305

APPENDIX- A

Symbols:

a Activity

a0,a1 and a2 Constants in excess volume-mole fraction

A, B and C Antoine constants

b0,b1 and b2 Constants in deviation in isentropic compressibility

Cp Heat capacity at constant pressure

d Strength of interaction parameter molecular diameter

E Energy equivalent

f Fugacity, frequency

g Acceleration due to gravity

G Gibbs free energy

GE/RT Excess Gibbs function

H Enthalpy

J Joule

K Kelvin

κ Compressibility

κs Isentropic compressibility

κsE Excess isentropic compressibility

Lf Free length in liquid

M Molecular mass

n Number of experimental points, mole number

P Pressure

p Number of parameters

R Gas constant

T Absolute temperature

u Sound speed

V Molar volume

Vm Molar volume of the mixture

x Mole fraction

ρ Density

Standard deviation, surface tension

306

Superscript

* Characteristic

E Excess property

G Group

l Liquid

M Mixing

o Pure state

s Size, Saturation pressure

Subscripts

1,2 Components

C Critical

Cal Calculated

Exp Experimental

i Component I

max Maximum

Mix Mixture

307

APPENDIX- B

List of Publications:

1. L. Venkatramana, K. Sivakumar, V. Govinda, K. Dayananda Reddy, Journal of

Molecular Liquids, 186 (2013) 163–170.

2. L. Venkatramana, K. Sreenivasulu, K. Sivakumar, K. Dayananda Reddy,

International Journal of Scientific & Engineering Research, 4 (2013) 1795- 1823.

3. L. Venkatramana, K. Sreenivasulu, K. Sivakumar, K. Dayananda Reddy,

Journal of Thermal Analysis and Calorimetry, 115 (2014) 1829-1834.

4. L. Venkatramana, R.L. Gardas, K. Sivakumar, K. Dayananda Reddy, Journal of

Thermochemica Acta (In Press), DOI: 10.1007/s 10973-013-3473-9.

5. L. Venkatramana, R.L. Gardas, K. Sivakumar, K. Dayananda Reddy, Journal of

Fluid Phase Equilibra (In Press) DOI: dx.doi.org/10.1016/j.fluid.2014.01.019

6. L. Venkatramana, R.L. Gardas, K. Sivakumar, K. Dayananda Reddy, Journal of

Chemical Thermodynamics (Communicated).

7. V. Syamala, L. Venkatramana, K. Sivakumar, P. Venkateswralu, Korean

Journal of Chemical Engineering (Communicated).

Author's personal copy

Study on solution properties of some industrially important solventswith an aromatic alcohol

L. Venkatramana a, K. Sivakumar b, V. Govinda c, K. Dayananda Reddy a,⁎a Department of Chemistry, P.V.K.N. Govt. Degree & P.G. College, Chittoor 517001, A.P., Indiab Department of Chemistry, S.V. Arts Degree & P.G. College (T.T.D'S), Tirupati 517502, A.P., Indiac Department of Chemistry, S.V. University, Tirupati 517502, A.P., India

a b s t r a c ta r t i c l e i n f o

Article history:Received 12 March 2013Received in revised form 6 April 2013Accepted 30 April 2013Available online 25 May 2013

Keywords:DensityExcess volumeSound velocityTheoretical analysisMolecular interaction

Densities (ρ) of pure liquids and their mixtures have been measured at 298.15 K to 313.15 K and atmosphericpressure over the entire composition range for the binary mixtures of benzylalcohol, with 1,2-dichlorobenzene,1,3-dichlorobenzene, and 1,2,4-trichlorobenzene by using Rudolph Research Analytical digital densitometer(DDH-2911 model). Further, the ultrasonic sound velocities for the above said mixtures were also measured at303.15 K and 313.15 K. The measured density data were used to compute excess molar volumes (VE) andthese were compared with Hwang equation. Isentropic compressibility (κS) and excess isentropic compressibil-ities (κSE) were evaluated from experimental sound velocity and density data. Moreover, the experimental soundvelocities were analyzed in terms of theoretical models namely collision factor theory (CFT) and free lengththeory (FLT). The experimental results were discussed in terms of intermolecular interactions between compo-nent molecules.

© 2013 Elsevier B.V. All rights reserved.

1. Introduction

Mixing effects of large number of compounds and their mixtureswhich are used in the process industry are rather difficult to be known,hence the investigation of thermodynamic properties such as densities,ultrasonic sound velocities, enthalpies and entropies which give an ideaof to what extent the deviations from non-ideality of organic mixturesat various temperatures is of great importance. Selection of systems forthermodynamic investigation should be based not only on the molecularstructure of the industrial components but also on their industrial andecological importance. A vast knowledge of thermodynamic propertiesbinary liquid mixtures is essential in many industrial applications suchas design calculation, heat transfer, mass transfer, fluid flow, etc. [1]. Fur-ther non-ideal thermodynamic behavior of liquid mixture may bediscussed in terms of differences in molecular size and shape, dispersionforces, polarity, polarizability, molecular association, etc. The liquid com-ponents selected as binary mixtures, are well-known organic liquidsand also had a wide range of applications at various fields of chemistrybesides being used in industries and routine analytical work. In thepresent study an attempt has been made to know the nature of mo-lecular interactions occurring between binary mixtures of ofbenzylalcohol with 1,2-dichlorobenzene,1,3-dichlorobenzene, and1,2,4-trichlorobenzene by measuring densities (ρ), at 298.15 K to313.15 K and speeds of sound (u) at 303.15 K and 313.15 K have

been measured over the entire composition range. Benzylalcohol isan important solvent for gelatin, cellulose acetate, and shellac [2].1,2-dichlorobenzene is used as an intermediate for dyes, and certainagricultural chemicals. 1,3-dichlorobenzene is widely used in themanufacture of poly resin, used as a room deodorant blocks andmoth control. 1, 2, 4-trichlorobenzene is used in the manufactureof the herbicide, in some pesticides, as a dye carrier in dielectricfield, as an organic intermediate and a chemical manufacture solventin lubricants [3]. From these density data, excess molar volumes (VE)and excess isentropic compressibility (κSE) were calculated. Further,the experimental sound velocity data were compared with theoreti-cal models proposed by Schaaff's collision factor theory (CFT) [4] andJacobson's free length theory (FLT) [5,6].

The present work was taken to know the effect of the introductionof a chloro group and their orientation in chlorobenzene moleculethat may influence both the sign and magnitude of excess volumeand excess isentropic compressibility.

2. Experimental

All the chemicals used in the presentworkwere of analytical reagentgrade procured from S.D. Fine Chemicals Ltd., India andMerck and theirpurities were as follows: benzyl alcohol 99.5%, 1,2-dichlorobenzene99.5%, 1,3-dichlorobenzene 99.5%, and 1,2,4-trichlorobenzene 99.6%.Prior to experimental measurements, all the liquids were purified asdescribed in the literature [7,8]. The purity samples were attained byfractional distillation and the purity of chemicals was checked by com-paring the measured densities and ultrasonic sound velocities, which

Journal of Molecular Liquids 186 (2013) 163–170

⁎ Corresponding author. Tel.: +91 9290080843 (mobile).E-mail address: sivakumarkasi64@gmail.com (K. Dayananda Reddy).

0167-7322/$ – see front matter © 2013 Elsevier B.V. All rights reserved.http://dx.doi.org/10.1016/j.molliq.2013.04.026

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Journal of Molecular Liquids

j ourna l homepage: www.e lsev ie r .com/ locate /mol l iq

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were in good agreement with literature values [9,10] and these aregiven in Table 1. The purity of the sample was further confirmed byGLC single sharp peak. Before use, the chemicals were stored over0.4 nm molecular sieves for about 72 h to remove water and werelater degassed.

