the numerical value of the pressure expressed in

newtons per square meter if such should be desired.

Temperatures will be expressed in degrees kelvin

which are related to temperatures in degreesCelsius by the following expression:

T=t+ 273.16 (1.9)

The value of the constant in eq (1.9) is based uponrecent international agreement concerning thetemperature in degrees kelvin of the triple point of

water [3], The nomenclature employed togetherwith the dimensions and units involved are givenbefore the introduction on p. vil. A short table ofconversion factors for the common dimensions andunits used is also presented, p. VIII.

A number of secondary tabulations have beenprepared involving the force-length-time systemof dimensions and engineering units. The appro-priate conversion factors may be found in the above-mentioned conversion table.

3 The NBS Office of Standard Reference Data, as administrator of the NationalStandard Reference Data System, has officially adopted the use of SI units for all

NSRDS publications, in accordance with NBS practice. This publication does not

use SI units because contractual commitments with the author predate establishment

of a firm policy on their use by NBS. However, conversion factors are given. We urgethat specialists and other users of data in this field accustom themselves to SI units

as rapidly as possible.

3

oCOro

Oro

LlI

(T

O 3C\J h-ro <

crLlI

CL

LJ

O HOro

OCOC\J

lOCVJ

OO

by\/ sjid\\\

LOn-

o loLO C\J

3IAimOA

4

FIGURE

1.1.

Variation

in

dew

point

volume

of

propane

with

temperature.

VOLUME

liters

/kg

2.5

0

- 2.5

- 5.0

FIGURE 1.2. Residual dew point volume ofpropane.

5

RESIDUAL

VOLUME

liters

/kg

VAPOR

PRESSURE

atm

0.25

0

-0.25

280 300 320 340 360

TEMPERATURE K

FIGURE 1.3. Vapor pressure of propane.

6

RESIDUAL

VAPOR

PRESSURE

atm

VAPOR

PRESSURE

atm

TEMPERATURE K

Figure 1.4. Vapor pressure-temperature diagram.

7

Table 1.1. Experimental values ofdew point volume a/or propane

Temperature

Reference

Temperature

Reference

Dana[4]

Sage

[5]

Reamer[6]

Helge-

son b[7]

Dana[4]

Sage

[5]

Reamer[6]

Helge-

son b[7]

K K255.4 169.2 343.5 15.4

260.9 141.7 344.3 15.2 15.4

266.5 118.6 346.4 14.3

272.0 99.9 346.9 14.0

277.6 85.5 82.8 349.8 13.2

283.2 73.7 72.7350.1 12.7

288.7 63.1 62.3352.7 12.1

293.9 52.4353.1 11.6

294.3 55.1 53.7355.4 11.3

299.8 48.1 46.4355.9 10.6

301.1 43.3

305 4 42.0 40.2 358.3 10.2

307 5 37.0 358.6 9.6

310 9 3A 9 34. ft 34. Q 360.9 9.8 9.5

313.3 32.2 361.3 8.8

363.6 8.5

313.5 32.6

316.5 32.5 30.4 363 8 8 0

318.6 28.3 366 3 7.3

322.0 28.7 26.5 368 4 6.6

323.4 25.3 368 8 6.5

370.0 4.5324.5 J 25.6

327 6 23.0 23.1

327.9 22.8

332.0 20.6 Estimated uncer-

332.1

333.2

20.5

20.2

tainty c, percent 1.0 0.2 0.2 0.2

336.1 18.6 Deviation

338.7 17.6 absolute d 1.07 0.31 0.28 0.34

339.6 16.8 algebraic e 1.07 -0.27 0.22 0.07

339.9 16.9 standard f1.4* 0.62 0.39 0.58

a Specific volumes expressed in liters/kg.b Specific volume calculated by application of Clapeyron equation to latent heat of

vaporization data.c Estimated uncertainty in experimental measurements.

d Absolute deviation defined by eq (2).e Average deviation defined by eq (1).

' Standard deviation defined by eq (3).

8

Table 1.2. Residual specific volume of dew point gas for propane

Temperature Reference

volume b

Residual volume a, liters/kg

Dana [4] Sage [5] Reamer[6]

Helgeson Smooth c

K

255.4 156.7 12.4 12.4

260.9 137.7 4.0 4.0

266.5 120.3 -1.7 -1.7

272.0 104.5 -4.6 -4.6

277.6 90.1 -5.4 -6.5 -5.4

283.2 77.3 -4.0 -5.3 -4.9

288.7 66.0 -3.4 -3.6 -3.6

293.9 56.7 -2.9 -2.3

294.3 56.1 -1.8 -2.3 -2.3

299.8 47.6 -1.2 -1.2 -1.1

301.1 45.8 -1.5 -0.9

305.4 40.3 -0.1 -0.2 -.1

307.5 37.8 -0.2 .1

310.9 34.2 .7 0.7 .5 .5

313.3 31.9 .5 .8

313.5 31.7 .7 .8

316.5 29.1 1.1 .7 1.0

318.6 27.5 .8 1.2

322.0 25.0 1.6 1.2 1.3

323.4 24.2 1.2 1.3

324.5 23.5 1.9 1.3

327.6 21.7 1.3 1.3 1.3

327.9 21.5 1.5 1.3

332.0 19.6 1.0 1.1

332.1 19.5 1.1 1.1

333.2 19.1 1.0 1.0

336.1 17.9 0.8 0.8

338.7 17.0 0.4 .5

339.6 16.6 0.4 .4

339.9 16.5 .5 .4

343.5 15.4 .1 -.1

344.3 15.1 -.3 -.3 -.2

346.4 14.5 -.4 -.4

346.9 14.3 -.2 -.5

349.8 13.5 -.7 -.8

350.1 13.4 -.6 -.8

352.7 12.6 -.9 -.9

353.1 12.5 -.8 -.9

355.4 11.8 -1.0 -1.0

355.9 11.6 -.9 -1.0

372-701 0 - 70 -39

Table 1.2. Residual specific volume of dew point gas for propane— Continued

Temperature Reference

volume b

Residual volume aliters/kg

Dana [4] Sage [5] Reamer[6]

Helgeson[7]

Smooth c

K

358.3 10.8 -1.0 -1.0

358.6 10.6 — 0.8 -1.0

360.9 9.8 -1.1 -0.9 -0.8

361.3 9.6 -.7 - 8

363.6 8.6 -0.5 -.4

363.8 8.6 -.5 -.4

366.3 7.4 -.1 .0

368.4 6.3 .3 4

368.8 6.0 .6 .6

370.0 5.3 -.8 .8

a Residual specific volume defined by Fg,— Vr.

b Reference volume expressed in liters/kg and defined by eq (4).c Critically chosen values of residual volume.

Table 1.3. Deviations of several sets of experimental data for

specific volume of dew point gas for propane

Deviation

Reference

Dana

[4]

Sage

[5]

Reamer[6]

Helge-

son [7]

Liters/ Liters/ Liters/ Liters/

kg kg kg kg

Absolute a 0.18 0.20 0.11 0.16

Algebraic b -.07 .02 .07 .08

Standard c .31 .27 .20 .32

Number of Points 13 20 14 16

a Absolute deviation defined by eq (2).

b Average deviation defined by eq (1).

c Standard error of estimate defined by eq (3).

10

Table 1.4. Experimental values of vapor pressure for propane

TemperatureK

Referencepressure,

equation

(1.7)

Dana [4] Sage [5] Reamer [6] Helgeson [7]

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

255 4 2 604 2.599 -0.005

260 9 3 150 3.130 -.020

266 5 3 779 3.776 -.003

272 0 4 501 4.511 .010

277 6 5 323 5.308 -.015 5.376 0.053

283 2 6 254 6.247 -.007 6.314 .061

288 7 7.302 7.288 -.014 7.335 .033

293 9 8 403 8.506 0.103

294 3 8.477 8.438 -.039 8.506 .029

299 8 9 786 9.717 -.069 9.805 .019

301 1 10.107 10.207 .100

305 4 11.239 11.160 -.079 11.248 .009

307 5 11.830 11.908 .078

310.9 12.843 12.724 -.119 12.840 -0.003 12.840 -.003

313.3 13.582 13.609 .027

313 5 13.634 13.609 -.025

316.5 14.608 14.426 -.182 14.596 -.012

318.6 15.322 15.310 -.012

322.0 16.542 16.331 -.211 16.515 -.026

323.4 17.032 17.011 -.022

324.5 17.448 17.011 -.047

327.6 18.652 18.610 -.042 18.610 -.042

327.9 18.785 18.713 -.072

332.0 20.474 20.414 -.060

332.1 20.498 20.414 -.084

333.2 20.949 20.910 -.039

336.1 22.243 22.115 -.128

338.7 23.438 23.408 -.030

339.6 23.854 23.816 -.038

339.9 23.986 23.816 -.170

343.5 25.739 25.517 -.222

344.3 26.128 26.116 -.012 26.116 -.012

346.4 27.234 27.218 -.016

346.9 27.493 27.218 -.275

349.8 29.027 29.049 .021

350.1 29.178 28.919 -.259

352.7 30.619 30.621 .002

353.1 30.838 30.621 -.217

355.4 32.142 32.226 .084

355.9 32.433 32.322 -.111

358.3 33.849 34.023 .174

358.6 34.050 34.023 -.027

11

Table 1.4. Experimental values of vapor pressure for propane a— Continued

TemperatureK

Referencepressure,

equation

(1.7)

Dana [4] Sage [5] Reamer [6] Helgeson [7]

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

Vaporpressure

Residualpressure b

360.9

361.3

363.6

363.8

366.3

368.4

368.8

370.0

35.479

35.686

37.162

37.269

38.898

40.311

40.576

41.413

35.710 .231 35.710 .231

35.724 .038

37.425 .263

37.425

39.126

.156

.228

40.827 .516

40.827 .251

42.011 .598

Estimated uncertainty,

percent 1.0 0.2 0.2 0.2

3 Pressures expressed in atmospheres.b Residual pressure calculated from eq (8).

Table 1.5. Deviations in experimental values of vapor pressure

for propane

Deviation a

Reference

Dana[4]

Sage

[5]

Reamer[6]

Helge-

son [7 ]

atm atm atm atm

Absolute b 0.059 0.129 0.173 0.044

Algebraic c -0.058 -0.031 0.082 0.024

Standard d 0.094 0.173 0.166 0.071

Number of Points 13 20 14 16

3 Deviations between experimental and predicted values.b Absolute deviation defined by eq (2).c Average deviation defined by eq (1).d Standard error of estimate defined by eq (3).

12

2. The fi-Pentane System

The vapor pressure of re-pentane has been studied

by numerous investigators [8-13] and the critical

properties have been measured many times [8, 9,

12, 14, 15]. The older data suffer from limitations

as to the purity of the samples of re-pentane em-ployed. For this reason, primary emphasis has beengiven to the latter measurements which have em-ployed markedly purer materials than those avail-

able prior to 1945. Table 1 reports critical properties

of re-pentane as measured by several investigators.

The critically chosen values are recorded in the

lower part of the table along with estimated meas-ures of uncertainty.

For the most part, the critically chosen values

follow closely those selected by the AmericanPetroleum Institute Project 44 [16]. It was thought

that Project 44 had an opportunity to review the

critical properties in somewhat greater detail than

was done in the present instance. The rather large

estimated uncertainty in the critical temperatureresulted from the significant variation in the critical

temperature reported by Beattie [12] and Ambrose[14]. Likewise, the critical pressure selected bythe American Petroleum Institute Project 44 wassignificantly different from that established fromthe experimental work of Beattie. For this reasonan uncertainty of 0.2 atm was selected. Ratherclose agreement in the critical volume as established

by Beattie [12] from direct volumetric measurementand that selected by the American PetroleumInstitute Project 44 [16] resulted in a somewhatsmaller estimate of uncertainty than otherwisewould haive been the case.

Following the graphical techniques that havebeen described in the introduction to this com-pilation, the vapor pressure interpolated from the

experimental measurements [11-13, 16] is reported

in a portion of table 2.2 at 10 degree K. intervals.

The residual vapor pressure of re-pentane is shownin figure 2.1. In this instance the reference vaporpressure was established from:

log„P r= 5.587347-

24^3 '45

(2.1)

The marked difference in the measurements of

Young [9] from those of the other investigators are

clearly indicated. Other measurements of Sage

[10, 11], Li [13], and Beattie [12] are in rather

good agreement. The average fractional deviation

and the standard deviation of each set of the ex-

perimental data from the critically chosen values

are set forth for the vapor pressure of re-pentane in

the upper part of table 2.3. It is most likely that the

measurements of Beattie [12] and Li [13] represent

the most accurate measurements. However, the

paucity of experimental points made it necessaryto place some reliance upon the measurements of

Sage [11]. Young’s measurements were not given

much credence because of their large deviations

from the significant body of more recent experi-

mental data which has accumulated. Again, the

current critically chosen data follow closely those

recommended by American Petroleum Institute

Project 44 [16]

.

Values of the specific volume of the saturated or

bubble-point liquid and the saturated or dewpointgas also have been recorded in a part of table 2.2.

