49

CHAPTER – 3

DENSITY AND VISCOSITY STUDIES OF BINARY LIQUID MIXTURES

3.1 GENERAL :

Due to recent developments made in the theories of liquid mixtures and

experimental techniques, the study of binary liquid mixtures, has attracted several

researchers in the field [1]. The prediction of the viscosity of liquid mixtures is a

goal of long standing, with both theoretical and practical importance. A truly

fundamental theory would predict the viscosity along with other thermodynamic

and transport properties from the knowledge of the intermolecular forces and

radial distribution function alone. Such a programme has had appreciable success

in application to pure simple liquids such as the liquefied rare gases [2], for

solutions however although the general theory has been formulated, It has not

been reduced successfully to numerical results.

One is thus forced to approximate approaches of which two general types

may distinguished. The first is that of continuous hydrodynamics, whose

application to molecular problem is identified with names of Einestein and stokes.

This approach, in which the discrete, molecular nature of solvent is

neglected, has been remarkably successful in explaining the viscosity o9f dilute

solutions of high polymers. It’s application to solutions in which both components

are of a comparable size is less appropriate.

The second general approach is to correlate the viscosity of liquid mixture

with the properties of pure components and the thermodynamic parameters

characteristic of the interactions, between components, since viscosity is a

property of liquid which depends on the intermolecular forces, the structural

aspects of liquids different concentrations and temperatures.

Viscosity date and excess thermodynamics functions of binary mixtures

have been widely used by various workers to know the nature of interactions

between their components. Relations between viscosity and excess

thermodynamic functions are also known and these functions can be determined

from the viscosity data of binary mixtures.

50

3.2 LITERATURE SURVEY :

Brown and smith [3] measured volume changes on mixing of benzene

with methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-2-propanol and hexanol

by using mixing cell, excess volume values increased with increases in

temperature and molecular weight of the alcohol.

Kinematic viscosities and densities were measured [4] experimentally in

the liquid system acetone-benzene-ethylene dichloride. Viscosities were obtained

between 25 and 55 oC. and densities between 25 and 45

oC.

Pardo and van Ness [5] determined excess molar volume at 25 and 45oC.

for binary mixture of ethanol with cyclohexane, toluene, o-xylene p-xylene and

molar volume were observed.

Kemal et al. [6] continuing a study of the effect of molecular structure on

refractive index-density relationships, mixtures of the three possible combinations

of the aromatics benzene, toluene, and xylene were investigated in the present

work The effect of composition and temperature on refractive index dispersion

and density measurement were presented for the mixture of benzene-toluene,

benzene-xylene and toluene-xylene at 20, 30 and 40 oC. Density measurement

provided a satisfactory means for analyzing for this system.

The excess volume of mixing of the binary system benzene-cyclohexane

were measured [7] as a function of composition at 25 and 40 oC. using a direct,

dilatometrictechnique. The results were compared with previous determinations,

and the comparison confirmed the superiority of the direct method of

measurement over the more usual indirect technique of calculating volume

changes from density measurements.

Nigam and Singh [8] determined excess volume for eight binary mixture

consisting of benzene, toluene, cyclohexane, CCl4 chloroform, bromobenzene and

chlorobenzene between 35-45 oC. They examined their results in terms of Apm

and Flory theory. They found Flory theory gave reasonable quantitative

agreement and correct sign of excess function.

51

The density viscosity and molecular interaction in binary mixture of

benzene and toluene with chlorobenzene and bromobenzene were measured [9]

at 25 to 35 oC. The studies showed the existence of specific interaction between

the components of the system.

The densities in air of cycloheptane, n-nonanol, 2- methylcyclohexanol,

benzaldehyde, chlorobenzene, and bromobenzene were measured [10] from about

25 to 100 oC. with a modified Robertson pycnometer. The experimental data for

each compound were fitted to nth degree polynomials in temperature for

interpolation and limited extrapolation. The agreement with the literature values

was satisfactory.

The viscosity of 10 binary systems, including polar and nonpolar

components, was determined [11] at 20 and 25 oC. The viscosity of the ternary

system heptane-iso-octanetoluene was also determined at 25 oC. Experimental

data were correlated by means of the method of McAllister and that of Heric.

Densities and molar volumes of solutions of nitrobenzene in 18 week

electron solvents were measured [12] as functions of concentration at 25 oC The

data were fitted by a least-squares method to a polynomial. No obvious

relationship was observed between the electron donating ability of the solvents

and densities of the solutions.

Densities of mixtures of benzene with four n-alkanes C6, C7, C10 and C16

were determined [13] at 25 and 50 oC. using a pycnometric method. The density

measurements were used to extend the corresponding states method of Rowlinson

and coworkers to systems containing benzene and long chain hydrocarbons.

Measurements of excess enthalpies in a flow microcalorimeter and of

excess volumes in a successive dilution dilatometer were carried out [14] at

298.15 K. For binary mixtures of chlorobenzene with benzene, toluene,

ethylbenzene, and xylene, m-xylene, and p-xylene.

The relationship between the composition of the ternary mixtures of

benzene-toluene-xylene and the refractive index, as well as density, was

determined [15] at 25 oC.

52

The viscosities for two systems, nitrobenzene-n-pentane and nitrobenzene-

n-heptane, were measured [16] for various concentrations and temperatures

between 20 and 40 oC. The viscosity in the neighborhood of critical point of

solution became anomalously large. The excess viscosity at the critical point lead

to a cusp rather than an infinity.

Ortega et al. [17] determined the excess volume of benzene with several

isomers of hexanol at 298.15 K. The results were fitted to a polynomial of

variable degree.

Rastogi et al. [18] measured excess molar volume for tetrachloro ethylene

+ toluene + p-xylene +CCl4 and + cyclohexane at 303.15 K. For some mixture an

inversion in sign in excess volume was observed.

Garrett and Pollock [19] measured the excess volume of benzene and

toluene with pyridine and methyl pyridine at 298.15 K. A linear correlation

between Pka and excess volume was found.

Nath and Singh [20] measured the excess molar volume at 293.15 K. for

mixture of tetrachloroethylene with benzene, toluene, p-xylene and CCl4. The

temperature coefficient of excess molar volume was determined.

Nath and Dubey [21] measured excess molar volume for trichloroethene

with benzene, toluene, p-xylene, tetrachloro methane and CHCl3 at 303.15 K. by

using dilatometer.

The volumes of mixing and dielectric constants of nitrobenzene-sulfolane

mixtures were measured, [22] at several temperatures ranging within 288.16-

333.16 K, over the entire composition range. The observed deflations from

ideality, decreasing with increasing temperature, were interpreted as not

indicative of significant interactions between unlike molecules.

Raman et al. [23] measured excess volume of n-alkanol with nitrobenzene

and chlorobenzene at 303. 15 K. Excess volumes were negative in mixture rich in

alkanol and positive else were. The results were attributed to the interaction

between unlike molecules.

53

Excess volumes of nonelectrolyte solutions of n-heptane, n-octane, and n-

nonane with chlorobenzene, nitrobenzene and benzonitrile were measured [24] at

313.5 K. by using a dilatometer.

Karvo [25] measured the excess enthalpies of sulpholane + benzene,

toluene, p-xylene and + meistylene at 303.15, 313.15 and 323.15 K. The value

were positive and increased with increasing hydrocarbon alkylation.

Viscosities of three binaries, viz., n -hexane-toluene, n -hexane-

chlorobenzene, and n -hexane-1-hexanol, were determined [26] at 30, 40, 50, and

60 oC. over the complete composition range. Experimental viscosities were

compared with values calculated by using equations based on the concept of

significant liquid structures as well as McAllister type three-body interactions.

Energies of activation for viscous flow were obtained and their variations with

composition were discussed.

Iloukhani et al. [27] measured excess volume of binary mixture of

substituted benzene with ethyl acetate at 313.15 K. The excess volumes were

positive over the entire range of composition.

Excess volume for binary mixture of methyl ethyl ketone with benzene,

toluene, chlorobenzene, bromobenzene and nitrobenzene were determined by

Jayalakshmi and Reddy [28] at 303.15 K, and 313. 15 K. The excess volume were

negative over the entire range of composition for all the system and both the

temperature. The data were examined in terms of Flory’s original theory.

The excess molar enthalpies of halogenobenzene + benzene or toluene and

of some dihalogen benzene were measureed [29] at atmospheric pressure and

303.15 K. The results were fitted to Redlich-Kister equation.

Singh et al. [30] measured viscosity and density of ternary liquid mixture

of ethyl benzene, bromobenzene and toluene. Mixture viscosities and densities of

the partially miscible ternary systems of toluene, chlorobenzene, and 1-hexanol

with their partially miscible binary subsystem n-hexane-benzyl alcohol were

measured at 30, 40, 50, and 60 oC. Activation enthalpies and entropies for

viscous flow were obtained and their variations with composition were discussed.

54

Rathnam [31] determined the excess volume of binary mixture at of ethyl

acetate with O-xylene. P-xylene at 303. 15 K, and 313. 15 K. Excess volume were

negative over the whole range of composition.

Viscosity coefficient measurements at saturated pressure were reported

[32] for ethyl acetate + o-xylene, ethyl acetate + p-xylene, ethyl acetate +p-

dioxane over the entire range of composition at 310.15 K. The value of mixture

viscosity were calculated for different composition by the application of Katti and

Chaudhri equation.

Marsh and Kim [33] reported the excess volume of binary system of 2-

methyl -2-propanol with water at 5 K interval from 303.15 to 323.15 K. The

partial molar volume of 2-methyl-2-propanol at infinite dilution in water was

extremely temperature dependent becoming more negative as temperature

increased.

Excess molar volumes for binary system of ethylbenzene with

chlorobenzene, nitrobenzene, aniline and benzene alcohol were measured [34] at

298. 15 K. using dilatometer. The excess volumes were negative for all systems

except for ethylbenzene + aniline. It was slightly positive at lower concentration

of aniline.

A number of excess functions were computed from the measured [35]

densities and viscosities of binary mixtures of bromoform with benzene, toluene,

p-xylene, acetonitrile, nitrobenzene and tetrahydrofuran at 298.15, 308.15

and318.15 K. Excess enthalpy and excess entropy of viscous flow were predicted

from the Arrhenius plots. Intermolecular interactions in the mixtures were

considered in the discussion of results.

Sinha et al. [36] measured the viscosity and density of ternary mixture for toluene,

ethylbenzene, bromobenzene and 1-Hexanol at 30, 40, 50, and 60 oC. the

nonidealities reflected in mixture viscosities were expressed and discussed in

terms of excess which were both positive and negative.

Aminabhavi et al. [37] measured excess volume, excess viscosity, excess

free energy of activation of flow, and contact interaction parameter were

55

computed for binary liquid mixtures of nitrobenzene with cyclohexane or N,N-

dimethylformamide from density and viscosity measurements in the temperature

interval of 298.15-313.15 K. The calculated quantities were discussed in terms of

the nature of the molecular interactions between the components. Attempts were

also made to test the validity of the viscosity models of Heric, Auslaender, and

McAllister in predicting the binary viscosity data.

Experimental measurements of density and viscosity of three binary

systems, viz., p –xylene, m -xylene, p-xylene, o -xylene, and m -xylene/o -xylene,

were performed [38] over the complete concentration ranges, for temperatures

between 273.15 and 303.15 K. For the same temperature interval, densities and

viscosities of three ternary mixtures of the isomers were obtained. Experimental

densities were compared with those predicted by the Hankinson-Brobst-Thomson

method, showing average deviations of about 0.3 %. The viscosity data were

correlated by the McAllister equations, producing excellent representations of

both binary and ternary data.

Excess volume and isentropic compressibilities of binary mixture of p-

chloro toluene with 2-propanol, 2-methyl -1- propanol and 3- methyl –1-butanol

were measured [39] at 303.15 K. The excess volume exhibits inversion in sign in

three mixture. The results were compared with those of there corresponding 1-

alkanols was more + ve for 1-alkanols group.

Excess molar volumes were determined [40] as a function of composition

at 308.15 K. for cycloalkanol with cyclohexane, benzene, toluene and p-xylene.

The results were interpreted on the basis of the structure breaking effect of

aromatic hydrocardon and weak specific interaction of the type OH- electron

between unlike molecules.

Aralaguppi et al. [41] determined the molar volume excess isentropic

compressibility and excess molar refraction of binary mixture of methyl

acetoacetate with benzene, toluene, m-xylene, mesitylene and anisole in the

temperature range 298. 15- 308.15 K. The excess molar volumes were explained

on the basis of the presence of weak dispersion type molecular interaction.

56

Excess molar volume VE of p-chlorotoluene with 1-propanol, 1-butanol, 1-

pentanol, 1-hexanol and heptanol were measured [42] at 303.15 K. VE were

negative in mixtures rich in alkanol and positive in those rich in p-chlorotoluene.

A comparison of these results with those for mixture of alkanols with toluene

showed that the algebraic value of VE were smaller in former group.

Kumar and Naidu [43] reported excess volume and isentropic

compressibilities of 1, 3 – dichlorobenzene + 2-propanol, + 2- methyl -1 propanol,

+ 3 methyl-1-butanol at 303.15 K. Both excess volume and deviation in isentropic

compressibilities were negative.

Yu and Tsai [44] determined the excess molar volume of binary mixture

or benzene and 1-alkonols ) at 298.15 K, and 308.15 K. The value of

molar volume were positive over the entire range of composition. The results

were compared with those predicted by the Hankinson-Brobst-Thomson

correlation (HBT) and the Spencer and Danner modified Rackett equation (SDR).

The HBT equation showed an average deviation of about 0.74% from the

experimental results while the SDR equation showed a 0.20% average absolute

deviation. The excess molar volumes, , calculated from the density values

were found to be positive for all the concentrations and temperatures considered.

Measurement of the densities for benzene + hexane using a high pressure

stainless steel pyconometer system at various temperatures between 298.15 and

473.15 K, were reported [45]. Excess molar volumes were found to be positive for

all concentrations and temperatures considered.