3. Measurements

All the binary liquidmixtures are prepared byweighing an appropri-ate amount of pure liquids in an electronic balance (Afoset, ER-120A,India) with a precision of ±0.1 mg by syringing each component intoairtight stopper bottles tominimize evaporation losses. The uncertaintyof the mole fraction was ±1 × 10−4. After mixing the sample, thebubble free homogenous sample was transferred into the U-tube ofthe densimeter through a syringe. The density measurements wereperformed with a Rudolph Research Analytical digital densimeter(DDH-2911 Model), equipped with a built-in solid-state thermostatand a resident program with accuracy of temperature of 303.15 K ±0.03 K. The uncertainty density measurement liquid mixtures are ±2 × 10−5 g.cm−3. Proper calibrations at each temperature wereachieved with doubly distilled, deionized water and with air as stan-dards. Amulti frequency ultrasonic interferometer (M-82Model, MittalEnterprise, New Delhi, India) operated at 2 MHz, was used to measurethe ultrasonic velocities of the binary liquid mixtures at 303.15 K and313.15 K by using a digital constant temperaturewater bath. The uncer-tainty in the measurement of ultrasonic sound velocity is ±0.3%.The temperature stability is maintained within ±0.01 K by circulatingthermostatic water bath around the cell with a circulating pump. Inorder tominimize the uncertainty of themeasurement, several maximaare allowed to pass and their number (50) in the present study iscounted. All maxima are recorded with the highest swing of the needleon themicrometer scale. The total distance d (cm)moved by the reflec-tor is given by d = nλ/2, where λ is the wave length. The frequency, ν,of the crystal being accurately known (2.0 MHz), the speed of sound, uin ms−1 is calculated by using the relation u = νλ.

4. Results and discussion

The non-ideal binary mixture behavior, represented by in terms ofexcess molar volume (VE), was computed from the experimentallydetermined density data using following equation

VE=cm3

:mol−1 ¼ x1M1 þ x2M2½ �=ρm– x1M1=ρ1 þ x2M2=ρ2½ � ð1Þ

where, xi is the mole fraction of component i(i = 1,2) in the mixture;Mi is the molar mass ρ and ρi are the measured density of the mixtureand the pure component i, respectively. The computed VE data wasalso given in Table 2 along with the predicted in terms of Hwang equa-tion [11]. Themethods and calculation of VE in terms of Hwang equationwere described earlier [12–15]. The VE data for all the binary systems ofbenzylalcohol with 1,2-dichlorobenzene, 1,3-dichlorobenzene and1,2,4-trichlorobenzene were graphically represented in Figs. 1–3.Further, the binary VE data for benzylalcohol and chlorobenzene mix-ture [16] was also represented in Fig. 4 at 303.15 K to study the effectof addition of the second/third chloro group in chlorobenzenemoleculeon how does it is influencing the sign and magnitude of excess volumeof binarymixtures thatwere under the present investigation. In general,the values of VE can be considered as arising from the two types of inter-actions between the component molecules:

i) A physical interaction consisting dispersion forces or weak dipole–dipole interactions, making a positive contribution

ii) A chemical or specific interaction, which includes charge–transferforce, forming H-bonding and other complex-forming interac-tions, resulting in a negative contribution to VE values.

Apart from these interactions, negative contributionmay also be dueto the different shapes and sizes of component molecules, whichmightallow them to fit into each other's structures, reducing volume andresulting in negative VE values. However, liquids of nearly equal molec-ular size usually mix to give a positive contribution to VE [17,18]. Aperusal of VE data in Table 2 shows that the factors that are responsiblefor positive contribution in all the binary mixtures of benzylalcoholwith di/trichlorobenzenes. It is evident from the plots in Figs. 1–3suggest that, VE data is positive for the mixtures of benzylalcohol withisomeric chlorobenzenes and negative in the mixture containingbenzylalcohol with chlorobenzene. The decrease in negative values ofVEwith increase in number of chloro groups in chlorobenzenemoleculereveals that dipole–dipole interactions are becoming weaker from1,2-dichlorobenzene to 1,2,4-trichlorobenzene.

Algebraic values of excess volumes for the systems of benzylalcoholwith chlorobenzenes fall in the order:

1,2-dichlorobenzene b 1,3-dichlorobenzene b 1,2,4-trichlorobenzene.The difference in VE values observed between dichloro and

trichlorobenzenes is probably because of the difference in theirshapes which leads to different alignments in the liquid mixture. Fur-ther, the chlorine atom at the 4th position in 1,2,4-trichlorobenzeneoffers the least steric hindrance to benzylalcohol molecules andthus the electron donor–acceptor interactions in it are lower thanthose of 1,2-dichlorobenzene and 1,3-dichlorobenzene. However, VE

values for mixtures of benzylalcohol with 1,2-dichlorobenzene,1,3-dichlorobenzene and 1,2,4-trichlorobenzene are algebraicallysmaller than those for mixtures of benzylalcohol with chlorobenzene[16]. This shows that the addition of the second or third chloro groupon chlorobenzene ring has influenced the sign and magnitude ofexcess volume to a significant extent. This observation is in line whichwere reported earlier for the binary mixtures of dimethylsulphoxideand dimethylformamide with di/trichlorobenzenes [19,20].

Furthermore, a comparison between experimental excess molarvolume and the predicted in terms of Hwang equation shows thatthe computed excess molar volumes give good estimation in all thebinary mixtures that are under the present investigation.

Table 1Densities (ρ) sound velocity (u), thermal coefficient (α) and heat capacity (cp) for purecomponent liquids at temperatures from 298.15 to 313.15 K along with the literaturevalues.

T/K ρ (g cm−3) u (m s−1) α (kK−1) Cp (J.mol−1.k−1)

Exp. Lit. Exp. Lit.

Benzylalcohol298.15 1.03851 1.03856 – – – –

303.15 1.03760 1.03700 [9] 1514 1511 [9] 0.7402 224.35 [22]308.15 1.02785 – – – – –

313.15 1.02691 – 1519 – 0.7456 227.62 [22]

1,2-dichlorobenzene298.15 1.30034 1.30090 [10] – – – –

303.15 1.29545 1.29540 [10] 1266 1265 [10] 0.8629 171.76 [10]308.15 1.28913 1.28970 [10] – – – –

313.15 1.27653 – 1237 – 0.8768 173.86 [22]

1,3-dichlorobenzene298.15 1.28345 1.28280 [10] – – – –

303.15 1.27772 1.27779 [10] 1237 1238 [10] 0.8862 171.25 [10]308.15 1.27219 1.27210 [10] – – – –

313.15 1.27210 – 1228 – 0.9685 173.24 [22]

1,2,4-trichlorobenzene298.15 1.44841 1.44841 [10] – – – –

303.15 1.44248 1.44243 [10] 1252 1256 [10] 0.8303 195.92 [10]308.15 1.43645 1.43645 [10] – – – –

313.15 1.41951 – 1232 – 0.8426 197.26 [22]

References: 1 Ref: [9], 2 Ref: [10] and 3 Ref [22].

