chapter 4 study of solute-solute and solute-solvent...

Chapter 4 Study of solute-solute and solute-solvent

interactions of l-histidine in aqueous-sucrose solutions at different temperatures using

volumetric, ultrasonic and viscometric methods

Chapter 4

92

4.1. INTRODUCTION The physicochemical properties of amino acids in aqueous solutions provide valuable information on solute-solute and solute-solvent interactions [1-6]. These interactions are important in understanding the stability of proteins, and are implicated in several biochemical and physiological processes in a living cell [7-9]. In continuation to our earlier studies [10-12] on amino acids in aqueous-carbohydrate solutions, we report here the results of our study on volumetric, ultrasonic and viscometric behaviour of l-histidine in aqueous-sucrose solutions. It is known [13,14] that polyhydroxy compounds helps in stabilizing the native globular structure of protein and reduce the extent of their denaturation by other substances. Carbohydrates located at cell surfaces, are important as receptors for the bioactive structures of enzymes, hormones, viruses, antibodies, etc. [15]. The protein-carbohydrate interactions are important for immunology, biosynthesis, pharmacology, medicine and cosmetic industry [16,17]. Thus, the properties of amino acids in aqueous-carbohydrate solutions are essential for understanding the chemistry of biological systems [18,19].

In this chapter, the densities, ρ, ultrasonic speeds, u, and viscosities, η of l-histidine in aqueous-sucrose (5, 10, 15 and 20 % of sucrose, w/w in water) at 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15 K and at atmospheric pressure, are reported. These experimental data have been used to calculate the apparent molar volume, apparent molar volume, Vφ , limiting apparent molar volume, Vφ° and the slope, Sv, apparent molar compressibiliity,

,sK φ , limiting apparent molar

compressibility, ,sK φ° and the slope, Sk, transfer volume,

,trVφ° , transfer

compressibility, , ,s trK φ° , Falkenhagen Coefficient, A, Jones-Dole coefficient, B and

temperature derivative of B-coefficient, dB/dT. These parameters have been used to discuss the solute-solute and solute-solvent interactions in these systems. 4.2. RESULTS AND DISCUSSION The experimental values of density, ρ, ultrasonic speed, u, and viscosity, η of l-histidine solutions in aqueous-sucrose solvents as functions of l-histidine concentration and temperature are listed in Table 4.1.

Chapter 4

93

4.2.1. Apparent Molar Volume and Compressibility The apparent molar volume, Vφ and apparent molar compressibiliity,

,sK φ of these solutions were calculated by using the relations

1000( )o

o

MVmφρ ρρρ ρ

−= +

(4.1)

,

1000( )os o s s

so

MKmφκ ρ κ ρ κρρ ρ

−= +

(4.2)

where m is the molal concentration of the solute (l-histidine), ρ and ρo are the densities of the solution and the solvent (aqueous-sucrose), respectively; M is the molar mass of the solute (l-histidine), and κs and sκ

° are the isentropic compressibilities of the solution and the solvent (aqueous-sucrose), respectively, calculated using the relation

κs = 1/u2ρ (4.3)

The values of Vφ and ,sK φ as functions of l-histidine concentration and

temperature are shown graphically in Fig. 4.1 and Fig. 4.2. It is observed that, for l-histidine in all the four aqueous-sucrose solvents, Vφ and

,sK φ vs. m curves (Fig. 4.1 and Fig. 4.2) were almost linear in the studied concentration range and at each investigated temperature.

4.2.2. Limiting Apparent Molar Volume and Compressibility

The values of limiting apparent molar volume, Vφ° and the slope, Sv, limiting apparent molar compressibility,

,sK φ° and the slope, Sk have been obtained using method of

linear regression of Vφ and ,sK φ vs. m of l-histidine in sucrose + water solvents from

the following relations [20]

vV V S mφ φ°= + (4.4)

, ,s s kK K S mφ φ°= + (4.5)

Chapter 4

94

where the intercepts, Vφ° or ,sK φ° , by definition are free from solute-solute interactions

and therefore provide a measure of solute-solvent interactions, whereas the experimental slope, Sv or Sk provides information regarding solute-solute interaction. The values of Vφ° , Sv, ,sK φ

° , and Sk along with the standard deviations of linear regression, σ for l-histidine in aqueous-sucrose solutions at different temperatures are listed in Table 4.2.