Excess volume for five ternary mixture of 2-methoxy ethanol + butyl

acetate + benzene + toluene, +chlorobenzene + bromobenzene and +nitrobenzene

measured [46] at 303.15 K. The excess volume exhibited positive deviation.

Jain et al. [47] determined excess molar volumes for the binary mixtures:

ethylbenzene + o-xylene, +m-xylene, + p-xylene; o-xylene + m-xylene, +p-xylene

and m-xylene +p-xylene were determined from density data obtained using

vibrating tube densimeter. The results were compared with literature values and

with Flory's theory.

57

The density and viscosity of binary mixtures of propanoic acid + benzene,

+ toluene, and + 0-, + m-, and + p-xylenes were measured [48] at 298.15 K.

Excess volumes were calculated. The interactions existing between the

components were discussed. The results were used to theoretically justify the

validity of the viscosity models.

The volume of mixing, speed of sound, and viscosity of binary liquid

mixtures composed of butyl acetate + o-xylene, + m-xylene, and + p-xylene were

measured [49] at 303.15 K. The excess volumes and deviations in isentropic

compressibility and viscosity were discussed in terms of molecular interaction

between like and unlike components.

Excess volume for binary mixture of ethyl acetate with toluene,

chlorotoluene and p-chloro toluene derivative were determined from density

measurement [50]. Negative excess volume was observed due to the interaction

occurring between unlike molecules.

Densities and viscosities of mixture of nitrobenzene with methanol,

ethanol, propan-1-ol, propan-2-ol, butan-1-ol, 2-methyl propan-1-ol and 2-methyl

propan 2-ol were measured [51] at 298.15 and 303.15 K. From these

measurement excess volume (VE) and deviation in viscosity ( ) were calculated

and the results were fitted to the Redlich-Kister polynomial.

Densities and speed of sound were measured [52] at 298.15, 303.15,

308.15 and 313.15 K. for the binary mixture of aniline with methyl alcohol and

ethyl alcohol, from these, excess molar volume, excess intermolecular free length

and isentropic compressibility deviation were calculated. The experimental and

calculated quantities used to discusse the mixing behavior of the components.

Gupta et al. [53] measured the excess molar volume of 1-propanol or 2-

propanol + aromatic hydrocarbon at 303. 15 K. The excess volume data for these

binary systems were interpreted in terms of Mecke-Kempter type association

model with Flory contribution terms.

Excess molar volumes of binary mixed solvents containing tetraethylene

glycol and benzene, toluene, acetone and acetonitrile were measured [54] as a

58

function of composition at 308.15K. The measurement were carried out with a

continuous-dilution dilatometer. The excess volumes were all negative over the

entire range of composition. The results were discussed in terms of the interaction

between components. The Flory model was used to calculate the excess volumes,

and were compared with experimental data for the four mixtures.

Gupta et al. measured [55] dielectric constants and refractive indices data

at 308.15 K. for 1-propanol with cyclohexane, benzene, toluene, o-, - and p-

xylene. The analysis of data showed the presence of strong specific interactions

between propanol and aromatic hydrocarbon. Frohlich equation was used to

calculate the apparent dipole moment of these binary mixtures

Densities, viscosities and refractive indices were measured [56] for 4-

chlorotoluene + methyl acetate, + ethyl acetate and + propyl acetate at 293.15,

298.15 and 303.15 K. The results were correlated by means of Redlich-Kister type

equation and discussed in terms of molecular interaction.

The excess volumes for 1-butanol or 2-butanol or 2-methylpropan-1-ol or

2-methylpropan-2-ol + o-xylene or m-xylene or p-xylene at 308.15 K. were

measured [57] overs the whole range of composition. The excess volumes vs

composition curves were skewed toward the low concentration of butanol. For

systems containing 1-butanol, curves were sigmoids and excess volumes values

changed sign in the 1-butanol (1) rich region (x1 > 0.8). For butanol + xylene

systems VE values varied in the order 2-methylpropan-2-ol > 2-butanol > 2-

methylpropan-1-ol > 1-butanol

Bhardwaj et al. [58] dilatometrically measured excess molar volume of

(butan-1-ol or butan-2-ol, or 2-methyl propan-1-ol or 2-methyl propan-2-ol

benzene + toluene) over the enter range of composition at the temperature 308.15

K. The results indicate the branching of an alkyl group of butanol near the

hydroxyl group make both the hydrogen bonding and electron donor accepter

interaction between butanol and benzene or toluene molecule less effective.

Excess molar volumes and excess molar heat capacities, were determined

[59] for mixtures of benzonitrile with chlorobenzene, or benzene, or toluene at the

temperatures 298.15 K, and 303.15 K. For all the systems the values of excess

59

molar volumes were negative over the whole range of compositions and

(∂VmE/∂T) were negative. The values of excess molar heat capacities were all

positive for the mixtures of chlorobenzene and toluene, while the sign for the

mixture with benzene changed from positive to negative with increasing mole

fraction of benzonitrile. The magnitudes of (∂Cp,E/∂T) were small, and the sign

depended on the system.

Excess molar volume measured [60] in a vibrating tube densimeter and

excess molar heal capacity measured in a flow calorimeter, were made for binary

mixture of ( ethanol + benzene or toluene or xylene or chlorobenzene) at a temp

295.15 K. The experimental results were interpreted in terms of self association of

ethanol and hydrogen bonds formed between ethanol and aromatic compound.

Venkatesu and Rao [61] determined the molar excess volume of binary

mixture of triethylamine with ethyl benzene, chlorobenzene, nitrobenzene,

bromobenzene at 308.15 K. The molar excess volume values were negative in all

the system over the entire range of composition. The results were interpreted on

the basis of intermolecular interaction between unlike molecule.

Swain et al. [62] systematically determined viscosities and densities of

ternary mixtures of tri-n-butyl phosphate + benzene + o-xylene at (30, 35, 40, and

45) oC. The deviations in the viscosity from a mole fraction average were fitted in

a Redlich-Kister-type equation, which included the contribution of each

constituent binary system along with a ternary contribution term.

The excess molar Gibbs energies of mixing for (2-methyl propan-2-o1 +

benzene or toluene or o, or m, or p-xylene ) at T =308.15 K. were calculated [63]

by the Barker method from vapour pressure data measured by static method.

Bhardwaj et al. [64] measured excess molar enthalpies at 308.15 K. for 2-

methylpropan-1-ol with benzene, toluene, o-, m- and p-xylene over the entire

range of composition. The analysis in terms of an athermal associated mixture

model Mecke–Kempter type with a Flory contribution term and quasi-chemical

model by Barker was described. Association model predicted good agreement

with VE data, while the prediction of both association model and quasi-chemical

model were fairly good for HE data.

60

Excess molar volume data on mixing for binary mixtures of sulfolane with

toluene, o-xylene, m-xylene, p-xylene, ethylbenzene and 1,2,4-trimethyl benzene

were measured [65] over the entire composition range at 298.15 K, and

atmospheric pressure in order to investigate interactions between molecules. A

vibrating tube density meter was used. All mixtures exhibited negative excess

volumes with a minimum which occurs approximately at = 0.5. The

experimental results were correlated using the Redlich–Kister equation.

Viscosities and densities of binary mixtures of tri-n-butyl phosphate (TBP)

with benzene, toluene and o-xylene were measured [66] at 30, 35, 40 and 45 oC.

The non-idealities reflected in mixture viscosities were expressed in terms of

excess viscosities. A Redlich-Kister-type equation was fitted to the binary -X-T

data for each system.

Excess molar enthalpies of (2-methyl propan 2- benzene or toluene or o,

m, or p-xylene ) were measured [67] in a flow micro calorimeter over entire

range of composition at 308.15 K. The results were analysed in terms of Mecke-

Kempter type association model with Flory contribution term.

Artigas et al. [68] measured densities and viscosities for mixture of some

hydrocarbon with 2-methyl -1-propanol at 298.15 and 313.15 K. The excess

molar volume and deviation in viscosity were found to be negative throughout the

entire range of composition.

The excess molar volume, excess molar enthalpies and excess molar heat

capacities were measured [69] as a function of mole traction at different

temperature for benzonitrile + benzene and benzonitrile + toluene. The results

were explained in terms of simple theory of complex formation.

Densities and refractive indices of the binary system ter butyl alcohol +

toluene +isooctane and + methyl cyclohexane and toluene + methyl cyclohexane

over entire range of composition were measured [70] at 298.15 K. Excess molar

volume and change of refractive indices were evaluated from empirical data. The

derived properties were fitted to variable degree polynomials.

61

Densities and viscosities were measured [71] for anisole with 2-butanol, 2-

methyl 1-propanol and 2-methyl 2-propanol binary liquid mixture with vibrating-

tube densimeter and Cannon-Fenske routine viscometer over the temperature

range between 303.15 and 323.15 K, and atmospheric pressure. Excess moral

volume and viscosity deviation were calculated at various temperatures. Both

excess molar volume and the viscosity deviation were negative for investigated

system. The isothermal excess molar volume and viscosity deviation were fitted

to a Redlich-Kister type equation.

New experimental data on densities and viscosities [72] for the systems 4-

methylpyridine + methanol, + ethanol, + propan-1-ol, + propan-2-ol, + butan-2-ol,

and + 2-methylpropan-2-ol were presented at 298.15 K, and ambient pressure

using a vibrating tube densimeter and an Ubbelohde viscometer. The results were

discussed qualitatively in terms of the association of the mixture components

caused by chainlike self-association of the alcohol molecules and cross-

association between alcohol and 4-methylpyridine.

Prabhavati et al. [73] measured excess volume for binary mixture of N-

methyl cyclohexylamine with benzene, toluene, o-xylene, m-xylene, and p-

xylene, chlorobenzene, bromobenzene and nitrobenzene at 303. 15 K. The excess

volume values were positive in mixture of N-methyl cyclohexylamine with o. m.

p-xylene, bromobenzene and nitrobenzene and an inversion of sing from negative

to positive was observed in the mixture of N methyl cyclohexylamine with

benzene, toluene. p-xylene and chlorobenzene. The experimental VE

were

analysed on the basis of molecular interaction between unlike molecules.

The densities in the temperature range 288.15 K. To 308.15 K, and the

viscosities in the temperature range 293.15 K. To 308.15 K, of the binary systems

-butyrolactone + o-xylene and m-xylene were measured [74]. Viscosity data

were correlated by the Heric, McAllister, and Hind-McLaughlin-Ubbelohde

equations. Viscosity deviations from mole fraction linearity and excess volumes

were calculated and found to be negative. Excess volumes were also fitted to a

Redlich-Kister type equation.

62

Molar excess volumes ) were evaluated for binary mixtures of

hexadecane and butanol in the temperature range of 303.15K to 318.15 K, at 5 K

intervals. values were computed [75] form density at various compositions.

negative over the entire range of composition and become less negative

at increasing temperatures. The results of excess molar volume were fitted to the

Redlich-Kister relation to estimate the adjustable parameters and standard

deviations. The results were discussed on the basis of intermolecular interactions

between unlike molecules.

Densities and viscosities were measured [76] for the binary mixture of

butan-2-o1 and 2-methyl propanol-2-ol with nitroethane at temperature from

293.15 K, to 313.15 K, and atmospheric pressure. McAllister’s three body

interaction model was used to correlate the binary kinematic viscosities.

Densities and viscosities for the binary liquid mixtures of anisole or

methyl tert-butyl ether (MTBE) with benzene, chlorobenzene, benzonitrile, and

nitrobenzene were measured [77] at 288.15, 293.15, and 298.15 K. These were

used to compute the excess volumes (VE) and deviations in viscosity ( ). These

properties were discussed with reference to the nature of interactions between the

unlike molecules.

Densities and viscosities of butanenitrile + 1-butanol, + 2-methyl 1-

propanol, + 2-butanol or + methyl 2-propanol were measured [78] at several

temperatures between 288.15 K, and 318.15. At each temperature, the

experimental viscosity data were correlated by means of the McAllister bi

parametric equation.

Tu et al. measured [79] densities and viscosities for the binary mixture of

methanol, propan-1-ol, propan-2-ol, butan 2-ol and 2methyl propan-2-ol with

nitro methane at temperatures from 293.15 K, to 313.15 K, and atmospheric

pressure. The results were fitted to McAllister three body interaction model to

correlate the binary kinematic viscosities.

Densities and viscosities of binary mixture of benzonitrile with methanol

ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, and 2-methyl 2-propanol were

measured by Nikam et al. [80] at 303.15, 308.15 and 313.15 K. From these data,

63

excess molar volume and deviation in viscosity were computed. These quantities

were fitted to a Redlich-Kister type polynomial.

The density, viscosity and ultrasonic velocity in binary mixture of propan-

l-ol, butan-l-ol and pentan-l-ol with 1,2-dibromoethane were determined [81] at

different temperatures from 298.15 to 313.15 K, over the whole composition

range. Using these parameters the excess volume ) excess viscosity ),

excess compressibility ), inter molecular free length ) and Grunberg and

Nissan parameter were evaluated. The butan-1ol + 1,2-dibromoethane system

were found to be negative at all temperature whereas for pentan-1-ol + 1,2-

dibromoethane the ) value were observed to be negative at low concentration

of pentan-1-ol (up to 0.1 molefraction).

Ouyana G, et al. [82] measured density for binary mixture of (2-propanal +

o-xylene, +m-xylene, + p-xylene, + 2methyl–2 propanol + o-xylene, +m-xylene, +

P-xylene ) at 298.15 K, and the excess molar volumes were derived.

Bahadur and Sastry [83] measured the densities and speed of sound of ten

ternary mixture of methyl acrylate (1) + 1-propranol (2) or 1-butanol (2) + n-

hexane (3) + n-heptane (3), + cylohexane (3) + benzene (3) + toluene (3) at

308.15 K. The excess volume, VE, and excess isentropic compressibility, Ks

E,

were estimated.

Aminabhavi et al. [84] determined densities, viscosities, and refractive

indices at (298.15, 303.15, and 308.15) K, and the speed of sound at 298.15 K, as

a function of mixture composition for the binary mixtures of ethyl chloroacetate +

cyclohexanone, + chlorobenzene, + bromobenzene, or + benzyl alcohol. Using

these data, excess molar volume and deviations in viscosity, molar refraction, and

speed of sound was calculated. These results were correlated with the Redlich and

Kister polynomial equation to derive the coefficients and standard errors.