These latter data were interpolated from selected

measurements [11-13],

Figure 2.2 depicts the bubble-point volume as a

function of temperature and presents the data of

Li [13], Sage [10, 11], and Young [9]. The data

shown in figure 2.2 were based upon direct measure-ments of the volume in the condensed liquid extra-

polated to the vapor pressure. In this instance, it

was not necessary to utilize the residual techniquesas the variation in the specific or molal volume with

pressure was sufficiently small that direct graphical

operations were satisfactory. The agreement of the

several sets of data for the volume of the bubble-

point liquid in comparison with the critically chosenvalues are set forth in the lower part of table 2.3.

Values of the vapor pressure and the specific

volume of the saturated liquid, together with applica-

tion of the Clapeyron equation to calorimetric meas-urements of the latent heat of vaporization of re-

pentane [17], were used to establish the volumeof the saturated gas at temperatures below 350 °K.

Figure 2.3 depicts the residual volume at dewpoint for re-pentane as established by several

methods. The volume of the gas was smoothed in

terms of the compressibility factor which is defined

by eq (2.2):

Z^— PVJbkT (2.2)

In this instance, residual graphical methods weredeemed sufficient to permit critically chosen valuesto be established without the need of analytical

techniques. The reference volume at dew point wasestablished from:

Vr= bkT/P (2.3)

It is apparent that the calorimetric measurements of

Kozicki, et al. [17] and the volumemetric data of

Li and Canjar [13] are in good agreement whilesome of the earlier measurements by Sage andLacey [10, 11] yielded larger values of the residual

volume.After a review of the information presented in

figure 2.3, primary emphasis was placed upon themeasurements of Kozicki [17] and Li [13] althoughthe data by Young [9] and Sage [10, 11] at the

higher temperatures, for the most part, were in goodagreement with the critically chosen values. Theagreement of the results obtained from the calori-

metric measurements of Kozicki [17] with the

13

directly measured values of Li [13] Young [9]

and Sage [10, 11] yields credence to the critically

chosen values.

The standard error of estimate of the smooth data

from the experimental values is recorded in table

2.3. This includes a comparison of the agreementof the directly-measured specific volume of the

dew-point gas with values calculated from the appli-

cation of the Clapeyron equation to the available

enthalpy changes upon vaporization established

from calorimetric measurements [17].

The same information presented in tables 2.1

and 2.2 is also depicted in tables 2.4 and 2.5 in the

force-length-time system of dimensions, and the

results tabulated in engineering units. The standard

errors of estimate are equal tor the data presentedin tables 2.1 and 2.2, and 2.4 and 2.5, respectively,

but they have been repeated in the different sets

of dimensions and engineering units in table 2.6

for the convenience of the user. The graphical

methods employed in interpolating these data havebeen applied with different levels of agreement at

various ranges of temperature, thus requiring

separate measures of uncertainty for each range.

Accuracy— There is recorded in table 2.7 the esti-

mated uncertainty for the vapor pressure, tempera-ture, and volume of the saturated gas and saturated

liquid as measured by each of the several investi-

gators. These have been evaluated by the current

authors for each of the several investigators, while

the over-all summary of the probable uncertainty

in the results reported in tables 2.1 and 2.2 is set

forth in the lower part of table 2.7. It should berecognized that a certain element of subjective

judgment is required in arriving at values of uncer-

tainty which have been ascribed to the several

variables. For the most part, uncertainties several

times those assigned by the original investigators

have been reported in table 2.7.

The measurements of Young resulted from tech-

niques involving confinement of the hydrocarbon in

glass over mercury. Likewise, the methods of

measurement of pressure were considered to besomewhat less accurate than had been stated byYoung. The sample purity was relatively poor by

present day standards but Young’s [9] measure-ments on the whole represented an outstanding

contribution to the knowledge of hydrocarbons at

the time the work was completed. Somewhat later

measurements by Sage [10, 11], in the light of

this review, probably suffered in the gas phase fromadsorption on the walls of the steel pressure vessel

within which the hydrocarbon was confined.

The purity of the sample was inadequate to permit

the vapor pressure to be established within the un-

certainty of the pressure measurements whichaccounted for the somewhat larger measure of

uncertainty indicated in table 2.7 for the vapor

pressure than was originally reported by the authors

[4]. These measurements of vapor pressure by Li

[13] and Beattie [12] are probably as good as anyreported and the sample purities were adequate to

permit the estimated accuracy of vapor pressure

measurements to be of the same order as that esti-

mated by the author [12]. Some difficulties fromadsorption undoubtedly influenced the volumetric

measurements by Li [13] and Beattie [12] but

these were less serious than those found by Sage

[11]. The measurements of vapor pressure byBeattie [12] with a sample of relatively high

purity are considered of good accuracy. Thevolumetric studies by Li [13] were not considered

as satisfactory as Beattie’s [12] techniques andfor that reason a larger measure of uncertainty than

that indicated by the author has been assigned.

Kozicki’s [17] calorimetric measurements offered

an interesting insight into the overall reliability of

the volumetric measurements of the dew-point

gas. However, since the first derivative of the vaporpressure with respect to temperature was required

to establish the volume of the dew-point gas, a higher

uncertainty was assigned to the derived volumetric

behavior than existed in the original calorimetric

measurements.There are a number of correlations and reviews

of the properties of the paraffin hydrocarbons that

include n-pentane which were not utilized in the

preparation of the tabular information submitted. In

table 2.8, however, the more useful reviews are

described briefly [18-27].

14

300TEMPERATURE K

350 400 450

(/)

CL

LUCC3COCOLUa:CL

ocoCL

2

<3QCOLUcr

5

4

3

2

0

2

-3

•4

1

—

6

1

—API 44

1 ~T~ ~T~ n T~

rfo-

?-o •

BEATTLI

SAGE

E

j

YOUNG&

00

J \-O 0

r

^ -

-u

T

j _

CRITICALk

0.35

030

0.25

0.20

0.15

0.10

0.05

0

- 0.05

- 0.10

- 0.15

-0.25

-0.30

00 200TEMPERATURE

300

Figure 2.1. Residual vapor pressure of n-pentane.

15

RESIDUAL

VAPOR

PRESSURE

atm

BUBBLE

POINT

VOLUME

ft3/lb

300TEMPERATURE

350K

400 450

4.25

4.00

3.75

3.50

3.25

3.00

2.75

2.50

2.25

2.00

1.75

1.50

FIGURE 2.2. Bubble point volume of n -pentane.

16

BUBBLE

POINT

VOLUME

liter/

kg

RESIDUAL

DEW

POINT

VOLUME

ft3/lb

TEMPERATURE K

300 350 400 450

FIGURE 2.3. Residual volume at dew point for n-pentane.

TABLE 2.1. Critical properties of n-pentane

Source Temperature Pressure Volume

K Atm Liters/kg Liters/kg-mol

Young [9] 470.4 33.0 4.31 310.9

Sage [11] 470.4 33.6 4.36 314.6

Beattie [12] 469.8 33.31 4.09 295

Ambrose [14] 469.5

Partington [15] 469.6

API 44 [16] 469.49 33.16 4.08 295

Critically chosen value 469.49 33.16 4.08 294.6

Estimated uncertainty 0.7 0.2 0.04 2.9

Estimated uncertainty, percent 0.1 0.5 1.0

17

372-701 0 - 70 -4

RESIDUAL

DEW

POINT

VOLUME

liter/kg

Table 2.2 Properties of the coexisting phases for n-pentane

Temperature

Vapor

pressure a

Volume

Dew point Bubble point

K Atm Liters/kg Liters/kg-mol Liters/kg Liters/kg-mol

280 0.32 970.9 70.06 X 10* 1.561 112.7

290 0.49 656.1 47.34 1.586 114.4

300 0.72 421.0 30.38 1.616 116.6

310 1.03 328.4 23.70 1.641 118.4

320 1.42 241.8 17.45 1.672 120.7

330 1.93 181.1 13.07 1.706 123.0

340 2.57 138.2 9.970 1.739 125.5

350 3.38 107.1 7.728 1.774 128.0

360 4.31 83.4 6.017 1.813 130.8

370 5.45 65.92 4.756 1.855 133.8

380 6.81 52.67 3.800 1.902 137.2

390 8.41 42.31 3.053 1.952 140.8

400 10.3 33.07 2.476 2.010 145.0

410 12.4 27.74 2.001 2.073 149.6

420 14.9 22.50 1.623 2.146 154.9

430 17.7 18.19 1.312 2.232 161.1

440 20.9 14.60 1.054 2.358 170.1

450 24.5 11.57 0.8347 2.525 1&2.2

460 28.6 7.791 .5621 2.792 201.4

469.49 b 33.16 4.08 .295 4.08 295

a (Atm) (1.013250 X 105)= A'/m 2

"Critical state [16]

18

TABLE 2.3. Agreement of interpolated and experimental data for n-pentane

Source Number of Average a Deviation Standard c

of points Fraction b

Vapor pressure, atm

Young [9] 24 -0.164 0.0102 0.248

Sage [11] 22 -.010 .0044 .019

Beattie [12] 4 .005 .0003 .010

Li [13] 2 .001 .0008

API 44 [16] 10 -.001 .0018 .003

Overall d 38 -.005 .0031 .015

Dew-point volume, liters/kg

Young e[9] .. 21 -0.27 0.0050 0.62

Sage [11] 23 .23 .0077 1.21

Li [13] 2 .08 .0056

Kozicki f[17]— |

11 -.42 .0024 0.97

Overall 57 -.08 .0056 .93

Bubble-point volume, liters/kg

Young e[9] 21 -0.0303 0.0124 0.002

Sage [11] 23 .00071 .0008 .062

Li [13] 2 -.0687 .0030

Overall 46 .0164 .0062 .041

“Average deviation defined by^

(Gexp— Csm) J/A

“Average fractional deviation defined byj ^ [ (CexD— Ggm )/Gexp]}/^V^

I

c Standard deviation defined byjj ^ (Gexp— C,m )

2

J/(A— 1)J

1 '2 where G = pressure or volume

d Excluding Young’s vapor pressure datae Values of deviations for Young not comparable since data employed had been smoothed.'Calorimetric data for temperatures between 311 and 350 K.

Table 2.4. Critical properties of the n-pentane system, engineering units

Source Temperature Pressure Volume

° F psia cu ft/lb cu ft/lb-mol

Young [9] 386.96 485.4 0.0690 4.98

Sage [11] 387 494 .0699 5.04

Beattie [12] 385.95 489.5 .0655 4.73

Ambrose [14] 385 41

Partington [15] 385 5

API 44 [16] ..." 385.41 487.3 .0654 4.72

Critically chosen value 385.41 487.3 0.0654 4.72

Estimated uncertainty 0.4 3.0 0.0007 0.05

Estimated uncertainty, percent 0.1 0.5 1.0

19

Table 2.5. Properties of the coexisting phases for n-pentane, engineering units

Temperature

Vapor

pressure a

Volume

Dew point Bubble point

°F psia cu ft!lb cu ft/lb-mol cu ft/lb cu ft/lb-mol

40 4.30 17.2 1240 0.02491 1.797

50 5.48 13.7 986 .02510 1.811

60 6.89 11.0 795 .02532 1.827

70 8.56 8.95 646 .02556 1.846

80 10.6 6.74 487 .02580 1.862

90 12.9 6.12 441 .02612 1.885

100 15.6 5.108 378.7 .02634 1.900

110 18.6 4.325 312.1 .02662 1.921

120 22.3 3.643 262.8 .02691 1.942

130 26.4 3.104 224.0 .02719 1.962

140 31.1 2.660 191.9 .02750 1.984

150 36.4 2.280 164.5 .02779 2.005

160 42.4 1.978 142.8 .02810 2.027

170 49.0 1.716 123.8 .02842 2.051

180 56.5 1.494 107.8 .02876 2.075

190 64.8 1.306 94.23 .02912 2.101

200 73.9 1.145 82.61 .02948 2.127

210 84.0 1.008 72.73 .02987 2.155

220 95.1 0.8886 64.11 .03028 2.185

230 107.2 .7877 56.83 .03072 2.216

240 120.4 .6966 50.26 .03143 2.268

250 134.7 .6184 44.62 .03166 2.284

260 150.3 .5498 39.67 .03219 2.323

270 167.3 .4892 35.30 .03273 2.362

280 185.6 .4353 31.41 .03333 2.405

290 205.4 .3875 27.96 .03396 2.450

300 226.7 .3452 24.91 .03467 2.501

310 249.7 .3067 22.13 .03548 2.560

320 274.3 .2718 19.61 .03641 2.627

330 300.8 .2405 17.35 .03752 2.707

340 329.1 .2118 15.28 .03884 2.802

350 359.4 .1853 13.37 .04043 2.917

360 392.0 .1600 11.54 .04246 3.064

370 426.8 .1348 9.726 .04548 3.281

380 461.3 .1106 2.980 .05109 3.686

385.41 b 487.3 .0654 4.73 .0654 4.72

‘ (Psia) (6.89475 x 103)= /V/m 2

.

b Critical state [16].