A perusal of Table 4.2 reveals that the Vφ° values are positive and Sv values are negative for l-histidine in aqueous-sucrose solutions indicating the presence strong solute-solvent interactions and weak solute-solute interactions in these systems. The trends observed in Vφ° values can be due to their hydration behaviour [21−25], which comprises of following interactions in these systems: (a) The terminal groups of zwitterions of amino acids, NH3

+ and COO− are hydrated in an electrostatic manner whereas, hydration of R group depends on its nature, which may be hydrophilic, hydrophobic or amphiphilic; and (b) the overlap of hydration co-spheres of terminal NH3

+ and COO− groups and of adjacent groups results in volume change. The Vφ° values increase due to reduction in the electrostriction at terminals, whereas it decreases due to disruption of side group hydration by that of the charged end.

The increase in Vφ° values (Fig. 4.3) with increase in temperature for l-histidine in aqueous-sucrose solutions can be explained by considering the size of primary and secondary solvation layers around the zwitterions. At higher temperatures the solvent from the secondary solvation layer of l-histidine zwitterions is released into the bulk of the solvent, resulting in the expansion of the solution, as inferred from larger Vφ°

values at higher temperatures [26,27]. Similar trends in Vφ° values were obtained in our earlier study [10] on interactions of l-histidine in aqueous-glucose solutions, however Vφ° values are found larger in case of aqueous-sucrose solvents as compared to aqueous-glucose solvents. Similar trends in Vφ° have also been reported by Ali et al. [17] for amino acids in aqueous-sucrose solutions and Pal and Kumar [2] for l-alanine and l-valine in water + sucrose solutions.

Chapter 4

95

The values of ,sK φ are negative (Table 4.2) for l-histidine in aqueous-sucrose

solutions, indicating that the water molecules around ionic charged groups of amino acids are less compressible than the water molecules in the bulk solution [28,29]. This further supports the conclusion that there exist strong solute-solvent interactions and weak solute-solute interactions in these systems. The values of

,sK φ° are negative

(Fig. 4.4) and Sk are positive (Table 4.2) for l-histidine in aqueous-sucrose solutions, indicating that there exist strong solute-solvent interactions and weak solute-solute interactions in these systems. This further supports the conclusion that the hydrophilic-ionic groups and hydrophilic-hydrophilic group interactions between OH groups of sucrose with l-histidine zwitterions dominate in these systems. The values of

,sK φ° increase with increase in temperature, indicating release of more water

molecules from the secondary solvation layer of l-histidine zwitterions into the bulk, thereby, are making the solutions more compressible.

4.2.3. Transfer Limiting Partial Molar Volume Limiting apparent molar properties of transfer provide qualitative as well as quantitative information regarding solute-solvent interactions without taking into account the effects of solute-solute interactions [30]. The transfer volumes,

,trVφ° of l-

histidine from water to aqueous-sucrose solutions were calculated by using the relation

o o o, , . s ,tr aq sucro e waterV V Vφ φ φ−= − (4.6)

where ,waterVφ° is the limiting apparent molar volume of l-histidine in water (Table

4.2). The ,trVφ° values for l-histidine from water to aqueous-sucrose solutions are

included in Table 4.2 and represented graphically in Fig. 4.5. Fig. 4.5 indicates that Vφ° of l-histidine in aqueous-sucrose are more than those in pure water, i.e.,

,trVφ°

values are positive. In general, the types of interactions occurring between l-histidine and sucrose can be classified as follows [23,24,31]:

Chapter 4

96

(a) The hydrophilic-ionic interaction between OH groups of sucrose and zwitterions of l-histidine.

(b) Hydrophilic-hydrophilic interaction the OH groups of sucrose and NH groups in the side chain of acid l-histidine mediated through hydrogen bonding.

(c) Hydrophilic-hydrophobic interaction between the OH groups of sucrose molecule and non-polar (−CH2) in side chain of l-histidine molecule.

(d) Hydrophobic-hydrophobic group interactions between the non-polar groups of sucrose and non-polar (−CH2) in side chain of l-histidine molecule.