George and Sastry [85] measured densities, speeds of sound, viscosities,

and relative permittivities for 21 binary mixtures of alkoxyethanols (2-

methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol) + benzene, + toluene, +

(o-, m-, and p-) xylenes, + ethylbenzene, and + cyclohexane at different

64

temperatures. The excess molar volumes, excess isentropic compressibilities,

deviations in dynamic viscosities, speeds of sound, and relative permittivities

were calculated across the mole compositions. The compositional variation of

excess and deviation functions has been expressed in terms of the Redlich-Kister

equation.

Densities and viscosities of ternary mixtures of N,N-dimethylformamide +

benzene + chlorobenzene and corresponding binary mixtures of N,N-

dimethylformamide + benzene, N,N-dimethylformamide + chlorobenzene, and

benzene + chlorobenzene were measured [86] at (298.15, 303.15, 308.15, and

313.15) K. From these data, excess molar volumes (VE) and deviations in

viscosity ( ) were calculated. Several empirical equations were used to predict

the excess molar volumes and deviations in viscosity of ternary mixtures. The

kinematic viscosities of binary and ternary liquid mixtures were also correlated

with mole fractions by McAllister’s equation.

George and Sastry [87] measured the densities, dynamic viscosities,

speeds of sound, and relative permittivities, for (dibutyl ether + benzene, or

toluene, or p-xylene) at different temperatures over the whole composition range

and at atmospheric pressure. The mixture viscosities were correlated with semi

empirical equations. Calculations of the speed of sound based on Nomoto’s

equation were found to be close to experimental values for the three mixtures and

at two temperatures. Excess functions such as excess molar volumes , excess

isentropic compressibilities , deviations in relative permittivities , and molar

polarizations were calculated and fitted to Redlich–Kister type equations.

Grunberg et al. [88] measured thermodynamic properties of non aqueous

binary mixture of benzene with corbon tetrachloride and chloroform at 298, 308,

318 K. The excess volume the excess viscosity, excess free energy of activation

of viscous flow and interaction parameter of Grunberg and Nissan were calculated

from experimental data as a function of composition and discussed.

The densities of (o-xylene, or m-xylene, or p-xylene + dimethyl sulfoxide)

were measured [89] at temperatures 293.15, 303.15, 313.15, 323.15, 333.15,

343.15, 353.15 K, and atmospheric pressure by means of a vibrating-tube

65

densimeter. The excess molar volume, , calculated from the density data

provided the temperature dependence of in the temperature range of 293.15 to

353.15 K. The results were correlated using the fourth-order Redlich–Kister

equation, with the maximum likelihood principle being applied for the

determination of the adjustable parameters. It was found that the in the

systems studied increase with rising temperature.

Yang et al. [90] measured excess molar volume and viscosity of binary

mixture of sulfolane with benzene, toluene, ethyl benzene, p-xylene, o-xylene at

303.13 and 323.15 K, and atmospheric pressure. The computed quantities were

fitted to Redlich–Kister equation to drive the coefficient and estimate the standard

error. The results were discussed in terms of intermoleclulor interactions.

Densities and speeds of sound were reported [91] for the binary mixtures

of (1,3-dioxolane or 1,4-dioxane) with (2-methyl-1-propanol or 2-methyl-2-

propanol) at the temperatures (298.15 and 313.15) K. Excess volumes and excess

isentropic compressibility coefficients were calculated from experimental data

and fitted by means of a Redlich–Kister type equation. The ERAS model was

used to calculate the excess volumes of the four systems at both temperatures.

Tanaka and Yokayama [92] measured apparent dipole movement of 1-

butanol, 1-propanol and chlorobenzene in cyclohexane or benzene and excess

molar volume al. 298.15 K. using Rohlich equation. The dipole-dipole

interactions observed for chlorobenzene were rather weak.

The viscosities and densities of binary mixture of ethyl benzene with

ethanol, 1-propanol, 1-butanol were determined [93] at 298.15 and 308.15 K. The

deviation in viscosity for all 3 system, were negative and the values decresed with

an increase in temperature which may be due to the reduction in dispersion force.

Singh et al. [94] measured the viscosities, densities, and speeds of sound

of binary mixtures of 4-methylpentan-2-one with o-xylene, m-xylene, p-xylene,

and isopropylbenzene at 298.15 K, over the whole composition range. Excess

volume, excess compressibility, and deviations in viscosity were calculated.

66

Singh et al. [95] measured viscosity and density of binary mixture of o-

xylene, m-xylene, and isopropyl benzene with 2- butanone at 298.15 K. The

deviation in viscosity were negative for the system containing o-xylene, m-xylene

and isopropyl benzene but for p-xylene, the deviation was positive.

Rathnam and Mohite measured [96] the viscosity density and refractive

indices of binary mixture of ethyl formate or ethyl benzoate with o-xylene, m-

xylene and ethyl benzene at 303.15 K, and 315.15 K, and atomsphric pressure for

the whole composition range. The experimental viscosities were fitted to an

empirical equation proposed by Frenkal.

Densities, viscosity and refractive indices of binary mixtures of anisole

with benzyl chloride, chlorobenzene and nitrobenzene were measured [97] al.

303.15 K. The variation of properties with composition suggested that the stegth

of intraction in these mixture followed the order, benzyl chloride > Nitrobenzene

> chlorobenzene.

The densities of binary mixtures formed by nitrobenzene with benzene or

toluene or ethyl benzene or styrene or o-xylene or m-xylene + nitrobenzene were

measure [98] in the temperature rang e of (298.15 to 353.15 K) and ambient

pressure using a vibrating tube densimeter. The results were correlated using

the fourth order Redlich-Kister equation. It was found that the in these system

studied, increases with rising temperature.

Densities and viscosities of 1-brombutane + 1-butanol, +2-methyl 1-

propanol, +2 butanol or + 2-methy-2 propanol were measured [99] at several

temperature. The experimental viscosities data were correlated by means of

McAllister bi parametric equation.

Density, viscosity, and refractive index, values for (tetradecane + benzene,

+ toluene, + chlorobenzene, + bromobenzene, + anisole) binary mixtures over the

entire range of mole fraction were measured [100] at temperatures 298.15,

303.15, and 308.15 K at atmospheric pressure. The speed of sound was measured

at 298.15 K, only. Using these data, excess molar volume deviations in viscosity,

Lorentz–Lorenz molar refraction, speed of sound, and isentropic compressibility

were calculated. These results were fitted to the Redlich and Kister polynomial

67

equation to estimate the binary interaction parameters and standard deviations.

Excess molar volumes exhibited both positive and negative trends in many

mixtures, depending upon the nature of the second component of the mixture. For

the (tetradecane + chlorobenzene) binary mixture, an incipient inversion was

observed. Calculated thermodynamic quantities were discussed in terms of

intermolecular interactions between mixing components.

Excess volumes, ultrasonic sound velocity, isentropic compressibilities

and viscosities ( ) were measured [101] for the binary mixture of DMSO with

1,2-dichlorobenze, 1,3-dichlorobenzene, 1,2,4 trichloro benzene, o-chlorotoluene,

m-chlorotoluene, p-chlorotoluene, o-nitrotoluene and m-nitrotoluene at 303.15 K.

Hasan et al. [102] measured density, viscosity and speed of sound studies

of binary mixture of methyl benzene with heptan-1-ol, octan-1-ol and decan-1-ol

at 303.15 and 313.15 K. The excess molar volume and excess isentropic

compressibility were positive for all three binaries studied over whole

composition where as deviation in viscosities were negative, and excess isentropic

compressibility were fitted to the Redlich-Kister polynomial equation The

Joyaban Acree model was used to correlate the experimental values of density,

viscosity and ultrasonic velocity at different temperatures.

The viscosities, densities, and speeds of sound of binary mixtures of

anisole with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene over

the entire range of mole fraction were measured [103] at temperatures 288.15,

293.15, 298.15, and 303.15 K, and atmospheric pressure. Excess compressibility

and deviations in viscosity were calculated and fitted to the Redlich-Kister

polynomial relation to estimate the binary coefficients and standard errors. The

deviations in viscosities and excess compressibilities were negative for all binary

systems. The speeds of sound were analyzed in terms of collision factor theory

and free length theory. The viscosity data were correlated with equations of

Grunberg and Nissan, Tamura and Kurata, Heric and Brewer, and McAllister.

Densities and viscosities of binary mixtures of aniline with benzene were

measured [104] over the entire range of composition, at atmospheric pressure,

and at 298.15, 303.15, 308.15, and 313.15 K. Excess molar volumes and

68

deviations in viscosity were calculated from the experimental data. Negative

excess molar volume and negative deviations in viscosity for aniline + benzene

systems were due to the interstitial accommodation of benzene molecules into

aggregates of aniline. The excess molar volumes and deviations in viscosity were

fitted to the Redlich–Kister polynomial equation. Furthermore, densities and

viscosities of ternary mixtures of aniline+benzene+N,N-dimethylformamide were

measured at atmospheric pressure, and at 298.15, 303.15, 308.15, and 313.15 K.

From these data, excess molar volumes and viscosity deviations were calculated.

McAllister's three-body interaction model has been used to correlate the

kinematic viscosities of binary and ternary liquid mixtures with mole fractions.

Several empirical equations were used to predict excess molar volumes and

deviations in viscosity of ternary mixtures.

Acoustical and excess properties of chlorobenzene + 1-hexanol or 1-

heptanol or 1-octanol or 1-nonanol or 1-decanol were studied by Adel et al. [105]

at 298.15, 303.15, 308.15, 313.15 K. The calculated excess and deviation

functions were fitted to polynomial relation to estimate the coefficient and

standard errors. The effect of n-alkan-1-ol chain length as well as temperature on

the excess molar volume were studies.

Ultrasonic speed, and viscosities of pure aniline, 1-propanol, 2-propanol,

2-methyl 2-propanol and their binary mixtures with aniline as a common

component over the entire composition range were measured [106] at 293.15,

298.15 303.15, 308.15, 313.15 and 318.15 K. From experiment data the deviation

in isentropic compressibility Ks and in viscosity, were calculated.

Densities and viscosities for N-formylmorpholine (NFM) with p-xylene,

m-xylene, and o-xylene were determined [107] over several temperatures at

atmospheric pressure. Density and viscosity data were used to compute the excess

molar volumes and viscosity deviations and they were fitted to the Redlich-Kister

equation

Excess volume of the binary liquid system of methyl formate, ethyl

formate, propyl formate, with bromo, chloro, and nitrobenzene were derived from

69

experimental density measurement [108] at (303.15, 308.15 and 313.15) K. The

excess volume were fitted to Redlich-Kister polynomial equation.

Bhaskarn and Kubendran [109] measured densities, viscosities, refractive

index, surface tension and ultrasonic velocity for p-anisaldehyde +chlorobenzene

at 303.15, 313.15 and 323.15 K. The excess values were fitted to the Redlich-

Kister polynomial equation.

Densities and viscosities for binary mixture of vitamin K3 +benzene,

toluene, ethylbenzene, o-xylene, m-xylene, p-xylene respectively were

determined by Song et al. [110] at 303.15 to 313.15 K. Results were fitted to

obtain appropriate parameter and standard deviation between the measured and

fitted values.

The densities, of binary mixtures of methyl acrylate (MA) with benzene,

toluene, o-xylene, m-xylene, p-xylene, and mesitylene, including those of pure

liquids, over the entire composition range were measured [111] at temperatures

(293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure.

From the experimental data, the excess molar volume, partial molar volumes, and

excess partial molar volumes, at infinite dilution were calculated. The values

were found negative over the whole composition range for all the mixtures and at

each temperature studied, except for MA + mesitylene which exhibit positive

values, indicating the presence of specific interactions between MA and

aromatic hydrocarbon molecules.

The experimental densities, dynamic viscosity and speed of sound of thirty

six binary mixture of ester + organic solvent (n-hexane, benzene, toluene, o, m, P-

xylene), + halogenated benzene (chloro bromobenzene), + nitrobenzene were

measured [112] over the complete composition range at atmospheric pressure and

temperature (295.15 to 313.15 K) excess molar volume, excess isentropic

compressibilities were calculated and fitted to Redlich-Kister type equation.

Densities for binary systems of (p-xylene or o-xylene + ethylene glycol

dimethyl ether) were measured [113] over the full mole fraction range at the

temperatures of (298.15, 303.15 and 308.15) K along with the densities of the

pure components. The excess molar volumes (VE) calculated from the density

70

data show that the deviations from ideal behaviour in the two binary systems were

negative, and they become more negative with the temperature increasing. The VE

were fitted to the Redlich–Kister polynomial equation.

The experimental densities and viscosities of binary mixture of 2-

pyrrolidone with butanol isomers were measured [114] at 293.15, 298.15 and

303.15 K, and atmospheric pressure over the whole mole fraction range. The

experimental results were correlated using Redlich-Kister polynomial equation.

Densities and speeds of sound of 2-propanone + aniline, + N-

methylaniline, or + pyridine systems were measured [115] at 293.15, 298.15, and

303.15 K, and atmospheric pressure using a vibrating tube densimeter and sound

analyzer (Anton Paar model DSA-5000). The data were interpreted assuming

strong acetone-amine interactions and weak structural effects.

Densities and viscosities for the binary mixtures of hexan-1-ol with p-

xylene were measured at a number of mole fractions [116] at 303.15, 313.15, and

323.15 K. The excess molar volumes and viscosity deviations were calculated

from the experimental results and were fitted to the Redlich-Kister polynomial

equation.