164 L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

Author's personal copy

Table 2Mole fraction of benzylalcohol (x1), densities (ρ), excess volumes (VE) and predictedexcess molar volumes (Hwang) at T = 298.15 K to 313.15 K for the binary mixturesof benzylalcohol with di/trichlorobenzenes.

x1 Density (ρ) (g.cm−3) VE (exp) VE (Hwang)

cm3 mol−1

Benzylalcohol (1) + 1,2-dichlorobenzene (2) T = 298.15 K0.0000 1.30034 0.000 0.0000.0990 1.27635 0.019 0.0180.1177 1.27179 0.022 0.0220.2180 1.24707 0.041 0.0410.2713 1.23379 0.049 0.0490.3215 1.22119 0.055 0.0570.4207 1.19601 0.065 0.0660.4890 1.17848 0.067 0.0690.5520 1.16215 0.067 0.0690.6598 1.13384 0.063 0.0620.7291 1.11540 0.056 0.0530.8012 1.09603 0.045 0.0410.8513 1.08245 0.034 0.0320.8993 1.06933 0.023 0.0220.9372 1.05889 0.014 0.0140.9575 1.05329 0.008 0.0091.0000 1.03851 0.000 0.000

T = 303.15 K0.0000 1.29545 0.000 0.0000.0990 1.27090 0.023 0.0220.1177 1.26636 0.027 0.0260.2180 1.24183 0.045 0.0450.2713 1.22862 0.055 0.0540.3215 1.21611 0.061 0.0610.4207 1.19111 0.070 0.0710.4890 1.17368 0.074 0.0740.5520 1.15745 0.075 0.0750.6598 1.12933 0.071 0.0700.7291 1.11103 0.063 0.0630.8012 1.09175 0.054 0.0520.8513 1.07827 0.042 0.0420.8993 1.06523 0.032 0.0310.9372 1.05489 0.020 0.0200.9575 1.04932 0.013 0.0141.0000 1.03760 0.000 0.000

T = 308.15 K0.0000 1.28913 0.000 0.0000.0990 1.26545 0.026 0.0270.1177 1.26091 0.033 0.0310.2180 1.23652 0.054 0.0530.2713 1.22341 0.064 0.0620.3215 1.21098 0.071 0.0690.4207 1.18616 0.079 0.0790.4890 1.16885 0.083 0.0820.5520 1.15274 0.083 0.0830.6598 1.12482 0.078 0.0780.7291 1.10664 0.070 0.0700.8012 1.08752 0.058 0.0590.8513 1.07410 0.049 0.0480.8993 1.06118 0.034 0.0350.9372 1.05089 0.024 0.0230.9575 1.04537 0.016 0.0161.0000 1.02785 0.000 0.000

T = 313.15 K0.0000 1.27653 0.000 0.0000.0990 1.25375 0.029 0.0290.1177 1.24941 0.034 0.0340.2180 1.22592 0.057 0.0560.2713 1.21330 0.067 0.0660.3215 1.20133 0.074 0.0730.4207 1.17737 0.086 0.0840.4890 1.16065 0.091 0.0890.5520 1.14508 0.092 0.0910.6598 1.11807 0.089 0.0880.7291 1.10048 0.081 0.0810.8012 1.08198 0.067 0.0700.8513 1.06899 0.056 0.0580.8993 1.05647 0.041 0.043

Table 2 (continued)

x1 Density (ρ) (g.cm−3) VE (exp) VE (Hwang)

cm3 mol−1

T = 313.15 K0.9372 1.04648 0.031 0.0290.9575 1.03980 0.021 0.0231.0000 1.02691 0.000 0.000

Benzylalcohol (1) + 1,3-dichlorobenzene (2) T = 298.15 K0.0000 1.28345 0.000 0.0000.0533 1.27143 0.022 0.0220.0933 1.26237 0.037 0.0370.1520 1.24895 0.059 0.0560.2041 1.23702 0.071 0.0710.2521 1.22590 0.082 0.0830.3272 1.20835 0.095 0.0960.4081 1.18924 0.102 0.1050.5269 1.16076 0.103 0.1060.6073 1.14116 0.096 0.0990.7127 1.11505 0.082 0.0820.7541 1.10471 0.072 0.0720.8030 1.09234 0.061 0.0600.8443 1.08167 0.064 0.0480.9164 1.06327 0.028 0.0261.0000 1.03851 0.000 0.000

T = 303.15 K0.0000 1.27772 0.000 0.0000.0533 1.26580 0.023 0.0240.0933 1.25680 0.041 0.0410.1521 1.24350 0.064 0.0610.2041 1.23166 0.078 0.0760.2521 1.22063 0.089 0.0880.3272 1.20321 0.102 0.1020.4081 1.18425 0.109 0.1110.5269 1.15598 0.111 0.1130.6073 1.13650 0.106 0.1060.7127 1.11060 0.091 0.0860.7541 1.10034 0.080 0.0810.8030 1.08809 0.067 0.0670.8443 1.07764 0.055 0.0560.9164 1.05921 0.035 0.0320.9511 1.04652 0.028 0.0271.0000 1.03760 0.000 0.000

T = 308.15 K0.0000 1.27219 0.000 0.0000.0533 1.26019 0.030 0.0310.0934 1.25123 0.049 0.0490.1521 1.23802 0.072 0.0730.2041 1.22623 0.089 0.0880.2521 1.21528 0.100 0.1010.3272 1.19801 0.114 0.1130.4082 1.17919 0.121 0.1220.5269 1.15115 0.122 0.1220.6073 1.13183 0.117 0.1160.7127 1.10613 0.101 0.1010.7541 1.09592 0.092 0.0920.8030 1.08375 0.080 0.0790.8444 1.07338 0.067 0.0670.9164 1.05516 0.040 0.0400.9511 1.04631 0.025 0.0241.0000 1.02785 0.000 0.000

T = 313.15 K0.0000 1.27210 0.000 0.0000.0533 1.25644 0.035 0.0340.0933 1.24747 0.054 0.0550.1521 1.23419 0.081 0.0820.2041 1.22239 0.098 0.1010.2521 1.21141 0.112 0.1130.3272 1.19407 0.130 0.1290.4081 1.17521 0.140 0.1380.5269 1.14713 0.143 0.1380.6073 1.12784 0.133 0.1310.7127 1.10220 0.111 0.1120.7541 1.09200 0.101 0.1010.8030 1.07986 0.085 0.086

(continued on next page)

165L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

Author's personal copy

Data formole fraction (x1) of benzylalcohol, density (ρ) of pure liquidsand their liquid mixtures of 1,2-dichlorobenzene, 1,3-dichlorobenzeneand 1,2,4-trichlorobenzene and experimental sound velocities (u), areincluded in columns 1–3 of Table 3. Isentropic compressibilities (κs) andexcess isentropic compressibilities (κsE), were also included in columns 4and 7 of Table 3. The excess isentropic compressibility data was alsorepresented graphically in Figs. 5–7. From the result of speed of sound(u), densities (ρ), and isentropic compressibilities (κS) were calculated as

κS ¼ u−2ρ−1: ð2Þ

Table 2 (continued)

x1 Density (ρ) (g.cm−3) VE (exp) VE (Hwang)

cm3 mol−1

T = 313.15 K0.8443 1.06951 0.071 0.0710.9164 1.05131 0.041 0.0420.9511 1.04245 0.027 0.0251.0000 1.02691 0.000 0.000

Benzylalcohol (1) + 1,2,4-trichlorobenzene (2) T = 298.15 K0.0000 1.44841 0.000 0.0000.0386 1.43511 0.014 0.0170.0773 1.42152 0.038 0.0340.1458 1.39714 0.071 0.0630.2218 1.36945 0.102 0.0930.2952 1.34211 0.124 0.1180.3472 1.32231 0.138 0.1320.4215 1.29347 0.152 0.1490.4962 1.26368 0.164 0.1610.5860 1.22689 0.165 0.1660.6784 1.18779 0.157 0.1610.7647 1.15012 0.138 0.1440.8096 1.13011 0.118 0.1280.8843 1.09599 0.086 0.0920.9175 1.08061 0.063 0.0711.0000 1.03851 0.000 0.000

T = 303.15 K0.0000 1.44248 0.000 0.0000.0386 1.42913 0.021 0.0240.0773 1.41554 0.051 0.0460.1458 1.39135 0.080 0.0790.2218 1.36379 0.113 0.1080.2952 1.33658 0.138 0.1310.3472 1.31686 0.154 0.1430.4215 1.28818 0.168 0.1570.4962 1.25860 0.175 0.1680.5860 1.22200 0.176 0.1740.6784 1.18310 0.169 0.1710.7647 1.14567 0.145 0.1560.8096 1.12577 0.124 0.1420.8843 1.09176 0.098 0.1040.9175 1.07652 0.069 0.0810.9575 1.04932 0.013 0.0141.0000 1.03760 0.000 0.000