The Vφ° values increase due to reduction in the electrostriction at terminals by positive contribution from the interactions of type (a) and (b), whereas it decreases due to disruption of side group hydration by that of the charged end by negative contribution from the interactions of type (c) and (d) mentioned above. The observed positive

,trVφ° values suggest that the hydrophilic-ionic group and hydrophilic-

hydrophilic group interactions dominate in these systems. The ,trVφ° values increase

with increase in sucrose concentration in the solutions (Fig. 4.5). This may be due to greater hydrophilic-ionic groups and hydrophilic-hydrophilic group interactions with increased concentrations of sucrose. The Similar trends in Vφ° and

,trVφ° with sucrose

concentration were also observed by Zhao et al. [4] from volumetric properties of arginine in aqueous-carbohydrate solutions at 298.15 K.

It is worth to compare the present results with those reported in chapter 3 on the behaviour of l-histidine in aqueous-glucose solutions [10]. The Vφ° and

,trVφ° values

are found much larger in case of aqueous-sucrose solvents as compared to aqueous-glucose solvents [10]. This may be due to greater hydrophilic-ionic groups and hydrophilic-hydrophilic group interactions, with the presence of more hydroxyl groups in sucrose molecules as compared to glucose molecules. Zhao et al. [4] also reported similar results from volumetric properties of arginine in aqueous-glucose/sucrose solvents at 298.15 K, wherein Vφ° and

,trVφ° values were found larger

in aqueous-sucrose solvents as compared to aqueous-glucose solvents. These authors also suggested similar order of interactions of arginine in aqueous-glucose/sucrose solvents. Our results are in agreement with the conclusions drawn by Zhao et al. [4].

Chapter 4

97

4.2.4. Transfer Limiting Partial Molar Compressibility The transfer compressibility of l-histidine from water to aqueous-sucrose solutions,

, ,s trK φ° were calculated by using the relation

, , , , s , ,s tr s aq sucro e s waterK K Kφ φ φ° ° °

−= − (4.7)

where , ,s waterK φ° is the limiting apparent molar volume of l-histidine in water (Table

4.2). The , ,s trK φ° values for l-histidine from water to aqueous-sucrose solutions are

included in Table 4.2 and represented graphically in Fig. 4.6. Table 4.2 indicates that ,sK φ° of l-histidine in aqueous-sucrose are more than those in pure water, i.e.,

, ,s trK φ°

values are positive. The observed positive , ,s trK φ° values suggest that the hydrophilic-

ionic groups and hydrophilic-hydrophilic group interactions dominate in these systems. The

, ,s trK φ° values increase with increase in sucrose concentration in the

solutions (Fig. 4.6). This may be due to greater hydrophilic-ionic group and hydrophilic-hydrophilic group interactions with increased concentrations of sucrose. The observed trends in

,sK φ and , ,s trK φ° further support the conclusions drawn from

Vφ° and

,trVφ° . The decrease in

,trVφ° and

, ,s trK φ° values with increase in temperature,

indicate that release of water molecules from the secondary solvation layer of l-histidine zwitterions into the bulk, becomes difficult with addition of sucrose in the solution due to greater hydrophilic-ionic groups and hydrophilic-hydrophilic group interactions as compared to those in water. 4.2.5. Analysis of Viscosity Data The viscosity data were analyzed by using Jones-Dole [32] equation of the form

1/ 21 Am Bmr

o

ηηη= = + +

(4.8)

where ηr is the relative viscosity of the solution, η and ηo are the viscosities of solution and the solvent (sucrose + water), respectively, m is molality of l-histidine in sucrose + water solvent, A and B are the Falkenhagen [33,34] and Jones-Dole [34] coefficients, respectively. Coefficient A accounts for the solute-solute interactions and

Chapter 4

98

B is a measure of structural modifications induced by the solute-solvent interactions [35,36]. The values of A and B have been obtained as the intercept and slope from linear regression of 1/ 2[( 1) / ]r mη − vs. m1/2 curves, which were found almost linear for these systems. The values of A and B along with the standard deviations of linear regression, σ are listed in Table 4.3. The values of A- and B-coefficients are positive, however, the A-coefficients are much smaller in magnitude as compared to B-coefficients, suggesting weak solute-solute and strong solute-solvent interactions in these solutions. Large and positive B-coefficients values, which increase with increasing concentration of sucrose, also indicate a structure to allow the co-solute (sucrose) to act on solvent [4]. B-coefficients increase (Fig. 4.7) when the water is replaced by sucrose, i.e., sucrose act as water structure-maker by H-bonding. B-coefficients increases (Fig. 4.7) with increasing concentration of sucrose, the reason may be that the friction increases to prevent water flow at increased sucrose concentration. The values of B-coefficients are found larger in case of aqueous-sucrose solvents as compared to aqueous-glucose solvents [10], which may be due to greater hydrophilic-ionic group and hydrophilic-hydrophilic group interactions, with the presence of more hydroxyl groups in sucrose molecules as compared to glucose molecules. Thus, the values of coefficients A and B support the behaviours of Vφ° ,