20

Table 2.6. Agreement of interpolated and experimental data for n-pentane, engineering units

Source

1 !Number Average a Deviation Standard c

of points fraction b

Vapor pressure, psia

Young [9] 24 -2.41 0.0102 3.65

Sage [11] 22 -0.15 .0044 0.28

Beattie [12] 4 .07 .0003 .14

Li [13] 2 .02 .0008

API 44 [16]... 10 -.02 .0018 .04

Overall d 38 -.08 .0031 .22

Dew-point volume, cu ft/lb

Young e[9] 21 -0.0043 0.0050 0.0099

Sage [11] 23 .0037 .0077 .0194

Li [13] 2 .0014 .0056

Kozicki f[17] 11 -.0067 .0024 .0156

Overall 57 -.0014 .0056 .0149

Bubble-point volume, cu ft/lb

Young e[9] 21 -0.00048 0.0124 0.00003

Sage [11] 23 .00011 .0008 .00100

Li [13] 2 -.0011 .0030

Overall 46 .00026 .0062 .00065

a Average deviation defined by (Gexp-Gsm )j/A.

b Average fractional deviation defined byj ^ j\cexp — Gsm )/GexpjJ/A'.

c Standard deviation defined by| j

^ (Gexp— Gsm )zj/(1V— 1 ) where G = pressure or volume.

“Excluding Young’s vapor pressure data.

“Values of deviations for Young not comparable since data employed had been smoothed.'Calorimetric data for temperatures between 100 and 170 °F.

Table 2.7. Accuracy of experimental background for n-pentane

Quantity Units Young [9] Sage [11] Beattie [12] Li [13] Kozicki [17]a

Sample purity mole fr 0 95 0 9970 0.9985 0.9988 0.9998b

Vapor pressure percent 5 3 .2 .2

Volumetric behavior percent .5 .5 .3 .4 .5

a Includes uncertainty in dew-point volume calculated from Clapeyron equation.b Reported by vendor. The specific weight of the liquid and the index of refraction agree closely with critically chosen values. The reported purity seems higher than would be

expected.

21

Table 2.8. Reviews of properties of the paraffin hydrocarbons

Subject Treatment Reference

Vapor pressure

Vapor pressure

Vapor pressure

Critical constants

Critical constants

Vapor pressure

Thermodynamic properties

Critical constants

Vapor pressure

Physical constants

Correlation. Equation of state

Review and re-evaluation of experimental data

Correlation. Empirical constants

Correlation. Van der Waals constants

Review of experimental data

Correlation. Semi-empirical equation

Re-evaluation of experimental data

Correlation. Van der Waals constants

Correlation. Semi-empirical equation of state..

Correlation. Statistical theory of liquids

[18]

[ 19 ]

[20 ]

[21 ]

[22 ]

[23 ]

[24 ]

[25 ]

[26 ]

[27 ]

3. The Methane-n-Pentane System

The methane-n-pentane system has been subject

to significant experimental study at temperaturesabove ambient. However, only a limited investiga-

tion is available for temperatures below 37.7 °C

[28],

The vapor pressure of methane has been studied

extensively [16, 29-32], and the critical state of

the hydrocarbon measured [16, 29, 33, 34]. Like-

wise, the vapor pressure of n-pentane was studied

by Young and others [8, 9, 12, 13], and the critical

properties determined [9, 12, 14, 16].

The phase behavior and the volumetric charac-

teristics of the coexisting phases in the methane-n-pentane system have been established [35-38].

A comparison of the phase behavior of several

hydrocarbon systems containing methane, withparticular emphasis on the critical states, also hasbeen presented [39]. In addition, a review wasmade of the phase equilibria data for the methane-n-pentane system, and of similar data for other

binary systems [40]. No new experimental datawere included in either of the above reviews.

Utilizing the graphical techniques which havebeen described in the introduction to this compila-

tion, the aforementioned experimental data weresmoothed with respect to pressure and temperature.The composition and the specific volume of the co-

existing phases also were interpolated as a function

of pressure and temperature. In table 3.1 are re-

corded the composition, molal volumes, specific

volumes, and molal equilibrium ratios of the

coexisting phases for mixtures of methane andn-pentane. The data are reported at temperaturesfrom 280 to 470 K. for pressures from the vaporpressure of n-pentane to a maximum of 170 atmos-pheres. The data have been recorded for even values

of pressure expressed in atmospheres for each 10 K.

temperature interval. The standard error of estimate

of the smooth curves employed for interpolating

these data from the experimental results are set

forth in table 3.2. The characteristics of the uniquestates, including the critical state, the point of maxi-mum temperature, and the maximum pressure for

mixtures of constant composition, aie listed in

table 3.3. These values of pressure and temperaturefor each of the three unique states, as well as a

rough estimate of the specific volume for the

critical state, are reported as a function of weightfraction methane. The data recorded in table 3.3

were obtained by suitable graphical operationsbased upon experimental volumetric and phaseequilibrium data. The estimated uncertainties for

each property have been included in the tabulation.

Since many persons having an occasion to utilize

this information are concerned with the force-

length-time system of dimensions, the above de-

scribed data expressed in these dimensions are

reported in conventional engineering units in tables

3.4 and 3.5. The composition and the specific

volume of the coexisting phases in the methane-n-pentane system are reported in table 3.4, and the

properties of the unique states in table 3.5.

The standard error of estimate of the smoothcurves used in the evaluation of these quantities

is identical with that reported in table 3.2. How-ever, for the sake of completeness, it has beenpresented in table 3.6 and expressed in the units

used in tables 3.4 and 3.5. In preparing the tabula-

tions shown in tables 3.1 to 3.2, an effort has beenmade to present the data in sufficient detail to permitthe use of four-point linear interpolation in order

to evaluate properties at any chosen temperature,and pressure or composition with a precision at

least equal to the accuracy of the data.

In order to illustrate the nature of the phasebehavior of this system, a pressure-temperaturediagram showing dew points and bubble points

for three mixtures of constant composition and the

vapor pressure of n-pentane is shown in figure 3.1.

In figure 3.1 the effect of temperature upon the

critical state of the methane-n-pentane systemhas also been shown. Since it was, from necessity,

estimated from the observed volumetric behaviorat states near the critical state, the data have beenindicated as an estimated quantity. The critical state

for a binary mixture can be considered to be that

22

state at which the properties of the coexisting phases

become continuously identical. For example, the

critical state can be approached by an increase in

temperature under isobaric conditions or by an

increase in pressure under isothermal conditions

or by any chosen polytropic path. In addition, the

estimated maximum pressure at which two phases

exist for a given temperature has been indicated.

This state often differs materially from the critical

state for a mixture of the same composition, as is

indicated for a mixture containing 0.50 mole frac-

tion methane. However, this state has been called

“maxcondenbar” as being the maximum condensa-

tion pressure for a given mixture. It should be

recognized that the maxcondenbar becomes equato the critical pressure at the maximum two-phase

pressure for the system as a whole. The maximumtwo-phase temperature for a mixture of a given

composition also has been shown and has been en-

titled the “maxcondentherm.” It is again em-phasized that the loci of the maxcondenbar and the

maxcondentherm as well as the critical represent

estimated quantities established from measuredvolumetric and phase behavior and not from direct

observation of these quantities.

In figure 3.2 is depicted the equilibrium ratio as a

function of pressure for each of several tempera-tures. The product of the pressure and the equilib-

rium ratio was employed in figure 3.2 to permit the

data to be presented with greater precision.

The molal equilibrium ratio, K, is detined in the

nomenclature and represents the ratio of the molefraction of a given component in the gas phase to

that in the coexisting liquid phase at the sametemperature and pressure. This quantity is often

employed to represent the phase behavior of the

system since the ratio can often be effectively

employed in phase equilibrium calculations to

greater advantage than values of the compositionsof the coexisting phases.

It should be recognized that the equilibrium ratio

always is unity at the critical state, Thus in the caseof figure 3.2 the critical locus is identified by a line

crossing the diagram in such a fashion that the

product of the pressure and the equilibrium ratio

and the pressure are everywhere equal. It also

should be recognized that the equilibrium ratio

for the less volatile component becomes equal to

unity when the pressure is equal to the vapor pres-

sure of that component. The lower pressureboundary of the heterogeneous region is thus

established by the vapor pressure of the less volatile

component.The effect of pressure upon the composition of the

coexisting phases and upon the critical state hasbeen shown in figure 3.3. The curves shown in this

figure represent the phase behavior for a particular

temperature as the pressure is changed. The critical

state in this instance represents the highest pressureat which two phases may coexist for a given tem-perature. Such behavior can also be seen in figure

3.1. However, it must be recognized that in casesof mixtures of a given composition the critical state

is neither the highest pressure nor the highesttemperature at which two phases can coexistthroughout most of the pressures and temperatureswhere heterogeneous equilibrium exists. The esti-

mated locus of maxcondenbar and maxcondenthermhave also been indicated in figure 3.3, and for a giventemperature represents the dew point gas, in this

instance, containing the largest mole fraction of

methane. Figures 3.4, 3.5, and 3.6 show the sameinformation in terms of the force-length-time systemof dimensions expressed in engineering units.

Accuracy— For those interested in the critical

evaluation of the experimental accuracy underlyingthe information presented in tables 3.1 to 3.5, acritical review of the uncertainties associated withthe measurements of the several investigators hasbeen made and is set forth in table 3.7. In any suchevaluation it is difficult to maintain objectivity. How-ever, it is believed that the values of uncertaintypresented in table 3.7 have been arrived at byconservative judgment and formal statistical

procedures, such as described in the introduction.

The uncertainties assigned to each of the variables

by the current authors are from two to four timesthat reported by the original investigators.

It should be recognized that the majority of the

values reported in table 3.7 do not apply to the

behavior in the vicinity of the critical state wherethe uncertainties may be many times as great, since

these states were not established by direct experi-

mental observation. There is need for additional

experimental work involving the determination of

the critical state by visual observation and byindirect measurements of the intensive properties

of the coexisting phases, in order to permit anobjective appraisal of the accuracy with which the

properties of the system near the critical state have

been established.

23

PRESSURE

atm

275 300 325 350 375 400 425 450 475TEMPERATURE K

Figure 3.1. Pressure-temperature diagram for methane-n-pentane system.

24

PRESSURE

•

EQU

ILI

BR

IUM

RATIO

PRODUCT

atm

FIGURE 3.2. Effect of pressure upon equilibrium ratio for methane-n-pentane system.

372-701 0 - 70-5

25

PRESSURE

atm

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

MOLE FRACTION METHANE

FIGURE 3.3. Pressure-composition diagram for methane-n-pentane system.

26

PRESSURE

psiQ

Figure 3.4. Pressure-temperature diagram for methane-n-pentane system, engineering units.

27

PRESSURE-EQUILIBRIUM

RATIO

PRODUCT

FIGURE 3.5. Effect of pressure upon equilibirum ratio for methane-n-pentane system, engineering units.

28

PRESSURE

psia

0.1 0.2 03 0.4 0.5 0.6 0-7 0-8 0.9

MOLE FRACTION METHANE

FIGURE 3 .6 . Pressure composition diagram for methane-n-pentane system, engineering units.

372-701 0 - 70 -6

29

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-<= CL.

2 1

t- z«soc

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E3cn O CM i^N'O'tO'O'OiC® n O CM 00 CM pH O' O n O' H N CO fH ^ fC\ 4- n 0 O' X CM X n- O 'O 4 n >0 n- 4

n cn 4- r- (Mcom^o^co^H O' n n >0 O ao O' 4- n mo® r- n m CM «H 0 0 cn n- cm NO pH n- CM X 0 >0 CM X05

ao >0 n U14444IM— O' 00 r*- >0 "0 m <n CM CM CM CM H F^ pH pH pH #H H •H H O' X X n- >0 >0 n n n 4 >* Xo 0 0 0 OOOOOOOOO 0 d d 0 0 0 OOO 0 600 O O O O O 0 O O 0 000 0 0 0 d 0 0 OOO

n n n n nnnnn-^'t^^ 4- 4- >1* 4- m m m m cn m CO m cn cn CO cn cn m cn cn m cn cn x m CM CM CM CM

o o o o OOOOOOOOO O O O OOO 0 0 0 0 OOO 0 0 0 0 0 0 0 0 0 OOO O 0 O OOO OOOLU LU UJ LU 111 111 UJ in ui ui 111 1 U 111 UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ UJ UJ UJc cn >0 ®NH>ofCi>tinofn n h- pH O' ao >o r*- 0 m m h N X cn CM m >0 CM X >0 nO n- O' pH 4 pH n n 0 n>0 GO CM S.D 4, M-lOh®fsj ao n m CM 0 n O O' F^ n O ® (M O' n m —a 0 x r*F v0 n cn cn CM H pH 0 0 4 X CM

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30

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

H H H H H H H pH pH H rgrgrgrgrgpgrgrgrgnjrgrgrgrgrgrgpgrgpg rg rg rg cm rg rg rg rg ph pH pH pH pH pH pH pH pH Oz ooooooooooooooooooooooooo O 000000 9 9 OOOOOOOOOOOOOh- III 111 111 L1J UJ LU UJ LU UJ LU LU UJ UJ ijj UJ UJ LU LU ill UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ LU UJ UJ LU UJ LU UJ UJ UJ LU LU UJz or\jooop> 4 oinp-p- NOMf*3 «OmoOOH 0 0 4- m in 0 45 rg O' m C30N 4 ro X pg •p in pi in rg O' OO PPI 4 Oa! O^^O’tO'Ul^iAO'ON^ 4- O ©inosinggg in 45 00 O' -- <M m X rg X rg O' f- x HN 4 43 S' CM m 0 0