Densities, speeds of sound, viscosities and refractive indices of binary

mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene were

measured over the entire range of composition [117] at 298.15 and 303.15 K, and

atmospheric pressure. From the experimental data, excess molar volumes VE,

isentropic compressibilities ΚS, excess isentropic compressibilities , and

deviations of speeds of sound D, were calculated at 298.15 and 303.15 K. These

excess functions were fitted to the Redlich–Kister polynomial equation. The

viscosity data were correlated using Kendall–Monroe, Grunberg–Nissan,

Tamura–Kurata, Hind–Mclaughlin Ubbelohde and Katti–Chaudhary viscosity

models, and McAllister's threebody interaction model at different temperatures.

The viscosities , densities , speeds of sound and refractive indices D

of binary mixtures of 1-decanol with o-xylene, m-xylene, p-xylene, ethylbenzene

and mesitylene were measured over the entire range of composition [118] at

298.15 and 308.15 K, and at atmospheric pressure. Excess molar volumes VE,

71

deviations of isentropic compressibilities , deviations of the speeds of sound

, viscosity deviations , excess free energies of activation for viscous flow

G*E and deviations of refractive indices D were calculated from the density ρ,

speed of sound , viscosity and refractive index D data. The calculated excess

and deviation functions were fitted to the Redlich–Kister polynomial equations

and the results analyzed in terms of molecular interactions and structural effects.

The viscosity data were correlated using McAllister's three body interaction

model at different temperatures.

The viscosities and the densities of binary mixtures of methylcyclohexane

+ nitrobenzene, methylcyclohexane + 1-bromobutane, and 1-bromobutane +

nitrobenzene and those of the constituent ternaries were measured [119] at 293.15

to 308.15 K, with the whole entire composition range and atmospheric pressure.

The excess molar volumes for the binary mixtures were fitted to the Redlich-

Kister equation to determine the appropriate coefficients. The experimental

viscosity data were correlated with the Grunberg Nissan equation too.

Papari et al. [120] computed densities and speed of sound for three binary

mixture with 2-phenylethanol with 1-butanol, 2-butanol and 2-methyl-1-propanol

at six temperatures from 298.15 K. To 323.15 K. The results, were used to discuss

the nature and strength of intermolecular interaction in these mixtures.

Kumar et al. [121] presented densities, viscosities and speed of sound for

binary mixture of cyclopentane with 2-methyl-1- propanol, 3-methyl 1-butanol

and 2-methyl 2-butanol and triethylene glycol ether with 2-mtheyl 1-propanol

densities were calculated these value fitted to Redlich kister equation.

3.2 RESULTS AND DISCUSSION :

Densities and viscosities for all binary mixtures at 298.15, 303.15, 308.15

and 313.15 K, and compositions are listed in tables 3.1 to 3.10.

The experimental densities of binary liquid mixtures of t-butanol with

benzene and substituted benzenes are plotted in Figure 3.1 against mole fraction

x1 of t-butanol at 298.15 K. No attempt was made to find the best smoothing

function to represent these results.

72

The excess molar volume values have been calculated using the density

values of the pure components and the binary mixture with the help of following

equation 3.1.

VE = (x1 M1 + x2 M2) /12 -(x1 M1/1) – (x2 M2 /2) ---(3.1)

where M1, x1, 1 and M2, x2, 2 are molecular weight, mole fraction and density of

components 1 and 2 respectively of binary mixtures, 12 is the mixture density.

The table 3.1 to 3.10 also include the excess molar volume values at four

temperature studied. At equimolar concentration (x1 = 0.5) the excess molar

volume value as 0.495 of t-butanol + benzene at 308.15 K, agree very

well with the reported values of 0.520 [58] similarly at 308.15 the

excess molar volume values as 0.418, 0.537 and 0.492 for o-xylene,

m-xylene and p-xylene agree very well with the reported values of 0.418, 0.537

and 0.493 [57] at (x1 = 0.5). The present 10 binary mixtures can be

classified into two groups, first electron donating groups attached to benzene ring

which consists of mixture of t-butanol with toluene, xylenes and aniline and

second mixtures of t-butanol with electron withdrawing group attached to benzene

which consists of o-chlorotoluene, p-chlorotoluene, chlorobenzene and

nitrobenzene.

The behaviour of excess molar volume values with the composition of (x1) of

t-butanol of all the binary mixture is depicted in Fig. 3.2 It is seen that excess

molar volume values for the mixture of t-butanol with benzene, toluene, o-xylene,

m-xylene, p-xylene, p-chlorotoluene and o-chlorotoluene are positive where as

the excess molar volume values for mixture of t-butanol with chlorobenzene,

nitrobenzene and aniline are negative. The positive excess molar volume values

follow the order m-xylene > p-xylene > benzene > toluene > o-xylene >

p-chlorotoluene > o-chlorotoluene where as the negative values of excess molar

volume follow the order aniline > nitrobenzene > chlorobenzene.

It has been shown that the excess molar volume values are determined by

three mains contributions namely physical, chemical and structural contributions.

Physical contributions include non polar intermolecular interactions for liquid

73

mixture having non polar constituents, dipole-dipole interactions for liquid

mixtures with polar constituents and dipole induced dipole interaction for binary

liquid mixtures in which one component is polar and other non polar. Chemical

contribution are mainly through H-bonding and electron donar-acceptor

interactions. The structural contribution arises from the breaking of self associated

liquid molecules, interstitial accommodation of one component into the empty

spaces of another component due to difference in size, shape and free volume of

the components.

t-butanol is a polar liquid and is self associated while the aromatic

hydrocarbon have a large quadruple-moment which causes molecular order in

them in the pure state. Mixing of t-butanol with these aromatic hydrocarbons

leads to breaking of the self association in t-butanol and the decrease in the

molecular order of hydrocarbon resulting in an expansion in volume and hence

the positive excess molar volume values are observed. As the electron donating

power of toluene is more than that of benzene due to the introduction of methyl

group, the hydroxyl hydrogen should interact more strongly with the electron

cloud of toluene than that of benzene thus the excess values for toluene should be

smaller than those of benzene.

The molar volumes of xylenes do not differ very much but the different

positions of methyl group change the geometry of xylene molecule, the position

of the substituted group play an important role on the electron density in the

aromatic ring. Among the three isomer of xylene, o-xylene seems to offer

minimum steric hindrance, thus increasing the electron donor-acceptor interaction

and making excess molar volume minimum among the three isomers of xylene.

The trend in the excess volume values for the binary mixture of t-butanol

with o-chlorotoluene and p-chlorotoluene could be explained on the basis of

strong hydrogen bonding between the hydroxyl hydrogen of t-butanol and chloro

group of the o-chlorotoluene because the electron cloud on the chloro group of the

o-chlorotoluene is more as compared to p-chlorotoluene

The excess molar volume values for t-butanol with chlorobenzene show a

sigmoid nature with excess molar volume values being negative at low t-butanol

74

mole fractions and becoming positive as the mole fraction of t-butanol in the

mixture increases. The excess moral volume values at equimolar mole fractions

go from negative to positive values. The excess molar volume values for t-butanol

with nitrobenzene and aniline are negative indicating a contraction in volume

when two components are mixed. It implies that the chemical contributions

predominate over the physical and structural contributions, this also implies that

the interactions between unlike molecule are stronger compared with the

intramolecular interactions.

The excess molar volume values show that the values for all the binary

mixture depend on the temperature of measurement.

The excess molar volumes were fitted to Redlich-Kister equation of the

type

VE = x1 x2

n

1i

ai (x1- x2)i ---(3.2)

where n is the degree of polynomial. Coefficients ai were obtained by fitting eq

3.2 to experimental results using a least-squares regression method. In each case,

the optimum number of coefficients is ascertained from an examination of the

variation in standard deviation ().Where was calculated using the relation

σ (VE) = [

∑(

)

]

---(3.3)

where N is the number of data points and n is the number of coefficients. The

calculated values of the coefficients ai along with the standard deviations are

given in Table 3.11.

Recently Jouyban and Acree (122,123) proposed a model for correlating

the density and viscosity of liquid mixtures at various temperatures. The proposed

equation is

lnm,T = f1ln1,T +f2ln2,T+ f1f2 [Aj (f1-f2) j/T] ---(3.4)

75

where m,T, 1,T and 2,T is density of the mixture and solvents 1 and 2 at

temperature T, respectively, f1and f2 are the volume fractions of solvents in case

of density, and mole fraction in case of viscosity, and Aj are the model constants.

The correlating ability of the Jouyban - Acree model was tested by

calculating the average percentage deviation (APD) between the experimental and

calculated density as

APD = (100/N) [(| exptl - calcd |) / exptl)] ---(3.5)

where N is the number of data points in each set. The optimum numbers of

constants Aj, in each case, were determined from the examination of the average

percentage deviation value. The calculated values of the coefficients Aj along with

the standard deviations () are given in table 3.12. It is seen that Jouyban and

Acree model represent the viscosity of binary mixtures to a very good extent.

The experimental viscosities of binary liquid mixtures of t-butanol with

benzene and substituted benzenes are plotted in Figure 3.3 at 298.15 K against

mole fraction x1 of t-butanol.

The viscosity deviations, , are obtained by means of;

= 12 - x11 -x22 ---(3.6)

where x1, 1 and x2, 2 are mole fractions and dynamic viscosities of constituents

1and 2 respectively of binary mixtures. 12 are viscosity of binary mixtures.

The values are listed in table 3.1 to 3. 10. Figure 3.4 depicts the

variation of with x1 at 298.15 K for binary mixtures of t-butanol with benzene

and substituted benzenes. Similar plots are obtained at other temperatures.

The values for all the binary mixtures of t-butanol with aromatic

hydrocarbons are negative, it is important to note here that values follow the

particular trends on the nature of the substituents on the benzene ring. The

values are large and close to each other for mixtures of t-butanol with benzene

and toluene but as one more methyl group is attached to toluene, the values

decreases sharply in absolute term for three isomers of xylene with nearly the

76

same values, similar trends is observed when one methyl group is substituted by

the chloro group in p–chloro and o-chlorotoluenes. The values are negative

for mixture of t-butanol with chlorobenzene, nitrobenzene and aniline. The

negative values of are characteristics for system in which dispersive force

like rupture of the self association in t-butanol are predominant. It is known that

the strength of intermolecular electron donar acceptor interactions is not the only

factor which influences the viscosity deviation in liquid mixtures. The other

factors such as the molecular size and shape of component and average degree of

association of the mixture also play on important role.

The values generally decrease in absolute terms with increase in

temperature.

Grunberg-Nissan, Tamura-Kurata, Hind et al. and Katti-Choudhari equations

have been used to determine the interaction parameters d, T12, H12, and Wvis.

These parameter were evaluated using least-square method and they are listed in

table 3.15.

The Grunberg-Nissan parameter d is negative for binary mixtures of

t-butanol with benzene, toluene, chlorobenzene, nitrobenzene, o-chlorotoluene

and aniline where as positive for p-chlorotoluene, o-xylene, m-xylene, and p-

xylene.

The Katti-Choudhari parameter Wvis not only shows the same trend as that of

d but also the magnetitud is of the same order. The d and Wvis values are negative

and large for mixtures of benzene, toluene, nitrobenzene and aniline and increase

in absolute terms with increase in temperature. It has been reported by Nigam and

Mahal [124], that [i] if > 0, d > 0 with large values then there would be strong

specific interaction between the component of liquid mixtures, [ii] if < 0 but d

> 0 then there would be weak specific interaction and lastly [iii] if < 0 with d

< 0 with large magnitude then dispersion forces would be dominant in the liquid

mixture.

77

The parameter T12 and H12 are negative for benzene and toluene and

positive for the other binary mixtures with almost similar magnitude, they also

increase in absolute term with increase in temperature.

The kinematic viscosities () of the binary liquid mixtures were obtained

from their dynamic viscosities and densities.

McAllister’s three-body and four body interaction models [125] have been

used to correlate the kinematic viscosities of binary liquid mixtures. The three-

body interaction model is given by

lnν = x13 ln ν1+ x2

3ln ν2 +3 x1

2 x2ln ν12 +3 x1 x2

2ln ν21- ln [x1+(x2M2/M1)] + 3 x1

2

x2 ln [(2/3) + (M2/3M1)] + 3x1x22 ln [(1/3) + (2M2/3M1)] + x2

3 ln (M2/M1). ---(3.7)

where ν12, ν21 are interaction parameters and M1 and M2 are molecular weights of

components1 and 2.

The four body interaction model is given by

ln x1ln + 4x1

3 x2 ln 1112 + 6x1

2x2

2 ln 1122 + 4x1x2

3 ln 2221+ x2

4 ln 2

- ln[x1+ x2M2/M1)] +4x13x2 ln[{3 + (M2/M1)}/4] + 6x1

2x2

2 ln[{1 + (M2/M1)}/2] +

4x1x23 ln[{(1 + 3M2/M1)}/4] + x

24 ln(M2/M1) ---(3.8)

where 12, 21, 1112, 1122, and 2221 are interaction parameters and M1 and M2 are

molecular weights of components 1 and 2.

The correlating ability of equations 3.7 and 3.8 was tested by calculating

the percent standard deviations ( %) between the experimental and calculated

viscosity as

σ % = [1/(n-m)∑ {(100(νexptl - νcalcd )/ νexptl)2)}

1/2 ] ---(3.9)

where n represents the number of experimental points and m represents the

number of coefficients.

Table 3.16 list the parameters for McAllister equation and percentage

standard deviations. From table 3.16, it is clear that McAllister’s four-body

78

interaction model gives a better result than the three-body model for correlating

the kinematic viscosities of the binary mixtures studied.

79

REFERENCES

1) Marcus Y, Induction to liquid State Chemistry, Wiley, Newyork, 1977.

2) Rice S A, Gray P, The statistical Mechanics of Simple liquid, Interscience,

Newyork, 1965.

3) Brown I, Smith F, J Phys Chem, 4 (1962).

4) Cronauer D C, Rothfus R R, Kermode R. I, J Chem Eng Data,

2 (1965) 131.

5) Pardo F, Vanness H C. J Chem Eng Data, 12 (1967) 217.

6) M Kemal, A. Sumer, Thompson R, J Chem Eng Data, 13 (1968) 31.

7) Powell R. J, Swinton F. L, J Chem Eng Data, 13 (1968) 261.

8) Nigam R K, Singh R P, Trans Farady Soc, 65 (1969) 950.