,sK φ° , Sv, Sk, ,trVφ

° and , ,s trK φ° , which suggest stronger solute-solvent interactions as

compared to solute-solute interactions in these solutions.

The temperature derivatives of B-coefficient (dB/dT) have also been calculated. The sign of dB/dT values is found to provide important information regarding structure-making or structure-breaking ability of the solute in solvent media [35,37]. In general, the dB/dT is negative for structure-maker and positive for structure-breaker solutes in solution [35,37]. The negative dB/dT values for l-histidine in aqueous-sucrose solvents indicate that l-histidine act as structure-maker in aqueous-sucrose solvents under study. Ali et al. [17] also reported similar structure-making behaviour of glycine in water + sucrose solutions and of l-histidine in aqueous-caffeine solvent [38]. Pal and Kumar [39] have also drawn similar conclusions for some amino acids in aqueous-urea solutions.

Chapter 4

99

4.3. CONCLUSIONS

The densities, ρ, ultrasonic speeds, u, and viscosities, η of solutions of l-histidine in aqueous-sucrose solvents (5, 10, 15 and 20 % of sucrose, w/w in water) were measured at different temperatures. From the experimental data, various parameters, viz., Vφ , Vφ° , ,sK φ ,

,sK φ° ,

,trVφ° ,

, ,s trK φ° , Falkenhagen Coefficient, A, Jones-Dole

coefficient, B and dB/dT were calculated. The results indicate that there exist strong solute-solvent (hydrophilic-ionic group and hydrophilic-hydrophilic group) interactions in these systems, which increase with increase in sucrose concentration. It is also observed that l-histidine act as structure-maker in these aqueous-sucrose solvents.

Chapter 4

100

Table 4.1: Densities, ρ, ultrasonic speeds, u, and viscosities, η of solutions of l-histidine in sucrose + water (5, 10, 15 and 20 % sucrose, w/w in water) solvents as functions of molality, m of l-histidine in sucrose + water solvents and temperature.

m (mol kg−1)

T /(K) 293.15 298.15 303.15 308.15 313.15 318.15

l-Histidine in 5 % aqueous-sucrose ρ /(kg⋅m−3) 0.0000 1018.91 1017.19 1015.45 1013.72 1011.98 1010.23 0.0249 1020.19 1018.47 1016.74 1015.01 1013.28 1011.54 0.0498 1021.46 1019.75 1018.03 1016.31 1014.58 1012.84 0.0749 1022.75 1021.05 1019.32 1017.61 1015.89 1014.16 0.0999 1024.03 1022.34 1020.62 1018.91 1017.19 1015.47 0.1250 1025.32 1023.63 1021.92 1020.21 1018.50 1016.78 0.1499 1026.60 1024.91 1023.20 1021.50 1019.79 1018.07 0.1749 1027.89 1026.20 1024.49 1022.79 1021.08 1019.37 0.1999 1029.17 1027.48 1025.78 1024.08 1022.37 1020.66 u /(m⋅s−1) 0.0000 1499.7 1514.3 1525.1 1535.7 1545.6 1554.5 0.0249 1503.9 1518.4 1529.0 1539.4 1549.1 1557.8 0.0498 1507.5 1521.8 1532.1 1542.3 1551.8 1560.2 0.0749 1510.5 1524.6 1534.5 1544.5 1553.6 1561.8 0.0999 1512.9 1526.7 1536.3 1546.0 1554.7 1562.6 0.1250 1514.6 1528.1 1537.3 1546.7 1555.0 1562.5 0.1499 1515.6 1528.8 1537.7 1546.7 1554.8 1561.9 0.1749 1515.9 1529.0 1537.3 1546.1 1553.8 1560.3 0.1999 1515.6 1528.4 1536.5 1544.8 1552.1 1558.4 103⋅η /(N⋅s⋅m−2) 0.0000 1.2137 1.0110 0.9129 0.8285 0.7457 0.6946 0.0249 1.2335 1.0264 0.9260 0.8394 0.7548 0.7026 0.0498 1.2513 1.0403 0.9372 0.8490 0.7627 0.7092 0.0749 1.2690 1.0539 0.9483 0.8582 0.7702 0.7155 0.0999 1.2865 1.0671 0.9592 0.8673 0.7778 0.7217 0.1250 1.3043 1.0809 0.9704 0.8764 0.7851 0.7278 0.1499 1.3216 1.0942 0.9815 0.8852 0.7923 0.7337 0.1749 1.3392 1.1078 0.9925 0.8941 0.7993 0.7396 0.1999 1.3574 1.1212 1.0032 0.9027 0.8062 0.7455