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rg eg cm cm rg N »H H H H »h fj pH pH pH 0 0 0 O O O O O O O O O 0 0 0 0 O O 0 0 0 0 O 0 O 0 0 O O O 0 O— LU= z o o oo o 00000 0 0 O 0 0 0 0 0 O O O O O O O O O 0 0 0 0 O O 0 0 0 0 O O O 0 0 O 0 O 0 OO' 11,1 111 liJ ill LU LU UJ UJ UJ LU UJ LU UJ UJ LU UJ UJ UJ UJ LU LU UJ UJ LU UJ LU LU LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ UJ UJ LU LU UJUJ ^ pH pH ^ ^ pH 45 7* in in m m co in in 0 r- r- 00 r- 4) h- O CM H in m in 00 4- pH O' O' 0 0 CM in h- 0 4 r- 0 4 0 CO 4 0

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r-t h O' ® g oj rg p-4 H H pH d 00 r- 0 m 4- d ro m ro m CM pg rg rg rg CM CM rg pH pH pH H pH ^H pH pH pH pH pH ^H

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T3 o o o o o 0 0 0 0 0 0 0 O O O O O 0 O O O O O O O O 0 0 0 O O 0 O O O O O 0 O O O O O O O OO

LU LU LU LU LU III 111 ill 111 HI UJ UJ UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ UJ LU LU UJ LU UJ UJ LU UJ LU UJ LU LU LU UJ UJ UJ LU LU UJ(jh ^ o O' S' O O O 0 O p-H rg rg co ro m >0 GO O' ph rg 4- in r- O' *H m in r- O' H 4 O CO ^H CO pg 0 O' rg X 4o in in m in in in in in in x -0 43 4) 4) >

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h-o—1 111 HI 111 UJ 111 111 111 III LU III UJ UJ UJ LU UJ UJ LU Ui UJ LU LU UJ UJ UJ UJ LU LU UJ LU LU UJ UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ44444444 fr'<n rg -1 -- O O' O' oo >o in 4* CM pH CO in ro -4 O O' 00 r- >0 4) X r— X O' *H 4 X 0 X H ^ cm m XO o ^ H H H H H H ^ H H —

1

pH O O O O 0 0 0 0 O' 00 45 in CO rg -- 0 O' X f*- 4) m m 4 co rg rg rg pH CM CM (O

s H »H <H pH c=) ^4 -J «=J H H ^4 pH o=3 pH pH pH H pH pH pH O' O' O' O' O' O' O' O' O' X X X X X X X X X X X X X X X_JCDCDO

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*: o o o o o OOOOOOOOOO 0000 O O 00000---- »H H pH pH H pH pH rg pg pg pg rg rg CO ro ro 4 in in

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_l UJ UJ UJ LU UJ LU UJ LU UJ LU LU UJ UJ UJ LU UJ LU UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ LU UJ LU UJ UJ LU UJ UJ UJ UJ<c co h n g so m O' 0 cm p- O' O pH co rg in rg O' m pH r- pg 0 pH pH 4) 4- 4- CM X X n n X r* O' rg in 33 rg r- pH in pH—

1

co O' m o no g p*g co 00 00 cO O' 43 4- rg *»h 00 cn PM m f- rg N» 4- pH GO 4D 4- CM pH O' X h- X in 4 ro <0 rg pH pH O O in O'

Q. s <0 rg rg —« -4 f4 H-4 incO rg rg p4 eH rH »-H rH oo r- >0 m 4- 4- ro ro m pg rg rg CM <M <H pH pH pH *H pH ^H pH pH pH pH pH pH O' X

LUOodooddoodd 0 0 O O O OOO O 0 0 O O 0 O odd O O O 0 0 0 d O O O O O O O 0 d 0 0

4 f«34 C0 Or^ 4 S'^S' rg O' m O' p-« O p-4 pH 4- m 0 4- 4) J0 GO 00 CO 00 CO r- 4 pH X 0^4 4 PS) O X ^ in X ro 4 O' h- O'

Li_ pm oo co r- pg in O' rg 4* in -1 m X r- o o -h m 4- m 45 43 0 43 45 45 45 4) 0 4) X 45 in in 4 CO rg pH O X r- in CO pH X CO 4 01—

OOhhN rg rg <0 in x t>- p- r- GO 00 00 oo 00 oo 00 00 00 00 GO ao X CO X X X X X X X X X X r- r- h- X X in X^ LUZc

o o o o o d 0 d 0 0 0 0 0 0 0 0 d O 0 0 d d 0 0 O 0 0 O 0 0 O O 0 0 0 0 0 0 0 odd O O 0 0 0 0

h-UJ

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n

0 in go 4“ 0s h rg fn 4 4 4 m in >0 4) 4) 45 O 43 45 45 4) 4) 45 45 >0 X X 43 x m m in 4 4 ro co rg pH 0 X 4 X_J

-- cm 4 4 m 4} 4) X CO GO O' O' 0 O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' S' O' O' O' O' O' O' O' O' O' O' O' X X O'

o2 6600006600 0 0 d d 0 0 0 0 0 0 0 0 d d 0 6 6 0 0 060 OOO 0 d 0 0 d 0 0 0 0 OOO 0

CT5 c V noLUZ >0 oo O rg g- 0 00 0 0 0 000 0 0 0 0 0 0 0 0 0000 O O O O 0 0 0 0 O 0 0 O 0 0 0 OOOO 0 0 co CO

aP O O H H H <h .h eg 4 X OOOMtO 00 0 in 0 in 0 m 0 in 0 in 0 n 0 in 0 m 0 in 0 in 0 in 0 in 0 m 0 in 0 in X X Xto <r pH >-4 H »—h rg rg m 4- 4- m in 4) >0 p- r- co X O' O' 0 O pH pH rg rg to CO 4 4 in m X X X X mCdQ_

pH pH pH pH pH pH pH •H pH pH pH pH pH •H pH

31

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLE

F

WTF

VOLUME

MOLE

F

WTF

VOLUME

EQUILIBRIUM

RATIO

b

ATM

METHANE

MOLAL

c

SPECIFIC

11

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

^,4.4p4*Hp4,4,4*4r4p4<MCM<M<MCM<M<MiMCMiMiMiM<M<M<M<MCMCMiMiMiM<MCMp4rHr4p4p4p4p4.4*4p4P40ooooooooooooooooooooooooooooooooooooooooooooooI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

mmLlJmmLi^yjijjmujiiJtjjijjijj'jjijjyj^ixiLUlUUJIiJIJJLUUJlJJliJUMUU^UUJ^lULJJlUUJUJUJUJUJUJUJUJUJ^o®'Oinaoi/M/iNO(Mfn 4, NMin>oo^N'ONmto>0 'O^Mn^©otf> 0'irun®'tfMio«tinfOOff>oCDNOfONN^O«tNOcO^OiN(3'r^OMiMfl>ONOOO<NJ't'00'M'ON©l/>OH(M^'OflOHi/>^ 0®0xr^xin-$->t, x<M^-4p4 00,00 h-o-xxxminintnininxxxxx^r,fc XXO'^*-<~*»4*4^cMCMX>frin*4

CM <M CM CM CM e4 H H *4 H H H H p4 0 O 0 O 0 0 0 O O 0 0 O 0 O O O 0 0 0 0 0 0 O O 0 0 O O 0 O 0O O O 0 O O O O O O 0 0 O O O 0 O 0 O 0 0 0 O O 0 O O O O O 0 O O 0 0 O 0 O O 0 0 O O 0 O OLU LU LU LU LU LU LU UJ LU LU LU LU LU LU UJ UJ UJ UJ LU LU LU UJ LU LU LU LU UJ LU LU UJ LU LU LU UJ LU LU LU UJ UJ UJ UJ LU LU UJ LU LUCM 00 00 p4 O' r- O >

0

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pH •4 *4 iH p4 p4 H 4 .4 4 H

1=1 r4 iH <=4 p4 H H H H *4 rH »4 pH *4 r4 *4 p-H 4 p4 4 4 4 4 p-4 p-4 t-4 4 ^4 4 p-4 ^4 r4 4 4 p-4 4 4 *4 rH 4 ^4 *4 *4 4O O O O O 0 O O 0 O O O O 0 0 O O O 0 0 O 0 O 0 O O 0 0 O O O 0 O O O O 0 0 0 O O 0 0 O 0UJ LU UJ of LU UJ UJ LU UJ LU LU LU LU UJ UJ UJ UJ LU UJ UJ UJ LU LU UJ UJ LU LU LU LU LU UJ UJ LU UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJP=H p4 H H p4 •4 CM CM CO CO CO H- H- in <0 >0 r- O' 0 CM CO in <o co 0 CM CO in r- O CM 0 co >0 p4 O' ^4 r- 0 >0 0 X *4

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^4 CM CM CM CM CM CM CM CM CM CM CM X0 0 660 6 6 6 0 0 0 O O 0 0 0 0 0 O 6 6 6 6 0 6 6 0 006 0 0 0 O 0 0 O O 0 6 0 O 6 0 0

cc\ x x x CO CO CO co CO CO CO CO CO co co CO <r\ r*i CO CO CO CO CO CM CM CM CM <M CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM0 O 000000 0 0 C O O 0 0 000 0 OOO 0 O 0 0 O 0 0 O 0 0 O O OOO O O O 0 0 0 0 0UJ UJ UJ UJ LU LU LU LU UJ LU LU LU LU UJ LU UU UJ UJ LU LU LU LU UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ LU LU UJ UJ LU UJ LU LU UJ•0 >0 0 -0 X <3 x in in >* CO CO CM CM *4 O O' 00 0 in CM O 0 O >0 n in -0 O- 00 O <M 'O H- 0 ^ H- h- in X*

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6 0 OOO 000 O 0 0 6 660066 0 0 0 6 0 0 0 6 0 6 0 OOOO 0 006 O OOOO 0 0 0

x0 0 -• -• H H -c >4* nO O' H- O' CM >fr h # in CM O' >0 >t CM O' 00 c CO CM CM cm CM CO in n 0 in 0 4 X 0 X X — 000000 0 0 0 O O *4 H i*4 ^4 (M CM CO co >* in in -a r- 00 ao O' O -* rsl rr\ in >0 GO O' p4 CM 00 0 H- X CM X

* 00000000 O O 0 0 O O 000000 0 0 OOOO *4 p-4 ^4 4 -4 p-4 4 *4 p-4 CM <M CM CM CM X X X in H-

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>* 00 CM CM co in O' >0 CM »4 j- O in 00 in ^4 (M in 0 in CO CO r* CM 0 O' O' O CM in in CO in *4 0 rO X >0 in in X 0 inin CM O' h- in CO H H >0 CO *4 in CO co in O' 00 O -t 0 O cO P-4 O' r- >0 in CO <M CM *4 0 GO CM >0 4 O p4 >0 CM X 0 X 0-i- h- x co CO CO CO CM pH p4 •-4 O' 00 0- vO in H- H- CO CO CM CM CM H 4 4 4 *-4 ^4 ^4 p-4 p-4 O' X ao O 0 in in in >* >*

0 O 6 0 O 0 O O O O O 0 0 0 0060 0 0 0 O 0 O 0 O 0 O 0 d O O 0 O 0 O 0 O O 0 0 0 0 0 0

in in m in in in in >t -t H- H- 4- H- H- >$ CO CO CO CO CO CO CO CO CO CO CO CO CO co CO CO CO CO CO co CO CO CC\ X X X X X CM0 0 0 0 0 0 0 0 O O O 0 000 0 OOO 0 0 0 O 0 0 0 0 0 0 O 0 0 0 0 0 O 0 O O 0 0 OOO OUJ UJ UJ UJ UJ LU LU LU UJ JJ LU UJ UJ LU UJ UJ LU UJ LU LU UJ UJ LU LU UJ UJ UJ LU UJ UJ UJ LU LU UJ LU UJ UJ LU UJ UJ UJ UJ UJ LU •JJ

O' O' O' 0 CO O O O' CO CO 0- 00 r- 0 0 -4 O' t h- 0 vO CM O in X) 0 NO co OJ ^0 >0 >fr H- n O' CM >0 O' X r*- *4 inO' x O' o- in O CM O O' O' CO O' >0 H- rO p-4 oj in n O' CO O in (M O' h- in CO CM 0 O' CO 0- >0 in <0 rO CM •4 *4 0 O H-CM CM H H H rH —4 >0 CO CM CM -4 f4 p-4 *4 O' 0- >0 in >fr rO ccs rO <M CM CM IM CM <M p-4 4 p-4 -• p4 4 <4 t4 -4 *4 4 4 p-4 O'

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CO H- >0 >0 O' 0 4 CM CO CO CO CO CO CO co CO CO CO CM CM •-4 4 O O' ao r- in 'T f\J 0 X >* O' CMO O H H cm 'm >* in >0 >0 C'- 0- r- oo 00 00 00 00 CO 00 ao 00 co CO 00 CO 00 00 00 OO ao X X in in

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32

See

footnotes

at

the

end

of

this

table,

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

“ a-© i

O' «C

<4 H *4 ^4 e4 ^4 H *4 H H H *4 H »4 e4 »4 4 <=a H •4 4 »4 H •4 r-4 •4 ^4 4 ^4 >4 *4 *4 •H 4 ^4 4 4o O o o <n o o O o o o o o o o o o O o o o o o o O o o o o o o o o o o O o o o o o o o oO