9) Nigam R K, Singh P P, Indian J Chem, 9 (1971) 671.

10) Nayar S, Kudchadker A P, J Chem Eng Data, 18 (1973) 356.

11) Marcel J, Mussche L, Verhoeye' A, J Chem Eng Data, 20 (1975) 46.

12) Miller L P, Wachter H N, Fried V, J Chem Eng Data, 20 (1975) 417.

13) Teja A S, Rice P, J Chem Eng Data, 21 (1976) 173.

14) Tanakat R, Benson G C, J Chem Eng Data, 21 (1976) 320.

15) Stevanovic J S, Simonovic D, J Chem Eng Data, 21 (1976) 456.

16) Sada E, Takahashi K, Hamada M, J Chem Eng Data, 22 (1977) 279.

17) Ortega J, Diazpena S N, J Chem Thermodyn, 9 (1977) 743.

18) Rastogi R P, Nath J, Singh B, J Chem Thermodyn, 9 (1977) 831.

19) Garrett P R, Pollock J M, J Chem Thermodyn, 9 (1977) 1045.

20) Nath J, Singh B, J Chem Thermodyn, 10 (1978) 307.

21) Nath J, Dubey S N, J Chem Thermodyn, 11 (1979) 1163.

22) Liliana J, Azzi A, Lopez A, Salello S, J Chem Eng Data, 25 (1980) 77.

23) Dharmaraju G, Swamy G N, Raman G K, J Chem Thermodyn,

12 (1980) 563.

24) Reddy S S, Reddy K D, Prabhakara Rao M V, J Chem Eng Data,

27 (1982) 173.

25) Karvo M, J Chem Thermodyn, 15 (1983) 821.

26) Singh P R, Singh C P, J Chem Eng Data, 29 (1984) 132.

27) Iloukhani H, Reddy K D, Rao M P, J Chem Eng Data, 29 (1984) 474.

80

28) Jayalakshmi T, Reddy K S, J Chem Eng Data, 30 (1985) 51.

29) Otin S, Toledo M J, Munoz J, Velasco I, Cutierrer L C,

J Chem Thermodyn, 17 (1985)935.

30) Singh R P, Sinha C P, Das J C, Ghosh P J, J Chem Eng Data,

31 (1986) 107.

31) Rathnam M V, Indian J Chem, 25 (1986) 1145.

32) Rathnam M V, J Chem Eng Data, 33 (1988) 14.

33) Marsh K N, Kim E S, J Chem Eng Data, 33(1988) 288.

34) Chaudhari S K, Katti S S, Indian J Chem, 24 (1988) 797.

35) Aminabhavi T M, Manjeshwar L S, Halligudi S B, Balundgi R H,

Indian J Chem 28A (1989) 217.

36) Sinha R P, Sinha C P, Das J C, Ghose P, J Chem Eng Data,

34 (1989) 335.

37) Joshi S S, Aminabhavi T M, Balundgi R H, J Chem Eng Data,

35 (1990) 185.

38) Serrano L, Silva J L, Farelo F, J Chem Eng Data, 35 (1990) 288.

39) Sreenlvasulu B, Kumar V C, Naidu P R, J Chem Eng Data, 37 (1992) 47.

40) Mahl B S, Kaur H, Bala P Chardwaj S S,Fluid Phase Equilib,

71 (1992) 313.

41) Aralagappi M I, Aminabhavi T M, Balandgi R H, Fluid Phase Equilib,

71(1992)313

42) Kumar K S, Naidu P R, J Chem Eng Data, 38 (1993) 156.

43) Kumar V C, Naidu P R, J Chem Eng Data, 38 (1993) 414.

44) Yu C-H, Tsai F – N, J Chem Eng Data, 39 (1994) 496.

45) Beg S A, Tukur N M, Dulaihan K, Harbe-Al, Haman E Z,

J Chem Eng Data, 40(1995) 74.

46) Krishanan K M, Rambabu K, Venkateshwarlu P, Raman G K,

J Chem Eng Data, 40 (1995) 128.

47) Jain D V S, Chadha R, Sehgal S K, Fluid Phase Equilib, 112 (1995) 151.

48) Singh M, Gupta P C, Kesharwani R N, J Chem Eng Data, 40 (1995) 358.

49) Ramachandran D, Kantipudi R, Kalahasti M K, Ponneri V, Gorijala K. R,

J Chem Eng Data, 40 (1995) 815.

81

50) Palaiologou M M, Molinou I E, J Chem Eng Data, 40 (1995) 880.

51) Nikam P S, Jadhav M C, Hasan M, J Chem Eng Data,40(1995) 931.

52) Nikam P S, Hasan M, Pathak R B, J Pure Appl Ultrason, 18(1996) 19.

53) Gupta V, Maken S, Kalra K C, Singh K C, Indian J Chem, 35 (1996) 508.

54) Pal A, Singh Y P, Indian J Chem, 35A (1996) 591.

55) Gupta V, Maken S, Kalra K C, Singh K C, Indian J Chem, 35A (1996) 974.

56) Palaiologou M M, J Chem Eng Data, 41 (1996) 1036.

57) Bharwaj U, Makan S, Singh K C, J Chem Eng Data, 41(1996) 1043.

58) Bhardwaj U, Makan S, Singh K C, J Chem Thermodyn, 28 (1996) 1173.

59) Tanaka R, Nakamichi T, J Chem Thermodyn, 29 (1997) 221.

60) Tanaka R, Toyama S, J Chem Eng Data, 42 (1997) 871.

61) Venkatesu P, Prabhakar Rao M V, Phys Chem Liq, 34 (1997) 895.

62) Swain N, Panda D, Singh S K, Chakravortty V, J Chem Eng Data,

42 (1997) 1235.

63) Bhardwaj U, Singh K C, Maken S, J Chem Theromodyn, 30 (1998) 109.

64) Bhardwaj U A, Maken S B, Singh K C, Fluid Phase Equilib,

142 (1998) 205.

65) Yu Y, Li Y G, Fluid Phase Equilib, 147 (1998) 207.

66) Swataa N, Panda D, Singh S K, Chakravortty V, J Mol Liq, 75 (1998) 211.

67) Bhardwaj U, Singh K C, Makan S, J Chem Thermodyn, 30 (1998) 253.

68) Artigas H, Domingauze M, Malnar A M, Lopez M C, Roya F M,

J Chem Eng Data, 43 (1998) 580.

69) Whihelm E, Vencour M, Roux A H, Polenlnicek M, Grolier J P E,

J Chem Thermodyn, 30 (1998) 1509.

70) Pena M P, Soria V M, Monton J B, Fluid Phase Equilib, 166 (1999) 53.

71) Wen L W, J Chem Eng Data, 44(1999) 188.

72) Haraschta P, Heints A L, Lehmann J K, Peters A, J Chem Eng Data,

44 (1999) 932.

73) Prabhavati C L, Sivakumar K, Venkateswarlu P, Raman G K,

Indian J Chem, 38(1999) 934.

74) Moumouzias G, Christos R, Ritzoulis G, J Chem Eng Data,

44 (1999) 1187.

82

75) Mehra R, Israni R, Indian J Pure Appl Phys, 38 (2000) 81.

76) Tu H, Liu C Y, Wang W F, Chou Y T, J Chem Eng Data, 45 (2000) 450.

77) Viswanathan S, Rao A M, Prasad D H L, J Chem Eng Data,

45 (2000) 764.

78) Martinez S, Garriga R, Perez P Gracia M, J Chem Eng Data,

45 (2000) 1182.

79) Tu C H, Lee S L, Peng I H, J Chem Eng Data, 46 (2001) 151.

80) Nikam P S, Jagadale B S, Sawant A B, Hasan M, J Chem Eng Data,

45 (2002) 214.

81) Rao S, Veeraiah N, Rambabu C, Indian J Chem, 41A (2002) 2268.

82) Ouyang G, Huang Z, Ou J, Wu W, Kang B, J Chem Eng Data,

48 (2003) 195.

83) Bahadur P. Sastry N V, Inter, J Themophy, 24 (2003) 447.

84) Nayak J N, Aralaguppi M I, Aminabhavi T M, J Chem Eng Data,

48 (2003) 628.

85) George J, Sastry N V, J Chem Eng Data, 48 (2003) 977.

86) Nikam P S, Kharat S J, J Chem Eng Data, 48 (2003) 1202.

87) George J, Sastry N V, J Chem Thermodyn, 35 (2003) 1837.

88) Grunberg B B, Chaudhary A, Roy M N, J Indian Chem Soc,

81(2004) 330.

89) Wang H, Liu W, Huang J, J Chem Thermodyn, 36 (2004) 743.

90) Yang C, Ma P, Zhou Q, J Chem Eng Data,49(2004) 881.

91) Villares A, Marti´N S, Haro M, Giner B, Artigas H, J Chem Thermodyn,

36 (2004) 1027.

92) Tanaka R, Yokayama T, J Solution Chem, 33 (2004) 1061.

93) Ratan V K, Singh S, Sethi B P S, J Chem Eng Data, 49 (2004) 1074.

94) Singh S, Sethi B P S, Katyal R C, Rattan V K, J Chem Eng Data,

49 (2004) 1373.

95) Singh S, Sethi B P S, Katyal R C, Ratan V K, J Chem Eng Data,

50 (2005) 125.

96) Rathnam M V, Mohite S, J Chem Eng Data, 50(2005) 325.

97) Ali A, Nain A K, Chand D, Lal B, Indian J Chem, 44 (2005) 511.

83

98) Wang H, Wu Y, Dong W, J Chem Thermodyn, 37 (2005) 866.

99) Anson A, Garreqa R, Martinez S,Perez P, Gracia M, J Chem Eng Data,

50 (2005) 1478.

100) Venkatesh M A, Manjeshwar L A, Malladi S B, Aminabhavi T M,

J Chem Thermodyn, 38 (2006) 1062.

101) Syamala V, Kumar K S, Venkateswar Lu P, J Chem Thermodyn,

38 (2006) 1553.

102) Hasan M, Shirude D F, Hiray A P, Kadam U B. Sawant A B,

J Chem Eng Data, 51 (2006) 1922.

103) Al-Kandary J A, Al-Jimaz A S, Abdul-Latif A M, J Chem Eng Data,

51 (2006) 2074.

104) Kharat S J, Nikam P S, J Mol Liq, 131 (2007) 81.

105) Adel S, Al-Jimaz,Jasem A, Alkandary, Abdul-Haq M, Abdul-Latif,

J Chem Eng Data, 52 (2007) 206.

106) Nain A K, Fluid Phase Equilib, 259 (2007) 218.

107) Yang T, Xia S, Song S, Xiaoxi F, Ma P, J Chem Eng Data, 52 (2007) 2062.

108) Manapragada V R, Singh R K R, Manparagada S K, J Chem Eng Data,

53 (2008) 265.

109) Baskaran R. Kubendran T R, J Chem Eng Data,53 (2008) 978.

110) Song C Y, Shen H Z, Zhao J H, Wang L C, Wang F A,

J Chem Eng Data, 53(2008) 1110.

111) Nain A A, Sharma S A, Anwar A B, Gopal S, J Mol Liq, 144 (2009) 124.

112) Sastry N V, Thakor R R, Patel M C, J Mol Liq, 13 (2009) 144.

113) Yang Y, Zhu Y, Peng J L, Chen J C, Feng P P, Huang Z Q,

J Chem Thermodyn, 41 (2009) 1000.

114) Farhan A M, Awwad A M, J Chem Eng Data, 54 (2009) 2095.

115) Alonso I, Alonso V, Mozo I, Fuente I G, Gonza´Lez J A, Cobos J C,

J Chem Eng Data, 55 (2010) 2505.

116) Habibullah M, Das K N, Ismail M M, Hasegawa H, Uddin M A,

J Chem Eng Data, 55 (2010) 5331.

117) Bhatia S C, Sangwan J, Bhatia J, J Mol Liq, 161 (2011) 95.

118) Bhatia S C, Ruman R, Bhatia R, J Mol Liq, 159 (2011) 132.

84

119) Shahram R, Seyyed H M, J Chem Eng Data, 56 (2011) 3949.

120) Papari M M, Ghodrati H, Fadaei F, Sedeghis R, Behrouz S, Soltani M. N,

J Mol Liq, 180 (2013) 121.

121) Kumar H, Singla M, Khasla A, J Solution Chem, 42 (2013) 428.

122) Jouyban A, Khoubnasabjafari M, Vaez-gharamaleki Z, Fekari Z, Acree Jr

W E, Chem. Pharm. Bull, 53 (2005) 519.

123) Jouyban A, Fathi – Azarbayjani A, Khoubnasabjafari M, Acree Jr W E,

Indian J Chem, 44 (2005) 1553.

124) Nigam R K, Mahl B S, Indian J Chem, 9 (1971) 1255.

125) McAllister R A, AIChE J, 6 (1960) 427.

85

Table 3.1 : Density (ρ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + Benzene.

Temp.