T = 308.15 K0.0000 1.43645 0.000 0.0000.0386 1.42315 0.027 0.0260.0773 1.40974 0.049 0.0510.1458 1.38555 0.090 0.0870.2218 1.35812 0.125 0.1190.2952 1.33107 0.149 0.1440.3472 1.31149 0.162 0.1580.4215 1.28291 0.181 0.1730.4962 1.25345 0.192 0.1840.5860 1.21705 0.193 0.1910.6784 1.17833 0.188 0.1860.7647 1.14114 0.160 0.1690.8096 1.12133 0.140 0.1540.8843 1.08758 0.105 0.1130.9175 1.07236 0.081 0.0870.9715 1.0471 0.039 0.0341.0000 1.02785 0.000 0.000

T = 313.15 K0.0000 1.43645 0.000 0.0000.0386 1.40660 0.040 0.0380.0773 1.39360 0.072 0.0710.1458 1.37033 0.114 0.1120.2218 1.34401 0.143 0.1430.2952 1.31800 0.162 0.1630.3472 1.29916 0.172 0.1730.4215 1.27165 0.184 0.1850.4962 1.24318 0.195 0.1950.5860 1.20785 0.207 0.2050.6784 1.17024 0.211 0.2090.7647 1.13399 0.200 0.1990.8096 1.11470 0.185 0.186

Table 2 (continued)

x1 Density (ρ) (g.cm−3) VE (exp) VE (Hwang)

cm3 mol−1

T = 313.15 K0.8843 1.08197 0.142 0.1420.9175 1.06723 0.111 0.1130.9715 1.04288 0.045 0.0461.0000 1.02691 0.000 0.000

0.0 0.2 0.4 0.6 0.8 1.00.00

0.03

0.06

0.09

x1

VE/c

m3 .

mo

l-1

Fig. 1. Variation of excess volume (VE) of the binary liquid mixture of benzylalcohol(1) with 1,2-dichlorobenzene (2) at 298.15 K (▲), 303.15 K (▼), 308.15 K (●) and313.15 K (■).

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

x1

VE/c

m3 .

mo

l-1

Fig. 2. Variation of excess volume (VE) of the binary liquid mixture of benzylalcohol(1) with 1,3-dichlorobenzene (2) at 298.15 K (▲), 303.15 K (▼), 308.15 K (●) and313.15 K (■).

166 L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

Author's personal copy

The corresponding excess isentropic compressibilities (κsE) wereobtained from the relation [21]

κEs ¼ κs−κids ð3Þ

where κsid is the ideal value of the isentropic compressibility and wascalculated from the following equation [21].

κids ¼X2i¼1

ϕi κs:i þ TVi α2i

� �=Cp:i

h i− T

X2i¼1

xiVi

! X2i¼1

ϕiαi

!2

=X2i¼1

xiCp:i

( ):

ð4Þ

Here, Cp.i and αi are the molar heat capacity and the thermal ex-pansion coefficient of the ith component respectively. The values ofCp.i and αi were obtained and evaluated from literature [10,22] andthese are mentioned in Table 1.

The value of κsE may be interpreted in terms of two opposingeffects:

i) loss of dipolar association and difference in size and shape of thecomponent molecule

ii) dipole–dipole, dipole-induced dipole, electron–donor–acceptor in-teractions and interstitial accommodation of the non-componentin the benzylalcohol lattice.

The former effects contribute to an increase in free length, de-scribed by Jacobson, this leads to negative deviations in sound veloc-ity positive deviation in excess isentropic compressibility [23]. Thelatter effects, on the other hand, lead to positive deviation in soundvelocity and negative deviation in excess isentropic compressibility.An examination of negative of κsE values in Figs. 5–7 suggests thatlatter effects are dominant in all the binary mixtures. On the basis ofmode of sound propagation given by Eyring and Kincaid [24] theincreased free-length in the solutions due to the process of mixing,results in the lowering of sound velocity due to closer approach ofunlike molecules leading to reduction in compressibility [25].

The algebraic values of κsE for the binary mixtures of benzylalcoholwith di/trichlorobenzenes fall in the order:

1,2-dichlorobenzene b 1,3-dichlorobenzene b 1,2,4-trichlorobenzene.The above order indicates that the intermolecular interactions in

ortho position become more than the meta and para isomers due towhich polar character will be more in ortho isomer [20].

The effects of increasing temperature result in the decrease of κSE

values suggesting the reduction of the specific molecular interactions.κSE data becomes less negative which may be due to low thermal dis-sociation of hetero-association in liquid mixtures and less interstitialaccommodation of one component into another [26].

Experimental ultrasonic sound velocities were analyzed in termsof collision factor theory (CFT) [4], free length theory (FLT) [5,6]and these were also included in Table 3 along with experimental ul-trasonic sound velocities. The pure component data namely, themolar volume (Vm), molar volume at absolute zero (V0), molar avail-able volume (Va), free length (Lf), surface area (Y), collision factor(S),average molecular radius (rm), actual volume of molecules per mole(B) and molecular sound velocity (R) that were used to calculatethe above said theories were collected from the literature [19]. Themethods and details of calculation of theories were discussed earlier[20,27] and these values are given in Table 4.

The details of various theories and relevant equations are given asfollows:

A comparison between experimental sound velocities and theoreti-cal values suggest that themodel proposed by Schaaff's CFT gives betterestimation of sound velocity data. The methods of calculation of thesetheories were described in earlier. The merits of these theories werecompared in terms of relative root mean deviation by using the follow-ing formula [28]

RMSD ¼ 1n∑n

i¼1yexp−ypred

yexp

" #2" #1=2: ð5Þ

The RMSD for all the binary system values given in Table 5 showsthat Schaaff's CFT model gives better estimation in sound velocity forthe binary mixtures under the investigation.

The experimental VE values and κSE data were fitted to Redlich–Kister type polynomial equation [29]

yE ¼ x1x2∑ni¼0ai x1−x2ð Þi ð6Þ

where YE = VE or κSE the subscription ‘i’ in the equation takes value from0 to 2; Ai is the adjustable parameter of the function and are determinedusing the least-squaresmethod. The corresponding standard deviationsσ(YE) have been computed using the relation.

σ YE� �

¼ Σ YEexp−YE

cal

� �2= m−nð Þ

� �1=2ð7Þ

where ‘m’ is the total number of experimental points and ‘n’ is the num-ber of coefficients in Eq. (6), and the standard deviations of all the bina-ry mixtures have been presented in Table 6.

0.0 0.2 0.4 0.6 0.8 1.00.00

0.06

0.12

0.18

x1

VE/c

m3 .

mo

l-1

Fig. 3. Variation of excess volume (VE) of the binary liquid mixture of benzylalcohol(1) with 1,2,4-trichlorobenzene (2) at 298.15 K (▲), 303.15 K (▼), 308.15 (●) and313.15 K (■).

0.0 0.2 0.4 0.6 0.8 1.0

-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

VE/c

m3 .

mo

l-1

x1

Fig. 4. Variation of excess volume (VE) of the binary liquid mixture of benzylalcohol(1) with chlorobenzene (■). 1,2-dichlorobenzene (▲) 1,3-dichlorobenzene (▼), 1,2,4-trichlorobenzene (●) at 303.15 K.