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ Ul UJ UJ4 4 4 4 4 in in >0 C** h- QO r- O' o <N co 4 <0 O' H co 4 <o 00 o OJ in h- o m <0 o 4 O' m Csl ^4 co o co m

O >0 o •o 'O <o •o <0 o 'O >0 vO >0 >o O r- r- r«- f~ GO GO 00 CO co O' O' O' O' o O o 4 H H eg co 4 in e- O' coUJ H c=4 •4 H •4 H H 5=3 H r4 *4 -* <4 r4 4 4 H 4 4 H »4 *4 H 4 CM eg eg <NJ fVJ eg eg IM eg eg eg eg co

a.UJocQ-

Oe4CO

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QC

CLXUJ

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

III III III 111 III Ml ’ll III III III III 111 I . I III III 111 111 III 111 111 III III III Hi III 111 III III 111 111 III III II 111 III 1 1 I 111 I 111 III III III III

fn<\iroh-M®0'04r'i-*040'Oin<'>joO'0-*{»)inr-0'<\i'004oo-*<\ir^4'0®04®inir>.oo

eg eg eg eg ^4 H 4 *4 4 r4 *4 H 4 o o o o o o o o o o o o O o o o o O o o o o o o o o o o o o oo O O O o o o o o o o o o o o o o o o o o o o o o O o O O o O o o o o o o o O o o o o oUl UJ Ul Ul UJ UJ UJ Ul UJ Ul UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ Ul UJ UJ UJ Ul Ul Ul UJ UJ UJ UJ Ul UJ UJh* »n GO in eg CO >0 GO *4 o e- o o eg <0 f*- o GO o eg 'i- o O' eg o eg o GO GO GO O' .4 CO in r- o CO x\ e- O' o O' oin co ^4 o 4 4 CO O' o ro eg o >0 oo •XI <0 o 4- o 't eg O' GO >0 in 4- eg 4 o O' O' GO h- x> -o in 4 CO eg eg o oi. *4 <4 «4 O' 4 co eg H »4 4 4 4 9.

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oooooooooooooooooooooooooooooooooooooooooooIII III 111 III III 111 III III III III III III III III III III 111 ill III III III III III III III III III 111 III III 111 HI III III III III III ill III III III III II

H^rfH-HH-HH^Hrt-HrfOOOOOOOO(MtNi^+flNN-lOO(f»(M>0-l^H H «4 H ^ H ^ H H ««4 ^4 H ^ H H H H H H *4 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ GO ® CO CO O O' O'

000000 3 OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO

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oooooooooooooo-*-**--<<M<\i<\i<\jr'j<nro<t>«nro44444minir»mifi.o.O'Or-r''-®f'-ooooooooooooooooooooooooooooooooooooooooooooo

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in Ul Hf mrOif*f>>o<Nir\Of“iftrrt'#, »*'*orN>OP»®<7'rr>®O»-*^h-O'r'J®i«n'i<\ir\jiriior-0'c^.oo<*lf,-Oosifi(<>N-irf04, OM<M*i(Mio®'ONOiftONn^aiO+(OrtOO'fflN^in^<*iffwMN-400(MrtrtHw0^mM(M-IH-l-l5'N^IOK\^^(»l(flffl(M(MMPgNN-lrf»4rii-lrf»l-l^F4rt-iHOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO

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• ¥ *0f\l4'0®OQOQOOQOOOOOOOOOOOOOQOOOOOOOOOOOOOOOOOO^-«inHHrf-HM't'0#ON*'0®OlftOH'OlflOiflOiflOiflOiflOiflOiflOK'Oi<'Ol/'OlflOlf'Otf''flN'f

33

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE

F

Ff

VOLUME

EQUILIBRIUM

RATIO

b

ATM

METHANE

MOLAL

c

SPECIFIC*

METHANE

MOLAL

c

SPECIFIC"

METHANE

N-PENTANE

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

111 111 til in ii* m m ill m hi in m m ill m ii* ill m in ill ill m ill ill ill 111 ill 111 in in ill 111 ill 111 iii m iif ^ iflp

CM eg H H pH pH pH H o o o o o o O o o o o O o o o o o O o o o o o o o o o o o oo o o o o o o o o o o o o o o o o o O o o o o O o o O o o o o o o o o o o o o o o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJCO 0- CO O' in O' in O' 4 'I- co in in 4- CO eg CO e- 4- 4- r- CO <6 o x 4 co 4 f- m m O' 5 ® oCNJ CO CO o 4> h- m 4 o o •c 4> co co O' o H H <0 h- 4- CM pH CM ro 4 o 00 O eg 4 o f- CO <o oCM o O' fM 4 0" o 4 eg o o f*p CO •h in 00 in CM o CO h* in 4- CO CM ^H O O' 00 r- 4> 4> in 4 co eg pH o o

1. 9. 4 (O CM pH H pH H pH CO >0 in in 4- 4- 3.co co m CM CM eg CM CM CM CM CM H pH H H -4 ^H

o o o o o o o o o o o o o O o o o o o O o o o o o o o o o o O o o o o O o o O o o pHo o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o O o o o o o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ4 4 m GO eg r~ H 43 -o CM p^ pH in o m o m CM p» 4 CM o o CO m o >0 m >0 H CO CM •o o eg eg h- o m o 4f* h- e- e* CD CO O' o o o H fO 4 o h- o o eg co in h- o pH co m t- o m >o o CO 00 CO o co ao pH o o CO>0 >0 <o o X <0 <o 43 h- e- P*» h- f» p^ CO co ® co co 00 o O o o o o o H •M eg co ro 4 43 CO o >0 <o

1. 1. 1. l. H H pH H H H pH c=4 pH pH H H 1. H eg eg 2, 2. 2. 2. 2. eg CM eg eg (\j <n3. 0.

CM CM eg eg eg eg eg eg CM eg eg eg eg eg eg eg eg CM CM eg eg cm eg eg eg pH H pH pH H pH H pH pH pH pH pH pH ^H CM fOo o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ

43 lO o cei e* -H in o 4 co cn O >0 (p( pH CO 4) eg pH o o O -1 o CO *H CM c o o in r*- eg o eg oo P- o <0 CO

o o o 0s ^ co co h* p» O in m cn eg ph o ® <0 m 4 cn eg m o eg CO m h- O eg 4 GO CO o o O' 4 h- -l oeg eg CM pH pH pH pH pH pH pH pH H H H pH pH O O o o O o o o o o GO ^ >o m in 4 CO CO CO CO eg co 4 <0 O -H

H pH pH pH pH *H pH <=} ^4 pH pH H pi H pH «=4 pH H pH H pH pH -H O o o ^ O' S' O' <y O' <7* ^ O ^ -i o

&

^ 00000000000000000000000-*-^>^^-.>H^-*.-i^r\ir\j(Ncg<\|('<3(r*44<'^• ooooooooooooooooooooooooooooooooooooooooooooUJa

®a5r^ir\-fo^<Mf^tNjao(*>r-h-ino'®ooir>'0(Nr-®h-r~^irif~fMOrr\f^f^r^oif'rrico(M(M» o^<M<\i<N<M-*-*ooff, i?'<\iifi®o<M4ir\in434N4<r'<Ni'-io<?'®®®®o,'»Hmo®04f>,-'0®rr

i

uj ooo—<<M®44'iNor-r^®-gr'3ir\®o<M4-o®o<M4'0®o-grriir>r,-0'^44><?'-g4®f'JOOQas oooooooooooo»*i-i'^>*<\i<'g<N<\i<\ir*'immrnm 444444 'rii/'mu'v®®«or»f'-®f'-3h»<

00 o O O o 00 o o o o 00 o 00 O 00 000 o 00 o o o o o o o o 00 00 o o O o

UJa. cm eg eg CM eg eg ^H pH pH pH pH ^H H pH »H pH pH H pH pH pH pH pH ^H pH pH pH pH pH o o o o o O o o o o o O pHs o o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o n o o o o o o1-=* UJ Ul UJ UJ Ul Ul UJ UJ (U UJ UJ UJ Ul UJ Ul UJ Ul Ul Ul UJ UJ UJ Ul UJ Ul UJ Ul UJ Ul UJ UJ UJ Ul UJ UJ UJ Ul UJ UJ UJ UJ UJ

eg co h- r- O' GO O' 00 o o o CO ® O' H O CM eg eg e* H O' 43 >0 o co CO o eg e- in o o eg CM CM O CD pH 4 00 4eg >fr r- in eg O' 4 00 CO CO CO CO CM o oo in 4 4 CD <0 pH o pH eg 4 h- O O' •H CO oo o 4 pH o e- D pH eg COco eg pH <0 co H >0 >* 4 h» pH >0 >o O* 4 O' 4> co -i O' >o in 4 co eg pH o o C0 CO eg e- CO ® 4 O' in pH O co

eg cm eg pH H ^H O' 00 0- o •a in 4 n CO CM CM eg eg ph pH pH pH *H H pH pH pH pH O'’ 00 oo e- n >0 >o in in in 4 4 o

4 4 4 CO CO co CO co CO CO CO CO eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg CO

O O O o o o o O o o o o O o o o o o o o o o-o o O O o o o o o o o o O o O o o o o OUJ UJ UJ UJ UJ Ul Ul UJ Ul UJ UJ Ul UJ Ul Ul UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ Ul UJ UJ UJ Ul UJ UJ Ul UJeg eg in 0- ^H CO o D CO •0 O' 00 (O o eg r- co o co co 4 CO o 0- o eg eg in pH O' in pH 4 M >

0

in e- eg 00 CO X COin 00 4 r*- o 4 pH 00 00 in e- CO eg eg o ® r- o ci 4 pH CO O O' CM co pH O' O' O pH m in CD ^H •n X eg CO oin co eg eg pH H in O o- in CO eg 00 •H O' O' eg 0- <SJ ® in eg O' in 4 eg •H o co >o n co CO eg ^H o pH

i. pH i. 6. 4. 3. eg eg 1. i. i. i. O' 00 Dinin^M'cococoegeg rg eg 2. eg eg i. i. i. i. i. i. i. pH ^H 1. pH 1. 0.

og04<\i<M4~<ff'CT''0-Hm®<Ni04-*ir\r-0'ooO'i3'®ir\<N®<\iinf^®®r-m<7'.<\iroo<y'44 o(M4’r>®®ir\>4'fr^orriir\®^m^.ir\u>triin<o®ir\irti/>mtrt^'<ff'i<M>400, ®<oinm^r>^<® -o

oooooooooooooooooooooooooooooooooooooooooo o

4Of-4-0<?'44>-.mir\4®r'-4®—•<\irri44444i'’'i ,N'*o«4Nn'i<?'4>-*-0'^443in-<®® 4Q H ^ ^ N ^ 00 CO 00 CO 00 CO ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ CO 00 00 CO 00 CD ^oooooooooooooooooooooooooooooooooooooooooo o

• V w®®000000000000000000000000000000000000000®irif0rtrtN^<ao(M<fj«oinoiftomoifioinoif>oifioinoiftOK'oiftOiftoinoiAOKMr'NN

34

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THEMETHANE-N-PENTANE

SYSTEM

-

CONTINUED

CO oCOCO

oUJQ

oc.