K

x1

ρ x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 0.8735 0.616 0.000 0.000

0.0923 0.8622 0.745 0.239 -0.224

0.2003 0.8503 0.842 0.402 -0.541

0.3009 0.8398 0.875 0.509 -0.893

0.4005 0.8300 0.931 0.566 -1.219

0.5011 0.8207 1.067 0.570 -1.468

0.6007 0.8119 1.320 0.539 -1.596

0.7011 0.8035 1.700 0.465 -1.601

0.8005 0.7956 2.329 0.353 -1.352

0.9008 0.7880 3.213 0.203 -0.852

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 0.8682 0.568 0.000 0.000

0.0923 0.8566 0.641 0.265 -0.186

0.2003 0.8446 0.644 0.432 -0.487

0.3009 0.8340 0.596 0.543 -0.818

0.4005 0.8242 0.558 0.593 -1.136

0.5011 0.8149 0.592 0.589 -1.385

0.6007 0.8061 0.741 0.551 -1.516

0.7011 0.7976 1.016 0.480 -1.523

0.8005 0.7896 1.551 0.371 -1.267

0.9008 0.7820 2.317 0.213 -0.783

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 0.8630 0.532 0.000 0.000

0.0923 0.8515 0.563 0.259 -0.164

0.2003 0.8397 0.573 0.408 -0.382

0.3009 0.8295 0.470 0.478 -0.697

0.4005 0.8200 0.382 0.484 -0.995

0.5011 0.8109 0.336 0.495 -1.253

0.6007 0.8023 0.417 0.406 -1.382

0.7011 0.7939 0.617 0.323 -1.394

0.8005 0.7858 1.039 0.225 -1.182

0.9008 0.7777 1.729 0.126 -0.704

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 0.8574 0.502 0.000 0.000

0.0923 0.8456 0.551 0.299 -0.099

0.2003 0.8336 0.525 0.478 -0.298

0.3009 0.8232 0.413 0.577 -0.572

0.4005 0.8135 0.293 0.624 -0.851

0.5011 0.8042 0.197 0.628 -1.109

0.6007 0.7955 0.186 0.584 -1.280

0.7011 0.7870 0.307 0.519 -1.320

0.8005 0.7790 0.659 0.415 -1.127

0.9008 0.7715 1.284 0.248 -0.663

1.0000 0.7648 2.106 0.000 0.000

86

Table 3.2 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + Chlorobenzene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 1.1005 0.757 0.000 0.000

0.0997 1.0718 0.780 -0.099 -0.345

0.2009 1.0413 0.877 -0.115 -0.621

0.2999 1.0107 1.057 -0.101 -0.806

0.4010 0.9789 1.334 -0.076 -0.902

0.5010 0.9469 1.701 -0.044 -0.904

0.6010 0.9145 2.152 -0.019 -0.821

0.7002 0.8817 2.672 0.027 -0.667

0.8009 0.8481 3.252 0.052 -0.459

0.9003 0.8146 3.851 0.058 -0.226

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 1.0956 0.721 0.000 0.000

0.0997 1.0666 0.735 -0.090 -0.251

0.2009 1.0359 0.754 -0.104 -0.501

0.2999 1.0052 0.855 -0.094 -0.663

0.4010 0.9732 1.016 -0.064 -0.771

0.5010 0.9410 1.290 -0.022 -0.763

0.6010 0.9085 1.616 0.003 -0.702

0.7002 0.8758 1.996 0.030 -0.586

0.8009 0.8421 2.449 0.060 -0.401

0.9003 0.8087 2.925 0.049 -0.189

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 1.0893 0.679 0.000 0.000

0.0997 1.0603 0.706 -0.081 -0.169

0.2009 1.0296 0.727 -0.084 -0.346

0.2999 0.9989 0.774 -0.062 -0.494

0.4010 0.9671 0.871 -0.039 -0.595

0.5010 0.9349 1.030 0.017 -0.632

0.6010 0.9026 1.259 0.037 -0.600

0.7002 0.8702 1.548 0.046 -0.505

0.8009 0.8367 1.894 0.071 -0.357

0.9003 0.8035 2.267 0.055 -0.179

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 1.0844 0.640 0.000 0.000

0.0997 1.0551 0.648 -0.061 -0.138

0.2009 1.0244 0.664 -0.072 -0.271

0.2999 0.9936 0.704 -0.046 -0.376

0.4010 0.9617 0.797 -0.017 -0.431

0.5010 0.9297 0.914 0.014 -0.460

0.6010 0.8972 1.061 0.054 -0.460

0.7002 0.8648 1.297 0.062 -0.369

0.8009 0.8314 1.516 0.077 -0.298

0.9003 0.7982 1.808 0.063 -0.152

1.0000 0.7648 2.106 0.000 0.000

87

Table 3.3 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + Toluene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 0.8618 0.555 0.000 0.000

0.1018 0.8524 0.561 0.250 -0.390

0.2034 0.8434 0.613 0.430 -0.733

0.3010 0.8353 0.737 0.514 -0.989

0.4022 0.8273 0.965 0.529 -1.155

0.5017 0.8195 1.301 0.513 -1.206

0.6006 0.8119 1.747 0.455 -1.144

0.7004 0.8040 2.308 0.401 -0.972

0.8007 0.7960 2.965 0.329 -0.705

0.9008 0.7882 3.691 0.209 -0.368

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 0.8576 0.527 0.000 0.000

0.1018 0.8479 0.553 0.267 -0.264

0.2034 0.8388 0.561 0.439 -0.546

0.3010 0.8305 0.601 0.527 -0.784

0.4022 0.8223 0.719 0.545 -0.955

0.5017 0.8144 0.933 0.519 -1.025

0.6006 0.8065 1.254 0.475 -0.986

0.7004 0.7985 1.685 0.411 -0.840

0.8007 0.7903 2.208 0.341 -0.603

0.9008 0.7823 2.789 0.222 -0.307

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 0.8532 0.492 0.000 0.000

0.1018 0.8434 0.498 0.274 -0.213

0.2034 0.8342 0.521 0.453 -0.408

0.3010 0.8259 0.618 0.534 -0.521

0.4022 0.8176 0.770 0.557 -0.587

0.5017 0.8097 0.878 0.523 -0.693

0.6006 0.8017 1.073 0.485 -0.710

0.7004 0.7936 1.361 0.425 -0.637

0.8007 0.7854 1.686 0.347 -0.528

0.9008 0.7773 2.176 0.232 -0.253

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 0.8484 0.486 0.000 0.000

0.1018 0.8388 0.489 0.246 -0.162

0.2034 0.8289 0.512 0.511 -0.304

0.3010 0.8195 0.613 0.730 -0.361

0.4022 0.8098 0.772 0.929 -0.366

0.5017 0.8005 0.949 1.070 -0.350

0.6006 0.7913 1.145 1.181 -0.314

0.7004 0.7829 1.376 1.153 -0.245

0.8007 0.7755 1.635 0.964 -0.148

0.9008 0.7694 1.898 0.584 -0.047

1.0000 0.7648 2.106 0.000 0.000

88

Table 3.4 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + o-Chlorotoluene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 1.0778 0.958 0.000 0.000

0.1005 1.0524 1.127 0.090 -0.181

0.1998 1.0266 1.348 0.151 -0.307

0.3024 0.9990 1.619 0.200 -0.393

0.3987 0.9722 1.909 0.230 -0.439

0.5001 0.9430 2.246 0.240 -0.456

0.6001 0.9131 2.618 0.233 -0.433

0.6999 0.8821 3.022 0.207 -0.377

0.7997 0.8499 3.459 0.156 -0.288

0.9011 0.8158 3.940 0.083 -0.160

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 1.0726 0.892 0.000 0.000

0.1005 1.0470 0.986 0.099 -0.156

0.1998 1.0210 1.122 0.169 -0.267

0.3024 0.9932 1.296 0.228 -0.348

0.3987 0.9663 1.488 0.258 -0.396

0.5001 0.9370 1.730 0.269 -0.406

0.6001 0.9070 1.997 0.265 -0.387

0.6999 0.8760 2.294 0.231 -0.339

0.7997 0.8438 2.627 0.174 -0.254

0.9011 0.8097 2.994 0.097 -0.139

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 1.0679 0.826 0.000 0.000

0.1005 1.0421 0.872 0.114 -0.137

0.1998 1.0160 0.945 0.189 -0.244

0.3024 0.9881 1.056 0.253 -0.319

0.3987 0.9611 1.188 0.290 -0.362

0.5001 0.9318 1.361 0.296 -0.373

0.6001 0.9018 1.563 0.289 -0.353

0.6999 0.8707 1.788 0.265 -0.309

0.7997 0.8386 2.048 0.195 -0.230

0.9011 0.8045 2.345 0.119 -0.117

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 1.0631 0.767 0.000 0.000

0.1005 1.0375 0.779 0.083 -0.123

0.1998 1.0116 0.814 0.127 -0.221

0.3024 0.9841 0.883 0.138 -0.289

0.3987 0.9574 0.974 0.132 -0.327

0.5001 0.9284 1.098 0.096 -0.339

0.6001 0.8987 1.251 0.046 -0.320

0.6999 0.8681 1.432 -0.044 -0.272

0.7997 0.8362 1.628 -0.146 -0.210

0.9011 0.8025 1.865 -0.278 -0.109

1.0000 0.7648 2.106 0.000 0.000

89

Table 3.5 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + p-Chlorotoluene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 1.0648 0.848 0.000 0.000

0.0953 1.0402 1.000 0.290 -0.191

0.1989 1.0148 1.251 0.344 -0.312

0.2901 0.9916 1.501 0.383 -0.390

0.3943 0.9643 1.832 0.392 -0.434

0.4902 0.9382 2.168 0.383 -0.443

0.5922 0.9094 2.561 0.349 -0.417

0.6981 0.8781 3.006 0.305 -0.353

0.7988 0.8472 3.458 0.220 -0.263

0.8997 0.8147 3.920 0.129 -0.164

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 1.0597 0.785 0.000 0.000

0.0953 1.0349 0.860 0.301 -0.172

0.1989 1.0093 1.015 0.363 -0.286

0.2901 0.9860 1.185 0.401 -0.353

0.3943 0.9585 1.414 0.420 -0.394

0.4902 0.9323 1.655 0.412 -0.402

0.5922 0.9034 1.944 0.379 -0.377

0.6981 0.8721 2.279 0.324 -0.317

0.7988 0.8411 2.619 0.243 -0.238

0.8997 0.8087 2.974 0.133 -0.145

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 1.0526 0.731 0.000 0.000

0.0953 1.0295 0.761 0.129 -0.152

0.1989 1.0038 0.849 0.224 -0.262

0.2901 0.9805 0.961 0.283 -0.324

0.3943 0.9531 1.129 0.313 -0.356

0.4902 0.9269 1.307 0.327 -0.361

0.5922 0.8980 1.524 0.318 -0.339

0.6981 0.8668 1.783 0.278 -0.282

0.7988 0.8359 2.049 0.211 -0.209

0.8997 0.8035 2.335 0.129 -0.115

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 1.0474 0.718 0.000 0.000

0.0953 1.0245 0.673 0.103 -0.177

0.1989 0.9992 0.724 0.149 -0.270

0.2901 0.9762 0.796 0.169 -0.325

0.3943 0.9490 0.914 0.173 -0.351

0.4902 0.9232 1.048 0.138 -0.350

0.5922 0.8947 1.223 0.079 -0.317

0.6981 0.8639 1.429 -0.011 -0.258

0.7988 0.8334 1.642 -0.128 -0.185

0.8997 0.8014 1.865 -0.261 -0.102

1.0000 0.7648 2.106 0.000 0.000

90

Table 3.6 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + o-Xylene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 0.8756 0.755 0.000 0.000

0.1003 0.8666 1.004 0.193 -0.121

0.2009 0.8576 1.297 0.331 -0.199

0.3016 0.8485 1.607 0.428 -0.261

0.3990 0.8396 1.925 0.482 -0.302

0.4999 0.8302 2.282 0.505 -0.318

0.5998 0.8208 2.659 0.480 -0.309

0.6988 0.8112 3.056 0.430 -0.278

0.7997 0.8013 3.493 0.329 -0.213

0.9003 0.7911 3.952 0.200 -0.125

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 0.8716 0.703 0.000 0.000

0.1003 0.8626 0.869 0.169 -0.102

0.2009 0.8536 1.067 0.283 -0.174

0.3016 0.8443 1.283 0.383 -0.227

0.3990 0.8353 1.509 0.427 -0.262

0.4999 0.8257 1.763 0.451 -0.278

0.5998 0.8161 2.035 0.426 -0.273

0.6988 0.8062 2.33 0.390 -0.243

0.7997 0.7961 2.657 0.287 -0.186

0.9003 0.7855 3.013 0.180 -0.099

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 0.8676 0.650 0.000 0.000

0.1003 0.8587 0.769 0.144 -0.081

0.2009 0.8496 0.903 0.260 -0.147

0.3016 0.8403 1.059 0.348 -0.192

0.3990 0.8312 1.226 0.393 -0.219

0.4999 0.8215 1.415 0.418 -0.231

0.5998 0.8118 1.622 0.393 -0.223

0.6988 0.8019 1.849 0.344 -0.193

0.7997 0.7916 2.094 0.253 -0.149

0.9003 0.7809 2.360 0.145 -0.083

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 0.8635 0.571 0.000 0.000

0.1003 0.8550 0.655 0.074 -0.070

0.2009 0.8461 0.757 0.150 -0.122

0.3016 0.8371 0.875 0.184 -0.159

0.3990 0.8283 1.001 0.176 -0.182

0.4999 0.8189 1.154 0.148 -0.184

0.5998 0.8094 1.318 0.086 -0.174

0.6988 0.7997 1.498 -0.001 -0.146

0.7997 0.7895 1.690 -0.116 -0.109

0.9003 0.7792 1.888 -0.286 -0.065

1.0000 0.7648 2.106 0.000 0.000

91

Table 3.7 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + m-Xylene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 0.8601 0.585 0.000 0.000