167L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

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5. Conclusion

In the present work excess volume data of binary mixture ofbenzylalcohol with 1,2-dichlorobenzene, 1,3-dichlorobenzene and1,2,4-trichlorobenzene are positive over the entire composition rangeat 298.15 K to 313.15 K and the property is positive in all the binary

Table 3Mole fraction (x1) of benzylalcohol, densities (ρ), sound velocities (u), isentropic com-pressibilities (κs), excess isentropic compressibilities (κsE) and theoretical sound veloc-ity values of benzylalcohol (1) with di/trichlorobenzenes (2) at 303.15 K and 313.15 K.

x1 ρ(g.cm−3)

u (exp)(m.s−1)

κs (TPa−1) UFLT UCFT κsE (TPa−1)

(m.s−1)

Benzylalcohol (1) + 1,2-dichlorobenzene (2) T = 303.15 K0.0000 1.29545 1266 482.6 – – 0.00.0990 1.27090 1289 473.5 1295 1298 −6.10.1177 1.26636 1294 471.6 1310 1308 −7.30.2180 1.24183 1320 462.1 1325 1328 −12.80.2713 1.22862 1335 456.6 1346 1349 −15.80.3215 1.21611 1349 451.8 1358 1354 −18.20.4207 1.19111 1376 443.4 1398 1400 −21.10.4890 1.17368 1394 438.4 1408 1403 −22.00.5520 1.15745 1411 433.9 1459 1463 −22.50.6598 1.12933 1439 427.6 1487 1489 −21.20.7291 1.11103 1455 425.1 1495 1496 −18.50.8012 1.09175 1472 422.7 1511 1513 −15.10.8513 1.07827 1485 420.5 1524 1521 −13.10.8993 1.06523 1494 420.6 1534 1532 −8.90.9372 1.05489 1502 420.2 1562 1565 −5.90.9575 1.04932 1505 420.7 1591 1590 −3.61.0000 1.03760 1514 420.4 – – 0.0

T = 313.15 K0.0000 1.27653 1237 511.9 – – 0.00.0990 1.25375 1264 499.2 1275 1272 −7.40.1177 1.24941 1270 496.2 1295 1293 −9.30.2180 1.22592 1299 483.4 1308 1305 −15.60.2713 1.21330 1316 475.9 1335 1333 −19.40.3215 1.20133 1330 470.5 1354 1357 −21.00.4207 1.17737 1361 458.5 1363 1368 −24.80.4890 1.16065 1382 451.5 1394 1389 −25.80.5520 1.14508 1400 455.5 1405 1401 −25.90.6598 1.11807 1433 435.5 1432 1435 −25.00.7291 1.10048 1453 430.4 1456 1458 −22.70.8012 1.08198 1472 426.5 1479 1476 −18.50.8513 1.06899 1485 424.2 1491 1493 −15.00.8993 1.05647 1498 421.8 1503 1499 −11.60.9372 1.04648 1506 421.3 1515 1510 −7.50.9575 1.04115 1509 421.8 1523 1526 −4.41.0000 1.02691 1517 420.8 – – 0.0

Benzylalcohol (1) + 1,3-dichlorobenzene (2) T = 303.15 K0.0000 1.27772 1237 510.6 – – 0.00.0533 1.26586 1253 503.2 1235 1232 −4.80.0933 1.25684 1265 497.2 1251 1254 −8.80.1521 1.24351 1282 489.3 1284 1281 −13.60.2041 1.23166 1299 481.1 1295 1297 −18.30.2521 1.22063 1314 474.4 1351 1355 −21.70.3272 1.20321 1335 466.3 1368 1369 −24.40.4081 1.18425 1360 456.5 1392 1394 −27.70.5268 1.15598 1394 445.1 1412 1416 −28.60.6073 1.13650 1418 437.6 1439 1438 −28.30.7127 1.11060 1447 430.0 1486 1491 −24.80.7541 1.10034 1456 428.7 1513 1508 −21.60.8030 1.08809 1470 425.3 1543 1538 −19.40.8443 1.07764 1479 424.2 1598 1594 −15.60.9164 1.05921 1496 421.8 1603 1607 −9.30.9511 1.05032 1503 421.4 1624 1619 −5.31.0000 1.02785 1514 420.4 – – 0.0

T = 313.15 K0.0000 1.27210 1237 522.8 – – 0.00.0533 1.25644 1246 512.6 1226 1228 −8.00.0933 1.24747 1260 504.9 1249 1248 −13.90.1521 1.23419 1278 496.1 1267 1263 −19.50.2041 1.22239 1295 487.8 1298 1304 −24.60.2521 1.21141 1310 481.0 1326 1325 −28.10.3272 1.19407 1334 470.6 1365 1361 −32.70.4081 1.17521 1358 461.4 1368 1365 −34.80.5269 1.14713 1395 447.9 1398 1394 −36.40.6073 1.12784 1418 440.9 1486 1489 −34.40.7127 1.10220 1449 432.2 1507 1503 −30.10.7541 1.09200 1460 429.6 1534 1538 −27.30.8030 1.07986 1473 426.8 1584 1591 −23.40.8443 1.06951 1482 425.7 1596 1593 −18.70.9164 1.05131 1501 422.1 1603 1160 −11.7

Table 3 (continued)

x1 ρ(g.cm−3)

u (exp)(m.s−1)

κs (TPa−1) UFLT UCFT κsE (TPa−1)

(m.s−1)

T = 313.15 K0.9511 1.04245 1510 420.9 1612 1613 −7.61.0000 1.02691 1517 420.8 – – 0.0

Benzylalcohol (1) + 1,2,4-trichlorobenzene (2) T = 303.15 K0.0000 1.44248 1252 439.5 – – 0.00.0386 1.42913 1267 435.9 1225 1221 −3.70.0773 1.41554 1280 431.2 1253 1255 −8.50.1458 1.39135 1301 424.6 1273 1269 −14.90.2218 1.36379 1324 418.3 1298 1300 −20.90.2952 1.33658 1345 413.6 1312 1316 −25.00.3472 1.31686 1358 411.8 1329 1325 −26.30.4215 1.28818 1377 409.4 1352 1356 −27.70.4962 1.25862 1396 407.7 1368 1363 −28.20.5860 1.22201 1416 408.1 1391 1394 −25.90.6784 1.18310 1438 408.8 1416 1410 −22.90.7647 1.14567 1458 410.6 1452 1450 −18.60.8096 1.12577 1466 413.3 1463 1467 −14.50.8843 1.09176 1485 415.4 1492 1489 −9.70.9175 1.07652 1495 415.6 1510 1509 −8.30.9715 1.05103 1507 418.9 1538 1535 −2.81.0000 1.03760 1514 420.4 – – 0.0

T = 313.15 K0.0000 1.41951 1232 464.1 – – 0.00.0386 1.40660 1248 456.5 1255 1253 −7.10.0773 1.39360 1262 450.5 1271 1275 −12.40.1458 1.37033 1287 440.6 1296 1292 −21.00.2218 1.34400 1312 432.2 1319 1315 −27.60.2952 1.31800 1334 426.4 1353 1348 −31.30.3472 1.29916 1349 423.0 1382 1385 −33.10.4215 1.27165 1370 419.0 1397 1394 −34.50.4962 1.24318 1392 415.1 1426 1421 −35.40.5860 1.20785 1415 413.4 1467 1469 −33.10.6784 1.17024 1438 413.2 1483 1488 −28.50.7647 1.13399 1460 413.7 1513 1515 −23.10.8096 1.11470 1470 415.2 1548 1545 −18.80.8843 1.08197 1491 415.7 1565 1562 −13.40.9175 1.06723 1498 417.6 1591 1587 −9.30.9715 1.04288 1511 420.0 1609 1606 −2.91.0000 1.02691 1517 420.8 – – 0.0

0.0 0.2 0.4 0.6 0.8 1.0-30

-20

-10

0

x1

KsE

/Tp

a-1

Fig. 5. Variation of excess isentropic compressibility (κSE) of the binary liquid mixture ofbenzylalcohol (1) with1,2-dichlorobenzene (2) at 303.15 K (▼) and 313.15 K (■).

168 L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

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mixtures. This data reveals that weak intermolecular interactions areprevailing in liquid mixtures. Further, negative κSE data in all the binarymixtures which arise due to changes of free volume in the real mixturesand presence of π-electrons in benzylalcohol result in the formation ofstrong intermolecular complexes leading to positive deviation insound velocity and negative excess isentropic compressibility.

Acknowledgment

The author expresses his sincere thanks to Prof. P. Venkateswarlu,Dept. of Chemistry, S.V. University, Tirupati for providing necessaryfacilities to carry out the present work.