3H-<0£UJaxUJ

<\J H .4 •H *4 H H o o o o o o o o o o o o o O o o o o o o o o o o o o o o oUJ o o O o O o o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o<c UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ Ul UJ UJ UJ JU Ul Ul Ul UJ Ul UJ UJX GO •o p- 4- O' o o> o O' CO CO >0 O' ^4 <o co O' CM 0- CM CM iH o in 00 •0 O' co 4- CM GO GO 4} 4> 4- oUJ o m n- m CO O' -0 p* 4^ CM CO in O' in 00 00 CM o CM m ^4 GO o in 4" 4- in in <o 00 o ^4 CO in in 4- oz o o CO in o 4- CM ^4 o co CP O' CM >0 CM 00 in CO O' p- >0 4- CO CM *4 o O' oo p- sO 'O in 4- CO CM ^4 o

•4 in CO CM CM ^4 «-4 H H 00 >0 in in 4- <* 1*1 CO CO co CM CM CM CM CM CM CM CM H *4 »4 f4 ^4 r*4 *-4 *“4 ^4

o o o o o o o o o o o o o o o O o o O o O O O O O O O O o o o o o o o o o o f-4

o o o o o o o o o o o o o o o o o o o O o o o o O O o O O o o o o o o o o o o oo

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ>0 o * 00 4^ oo 4- GO CO O' CM m o in o m H 00 in CO CO 4- >0 O' CO H *4 in CO o n P- in oo r- 00 f«4o o CM CM CO CO 4- X* <0 p» O' o CM co in •O 00 o CM 4- <o GO ^4 4- P- o 4^ 00 CO oo in 4- in O' CM O'

UJQ-

p- p» h- p* P- p*- P» P- r*- p- p- 00 00 00 00 oo 00 O' O' O' O' cp o o o •4 ^4 rW CM CM CO 4> m 4> O' CM CO

- <4 -4 H *4 c—

«

H H -4 H *4 r*4 s4 h f4 c4 f=4 ^4 o=4 CM CM CM CM CM CM CM CM CM CM CM CM CM PO o

CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM *4 f4 f-4 f4 *4 *4 f4 f-4 t4 r4 CM COO o O o o o o o O O O o O O O O O o O o O O O o O o o o o o o o o o o o o O O

_l UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ Ul UJ Ul UJ UJ Ul UJ UJ UJ UJ Ul Ulo 4- 00 cm p- .4 >o o 4- CP .0 CM o p- in CM o O' 00 oo OO O' o CM 4- p- P- O' P- in 4- 4- <o *o 4- 4>

o PO CM ^ o o O' O' 00 p» m 4- CM h o O' p* o m 4- CO CO <M O O' CO p» O' CM 0- *0 o f4 00 CM H o2 <N CM CM CM CM CM H H .-4 f4 <=4 •—4 o o o o o o O O o o O' O' 00 p» P- o «

0

>0 P* O' o *4

H H H H H H H H H H H H H H ^ H ^ »4 H H H H ^ H H H H ^ ^4 H f4 H »4 H ** f4 OoooooooooooooooooooooooooooooooooooooooI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

III ill III ift f

i^i qi III ill m m Hf 11 1 m ||| III ill III HI 111 til Hi til III III III 111 m III II* ill 1 1 1 I|f III H

^III

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0<''J't'Oco»-f*>i/>F-oif'-<®4'0*“4--*coif'<\lOF-if><*if\ii-i-*-HfriF'-»*h-ift^i**<sjr'-.o4-

OOOOOHWHrtNMn®^UMflONN®J'OOHNM'tK\^^®O^Cl®«IMI'O0'OOOOOOOOOOOOOOOOOOOOO-H-i—i-i-i-H.-i-i^.j<\|i\l<\l<\lcgf*ir<1 .1-<\|

oooooooooooooooooooooooooooooooooooooooo

^O^0'(M«NHrtHNOHJ'n^N.f^^0^®O>0(fN+®HMflOmNN<|No-<-iNmj’in®f'aoNii>so'^rtrf\Nff'iHrti/\s®oN^®eoK>iA»oi,'®rtaiftOOOOOOQOOO'<HrtHHniN(MNNK\®®mrt<'^*4’4, lfl®®lft«4).ONN40. o 0, o O o o 0. 0. 0. 0. 0. o 0. 0. o 0. 0. 0. 0. 0. o o 0. 0. 0, 0. 0. 0. 0. 0. 0. 0. o o 0.

o<0. 0.

CM CM CM CM ^4 ^4 f4 f4 ^4 f-4 1*4 f4 fH f=4 «4 •4 »4 e4 *4 f4 4 *4 f4 «4 f4 f4 O o o o o O O o o O o O *4O O o O o o o o o o o o o o o o o o o o o o o o o o O o o o o o o o o o o o oUl UJ UJ Ul Ul UJ ULI Ul UJ UJ Ul Ul Ul Ul Ul UJ Ul UJ Ul Ul Ul UJ Ul Ul Ul UJ Ul UJ UJ UJ Ul Ul UJ UJ Ul Ul Ul UJ UJGO 00 4- in o h- CM in 00 f—4 X C0 CM o 4- 4- o o oo co 4) O' co f*- O' 'o PO in p- CO p- X p- PO 4 O' in 4o in -4 co H O CM in oo O' -o *4 *4 CM o 4- CM co NO CM o o o *4 CO >0 4- >0 PO CM 4- X in 4- 4- CM O'00 4^ (M r> o O' ^4 4- 00 co 4- 00 CO O >o CO ^4 O' >0 in CO P0 CM c=3 o O' CO CM P* CM p» co O' in **3 >0 CO

1. *4 •^4 O' r*-6. 5. 5. 4 3. 3. 2.

CM CM CM 4 *4 •4 i. *4 ^4 *4 *4 1. 9.O'

8. X P» 7, o >0 in5. 5. 0,

4- CO CO CO CO co PO CO CO CO CO CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM <M CM CM CM cm CM CM CM POo O o O o o o O o o o o o o o O o o O o O o O O O o o o o O o O o O o o o O oUJ UJ UJ UJ UJ Ul UJ Ul Ul Ul UJ Ul UJ Ul UJ UJ UJ UJ Ul Ul Ul UJ UJ Ul Ul UJ Ul Ul Ul UJ UJ UJ Ul UJ UJ Ul UJ UJ UlCO 00 4- CM O' 00 O' oo o CM o *4 r*- O' h- f4 O' oo O' o oo 30 CO o >0 in o o 4- >o in PM X O' CM in 4- P->0 oo *4 >o PO CM O' CM P- f-4 *4 p- >0 p- h- m in O' p- GO >4 in ^4 X p- -0 >o p^ O' 4 co 43 O CO oCM CO CM CM in CO in 4- CM o PO *4 f4 4- 00 CO O' o C0 o 00 n0 in co CM o O' X >0 n in 4- CO P0 CM f4 »4

4 N0 4- (O CM <M f4 f4 H *-41. 8. 7.

>0 5. 4- 3. 3. 3. 3. 2. 2. CM cm CM 2. 1. 1. •4 i. i. *4 4 *4 1. 1. 4 o

MO‘-<ONO'WirMflifiBMMHifi®ac®oo-<N^iri®-i(r.®sBifiPuao'ON®0‘^Oa'f-®Sf-9'®®n^aO®(M®^NSN®^FlJ)ON4®®K>O®»(M»n®o«OMfla-<^'OBNirw'®ooH-i-i-iHri-i-HootMoi'iin4MOff'>o^<i

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO

oif\*'sjf>-a'aD4-^ir\rri^-friooo>of^aoa'000'0'®r~ir\rooh-oo'^, oo<Mir\f^or'h-

o in*jn-p*-xxxxxxxcpo'^o»O'O'a'<7'O'a‘(7'O'0'0'O‘<7'O'C7'XXxxxxxxn-ooooooooooooooooooooooooooooooooooooooo

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35

See

footnotes

at

the

end

of

this

table.

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE

F

WTF

VOLUME

"

EQUILIBRIUM

RATIO

b

ATM

METHANE

MOLAL

c

SPEaFIC

d

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

H H »-4 H H H H *“4 H H H H H H H H H H H H H H H H H H H H H H H ^ H OooooooooooooooooooooooooooooooooooooooI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

UJUJUJUJUJUJUJUJUJUiUJUiliJUiUJUJUJUJUiUillJUJUJUJUJUJUJUJUiUJUiUilUlilUiUiUiiiJ

H c—1 «=4 H H o o o o o O O O o o o o o o o o o O O o o o o o o o o o oo o o o o o o O o o o o o o o o o o o o o o o o o o O O o o o o o o o o o oUJ UJ UJ UJ Ui UJ UJ UJ UJ UJ Ui UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ UJ UJ UJo o cm in m CO 4- —

1

o O' O' in m GO ^ o rr\ CM h- r- 4- CM GO CM O' O' o ift 4- O' in h* r** cm oo in O' r*» m GO O 'O 4- ^4 m in CM in O' <\l CM •0 4- m ® <*) o GO •o o n in >0 <0 GO O' h *4 o a oH 4- in o r- 4- cr> •4 O 4- o o m h- «M O' <0 *»4 O' f- o m m CM *4 O O' GO r- ® in 4- 4- fOCMO om 3. eg <M -i H H H 8.

h- •o in 4- 4- <»>3. 3. 3. 2. 2.

CM2. 2.

CM IM2. 1. •4 H H ^4 *4 H H *4 H -4

o O O O o o o O o o o o o o o o O o O o o o o o o o o o o o o o o o O o o •Ho o o o o o o o o o o o o o o o o o O o o o o o o o o o © o o o o o o o o oUJ UJ UJ UJ UJ UI UJ UJ UI Ui UI UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UI UJ UJ UI UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJm r- CM o in o in o 4* 1^ CM GO m H o m <M O o 4* GO 4- CM PO CO >0 H CM o 4- in O' * 4- in O'4* 4> in in o >0 r* GO O' o CM m in GO o CM 4* o GO o CM in GO ^4 4- GO m CO 4- p4 o CM 4 O' ^4 O'h- h- h- r- h- r- 00 00 00 GO GO GO O' O' O' O' O' o o o o *4 H CM CM m 4- in >0 GO O -o m

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOm ill III m III m HI III HI ill m ill ill m HI in ill III ill til ill III III III in III m ill ill m ill ill III Hi HI III HI ill

o4-0, <','r-'-, u'\oir\<\io'.o4'<Nj—<0> ®®®0'O<M4, f-Of^r~-*4, ®ci,i-*»^o®0'r-4-

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o4-

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^4 H ^ H H H m m ^ ^ vn4- <M4 r-

36'Z

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE

F

WT

F

VOLUME

EQUILIBRIUM

RATIO

b

ATM

METHANE

MOLAL

c

SPECIFIC

11

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

^4 ^4 pH pH H H H H H —4 H pH H H pH p4 pH H H H sd pH pH pH pH *4 H ^4 H pH pH p4 ^4 pH pH 0009 0000 0 0 O O O O O O O O O OOOO O O O O O O O O 0 O O O 0 0 0LU UJ UJ LU UJ UJ UJ UJ LU LU UJ UJ UJ UJ LU LU UJ LU UJ UJ UJ LU LU LU LU LU UJ UJ LU UJ LU LU UJ UJ UJ UJ UJun co eg 0 co r» eg >0 0 vO 0 ro 0 0 4 'O 30 *4 4 in —< o> ao O' 0 CO CO e- CO CM O' CO ^4 UN eg 0r- ® ® >0 CO UN pH O UN 0 (M eg e- rO ^4 rsj lA ® (NI N pH p» 4 (A CO 4 ao LA >0 CO >0 0 O' UN 0co c 4 -O i-H ® ® 4* eg O' 00 r** ® 0 0 0 o <ONN ao ao a* O H fNJ CO UN O CO CO CO eg CM 006 1n 4 3. 3. 2

.

2.2.

2.pH .H h pH H »4 1—

«

H H »4 pH pH pH pH CM 2.

eg 2.(NI 2

.3, 3

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40

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at

the

end

of

this

table,

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

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POINT

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41

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footnotes

at

the

end

of

this

table.

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

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CONTINUED

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42

See

footnotes

at

the

end

of

this

table

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

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in 4 4 eg m m ^4 o O' O O' m 00 4 4 m oo CO eg m oo in 4 rO •4 O' r*- in 4 eg eg o o 4 o o m 4 4eg eg 2

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o o o o o o O o o o o o o o o O o o o o O o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ yy UJ yj UJ UJC eg oo 4 o o in •4 eg m o ^4 O' o O in CO 4 m in 4O O' eg O' in eg o eg o h- in £> CD eg 00 e- m e-oo in 4 eg o oo g> O' m 00 m O' >0 -4 CO 4 eg o 00 ^4

H H 1.i. i 00

7. 6. 5. 5. 4 4.3. 3. 3. 3. 2. 2. eg eg eg ^4 C.

ffi(fiWHH^ONS#® ,tO’OOO^NOOlflOoinr“®-*inino-*® — -*®-*®<MO'<\i4<M4in® mni4-0®m®^<M4inp“«®0'0'0'®®^'®4''*0' O'OOOCiHHHNNrgMIMNIMNMftlNNNIMM^ f\)

OOOOOOOOOOOOOOOOOOOOOOO o

f'inin<\|.»-<N—<0-0-—<-0f'-m0'O0'-00'a'4(\lrM.0 —I®f“ 400 f^<\lin®^M® 44 m,*,$-mi\|»*(T-m(\| ino-*<Nr-i44ininin'0-0'0'0-0-0'0-0'0'0-0minin -o

OOOOOOOOOOOOOOOOOOOOOOO o

• Vi W00000©0000000000000000'0»^4^taomoino^oiAOinoiftoino^oiAooc1 orf ^,^oj<MOi^i^-^-unir\®vOi>^F^®®a'0'oo-i'-<®r~

43

See

footnotes

at

the

end

of

this

table.

o oo o © o o o o o o o o o o o O o O o o o o o o o o o o o o o o o O o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

O' o o o * in o o ^4 co 4 4- 4- o m O' o o CO o co o m UN sO <o UN <NJ 00 *0 o O o*4 •o 4 4 h» (M cm •o O' O' UN O (NJ UN r*> m O' o <N m 4- CO fNI in UN (NJ 00 CNJ (NJ o 4) o 4- oin 00 CM rsj m o p- in on CNJ CM cn 4 <£ 00 ^4 4) ^4 o © co CM 4-

O' m co (NJ •-4 (M «N m CNJ O o• 9 • • • • • • • • • • 9 9 • • • • • • # • • • • • • • • • • • • • a

O' 00 CO >

0

o m in in UN UN m in UN in 4) 4> r* © O' 00 r* 41 '

0

4) '

0

<0 o o <o 4) CO •4

^4 o o o o o o O o o o O o O O o o o o o o o o o o o O o o o O o o o oo o o o o o o O o o o o o O O o o o o o o o o o o o o o o o O o o o oUJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

(«N o * UN 00 4 o * UN © ^4 © o UN o >0 o 4 00 UN * CD O' o >6 O' p- (NJ o>0 m © © © CO O' GO CO ft\ o 4-