0.0957 0.8524 0.807 0.248 -0.147

0.1947 0.8447 1.079 0.419 -0.258

0.2956 0.8369 1.395 0.537 -0.331

0.4002 0.8287 1.757 0.619 -0.373

0.5001 0.8210 2.131 0.626 -0.384

0.6001 0.8131 2.539 0.605 -0.362

0.7003 0.8052 2.973 0.525 -0.315

0.7994 0.7972 3.437 0.412 -0.234

0.8995 0.7891 3.922 0.240 -0.135

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 0.8555 0.553 0.000 0.000

0.0957 0.8479 0.679 0.219 -0.144

0.1947 0.8402 0.853 0.375 -0.250

0.2956 0.8323 1.069 0.490 -0.319

0.4002 0.8240 1.326 0.570 -0.358

0.5001 0.8160 1.604 0.600 -0.362

0.6001 0.8081 1.905 0.560 -0.344

0.7003 0.8000 2.242 0.487 -0.290

0.7994 0.7918 2.597 0.381 -0.215

0.8995 0.7836 2.980 0.200 -0.115

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 0.8518 0.501 0.000 0.000

0.0957 0.8443 0.602 0.191 -0.104

0.1947 0.8365 0.717 0.346 -0.201

0.2956 0.8286 0.872 0.446 -0.262

0.4002 0.8202 1.067 0.523 -0.291

0.5001 0.8122 1.271 0.537 -0.301

0.6001 0.8041 1.507 0.507 -0.279

0.7003 0.7959 1.764 0.430 -0.236

0.7994 0.7876 2.038 0.319 -0.175

0.8995 0.7789 2.336 0.183 -0.091

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 0.8474 0.474 0.000 0.000

0.0957 0.8403 0.534 0.124 -0.096

0.1947 0.8329 0.611 0.214 -0.181

0.2956 0.8252 0.719 0.277 -0.237

0.4002 0.8172 0.862 0.290 -0.265

0.5001 0.8095 1.022 0.256 -0.268

0.6001 0.8017 1.204 0.179 -0.249

0.7003 0.7937 1.409 0.069 -0.208

0.7994 0.7856 1.627 -0.074 -0.152

0.8995 0.7771 1.859 -0.241 -0.083

1.0000 0.7648 2.106 0.000 0.000

92

Table 3.8 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + p-Xylene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 0.8562 0.602 0.000 0.000

0.0994 0.8487 0.835 0.234 -0.149

0.1972 0.8415 1.123 0.393 -0.237

0.2992 0.8340 1.443 0.509 -0.309

0.4004 0.8265 1.798 0.580 -0.343

0.4976 0.8193 2.162 0.598 -0.352

0.6002 0.8117 2.575 0.564 -0.334

0.6968 0.8044 2.991 0.497 -0.289

0.7993 0.7966 3.455 0.376 -0.219

0.8980 0.7889 3.924 0.226 -0.129

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 0.8522 0.564 0.000 0.000

0.0994 0.8447 0.716 0.212 -0.128

0.1972 0.8374 0.905 0.362 -0.214

0.2992 0.8298 1.133 0.467 -0.273

0.4004 0.8222 1.384 0.527 -0.307

0.4976 0.8148 1.650 0.548 -0.315

0.6002 0.8070 1.958 0.514 -0.296

0.6968 0.7995 2.267 0.448 -0.258

0.7993 0.7913 2.627 0.350 -0.187

0.8980 0.7834 2.982 0.195 -0.110

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 0.8473 0.527 0.000 0.000

0.0994 0.8400 0.624 0.183 -0.113

0.1972 0.8328 0.752 0.320 -0.192

0.2992 0.8252 0.915 0.425 -0.245

0.4004 0.8177 1.101 0.471 -0.273

0.4976 0.8103 1.301 0.492 -0.278

0.6002 0.8024 1.538 0.470 -0.258

0.6968 0.7949 1.783 0.403 -0.218

0.7993 0.7867 2.059 0.304 -0.159

0.8980 0.7787 2.339 0.160 -0.087

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 0.8437 0.489 0.000 0.000

0.0994 0.8367 0.553 0.120 -0.097

0.1972 0.8297 0.637 0.210 -0.171

0.2992 0.8224 0.756 0.253 -0.217

0.4004 0.8151 0.895 0.253 -0.241

0.4976 0.8080 1.057 0.215 -0.237

0.6002 0.8004 1.245 0.135 -0.215

0.6968 0.7930 1.436 0.038 -0.180

0.7993 0.7851 1.659 -0.118 -0.122

0.8980 0.7770 1.876 -0.265 -0.065

1.0000 0.7648 2.106 0.000 0.000

93

Table 3.9 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + Nitrobenzene.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 1.1982 1.801 0.000 0.000

0.0929 1.1633 1.509 -0.101 -0.538

0.1964 1.1228 1.519 -0.129 -0.801

0.3000 1.0818 1.601 -0.178 -0.993

0.3940 1.0438 1.641 -0.204 -1.202

0.5000 1.0004 1.649 -0.249 -1.474

0.6008 0.9577 2.194 -0.220 -1.196

0.6998 0.9148 2.652 -0.158 -0.999

0.8009 0.8701 3.011 -0.070 -0.908

0.8995 0.8256 3.556 0.049 -0.623

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 1.1933 1.618 0.000 0.000

0.0929 1.1587 1.381 -0.148 -0.401

0.1964 1.1179 1.289 -0.170 -0.675

0.3000 1.0768 1.225 -0.228 -0.921

0.3940 1.0387 1.159 -0.261 -1.153

0.5000 0.9968 1.101 -0.472 -1.398

0.6008 0.9534 1.325 -0.389 -1.351

0.6998 0.9097 1.623 -0.255 -1.227

0.8009 0.8656 2.262 -0.241 -0.766

0.8995 0.8202 2.768 -0.024 -0.434

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 1.1883 1.430 0.000 0.000

0.0929 1.1533 1.118 -0.120 -0.425

0.1964 1.1129 0.984 -0.184 -0.684

0.3000 1.0719 0.924 -0.258 -0.870

0.3940 1.0339 0.927 -0.305 -0.981

0.5000 0.9901 1.017 -0.330 -1.019

0.6008 0.9474 1.193 -0.313 -0.965

0.6998 0.9047 1.460 -0.280 -0.818

0.8009 0.8602 1.788 -0.216 -0.613

0.8995 0.8160 2.201 -0.131 -0.319

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 1.1834 1.252 0.000 0.000

0.0929 1.1489 0.886 -0.176 -0.445

0.1964 1.1083 0.873 -0.234 -0.547

0.3000 1.0670 0.773 -0.290 -0.735

0.3940 1.0291 0.755 -0.354 -0.833

0.5000 0.9854 0.811 -0.396 -0.868

0.6008 0.9424 0.937 -0.353 -0.828

0.6998 0.9009 1.139 -0.453 -0.711

0.8009 0.8551 1.407 -0.244 -0.529

0.8995 0.8111 1.730 -0.177 -0.290

1.0000 0.7648 2.106 0.000 0.000

94

Table 3.10 : Density ( ),Viscosity ( ),Excess Molar Volume (VE) and Deviations

in Viscosity (∆ ) for t-Butanol + Aniline.

Temp.

K

x1

x10-3

kg.m-3

mPa.s

VEx106

m3.mol-1

∆

mPa.s

298.15

0.0000 1.0171 3.375 0.000 0.000

0.1007 0.9946 3.293 -0.190 -0.190

0.1985 0.9723 3.028 -0.325 -0.559

0.2962 0.9496 2.829 -0.410 -0.863

0.3979 0.9257 2.707 -0.459 -1.094

0.4986 0.9018 2.716 -0.469 -1.193

0.5998 0.8776 2.826 -0.441 -1.191

0.6998 0.8535 3.050 -0.373 -1.074

0.7992 0.8295 3.365 -0.277 -0.865

0.9003 0.8051 3.831 -0.154 -0.507

1.0000 0.7810 4.445 0.000 0.000

303.15

0.0000 1.0121 3.141 0.000 0.000

0.1007 0.9898 2.672 -0.226 -0.493

0.1985 0.9674 2.394 -0.368 -0.794

0.2962 0.9446 2.184 -0.458 -1.027

0.3979 0.9206 2.049 -0.512 -1.187

0.4986 0.8966 2.007 -0.524 -1.253

0.5998 0.8722 2.084 -0.486 -1.200

0.6998 0.8480 2.246 -0.416 -1.062

0.7992 0.8239 2.483 -0.316 -0.848

0.9003 0.7993 2.890 -0.175 -0.465

1.0000 0.7750 3.379 0.000 0.000

308.15

0.0000 1.0087 2.521 0.000 0.000

0.1007 0.9863 2.311 -0.240 -0.222

0.1985 0.9638 2.005 -0.395 -0.540

0.2962 0.9409 1.818 -0.496 -0.739

0.3979 0.9169 1.658 -0.571 -0.911

0.4986 0.8927 1.591 -0.581 -0.990

0.5998 0.8682 1.620 -0.551 -0.974

0.6998 0.8438 1.746 -0.475 -0.860

0.7992 0.8195 1.958 -0.367 -0.660

0.9003 0.7947 2.267 -0.215 -0.363

1.0000 0.7700 2.642 0.000 0.000

313.15

0.0000 1.0049 2.400 0.000 0.000

0.1007 0.9829 2.000 -0.300 -0.370

0.1985 0.9609 1.725 -0.525 -0.617

0.2962 0.9383 1.513 -0.678 -0.800

0.3979 0.9145 1.339 -0.797 -0.944

0.4986 0.8906 1.275 -0.862 -0.978

0.5998 0.8663 1.288 -0.877 -0.936

0.6998 0.8421 1.390 -0.847 -0.804

0.7992 0.8179 1.553 -0.774 -0.612

0.9003 0.7931 1.807 -0.646 -0.328

1.0000 0.7648 2.106 0.000 0.000

95

Table 3.11 : Least Square Parameters of Redlich-Kister Equation and Standard

Deviations, σ (VE) for Binary System at Different Temperatures.

System

t-Butanol +

Temp.

K a0 a1 a2 a3 a4 σ

Benzene

298.15 2.2631 -0.3071 0.4112 - - 0.0067

303.15 2.3403 -0.4103 0.6166 - - 0.0075

308.15 1.8794 -0.8785 -0.0193 -0.2195 0.8736 0.0023

313.15 2.5023 -0.2658 0.5400 -0.2658 0.7290 0.0061

Chlorobenzene

298.15 -0.1892 0.6115 0.0524 0.7472 -0.1790 0.0039

303.15 -0.1096 0.6798 -0.1655 0.4527 - 0.0050

308.15 0.0229 0.6172 -0.2492 0.5122 - 0.0089

313.15 0.0621 0.6322 -0.0929 0.6322 - 0.0052

Toluene

298.15 2.0251 -0.8115 1.0493 0.8777 -0.3895 0.0047

303.15 2.0845 -0.7874 0.9268 0.8024 0.0591 0.0023

308.15 2.1145 -0.8074 1.0590 0.8536 - 0.0040

313.15 4.3154 2.5467 1.2013 2.5467 -1.1704 0.0090

o-Chlorotoluene

298.15 0.9639 0.0771 -0.0022 -0.1776 - 0.0017

303.15 1.0841 0.0500 0.0032 -0.0834 - 0.0024

308.15 1.1916 0.0433 0.1376 - - 0.0046

313.15 0.3639 -0.4667 -0.0075 -0.4667 -3.5108 0.0190

p-Chlorotoluene

298.15 1.5469 -0.2065 -0.0508 -1.4654 2.0533 0.0129

303.15 1.6571 -0.1560 0.0041 -1.6159 1.9177 0.0124

308.15 1.3009 -0.0515 0.2312 - - 0.0032

313.15 0.5248 -0.4768 -0.3248 -0.4768 -2.8452 0.0199

o-Xylene

298.15 2.0147 -0.0332 -0.0088 0.1307 0.4214 0.0036

303.15 1.7747 0.0566 0.2051 - - 0.0076

308.15 1.6496 -0.0064 -0.0842 - - 0.0033

313.15 0.5411 -0.4675 0.4090 -0.4675 -4.8168 0.0227

m-Xylene

298.15 2.5050 -0.1093 0.3694 - - 0.0052

303.15 2.3604 -0.1178 0.0187 - - 0.0082

308.15 2.1499 -0.1750 -0.3200 0.0848 0.4180 0.0045

313.15 1.0017 -0.6529 -0.4165 -0.6529 -3.2933 0.0201

p-Xylene

298.15 2.3913 -0.1259 -0.1439 0.0565 0.5905 0.0023

303.15 2.1694 -0.1275 0.1313 - - 0.0037

308.15 1.9602 -0.0661 0.1031 -0.1824 -0.3220 0.0045

313.15 0.8317 -0.7951 -0.2601 -0.7951 -3.5772 0.0144

Nitrobenzene

298.15 -0.9599 -0.3530 0.9962 2.1756

0.0127

303.15 -1.4858 -1.1743 0.7953 3.1325

0.0654

308.15 -1.3212 -0.1929 0.5352 0.2314 -1.0851 0.0065

313.15 -1.5058 -0.1016 -0.6507 - - 0.0461

Aniline

298.15 -1.8691 0.2446 -0.0530 - - 0.0020

303.15 -2.0823 0.2388 -0.0334 0.1571 -0.2966 0.0027

308.15 -2.3312 0.1635 0.0973 -0.0057 -0.6246 0.0036

313.15 -3.4711 -0.3198 -0.3245 -0.3198 -3.8321 0.0206

96

Table 3.12 : Parameters of Jouyban-Acree Model and Average Percentage Deviation

for Density.

System t-Butanol + A0 A1 A2 A3 A4 APD

Benzene -7.5608 1.5463 -0.5970 0.9474 -2.4376 0.0114

Chlorobenzene 25.9583 1.7109 0.8384 -1.4711 0.1095 0.0040

Toluene -2.7871 -1.0295 -2.5249 - - 0.0449

o-Chlorotoluene 34.0164 7.0329 1.4839 3.0088 2.7111 0.0291

p-Chlorotoluene 32.1527 7.2830 1.6631 4.7510 -0.3101 0.0453

o-Xylene 6.5692 1.4566 0.2419 2.3019 2.8063 0.0424

m-Xylene 3.8135 1.2853 0.6602 2.6245 2.0321 0.0443

p-Xylene 3.9481 1.4487 0.2635 2.5147 2.7710 0.0439

Nitrobenzene 42.2353 8.4298 -1.3387 -4.8398 2.6946 0.0341

Aniline 15.6782 0.1823 0.2501 2.4894 3.9346 0.0479

97

Table 3.13 : Least Square Parameters of Redlich-Kister Equation and Standard

Deviations, ) for Binary System at Different Temperatures.

System

t-Butanol +

Temp.