0.0 0.2 0.4 0.6 0.8 1.0-40

-30

-20

-10

0

X1

KsE

/Tp

a-1

Fig. 6. Variation of excess isentropic compressibility (κSE) of the binary liquid mixture ofbenzylalcohol (1) with 1,3-dichlorobenzene (2) at 303.15 K (▼) and 313.15 K (■).

0.0 0.2 0.4 0.6 0.8 1.0-40

-30

-20

-10

0

X1

KsE

/Tp

a-1

Fig. 7. Variation of excess isentropic compressibility (κSE) of the binary liquid mixture ofbenzylalcohol (1) with 1,2,4-trichlorobenzene (2) at 303.15 K (▼) and 313.15 K (■).

Table 4Calculated values of the molar volume (Vm), molar volume at absolute zero (V0), molar available volume (Va), free length (Lf), surface area (Y), collision factor (S), average molec-ular radius (rm), actual volume of molecules per mole (B) of pure liquid compounds at 303.15 K and 313.15 K.

Compound Vm Vo Va Lf Y S rm B

cm3.mol−1 A0

303.15 KBenzylalcohol 104.22 83.96 16.41 0.4092 80.173 1.8137 2.7486 52.3641,2-dichlorobenzene 108.84 95.35 17.80 0.4380 81.277 1.6054 0.28054 55.6641,3-dichlorobenzene 115.05 96.56 18.54 0.4488 82.638 1.5748 0.28246 56.8241,2,4-trichlorobenzene 125.79 107.29 18.52 0.4167 88.902 1.5305 0.29509 64.793

313.15 KBenzylalcohol 104.99 87.13 17.87 0.4165 85.828 1.8945 2.7525 52.6171,2-dichlorobenzene 110.46 97.43 18.09 0.4597 84.286 1.7281 0.2875 55.8981,3-dichlorobenzene 115.55 97.94 20.57 0.4672 85.583 1.5976 0.3482 57.7351,2,4-trichlorobenzene 127.83 109.64 20.61 0.4372 91.804 1.5830 0.3581 64.934

Table 5RMSD of speed of sound (u) of benzylalcohol with chloro substituted benzene at T =303.15 K and 313.15 K from different relations.

RMSD 303.15 K 313.15 K

Benzylalcohol (1) + 1,2-dichlorobenzene (2)CFT 0.016 0.006FLT 0.024 0.027

Benzylalcohol (1) + 1,3-dichlorobenzene (2)CFT 0.031 0.034FLT 0.029 0.038

Benzylalcohol (1) + 1,2,4-trichlorobenzene (2)CFT 0.033 0.034FLT 0.103 0.109

Table 6Coefficients Ai of Redlich–Kister Eq. (6) and the corresponding standard deviations (σ)of all the systems.

Temperature Function A0 A1 A2 σ(VE)

Benzylalcohol (1) + 1,2-dichlorobenzene (2)VE

289.15 K 0.279 0.025 −0.084 0.002303.15 K 0.299 0.050 −0.007 0.001308.15 K 0.333 0.048 0.023 0.001313.15 K 0.359 0.09 0.073 0.002

κsE

303.15 K −89.9 −17.6 11.5 0.3313.15 K −105.0 −21.1 4.1 0.4

Benzylalcohol (1) + 1,3-dichlorobenzene (2)VE

289.15 K 0.430 −0.048 −0.052 0.003303.15 K 0.454 −0.040 −0.010 0.002308.15 K 0.493 −0.040 0.091 0.002313.15 K 0.559 −0.060 0.066 0.002

κsE

303.15 K −117.0 −9.5 11.6 0.5313.15 K −143.0 2.8 −19.2 0.4

Benzylalcohol (1) + 1,2,4-trichlorobenzene (2)VE

289.15 K 0.646 0.246 0.098 0.005303.15 K 0.674 0.235 0.268 0.001308.15 K 0.740 0.244 0.280 0.005313.15 K 0.783 0.280 0.649 0.001

κsE

303.15 K −112.0 9.137 8.068 0.808313.15 K −138.0 33.9 −13.2 0.6

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170 L. Venkatramana et al. / Journal of Molecular Liquids 186 (2013) 163–170

Thermodynamic properties of binary mixtures containing1-alkanols

L. Venkatramana • K. Sreenivasulu •

K. Sivakumar • K. Dayananda Reddy

Received: 1 May 2013 / Accepted: 9 October 2013 / Published online: 7 November 2013

� Akademiai Kiado, Budapest, Hungary 2013

Abstract Densities (q) of pure liquids and their mixtures

have been measured at 303.15 and 313.15 K and atmospheric

pressure over the entire composition range for the binary

mixtures of benzylalcohol with 1-propanol, 1-butanol,

1-pentanol, and 1-hexanol by using Rudolph Research Ana-

lytical digital densitometer (DDM-2911 model). Further, the

ultrasonic sound velocities for the above said mixtures were

also measured at 303.15 and 313.15 K. The measured density

data were used to compute excess molar volumes (VE) and

these were compared with the values obtained by Hwang

equation. Isentropic compressibility (jS) and excess isentro-

pic compressibilities (jSE) were evaluated from experimental

sound velocity and density data. Moreover, the experimental

sound velocities were analyzed in terms of theoretic models

namely, collision factor theory and free length theory. The

experimental results were discussed in terms of intermolec-

ular interactions between component molecules.

Keywords Density � Excess volume � Sound

velocity � Theoretic analysis � Molecular interaction

Introduction

The important role played by solvents in chemistry has

long been recognized. Mixing effects for a large number of

compounds and their mixtures used in the petroleum

processing industry are rather difficult be known, hence

knowledge of thermodynamic properties such as densities,

ultrasonic sound velocity, viscosity and refractive index of

many organic mixtures at various temperatures is of great

importance and consideration. Mixing of the compounds

with different and complex molecular structure causes

various intermolecular interactions, resulting in non-ideal

behavior [1–5]. We report here the excess volume and

excess isentropic compressibilities data of binary mixture

of benzylalcohol with 1-propanol, 1-butanol, 1-pentanol,

and 1-hexanol at 303.15 and 313.15 K. The organic liquids

that were used in the present investigation are having many

industrial applications. Benzylalcohol is an important as a

solvent for gelatin, cellulose acetate, shellac [6, 7].

1-Alkanols are interesting simple examples of biologic and

industrial important amphiphilic materials [8]. Further, it

has been reported [9–11] that the strength of association in

alkanols decreases as the carbon chain length in the mol-

ecule increases for 1-propanol, 1-butanol, 1-pentanol, and

1-hexanol. A survey of the literature has shown that the

thermodynamic properties for binary liquid mixtures of

benzylalcohol with aromatic hydrocarbons [12], 1-propa-

nol, and 1-octanol [13] were reported earlier. To our best of

knowledge, no systematic studies on excess volumes (VE)

and excess isentropic compressibility (jSE) were reported

for a series of 1-alkanols with benzylalcohol, and hence,

we report here new VE and jSE data for the binary mixtures

of benzylalcohol with 1-alkanols (c3–c6). Further, the

experimental sound velocity data were also compared with

theoretic models proposed by Schaaff’s collision factor

theory (CFT) [14] and Jacobson’s free length theory (FLT)

[15, 16]. The present study was under taken to know the

effect of temperature and chain length of 1-alkanols when

mixed with benzylalcohol that may induce changes in sign

and magnitude of excess thermodynamic functions.

L. Venkatramana � K. Dayananda Reddy (&)

Department of Chemistry, P.V.K.N. Govt. Degree & P.G.