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o o o o O O o o o o o o o o O o o o *4 o O O O O © O O o o O O O O o ^4

o o o o o o o o o o o o o o o o o o o o O o o O O o o o o © O o o o ©UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ00 p- UN CO CNJ O' O' -4 O' O' UN in ^4 00 CNJ 43 co in 00 m 4- CNJ o CM o *4 O' m CO 'o CM 4- p* 00

>0 00 o co UN 00 CNJ UN O' 4- O' m CO o ^4 00 in o 43 f>- o co 43 O' 4- CO 4- o CD CO O' o44 ^4 #4 (NJ (NJ (NJ fM ro pin co 4- 4- in in h- 00 O' CNJ 4- CM CNJ ro co co 4- 4- in 43 >0 h- O' o 4- 4

• • • • • • • • • • • • 9 • • •

2 2 2 2 2 2 2 2 2 2 2 2 CNJ 2 2 2 2 3 0 (M CM CM CM CM CM CM CM (NJ CM CM CNI CM ro co o

CM CM CNJ CM PM CM CM CM CM CM CM CM CM CM CM CM CM CM co CM (M CM (M (M CM CM CM CM PM CM CM CM CM CM CO

o o o o o o o o o o o o o o o o o o o O o o o O o o o o o o o o O o oUl Ul UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJib m 0 O' ® O' in o f- >0 00 •O l>- 4 >0 o >0 CM 00 o O CM <0 m UN O' 4 r- CO (O <0 p* ^4in in >*• co pm •4 4 o o © © © O' 00 00 <£ 00 CO PM CM *4 o O' © O' O' O CO h* (M ^4 oin in m m in m m m in 4 4 4 4 4 in ^ in oh •0 >0 •c o <0 in UN UN in <0 >

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c P- 00 CM

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0

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o o o o o o o o o o o © o o o o o o

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o 00 p*- UN <0 PM UN UN 4 •c © h- 4 ^4

in co CM 4- 4) p*- O' o CM 4 UN h- O' CM m o 00 •O CM O' » ^4 © 4 4 h- o CO •o © OJ vO CM PM 00 ©o H CM 4- >0 00 o m r* O' ^4 co <0 oo ^4 co CO Ul o © CO in © (M >0 00 •4 (O >o O' (O © in

o o O © o o 4 ^4 4 ^4 ^4 CM CM CM CM CO CO co CM BL o o o O o «4 4 *4 ^4 (M PM (M PM CO 4 PM• • • • • • • • • • • • • • • • • • • • © • • • • • • • • • • • • • • 9 9 9

o o o o o o o o o o o o o O o o o o 00 h-<

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o o o o o o o o o o o o o O o oUJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJM) O- O' o PN UN ^4 O' >0 ^4 ^4 ~0 4 00 co UN UN 00 CM 00 (M oo 0- O' UN 4 (M O' o o (M 4 CD

h- © CM in O o UN cn 4 UN >0 in in CM p- ^4 ^4 UN o #4 CO 00 UN UN UN >0 o 4 (O m CO CD h- O44 O © CO r- in 4 cn 4 o © CM 4 co ^4 in 4 CO h- m 4 CO fM r4 o © o (M 4 O' ^4 42. 2.

CM r4 «4 4 >4 4 #4 ^4 © 00 00 c*- >0 vO in O 4 4 4 4 ^4 H ^4 © O' 00 >0 in UN o

co co (O CO CM CM PM CM CM (M CM CM (M CM PM PM CM CM CO CO co CM CM (M CM (M CM CM CM PM CM PM CM PM CO

o o o o o o o o o o o o o o o o o o o o o o o o o O © o o o o o O o oUl UJ Ul UJ UJ Ul UJ Ul Ul 111 111 HI 111 111 in UJ UJ Ul UJ UJ UJ UJ Ul UJ Ul Ul UJ UJ UJ UJ UJ Ul UJ UJ UJin >o *o in f- ® o 4 ,h « ® in m 4 ^4 oo ao © o P^ o P^ © CO CM 44 CO CO O' <0 44o MD ^ 4 «0 N UN N P^ CO in CM CO UN CM GO 00 co O' 00 (M fM CO 00 ^4 co UN ^4 CM o p- oUN CO m o in (*i 4 K h >o psi oo in pm © P- (M 4 CM -4 '

0

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UN O' 4 o O PM © o co CM9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

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ro©o04f^40GO>or^co(M© CO P*" 44 © OO O 4 CO GO O' <0 0 OO 4 O O 0 fO CMM © O O 4 Hi40N0lA®« >0 O 4 UN >0 O' 00 ro 4 4 (O © CO PsJ O' CO 4 PM O PO PM *HKIlMMM mKO'HIMKWM'in 1*1 m i\i h ^ CO O 44 UN 00 44 CO 4 p- h- CD 00 GO P- M3 CO 00

o o o o -« 4s44N(M(MNN(\ (M PM (M (M ^ CM 0 O O 0 ^4 ^4 ^4 4 »4 44 4 4 4 44 44 ^4

o o 6 o o 60666600600000 0 O 0 O 0 O 0 O O 0 © O O O O O O 0

« imj Mhrl J'f»OMN4l*l © pm r- © PM PM 4 00 in CM 0- © m ao UN •0 UN 4NinHN(Mnoj'inm4H4inH40HN in co -0 4 CM O ^4 «

0

4 UN 44 CO 44 O 0- M> COin(M0'O®40'*H4'0h»®®® 00 N M) UN S 00 0 P*» 0 © O ^4 •0 co © 0 O 0 © 0 O OO44P0(0^>ruNinuNUNinuNin in m m m 4 UN © O (M CM CO 4 >r UN in in 4 in

9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9oddoodoooooooo d 0 0 0 0 0 © 0 0 O 0 O 0 0 O 0 0 0 0 © O O 0

0 O 0 © O 0 O O O 0 O 0 O O 0 0 OC Vi to

0 m 0 p- O O O O O 0 O 0 O 0 O O O O• *« to0 © co m

• 9 9 9 9 9 • 9 9 9 9 9 9 9 9 9 9 9999 9 9 9 9 9 • 9 9 9 « 9 9 9 9 9999«

0

co O UN O UN O m O UN O UN O in O in O UN © ^4 CO GO O UN O in 0 in 0 UN 0 UN C UN © in ^ pm ©4 4 CM PM CO ON 4* 4* m UN >0 M3 h- p- 00 GO © © © GO P*“ 44 CM PM co co 4 UN UN 'O O P^ CD GD <D r- M3

44

See

footnotes

at

the

end

of

this

table,

TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THEMETHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEWPOINT

BUBBLE

POINT

PRESSURE

3

MOLE

F

WTF

VOLUME

MOLE

F

WTF

VOLUME

"

EQUILIBRIUM

RATIO

b

ATM

METHANE

MOLAL

c

SPEaFIC

d

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

o4-4-

*•

Oaia

cc3<CC

H H H H H H H ^ H H OooooooooooooI I I I I I I I I I I

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O'aor-r-r-r-r-f'-r-f-O'-*

oooooooooooooooooooooooohi n i 1

1

I iii hi i)i in ni ill m ill m0!'*000'00®—if'-'OO^NOnONNOCW'lOO

OOOOOOOOOOO-iOOOOOOOOOOOOHI Hf yj yi >11 III HI III III III ill

UTfO N >0 fO ^ O' O IfN O 00

4-4->$*inin>or*-aoo‘eg>o^®oo®*oo©oooocMegcgegegegcgegegcocoo

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1

f ill iii hi hi 1 1

1

1. 1 1 ill niN>0«t^C0Q04, 't^a0OO^oooOHioinoN®^h-e-e-r^p*»e^e-r^aocoO'og

H H H H H H H H H rt H O

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^^co>ON^ir®^o>ts-~g^, 0'eg'00''$’—<inin*-<*H-g yt 'Offl^mma^'to^oDOOO^^HHNN^mN• ••••••••••«•DOOOOOOOOOOOO

oin>*

oUJo

LUoc

HHrtHHHHHOoooooooooI I I I I I I I

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O'<N)h-4, fVJfNjm0DO• ••••••••

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oooooooooooooooooomi hi mi hi ni ni mi mi hif-ITi—l^(M(\jO—lO—t^>«M<Biri(Mcrif>o• •«••••••

<—i—

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W fO fO CO CO fO fOoooooooooLUUJUJUJUJUJUJUJUJegcgcgfOincoegmO'aoGocoaooocoo'Ocn

ooooooooo

0'0eg0'in^g0'00h»e-OOHHNrt(^'t'0(f»oooooooooooo©oooooo©oooooooooo

NNN®f^'0'tin«tNO<NJ»n^OCMlAC0^>tOOOO^HHHNHOOOOOOOOOO

H H o o o o a o O c=45 ft. eg eg H f-4 H H H HO o o o o o o o o o o o £ o o o O o o o o oUj UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ 1= UJ UJ UJ UJ UJ UJ UJ Ul UJ4- H O' co 4- eg o in o eg GO 00 >0 in co 4- H o O' GO4- CO CO -o 4- O' O' n o ee co o H o m o eg co 4- oco eg o GO o eg j- •o e- <0 4- ©9 o> co GO p- 4> in 4-

9 • 0 0 ® • 9 9 •H *-g »=l ^g o* O' GO r*» o in >4- o o o O o o o o o O

CNJ rvj eg eg eg eg eg eg eg eg eg co CO co co co co co ro CO coo o o O o O o o o o o o o o o o o o o o ouu UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ4- eg o o m 4- in eg •4- o o O' eg 00 © e- >o >0 e- O'GO GO o r- co O' ^g e- in r*» eg <=—

<

<»> O' O' eg >o o in o mO' ITN in e- H m *«g o eg CO 4- eg ao >0 in in 4- 4- co ro eg• • • © • 0 9 9 © © 9 9 • • © © 0 © © ®

GO <0 in m 4- •i- co co eg eg o o o O o o o o o o

O't

oUJo

UJQCol-<(XUJft,

XLU

o •g 4) <o 4- o o O' -0 inO' eg co o eg o CO eg O' O' O' CO CM 4- CO o eg o 4- O' 4-

O' o eg co CO CO eg o O' CO o eg 4- >0 r- GO 00 r- >0 GOo o o H *-g H ^g —4 *»g o <g o O o o o o o o o o9 9 9 9 9 9 9 9 9 9 9

o o o o o o o o o o o o o o o o o o o o o o

o eg eg in O' eg O ~g00 O' e* >o in H GO GO ^g vO H GO O' o GO CO o o H o 4- egGO in *H in GO o o o o in <o O o o •o eg >o GO O' GO 4- O'r*g eg co co co -g* 4- 4- 4- (O CO 4’ o »g H eg eg eg eg eg eg eg9 • 0 9 9 G 9 © 9 © 9 9 9 9 9 9 9 9 9 9 e 9

o o O o o o o O o o o O o o o Q o o o o O O

• *« 1« • *4 Wo o o o o o o o o O CO 4- CO o o o O o o o 0 5 O' O'

1 • 9 e 9 9 9 9 9 9 9 9 9 9 © 9 9 9 9 9 9 9 9 9 9

o in O in o in o in o in in CO CO in o in o in o in O eg CO in1CO co 4- 4- m in 4> <0 h* h- <0 4) eg CO CO 4 4- in in >0 o n in

45

Table 3.2. Agreement of interpolated and experimental data for the methane-n-pentane system

Source Numberof points

Average a Deviation

fraction b

Standard c

Composition d

Taylor [36] 14 0.0021 0.0042 0.0116

Dourson [37] — 4 .0078 .0198 .0164

Sage [38] 32 .0007 .0035 .0037

Pressure e

Sage [38] 34 -0.05 0.0054 0.33

Sage [35] 9 4.8 .0395 5.5

“ Average deviation defined by£^ (Gt exp -Gk sm]lN.

b Fractional deviation defined by

' Standard deviation defined by

l|[

([?

(C* exp Cfcsm ) /Gke .])«».

(^frexp ^sm)2]/(AT—

1)|111 where G = either composition or pressure.

d Composition in weight fraction methane.e Pressure in atm.

Table 3.3. Unique states for the methane-n-pentane system

Methane Critical Maxcondenbar Maxcondentherm

Mole

fraction

Weight

fraction Temperature Pressure a

Volume

Temperature Pressure a Temperature Pressure a

Molal b Specific c

K atm K atm K atm

0.0 0.0 d 469.49 33.16 294.6 4.08 469.49 33.16 469.49 33.16

.333 .1 439.9 75.9 218 4.08 408.4 91.5 446.6 58.6

.529 .2 409.7 111.3 173 4.08 355.9 133.5 427.0 70.9

.658 .3 380.6 139.0 144 4.08 328.4 152.4 408.6 76.7

.750 .4 351.4 156.4 122 4.04 310.8 162.4 390.0 78.9

.818 .5 311.7 166.5 99 3.78 e 294.7 167.5 371.5 78.4

.871 .6e 275.0 169.2 275.3 169.2 353.3 75.8

.913 .7 253.0 167.0 253.0 167.0 333.8 71.2

.947 .8 232.3 155.9 232.3 155.9 e 309.7 64.4

.976 .9 211.2 129.4 211.2 129.4 279.3 55.7

1.0 1.0 d 190.63 45.57 99.3 6.18 190.6 45.5 190.6 45.5

.1 .024 462.8 44.2 272 4.08 457.9 46.1 463.8 41.4

.2 .053 454.2 57.0 249 4.08 439.9 63.1 456.7 49.2

.3 .087 443.8 70.7 226 4.08 417.0 83.5 449.4 56.4

.4 .129 430.9 86.7 203 4.08 390.3 106.4 440.7 63.2

.5 .182 414.8 105.1 180 4.08 362.9 128.2 430.3 69.3

.6 .250 394.7 126.6 157 4.08 339.7 144.9 417.8 74.4

.7 .342 368.6 147.5 134 4.08 320.7 157.1 400.7 78.0

.8 .471 327.5 164.0 106 3.90 e 299.5 166.6 376.9 78.7

.9 .667 260.2 168.4 260.2 168.4 340.2 73.0

Estimated

uncertainty f1.0 1.0 3.0 2.0 4.0 2.0 3.0

d API 44 [16].

e Values at this and lower temperatures extrapolated.