K a0 a1 a2 a3 a4 σ

Benzene

298.15 -5.8439 -4.2338 -0.3952 - - 0.0096

303.15 -5.5352 -4.0753 0.0402 - - 0.0087

308.15 -4.9618 -3.8944 0.0564 - - 0.0210

313.15 -4.4280 -4.7248 -0.4705 1.3127 0.9879 0.0099

Chlorobenzene

298.15 -3.6182 0.8260 0.6812 - - 0.0003

303.15 -3.0709 0.5561 0.3907 -0.1930 0.8976 0.0078

308.15 -2.5267 -0.0691 0.9174 -0.0020 - 0.0000

313.15 -1.8585 -0.1024 -0.0161 - - 0.0097

Toluene

298.15 -4.8250 0.0788 0.9916 0.0117 - 0.0000

303.15 -4.0982 -0.3546 1.4696 0.0054 - 0.0000

308.15 -2.6724 -1.0167 -1.3148 1.0832 2.2446 0.0226

313.15 -1.3997 0.6806 -0.5134 0.1662 1.4123 0.0062

o-Chlorotoluene

298.15 -1.8170 0.0680 -0.0831 0.0962 -0.0721 0.0012

303.15 -1.6275 0.0406 -0.0193 0.0954 - 0.0020

308.15 -1.4883 0.0358 -0.0871 0.1354 0.3142 0.0021

313.15 -1.3552 0.0786 -0.0161 - - 0.0024

p-Chlorotoluene

298.15 -1.7789 0.2758 0.2550 -0.0542 -0.9516 0.0038

303.15 -1.6075 0.2654 0.1582 -0.0442 -0.7019 0.0018

308.15 -1.4408 0.2630 -0.0479 0.0615 -0.1071 0.0018

313.15 -1.3944 0.3612 0.1651 0.3087 -0.7119 0.0025

o-Xylene

298.15 -1.2774 -0.1165 0.0916 0.1294 -0.3581 0.0022

303.15 -1.1121 -0.1421 -0.0484 0.2445 0.0634 0.0012

308.15 -0.9216 -0.0149 0.0132 - - 0.0010

313.15 -0.7430 0.0967 0.1546 -0.0985 -0.2579 0.0013

m-Xylene

298.15 -1.5277 0.1318 -0.0956 - - 0.0019

303.15 -1.4563 0.1602 -0.0172 0.1301 - 0.0014

308.15 -1.1892 0.1762 -0.1098 -0.0742 0.3702 0.0030

313.15 -1.0714 0.2076 0.0199 -0.1297 0.1064 0.0015

p-Xylene

298.15 -1.4145 0.0916 0.0972 0.0969 -0.4460 0.0028

303.15 -1.2620 0.1180 0.0986 0.0451 -0.2815 0.0024

308.15 -1.1086 0.1634 0.0543 0.0513 -0.0784 0.0007

313.15 -0.9528 0.2448 -0.0161 - - 0.0015

Nitrobenzene

298.15 -5.3655 -0.1167 3.9204 -0.5722 -9.1860 0.0885

303.15 -5.5182 -1.8616 4.0892 2.9173 -4.4262 0.0472

308.15 -4.0727 0.0044 0.3943 1.3718 -1.0699 0.0108

313.15 -3.5454 -0.5037 1.8979 2.5343 -4.4564 0.0354

Aniline

298.15 -4.7678 -0.8064 0.3176 -2.2000 1.6892 0.0082

303.15 -4.9488 -0.4032 -0.5443 0.8302 - 0.0162

308.15 -3.9266 -0.4184 0.0101 -0.8558 1.6231 0.0172

313.15 -3.9205 -0.0872 0.4880 0.5360 -0.6496 0.0088

98

Table 3.14 : Parameters of Jouyban-Acree Model and Average Percentage Deviation

for Viscosity.

System

t-Butanol + A0 A1 A2 A3 A4 APD

Benzene -1226.6705 -824.8637 1213.6728 677.4755 - 8.4310

Chlorobenzene -248.0900 353.5325 49.1295 -159.5153 - 2.0817

Toluene -260.8114 449.5131 -256.1451 -149.1346 406.9507 2.4181

o-Chlorotoluene -46.4569 90.2659 -43.3004 16.4252 13.4101 2.5573

p-Chlorotoluene -4.7727 168.4881 -150.8322 - - 2.9115

o-Xylene 147.3911 -26.1343 -2.0584 - - 2.0186

m-Xylene 168.3289 21.4135 -23.2300 - - 2.6183

p-Xylene 187.0899 12.6179 -36.7927 - - 2.8323

Nitrobenzene -781.5835 178.2885 769.9588 303.9002 -1121.3646 3.6286

Aniline -576.7822 -47.5581 200.7802 -14.5218 -15.2652 2.2070

99

Table 3.15 : Interaction Parameter for Binary System.

System

t-Butanol +

Temp.

K

d

σ

T12

mPa.s

σ

Wvisc/

RT

kj.mol-1

σ

H12

mPa.s

σ

Benzene

298.15 -1.4088 0.09 -0.4924 0.32 -1.4448 0.09 -0.4354 0.31

303.15 -2.7054 0.14 -0.8380 0.45 -2.6759 0.15 -0.7961 0.43

308.15 -3.7788 0.17 -0.9209 0.38 -3.7223 0.17 -0.8880 0.36

313.15 -4.9985 0.33 -0.9427 0.59 -4.9537 0.33 -0.9167 0.57

Chlorobenzene

298.15 -0.4225 0.11 0.9284 0.06 -0.6040 0.11 0.8576 0.04

303.15 -0.8192 0.11 0.6378 0.05 -0.8178 0.11 0.5867 0.04

308.15 -0.9335 0.04 0.5236 0.02 -0.9238 0.05 0.4837 0.02

313.15 -0.9267 0.03 0.5060 0.01 -0.9340 0.04 0.4759 0.01

Toluene

298.15 -0.8759 0.15 0.3006 0.04 -0.9011 0.14 0.1826 0.03

303.15 -1.2906 0.13 0.1309 0.07 -1.2615 0.13 0.0443 0.09

308.15 -1.0509 0.05 0.2573 0.04 -1.0318 0.05 0.1890 0.05

313.15 -0.4312 0.08 0.6511 0.06 -0.4091 0.08 0.6001 0.05

o-Chlorotoluene

298.15 0.3107 0.01 1.9805 0.02 0.1739 0.02 1.7824 0.06

303.15 -0.0472 0.02 1.4621 0.01 -0.0148 0.03 1.3202 0.04

308.15 -0.3485 0.02 1.0975 0.01 -0.3029 0.02 0.9923 0.03

313.15 -0.5923 0.03 0.8448 0.01 -0.5757 0.03 0.7668 0.03

p-Chlorotoluene

298.15 0.4602 0.01 1.9589 0.03 0.3382 0.03 1.7434 0.02

303.15 0.0590 0.04 1.4216 0.03 0.1006 0.04 1.2658 0.02

308.15 -0.2683 0.03 1.0779 0.02 -0.1225 0.03 0.9629 0.02

313.15 -0.6913 0.05 0.7917 0.04 -0.5738 0.05 0.7090 0.03

o-Xylene

298.15 0.9020 0.03 2.1984 0.07 0.8893 0.03 1.9565 0.04

303.15 0.5418 0.01 1.6590 0.06 0.5878 0.01 1.4829 0.04

308.15 0.3064 0.07 1.3187 0.05 0.3667 0.02 1.1865 0.01

313.15 0.1936 0.06 1.0742 0.08 0.2226 0.06 0.9718 0.03

m-Xylene

298.15 1.1365 0.03 2.0144 0.02 1.1418 0.03 1.7418 0.09

303.15 0.6005 0.01 1.4355 0.03 0.6559 0.01 1.2358 0.02

308.15 0.3742 0.02 1.1350 0.02 0.4764 0.06 0.9792 0.08

313.15 0.0468 0.02 0.8783 0.02 0.1178 0.02 0.7594 0.09

p-Xylene

298.15 1.1528 0.03 2.0858 0.02 1.1609 0.03 1.8087 0.01

303.15 0.7177 0.08 1.5425 0.02 0.7726 0.04 1.3390 0.01

308.15 0.3735 0.01 1.1863 0.02 0.4692 0.01 1.0338 0.01

313.15 0.1299 0.02 0.9483 0.03 0.1940 0.02 0.8313 0.02

Nitrobenzene

298.15 -1.7791 0.09 0.5151 0.06 -2.0107 0.09 0.4613 0.06

303.15 -2.4438 0.08 -0.0031 0.09 -2.4543 0.09 -0.0388 0.09

308.15 -2.4728 0.07 0.0280 0.03 -2.4318 0.06 0.0077 0.01

313.15 -2.6649 0.06 -0.0609 0.04 -2.6450 0.06 -0.0740 0.03

Aniline

298.15 -1.2979 0.04 1.6149 0.04 -1.4593 0.03 1.6237 0.04

303.15 -1.8587 0.02 0.7314 0.01 -1.8807 0.01 0.7330 0.01

308.15 -1.7518 0.03 0.6881 0.02 -1.7401 0.03 0.6907 0.02

313.15 -2.1090 0.02 0.3230 0.01 -2.1298 0.02 0.3227 0.06

100

Table 3.16 : McAllister 3 and 4 Body Interaction Parameters for Binary Systems.

System

t-Butanol +

Temp.

K

3 Body 4 Body

ν12 ν21 σ% ν1112 ν1122 ν2221 σ%

Benzene

298.15 1.3652 1.2171 7.79 2.675 0.660 1.420 0.5364

303.15 0.7238 0.7759 16.00 2.000 0.203 1.275 0.7829

308.15 0.3721 0.5714 16.80 1.440 0.070 1.327 3.1524

313.15 0.1358 0.5996 29.63 0.977 0.016 2.082 7.4917

Chlorobenzene

298.15 3.2976 0.7306 3.80 3.698 1.638 0.677 0.1373

303.15 2.5692 0.6274 2.01 3.014 0.946 0.651 0.7859

308.15 1.7743 0.6426 2.06 2.356 0.645 0.716 0.6470

313.15 1.4470 0.5912 1.01 1.787 0.651 0.621 0.5165

Toluene

298.15 3.4625 0.5619 2.55 3.766 1.455 0.561 0.5580

303.15 2.2517 0.5339 5.67 3.211 0.637 0.670 1.2883

308.15 1.7528 0.5639 1.90 2.043 0.927 0.553 1.2878

313.15 2.2080 0.5374 2.04 2.165 1.168 0.502 0.8621

o-Chlorotoluene

298.15 3.1421 1.6497 2.30 3.785 1.928 1.402 0.1589

303.15 2.6493 1.2619 0.75 2.910 1.436 1.102 0.1296

308.15 2.0695 0.9708 0.28 2.324 1.068 0.905 0.1251

313.15 1.6256 0.7814 0.26 1.837 0.845 0.758 0.1438

p-Chlorotoluene

298.15 3.2294 1.5914 2.95 3.727 2.017 1.257 0.4148

303.15 2.7437 1.1566 1.93 2.836 1.538 0.938 0.3596

308.15 2.1970 0.8598 1.18 2.281 1.155 0.755 0.2843

313.15 1.8450 0.5944 1.93 1.785 1.008 0.544 0.5586

o-Xylene

298.15 3.5669 2.4119 0.35 4.147 2.379 1.922 0.1231

303.15 2.8691 1.7619 0.33 3.180 1.842 1.451 0.1372

308.15 2.2864 1.378 0.11 2.523 1.463 1.180 0.0606

313.15 1.8664 1.0944 0.29 2.015 1.224 0.946 0.1279

m-Xylene

298.15 3.563 2.2587 0.20 4.073 2.401 1.628 0.1004

303.15 2.9288 1.4322 1.03 3.072 1.905 1.081 0.2144

308.15 2.3034 1.1252 0.48 2.487 1.389 0.926 0.2574

313.15 1.8595 0.8397 0.74 1.962 1.127 0.727 0.2151

p-Xylene

298.15 3.6089 2.3282 0.49 4.083 2.419 1.731 0.1356

303.15 2.9046 1.6062 0.55 3.108 1.883 1.242 0.1701

308.15 2.3677 1.1551 0.61 2.464 1.492 0.947 0.1823

313.15 1.9321 0.8896 0.65 2.004 1.184 0.766 0.1350

Nitrobenzene

298.15 2.3016 0.8625 6.73 2.762 1.544 0.914 2.3132

303.15 1.5982 0.7255 9.51 2.600 0.460 1.091 1.9936

308.15 1.5811 0.4711 1.17 2.002 0.576 0.632 0.4796

313.15 1.2677 0.3499 3.27 1.421 0.581 0.443 2.2118

Aniline

298.15 2.5554 2.8182 2.37 3.737 1.858 3.451 0.4634

303.15 2.1265 1.8161 1.38 2.648 1.583 2.165 0.3094

308.15 1.5419 1.7551 2.56 2.220 0.994 2.258 0.2909

313.15 1.2578 1.2669 2.05 1.703 0.871 1.653 0.4808

101

Figure 3.1 : Density at 298.15 K for (x1) t-Butanol + (1-x1) Benzene ( ),

Chlorobenzene ( ), Toluene ( ), o-Chlorotoluene (), p-Chlorotoluene (),

o- Xylene ( ), m-Xylene (), p-Xylene (-), Nitrobenzene (), Aniline ().

x1

102

Figure 3.2 : VE values at 298.15 K for (x1) t-Butanol + (1-x1) Benzene ( ),

Chlorobenzene ( ), Toluene ( ), o-Chlorotoluene (), p-Chlorotoluene (),

o- Xylene ( ), m-Xylene (), p-Xylene (-), Nitrobenzene (), Aniline ().

x1

103

Figure 3.3 : Viscosity at 298.15 K for (x1) t-Butanol + (1-x1) Benzene ( ),

Chlorobenzene ( ), Toluene ( ), o-Chlorotoluene (), p-Chlorotoluene (),

o- Xylene ( ), m-Xylene (), p-Xylene (-), Nitrobenzene (), Aniline ().

x1

104

Figure 3.4 : ∆η values at 298.15 K for (x1) t-Butanol + (1-x1) Benzene ( ),

Chlorobenzene ( ), Toluene ( ), o-Chlorotoluene (), p-Chlorotoluene (),

o- Xylene ( ), m-Xylene (), p-Xylene (-), Nitrobenzene (), Aniline ().

x1