Chapter 4

101

Table 4.1 (Continued)

m (mol kg−1)

T /(K) 293.15 298.15 303.15 308.15 313.15 318.15


Chapter 4

102


m (mol kg−1)

T /(K) 293.15 298.15 303.15 308.15 313.15 318.15


Chapter 4

103


m (mol kg−1)

T /(K) 293.15 298.15 303.15 308.15 313.15 318.15


Chapter 4

104

Table 4.2: Limiting apparent molar volume, Vφ° , slope, Sv, transfer volume, ,trVφ° , Limiting

apparent molar compressibility, ,sK φ° , slope, Sk, transfer compressibility,

, ,s trK φ° and standard

deviations of linear regression, σ for l-histidine in sucrose + water (5, 10, 15 and 20 % sucrose, w/w in water) solvents at different temperatures.

Property T /(K) 293.15 298.15 303.15 308.15 313.15 318.15

l-Histidine in water [10] 105⋅ Vφ° /m3

⋅mol−1 9.806 9.828 9.852 9.870 9.895 9.917 10 ⋅ σ for equation (4.4) 0.033 0.021 0.037 0.036 0.037 0.033 105⋅ Sv /m3

⋅mol−1⋅kg−1 -1.174 -1.162 -1.174 -1.165 -1.174 -1.179 1012⋅

,sK φ° /m5

⋅N−1⋅mol−1 -2.043 -1.916 -1.790 -1.646 -1.518 -1.405

σ for equation (4.5) 0.004 0.005 0.013 0.011 0.012 0.008 1012⋅ Sk /m5

⋅N−1⋅mol−1⋅kg−1 6.938 7.159 7.414 7.233 7.069 7.098

l-Histidine in 5 % aqueous-sucrose 105⋅ Vφ° /m3


⋅mol−1⋅kg−1 -1.101 -1.062 -1.029 -0.953 -0.899 -0.868 106⋅

,trVφ° /m3

⋅mol−1 1.076 1.013 0.952 0.890 0.821 0.760

1012⋅,sK φ° /m5

⋅N−1⋅mol−1 -1.461 -1.406 -1.340 -1.286 -1.230 -1.179

σ for equation (4.5) 0.001 0.004 0.008 0.006 0.010 0.010 1012⋅Sk /m5

⋅N−1⋅mol−1⋅kg−1 2.991 3.056 3.151 3.205 3.305 3.409

1012⋅, ,s trK φ° /m5

⋅N−1⋅mol−1 0.582 0.510 0.421 0.360 0.288 0.226

l-Histidine in 10 % aqueous-sucrose 105⋅ Vφ° /m3


⋅mol−1⋅kg−1 -1.167 -1.115 -1.067 -1.012 -0.980 -0.927 106⋅

,trVφ° /m3

⋅mol−1 1.810 1.736 1.679 1.627 1.578 1.523

1012⋅,sK φ° /m5

⋅N−1⋅mol−1 -1.249 -1.210 -1.150 -1.115 -1.088 -1.050


⋅N−1⋅mol−1⋅kg−1 2.386 2.355 2.239 2.299 2.394 2.408

1012⋅, ,s trK φ° /m5

⋅N−1⋅mol−1 0.794 0.706 0.611 0.531 0.431 0.355

Chapter 4

105


Property T /(K)