'Estimated uncertainty expressed in percent.

a (Atm) (1.013250 X 105) = N/m 2

.

"Volume expressed in liters/kg-mol.

c Volume expressed in liters/kg.

46

TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

ooooooooooooooooooooooI I I I I I I I I I I I I I I I I I I I I

III in ill III in in m III I n l-il 1 111 111 111 111 111 111 111 III 11 J HIin«oiftoo^Oi»'OiA(fiO'tnN-4iftoo'f-NOM)lMOONO^Oi0^OMn94NO'49'OO

H.H H H H r-l -< o o O O o o o O o o o oO o o o o o o o o o o o o o o o o o o o o oUJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ<o cn Ot<NO O' fO o 00 in O' o o -l O' o if r- oo oH 00 ^ ^ ^ N it m CM CM cn m oo «t -4 00 h» in H o1.

in cn cm cm ^ i. -* -o •4-3. 2. CM CM e-4 H i.

1. 1.

H H H H H H t-4 H H H Ho 0 o

1 1

o oA

01

01

o 01

o o oA

01

ofl

oo

01

oII

og

01

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1

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UJ1

UJ1

UJ1

UJ UJ1

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UJ1

UJ1

UJ UJB

UJ1

UJ UJ1

UJ UJ1

UJo o o H CM cn ro 4* o >0 cn o O' 00 00 H O' O' min in in in in in in in in in >o >0 r- oo 00 O' o CM m >o cnCM CM cm CM CM CM CM CM CM CM CM CM CM CM CM CM cn cn cn «n

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o o o oUJ Hi UJ UJit O' cn inh»«or- it «*» cn

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UJ UJ UJ UJO' co O'H COO (NlH 0s GD 'O

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ooooooooooooooooooooo

(Minin>rr-inh-->OOcn'^cn^^mh->0^4, CMcno mNO'^M\l>0©ONfn(7'00000'®«0(VjN®a' oc\j>t'Ovor^rs.f^cocoooaoo'Os O'0'aoaocoaor->oir» o'

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h-maororo>Ofoa'-4-f^4, r^r^r^r^mfMir\krvaor^vO r-

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® S4 Mooooooooooooooooooooomin-oIM't'ODOOMtiHOOOOOOOOOOOO®#^rf^^_lHN-t'0®OMt'0®OM't-t'ta3^HririHNlMNNN

47

See

footnotes

at

the

end

of

this

table.

TABLE

14.

PROPERTIES

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THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

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48

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footnotes

at

the

end

of

this

table,

TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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49

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footnotes

at

the

end

of

this

table,

TABLE

14.

PROPERTI

ESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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50

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footnotes

at

the

end

of

this

table

TABLE

3.4.

PROPERTIESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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51

See

footnotes

at

the

end

of

this

table

TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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52

See

footnotes

at

the

end

of

this

table,

TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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53

See

footnotes

at

the

end

of

this

table,

TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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54

See

footnotes

at

the

end

of

this

table

TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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55

See

footnotes

at

the

end

of

this

table.

TABLE

3.4.

PROPERTIESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

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CONTINUED

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56

See

footnotes

at

the

end

of

this

table,

TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

^ °rO <

s

£

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57

See

footnotes

at

the

end

of

this

table,

TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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table.

TABLE

14.

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IN

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METHANE-N-PENTANE

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this

table,

TABLE

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the

end

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14

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PROPERTIES

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THE

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64

TABLE 3.5. Unique states for the methane-n-pentane system, engineering units

Methane Critical Maxcondenbar Maxcondentherm

Mole

fraction

Weight

fraction Temperature Pressure a

Volume

Temperature Pressure a Temperature Pressure a

Molal b Specific c

° F psia °F psia °F psia

0.0 0.0d 385.41 487.3 4.72 0.0654 385.41 487.3 385.41 487.3

.333 .1 332.1 1115 3.50 .0654 275.5 1344 344.2 862

.529 .2 277.8 1635 2.78 .0654 181.0 1962 308.9 1042

.658 .3 225.4 2043 2.30 .0654 131.5 2240 275.7 1127

.750 .4 172.9 2298 1.95 .0648 99.8 2387 242.3 1159

.818 .5 101.3 2447 1.59 .0605 e 70.7 2462 209.0 1152

871 .6e 35.4 2486 35.9 2486 176.3 1114

913 .7 -4.2 2454 -4.2 2454 141.2 1047

947 .8 -41.5 2291 -41.5 2291 e 97.8 947

976 .9 -79.5 1902 -79.5 1902 43.1 818

1.0 1.0d -116.54 669.7 1.59 .0990 -116.54 669.7 -116.54 669.7

.1 .024 373.4 650 4.35 .0654 364.5 678 375.1 608

.2 .053 357.8 838 3.98 .0654 332.1 927 362.3 723

.3 .087 339.2 1039 3.62 .0654 291.0 1227 349.2 829

.4 .129 316.0 1274 3.25 .0654 242.8 1564 333.5 929

.5 .182 287.0 1545 2.88 .0654 193.6 1884 314.9 1018

.6 .250 250.7 1860 2.52 .0654 151.8 2129 292.4 1093

.7 .342 203.7 2168 2.15 .0653 117.6 2309 261.7 1146

.8 .471 129.8 2410 1.70 .0624 e 79.5 2448 218.8 1157

.9 .667 8.7 2475 8.7 2475 152.6 1073

Estimated

uncertainty f 1.0 1.0 3.0 2.0 4.0 2.0 3.0

“(Psia) (6.894757 Xl03)= N/m 2

.« API 44 [16].

b Volume expressed in cu ft/lb-mol. c Values at this and lower temperatures extrapolated.c Volume expressed in cu ft/lb. ' Estimated uncertainty expressed in percent.

TABLE 3.6. Agreement of interpolated and experimental data for the methane-n-pentane

system, engineering units

Source

Numberof points

Deviation

Average a Fraction b Standard c

1

Composition d

Taylor [36]

—14 0.0021 0.0042 0.0116

Dourson [37] 4 .0078 .0198 .0164

Sage [38] 32 .0007 .0035 .0037

Pressure e

Sage [38] 34 -0.7 0.0054 4.9

Sage [35] 9 69.9 .0395 80.8

a Average deviation defined by I ^ (C* exp —Gk ,m ) I//V.

1^

b Fractional deviation defined by[ £ ^(C* exp-C ,J/Gk exJ^IN.

c Standard deviation defined bv{j^

(Gk„B- Ck sJ 2j/(V-l)

j

dComposition in weight methane.e Pressure in psia.

1,2 where G — either composition or pressure.

65

Table 3.7. Accuracy of experimental backgroundfor the methane-n-pentane system

Quantity Units Taylor [36] Dourson [37] Sage [35] Sage [38]

Sample purity

Methane Mole 0.990 0.997 0.997 0.997

n-Pentane fraction .995 .995 .992 .992

Composition

Volumetric a Atm 0.2

Phase measurements Weight

fraction 0.01-0.02 0.005 .005

Volumetric behavior Percent 0.3-3.

0

0.4 0.5

Unique states

Temperature K 1.0

Pressure Atm 0.8

Volume Percent 5

a Phase boundaries determined from first derivative of volume versus pressure. All error assumed to be in pressure.

4. References

[1] “Thermodynamic Property Values of Ordinary WaterSubstance,” International Secretariat, Sixth Inter-

national Conference on the Properties of Steam, Amer-ican Society of Mechanical Engineers, United Engineer-ing Center, New York 1967.

2] Antoine, Charles, Compt. Rend. 107 ,681—684 (1888).

3] Rossini, Frederick D., Pure and Applied Chemistry 9,453-459 (1965).

[4] Dana, L. I., Jenkins, A. C., Burdick, J. N. and Timm, R. C.,

Refrigerating Engineering 12, 387^405 (1926).

[5] Sage, Bruce H., Schaafsma, J. G. and Lacey, William N.,

Ind. Eng. Chem. 26, 1218-1224 (1934).

[6] Reamer, H. H., Sage, B. H. and Lacey, W. N., Ind. Eng.Chem 4 1 482-484 H9491

[7] Helgeson, N.’ H. and Sage, B. H„ J. Chem. Eng. Data 12,47-49 (1967).

[8] Rose-Innes, J. and Young, Sydney, Phil. Mag. Ser. 5, 47,353 (1899).

[9] Young, Sydney, Sci. Proc. Roy. Dublin Soc. 12, No. 31,

374 (1910).

[10] Sage, B. H., Lacey, W. N. and Schaafsma, J. G., Ind. Eng.Chem. 27,48 (1935).

[11] Sage, B. H. and Lacey, W. N., Ind. Eng. Chem. 34, 730

(1942).

[12] Beattie, J. A., Levine, S. W. and Douslin, D. R., J. Am.Chem. Soc. 73, 4431 (1951).

[13] Li, Kun and Canjar, L. N., Chem. Eng. Progr. Symp Ser.

No. 7, 49, 147 (1953).

[14] Ambrose, D., Cox, J. D. and Townsend, R., Trans. Faraday

Soc. 56, 1452 (1960).

[15] Partington, E. J., Rowlinson, J. S. and Weston, J. F., Trans.

Faraday Soc. 56, 479 (1960).

[16] Am. Petroleum Inst. Research Project 44, ChemicalThermodynamic Properties Center, Texas A & MUniversity, “Selected Values of Properties of Hydro-carbons and Related Compounds.”

[17] Kozicki, W. and Sage, B. H., J. Chem. Eng. Data 5, No. 3,

331 (1960).

[18] Benedict, M., Solomon, E., and Rubin, L. C., Ind. Eng.Chem. 37, 55 (1945).

[19] Stull, Daniel R., Ind. Eng. Chem. 39, No. 4, 517 (1947).

[20] Perry, R. E. and Thodos, George, Ind. Eng. Chem. 44No. 7, 1649 (1952).

[21] Michael, G. V. and Thodos, George, Chem. Eng. Progr.

Symp. Ser. No. 7, 49, 131 (1953).

[22] Kobe, K. A. and Lynn, R. E., Jr., Chem. Rev. 52. 131 (1953).

[23] Frost, A. A. and Kalkwarf, D. R., J. Chem. Phys. 21No. 2, 264 (1953).

[24] Brydon, J. W., Walen, N. and Canjar, L. N., Chem. Eng.Progr. Symp. Ser. No. 7, 49, 151 (1953),

[25] Thodos, George, A.I.Ch.E. J. 1 No. 2, 168 (1955).

[26] Erpenbeck, J. J. and Miller, D. G., Ind. Eng. Chem. 51No. 3, 329 (1959).

[27] Nakanishi, K., Kurata, M. and Tamura, M., J. Chem.Eng. Data 5, No. 2, 210 (1960).

[28] Boomer, E. H., Johnson, C. A. and Piercey, A. G. A., Can.

J. Res. B 16, 319 (1938).

[29] Armstrong, G. T., Brickwedde, F. G. and Scott, R. B.,

unpublished report (1954)

[30] Cardoso, E., J. Chim. Phys. 13, 312 (1915).

[31] Keyes, F. G., Taylor, R. S. and Smith, L. B., J. Math. Phys.1 211 (1922).

[32] Volova, L. M., J. Phys. Chem. (USSR) 14, 268 (1940).

[33] Bloomer, O. T. and Parent, J. D., Inst. Gas Tech. Bull. 17(1952).

[34] Bennewitz, K. and Andreewa, N., Z. Physik Chem. A 14237 (1929).

[35] Sage, B. H., Webster, D. C. and Lacey, W. N., Ind. Eng.Chem. 28, 1045 (1936).

[36] Taylor, H. S., Wald, G. W., Sage, B. H. and Lacey, W. N.,

Oil Gas J. August 10, 1939, 38, 46-49.

[37] Dourson, R. H., Sage, B. H. and Lacey, W. N., Am. Inst.

Mining Met. Engrs. Tech. Pub. 1490 (1942).

[38] Sage, B. H., Reamer, H. H., Olds, R. H. and Lacey, W. N.,

Ind. Eng. Chem. 34, 1108 (1942).

[39] Velikovskii, A. S., Stepanova, G. S., and Vybornova, Ya I.,

Gaz Prom. (Gas Industiy) 9 No. 2, 1-6 (1964).

[40] Savvina, Ya D. and Velikovskii, A. S., Gaz Prom. (Gas

Industry) No. 2 26, 1-6 (1957).

66

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