College, Chittoor 517001, AP, India

e-mail: ramanapvkn@gmail.com

K. Sreenivasulu � K. Sivakumar

Department of Chemistry, S.V. Arts Degree & P.G. College

(T.T.D’S), Tirupati 517502, AP, India

123

J Therm Anal Calorim (2014) 115:1829–1834

DOI 10.1007/s10973-013-3473-9

Author's personal copy

Experimental

Materials and apparatus

All the chemicals used in the present study were of ana-

lytical reagent grade procured from S.D.Fine chemicals

Ltd., India and Merck, and their purities were as follows:

benzylalcohol 99.5 %, 1-propanol 99.5 %, 1-butanol

99.5 %, 1-pentanol 99.6 %, and 1-hexanol 99.5 %. Prior to

experimental measurements, all the liquids were purified as

described in the literature [17]. The purity samples were

attained by fractional distillation, and the purity of chem-

icals were checked by comparing the measured densities

and ultrasonic sound velocities, which were in good

agreement with the literature values [12, 18, 19] and these

are given in Table 1. The purity of the sample was further

confirmed by GLC single sharp peak. Before use, the

chemicals were stored over 0.4 nm molecular sieves for

about 72 h to remove water and were later degassed.

All the binary liquid mixtures are prepared by weighting

an appropriate amount of pure liquids and an electronic

balance (Afoset, ER-120A, India) with a precision

of ±0.1 mg by syringing each component into airtight

stopper bottles to minimize evaporation losses. The

uncertainty of the mole fraction was ±1 9 10-4. After

mixing the sample, the bubble free homogenous sample

was transferred into the U-tube of the densimeter through a

syringe. The density measurements were reported earlier

[20] with a Rudolph Research Analytical digital densimeter

(DDM-2911 Model). A multi frequency ultrasonic inter-

ferometer (M-82 Model, Mittal Enterprise, New Delhi,

India) operated at 2 MHz, was used to measure the ultra-

sonic velocities of the binary liquid mixtures at 303.15 and

313.15 K as described earlier in the literature [21, 22].

Results and discussion

The experimental values of densities (q) and ultrasonic

sound velocities (u) were used to calculate excess molar

volume (VE) and excess isentropic compressibilities (jSE) for

Table 1 Densities (q), sound velocity (u), thermal coefficient (a), and heat capacity (cp) for pure component liquids at temperatures from 298.15

to 313.15 K along with the literature values

q/g cm-3 u/m s-1

T/K Exp. Lit. Exp. Lit. a/kK-1 Cp/J mol-1 k-1

Benzylalcohol

303.15 1.03760 1.03700 [12] 1,514 1,511 [12] 0.7402 224.35 [24]

313.15 1.02691 1,519 0.7456 227.62

1-Propanol

303.15 0.79559 0.79597 [18] 1,192 1,189 [18] 0.76827 147.80 [18]

313.15 0.78720 0.78770 [18] 1,158 1,155 [18] 0.53083 153.58 [18]

1-Butanol

303.15 0.80206 0.80209 [18] 1,226 1,222 [18] 0.94756 177.10 [18]

313.15 0.79409 0.79430 [18] 1,191 1,189 [18] 0.89640 184.28 [18]

1-Pentanol

303.15 0.80656 0.80650 [19] 1,262 1,258 [19] 0.89945 212.26 [19]

313.15 0.79905 0.79905 [19] 1,225 1,225 [19] 1.09881 220.94 [19]

1-Hexanol

303.15 0.81215 0.81212 [19] 1,287 1,288 [19] 0.80783 245.30 [19]

313.15 0.80451 0.80451 [19] 1,254 1,252 [19] 0.98693 255.50 [19]

0.0 0.2 0.4 0.6 0.8 1.0

–0.2

–0.1

0.0

0.1

0.2

x1

VE

/cm

3 mol

–1

Fig. 1 Variation of excess volume (VE) of the binary liquid mixture

of benzylalcohol with 1-propanol (filled square), 1-butanol (filled

circle), 1-pentanol (filled triangle), 1-hexanol (filled diamond) at

303.15 K and benzylalcohol with 1-propanol (unfilled square),

1-butanol (unfilled circle), 1-pentanol (unfilled triangle), 1-hexanol

(unfilled diamond) at 313.15 K, respectively

1830 L. Venkatramana et al.

123

Author's personal copy

the binary liquid mixtures of benzylalcohol with 1-alcohols

(c3–c6) at 303.15 and 313.15 K. The VE data are graphically

represented in Fig. 1 and jSE data in Fig. 2 for all the binary

mixtures at two temperatures. The excess molar volume data

of all the binary mixtures were calculated from the measured

densities by using the following equation

VE ¼ x1M1 þ x2M2½ �=q� x1M1=q1 þ x2M2=q2½ � ð1Þwhere q is the density of the mixture, and x1, M1, q1 and x2,

M2, q2 are the mole fractions, molecular masses and den-

sities of pure components 1 and 2, respectively.

From the result of ultrasonic sound velocities (u) and

densities (q), isentropic compressibilities (jS) were calcu-

lated as

jS ¼ u�2q�1 ð2ÞThe corresponding excess isentropic compressibilities

(jSE) were obtained from the relation [23]:

jEs ¼ js� jid

s ð3Þwhere jS

id is the ideal value of the isentropic

compressibility and was calculated from the following

equation [23]:

jids ¼

X2

i¼1

ui js:i þ TVi a2i

� �=Cp:i

� �

� TX2

i¼1

xiVi

! X2

i¼1

uiai

!2,X2

i¼1

xiCp:i

8<:

9=; ð4Þ

Here, Cpi and ai are the molar heat capacity and the

thermal expansion coefficient of the ith component,

respectively. The value of Cpi and ai obtained and

evaluated from the literature [18, 19, 24] and these are

mentioned in Table 1.

An examination of VE data given in Fig. 1 show that it is

negative over the entire composition range for the binary

mixtures containing 1-propanol and 1-butanol whereas VE

data exhibit an inversion in sign in the mixtures containing

1-pentanol and 1-hexanol. The sign of excess volume (VE)

of system depends on the relative magnitude of expansion

and contraction of two liquids. If the factors that cause

expansion in volume dominate the factors creating con-

traction, then VE becomes positive. On the other hand, if

the contractive factors dominate the expansive factors than

VE become negative.

The factors those are responsible for expansion in vol-

ume, which are as follows:

(i) Loss of dipolar association i.e. rupturing of

H-bonding of component by the other or breaking up of

associates held by weaker forces, namely dipole–dipole or

dipole-induced dipole interactions or by Vander Waals

forces. (ii) The geometry of molecular structure which

does not allow fitting of the one component into others.

(iii) Steric hindrance which opposes proximity of the

constituent molecules.

While the negative VE values arise due to dominance of

the following factors:

(i) Chemical interactions between constituent mole-

cules, such as hetero molecule association through the

formation of H-bond known as strong specific interactions.

(ii) Accommodation of molecules of one component into

the interstitials of the molecules of the other components.

(iii) Geometry of the molecular structure that favors

fitting of the component molecules with each other [25].

From the Fig. 1, it is evident that the factors which are

responsible for negative VE values which are dominant in

the mixtures of benzylalcohol with 1-propanol and

1-butanol. On the other hand, the factors those are

responsible for both the positive and negative VE data

which are competing with each other in the binary mixtures

containing 1-pentanol and 1-hexanol. Further, it is

observed that the magnitude of negative VE data decreases

with increase in composition of benzylalcohol. According

to Marcus [11], the molecules of 1-alkanols are associated

through hydrogen bonding in pure state. When these alk-

anol molecules are mixed with polar molecule like ben-

zylalcohol would induce mutual dissociation of the

hydrogen-bonded structures present in pure alkanols with

subsequent formation of strong intermolecular hydrogen

bonding (O…H–O), relatively weak hydrogen bonding (p–

H) between p-electrons of the benzene ring of benzylal-

cohol and protons of 1-alkanols [13]. Further, the curves in

Fig. 1 also reveal that as the chain length of 1-alkanol

molecule increases from 1-propanol to 1-hexanol, the

0.0 0.2 0.4 0.6 0.8 1.0

–90

–80

–70

–60

–50

–40

–30

–20

–10

0

x1

sE /

TP

a–1κ

Fig. 2 Variation of excess isentropic compressibility (jSE) of the

binary liquid mixture of benzylalcohol with 1-propanol (filled

square), 1-butanol (filled circle), 1-pentanol (filled triangle), 1-hex-

anol (filled diamond) at 303.15 K and benzylalcohol with 1-propanol

(unfilled square), 1-butanol (unfilled circle), 1-pentanol (unfilled

triangle), 1-hexanol (unfilled diamond) at 313.15 K, respectively

Thermodynamic properties of binary mixtures containing 1-alkanols 1831

123

Author's personal copy

negative excess volume tends to shift toward positive

excess volume which implies that dipole–dipole interac-

tions are becoming weak in higher 1-alkanols owing to the

decrease in their polarizability [26]. Also the positive

excess volumes suggest that the higher 1-alkanols pose less

proton donating ability than the lower alkanols, and hence

hetero-association effects decree in the binary mixtures

with an increase of chain length of linear alkanols [27, 28].