293.15 298.15 303.15 308.15 313.15 318.15 l-Histidine in 15 % aqueous-sucrose

105⋅ Vφ° /m3⋅mol−1 10.036 10.053 10.070 10.084 10.103 10.119

10 ⋅ σ for equation (4.4) 0.023 0.025 0.027 0.025 0.019 0.027 105⋅ Sv /m3

⋅mol−1⋅kg−1 -1.175 -1.113 -1.088 -1.033 -1.003 -0.945

106⋅ ,trVφ° /m3

⋅mol−1 2.302 2.244 2.184 2.135 2.079 2.026

1012⋅ ,sK φ° /m5

⋅N−1⋅mol−1 -1.083 -1.062 -1.038 -1.014 -0.984 -0.961


⋅N−1⋅mol−1⋅kg−1 1.670 1.708 1.743 1.741 1.685 1.715

1012⋅, ,s trK φ° /m5

⋅N−1⋅mol−1 0.960 0.854 0.723 0.632 0.534 0.444

l-Histidine in 20 % aqueous-sucrose

105⋅ Vφ° /m3⋅mol−1 10.084 10.101 10.118 10.130 10.150 10.167

10 ⋅ σ for equation (4.4) 0.020 0.015 0.013 0.013 0.026 0.019 105⋅ Sv /m3

⋅mol−1⋅kg−1 -1.107 -1.068 -1.036 -0.944 -0.907 -0.824

106⋅ ,trVφ° /m3

⋅mol−1 2.783 2.724 2.662 2.599 2.553 2.504

1012⋅ ,sK φ° /m5

⋅N−1⋅mol−1 -0.933 -0.924 -0.913 -0.902 -0.893 -0.880


⋅N−1⋅mol−1⋅kg−1 1.171 1.203 1.254 1.299 1.351 1.370

1012⋅, ,s trK φ° /m5

⋅N−1⋅mol−1 1.110 0.992 0.848 0.744 0.625 0.525

Chapter 4

106

Table 4.3: Falkenhagen coefficient, A, Jones-Dole coefficient, B and standard deviations of linear regression, σ for l-histidine in sucrose + water (5, 10, 15 and 20 % sucrose, w/w in water) solvents at different temperatures.

Property T /(K)

293.15 298.15 303.15 308.15 313.15 318.15 l-Histidine in water [10] 105⋅ A /kg1/2⋅mol−1/2 1.221 1.480 1.598 1.704 1.868 2.236 104⋅ B /kg⋅mol−1 5.018 4.369 3.843 3.292 2.800 2.217 10 ⋅σ for equation (4.8) 0.005 0.014 0.007 0.005 0.010 0.010 l-Histidine in 5 % aqueous-sucrose 105⋅ A /kg1/2⋅mol−1/2 1.470 1.604 1.808 2.026 2.138 2.399 104⋅ B /kg⋅mol−1 5.564 5.082 4.535 4.041 3.605 3.136 10 ⋅σ for equation (4.8) 0.008 0.006 0.008 0.005 0.008 0.003 l-Histidine in 10 % aqueous-sucrose 105⋅ A /kg1/2⋅mol−1/2 1.627 1.794 1.905 2.099 2.244 2.481 104⋅ B /kg⋅mol−1 5.971 5.496 4.986 4.455 3.978 3.475 10 ⋅σ for equation (4.8) 0.007 0.003 0.006 0.008 0.004 0.008 l-Histidine in 15 % aqueous-sucrose 105⋅ A /kg1/2⋅mol−1/2 1.743 1.933 2.017 2.139 2.390 2.549 104⋅ B /(kg⋅mol−1) 6.497 5.847 5.352 4.791 4.318 3.865 10 ⋅σ for equation (4.8) 0.014 0.026 0.016 0.011 0.010 0.005 l-Histidine in 20 % aqueous-sucrose 105⋅ A /kg1/2⋅mol−1/2 1.974 2.089 2.178 2.274 2.477 2.605 104⋅ B /kg⋅mol−1 6.999 6.371 5.798 5.225 4.721 4.270 10 ⋅σ for equation (4.8) 0.023 0.015 0.015 0.010 0.018 0.004

Chapter 4

107

Figure 4.1: Variations of apparent molar volume, Vφ vs. molality, m of l-histidine in sucrose + water (w/w) solutions, (a) 5% sucrose, (b) 10% sucrose, (c) 15% sucrose, (d) 20% sucrose, at temperatures, At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○. The points represent experimental values and lines represent values calculated from equation (4.4).