The algebraic values of VE for the mixtures of benzylal-

cohol with 1-alkanols fall in the order:

1-hexanol [ 1-pentanol [ 1-butanol [ 1-propanol

A perusal of jSE data in Fig. 2 suggests that the property is

negative over the entire composition range for all the binary

mixtures of benzylalcohol with 1-alkanols at both the tem-

peratures. The jSE values ascribed to the changes in inter-

molecular free space defined by Jacobson. These changes

occur due to structure-breaking and structure-making effects

of the components and the consequent change in geometrical

factors. Structure-breaking effect contributes to increases in

free space between the molecules and these results in the

sound waves covering shorter distance in mixtures. This

leads to the positive deviation in compressibilities. On the

other hand, structure-making effects would contribute to

decrease in free space and a negative deviation in isentropic

compressibility. The actual deviation would depend upon

the balance between the two opposing effects. The experi-

mental results indicate that the structure-making effect is

dominated in all binary mixtures of benzylalcohol with

1-alkanols. The algebraic jSE values fall in the order:

1-hexanol [ 1-pentanol [ 1-butanol [ 1-propanol

The above order indicates that as the chain length of

alkanol increases, the hetero-association decreases due to

decrease in polarity of alcohols molecules. Further, it is

concluded that algebraic values of excess volume (VE) and

excess isentropic compressibility (jSE) decrease not only the

increasing the chain of 1-alkanols but also decrease in

polarizability values of 1-propanol (3.09 D); 1-butanol

(1.75 D); 1-pentanol (1.7 D); 1-hexanol (1.55 D) [17].

An examination of jSE data in Fig. 2 suggests that mix-

ing of benzylalcohol with 1-alkanols leads to interstitial

accommodational molecules. This leads to decreasing

intermolecular free space between component molecules

and formation of closer molecular aggregates [29]. The

effects of increasing temperature appear the increasing jSE

values suggesting the increasing the specific molecular

interactions. jSE data become more negative which may be

due to high thermal dissociation of hetero-association in

liquid mixtures and more interstitial accommodation of one

component into another [30]. Over the entire investigated

conditions, the absolute values of excess volumes and

excess isentropic compressibilities are increased with

increasing the temperature in all the binary systems of

benzylalcohol with 1-alkanols.

Experimental speeds of sound were analyzed in terms of

the CFT [14] and FLT [15, 16]. The pure component data

namely, the molar volume (Vm), molar volume at absolute

zero (V0), molar available volume (Va), free length (Lf),

surface area (Y), collision factor (S), average molecular

radius (rm), actual volume of molecules per mole (B), and

molecular sound velocity (R), which were used to calculate

the above said theories were collected from the literature

[31]. The methods and details of calculation of theories

were discussed earlier [32]. The details of various theories

and relevant equations are given as follows: A comparison

between experimental speed of sound and theoretic speed

of sound values suggests that the model proposed by

Schaaff’s CFT gives better estimation of sound velocity

data. The methods of calculation of these theories were

0.000

0.005

0.010

0.015

0.020

0.025

% R

MS

D

A B C D

Fig. 3 Graphical representations of theoretical models FLT (unfilled

square) and CFT (filled square) of benzylalcohol with 1-propanol (a);

1-butanol (b); 1-pentanol (c); 1-hexanol (d) at 303.15 K

0.000

0.005

0.010

0.015

0.020

% R

MS

D

A B C D

Fig. 4 Graphical representations of theoretic models FLT (unfilled

square) and CFT (filled square) of benzylalcohol with 1-propanol (a);

1-butanol (b); 1-pentanol (c); 1-hexanol (d) at 313.15 K

1832 L. Venkatramana et al.

123

Author's personal copy

described in earlier. The merits of these theories were

compared in terms of relative root mean deviation by using

the following formula [19].

RMSD ¼ 1

n

Xn

i¼1

yexp � ypred

yexp

� �2" #1=2

ð5Þ

It is evident from the Figs. 3 and 4 that the RMSD data

for all the binary systems, CFT model gives better

estimation in speed of sound for the liquid mixtures

under the investigation.

The experimental VE values and jSE data have been fitted

to Redlich–Kister type polynomial equation [33]

yE ¼ x1 x2

Xn

i¼0

ai x1�x2Þð i ð6Þ

where yE are VE and jSE, and while x1 and x2 refer to the

mole fractions of the pure components. The equation takes

value from 0 to 2; ai is the adjustable parameter of the

function and is determined using the least-squares method.

The corresponding standard deviations r (yE) have been

computed using the relation.

r yE� � ¼ R yE

exp � yEcal

� 2

m� nð Þ� �1=2

ð7Þ

where m is the total number of experimental points, and

n is the number of coefficients in Eq. (6), and the standard

deviations of all the binary mixtures have been presented in

Table 2.

Acknowledgements The authors express his sincere thanks to

Prof. P. Venkateswarlu, Department of chemistry, S.V. University,

Tirupati for providing necessary facilities to carry out the present study.

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Temperature/

K

Function a0 a1 a2 r (yE)

Benzyl alcohol (1)?1-propanol (2)

VE

303.15 -0.797 0.157 -0.043 0.001

313.15 0.917 0.176 -0.388 0.005

jSE

303.15 -294.27 34.62 78.747 2.264

313.15 -335.61 18.62 -77.932 1.727

Benzyl alcohol (1)?1-butanol (2)

VE

303.15 -0.621 0.085 0.073 0.003

313.15 -0.781 0.102 -0.081 0.002

jSE

303.15 -183.86 23.73 -11.89 0.497

313.15 -213.65 6.34 -67.95 1.615

Benzyl alcohol (1)?1-pentanol (2)

VE

303.15 -0.443 1.069 0.854 0.003

313.15 -0.668 1.832 1.271 0.001

jSE

303.15 -137.68 -10.93 -43.21 0.982

313.15 -165.26 -12.51 -54.13 1.403

Benzyl alcohol (1)?1-hexanol (2)

VE

303.15 0.599 0.471 -0.771 0.007

313.15 0.791 0.662 -0.549 0.009

jSE

303.15 -115.71 -4.671 -31.280 0.685

313.15 -128.96 -4.604 -44.952 1.039

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1834 L. Venkatramana et al.

123

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Ms. Ref. No.: TCA-D-13-00694R2 Title: Effect of chain length of alcohol on thermodynam~c properties of their binary mixtures with benzylalcohol Thermochimica Acia

Dear Ramesh Gardas.

I am pleased to confirm that your paper 'Effect of chain length of alcohol on therrnodvnarnic ~rooerties of their b l n a ~ mlxtures with benzvlalcohol" has been accepted for publlcat~on In ~hermochlrnlca Acta

When vour DaDer IS ~ubltshed on ScmnceDlrect w u want to make sure ~t gets the attention it deserves: To help you get your message across, Eisevier has developed a new, free service called AudioSlides: brief. webcast-stde oresentations that are shown (publicly available) nexl to your published article. his k r k t gives you the opportunity to explain your research in your own words and attract Interest You will receive an lnvltat~on emall to create an Aud~oSl~des oresentat~on shortlv For more lnformat~on and examples, please visit -&.

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