9.60

9.70

9.80

9.90

10.00

0.00 0.05 0.10 0.15 0.20 0.25

V φ /10-5

m3mo

l-1

9.70

9.80

9.90

10.00

10.10

0.00 0.05 0.10 0.15 0.20 0.25

V φ /10-5

m3mo

l-1

9.75

9.85

9.95

10.05

10.15

0.00 0.05 0.10 0.15 0.20 0.25

V φ /10-5

m3mo

l-1

9.80

9.90

10.00

10.10

10.20

0.00 0.05 0.10 0.15 0.20 0.25

V φ /10-5

m3mo

l-1

m/(mol kg-1)

(a)

(b)

(c)

(d)

Chapter 4

108

Figure 4.2: Variations of apparent molar compressibility,

,sK φ vs. molarity, m of l-histidine in sucrose + water (w/w) solutions, (a) 5% sucrose, (b) 10% sucrose, (c) 15% sucrose, (d) 20% sucrose, at temperatures, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○. The points represent experimental values and lines represent values calculated from equation (4.5).

-1.50

-1.30

-1.10

-0.90

-0.70

-0.50

-0.30

0.00 0.05 0.10 0.15 0.20 0.25

K s,φ / 10

-12m5 N-1

mol-1

-1.30

-1.10

-0.90

-0.70

-0.50

0.00 0.05 0.10 0.15 0.20 0.25

K s,φ / 10

-12m5 N-1

mol-1

-1.10

-1.00

-0.90

-0.80

-0.70

-0.60

-0.50

0.00 0.05 0.10 0.15 0.20 0.25

K s,φ / 10

-12m5 N-1

mol-1

-0.95

-0.85

-0.75

-0.65

-0.55

0.00 0.05 0.10 0.15 0.20 0.25

K s,φ / 10

-12m5 N-1

mol-1

m/mol kg-1

(a)

(b)

(c)

(d)

Chapter 4

109

Figure 4.3: Variations of limiting apparent molar volume, Vφ° vs. mass % of sucrose for l-histidine in sucrose + water solutions at temperatures, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○.

9.8

9.9

10.0

10.1

10.2

0 5 10 15 20 25

V φ°/1

0-5m3

mol-1

Mass % of sucrose

Chapter 4

110

Figure 4.4: Variations of limiting apparent molar compressibility,

,sK φ° vs. mass % of

sucrose for l-histidine in sucrose + water solutions at temperatures, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○.

-2.2

-2.0

-1.8

-1.6

-1.4

-1.2

-1.0

-0.8

0 5 10 15 20 25

K s,φ°/

10-12

m5N-1

mol-1

Mass % of sucrose

Chapter 4

111

Figure 4.5: Variations of transfer volume,

,trVφ° vs. mass % of sucrose for l-histidine in

sucrose + water solutions at temperatures, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○.

0.6

1.2

1.8

2.4

0 5 10 15 20 25

V φ° tr/

10-5

m3mo

l-1

Mass % of sucrose

Chapter 4

112

Figure 4.6: Variations of transfer compressibility,

, ,s trK φ° vs. mass % of sucrose for l-

histidine in sucrose + water solutions at temperatures, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○.

0.2

0.4

0.6

0.8

1.0

1.2

0 5 10 15 20 25

K s,φ° t

r/10-1

2m5

N-1mo

l-1

Mass % of sucrose

Chapter 4

113

Figure 4.7: Variations of Jones-Dole coefficient, B vs. mass % of sucrose for l-histidine in sucrose + water solutions at temperature, T/K = 293.15, ♦; At T/K = 293.15, ♦; T/K = 298.15, ■; T/K = 303.15, ▲; T/K = 308.15, □; T/K = 313.15, ∆; T/K = 318.15, ○.

2

3

4

5

6

7

0 5 10 15 20 25

B /10

-4kg

mol-

1

Mass % of sucrose

Chapter 4

114

REFERENCES

[1] C. Zhao, P. Ma, J. Li, J. Chem. Thermodyn. 37 (2005) 37. [2] T. S. Banipal, J. Kaur, P. K. Banipal, K. Singh, J. Chem. Eng. Data 53 (2008)

1803. [3] A. Ali, S. Khan, S. Hyder, A. K. Nain, Phys. Chem. Liq. 44 (2006) 655. [4] A. Ali, S. Sabir, A. K. Nain, S. Hyder, S. Ahmad, R. Patel, J. Chin. Chem.

Soc. 54 (2007) 659. [5] K. Zhuo, Q. Liu, Y. Yang, Q. Ren, J. Wang, J. Chem. Eng. Data 51 (2006)

919. [6] A. Ali, R. Patel, Shahjahan, V. Bhushan, Z. Naturforsch. A 64a (2009) 758. [7] A. M. Ronero, E. Moreno, J. L. Rojas, Thermochim. Acta 328 (1999) 33. [8] Z. Yan, J. Wang, W. Kong, J. Lu, Fluid Phase Equilib. 215 (2004) 143. [9] F. J. Millero, A. Lo Surdo, C. Shin, J. Phys. Chem. 82 (1978) 784. [10] A. K. Nain, R. Pal , R. K. Sharma, J. Chem. Thermodyn., 43 (2011) 603. [11] A. Ali, S. Hyder, S. Sabir, D. Chand, A. K. Nain, J. Chem. Thermodyn. 38

(2006) 136. [12] A. K. Nain, D. Chand, J. Chem. Thermodyn. 41 (2009) 243. [13] J. F. Back, D. Oakenfull, M. B. Smith, Biochemistry 19 (1979) 5191. [14] Y. Fujita, Y. Iwasa, Y. Noda, Bull. Chem. Soc. Jpn. 55 (1982) 1896. [15] D. E. Metzler, The Chemical Reactions in Living Cells, vol. 1, Academic

Press, New York, 1077. [16] M. Wusteman, S. Boylen, D. E. Pegg, Cryobiology 33 (1996) 423. [17] S. Li, W, Sang, R. Lin, J. Chem. Thermodyn. 34 (2002) 1761. [18] A. Pal, N. Chauhan, Indian J. Chem. 48A (2009) 1069. [19] G. A. Kulikova, E. V. Parfenyuk, J. Solution Chem. 37 (2008) 835. [20] D. O. Masson, Phil. Mag. 8 (1929) 218. [21] D. P. Kharakoz, Biophys. Chem. 34 (1989)115−125; J. Phys. Chem. 95 (1991)

5634.

Chapter 4

115

[22] A. Zhao, P. Ma, J. Li, J. Chem. Thermodyn. 37 (2005) 37. [23] G. R . Hedwig, H. Hoiland, J. Chem. Thermodyn. 25 (1993) 349. [24] A. K. Mishra, J. C. Ahluwalia, J. Phys. Chem. 88 (1984) 86. [25] J. C. Ahluwalia, C. Cstiguy, G. Perron, J. Desnoyers, Can. J. Chem. 55 (1977)

3364. [26] R. K. Wadi and P. Ramasami, J. Chem. Soc., Faraday Trans. 93 (1997) 243. [27] A. Ali, S. Khan, F. Nabi, J. Serb. Chem. Soc. 72 (2007) 495. [28] H. Rodriguez, A. Soto, A. Arce, M. K. Khoshkbarchi, J. Solution Chem. 32

(2003) 53. [29] A. Soto, A. Arce, M. K. Khoshkbarchi, J. Solution Chem. 33 (2003) 11. [30] S. Banerjee, N. Kishore, J. Solution Chem. 34 (2005) 137. [31] R. Bhat, N. Kishore, J. C. Ahluwalia, J. Chem. Soc., Faraday Trans. I 88

(1988) 2651. [32] G. Jones, M. Dole, J. Am. Chem. Soc. 51 (1929) 2950. [33] H. Falkenhagen, M. Dole, Z. Phys. 30 (1929) 611. [34] H. Falkenhagen, E. L. Vernon, Z. Phys. 33 (1932) 140. [35] A. Feakins, D. J. Freemantle, K. G. Lawrence, J. Chem. Soc., Faraday Trans.

70 (1974) 795. [36] S. C. Bai, G. B. Yan, Carbohydr. Res. 338 (1999) 2921. [37] M. Kaminsky, Discuss. Faraday Soc. 24 (1957) 171. [38] A. Ali, S. Sabir, A. K. Nain, S. Hyder, S. Ahmad, R. Patel, J. Indian Chem.

Soc. 83 (2006) 581. [39] A. Pal, S. Kumar, J. Mol. Liq. 109 (2004) 23.

chapter 4 study of solute-solute and solute-solvent...

Documents