ISSN: 2456–5474 RNI No.  UPBIL/2016/68367 VOL.- VII , ISSUE- XI December  - 2022
Innovation The Research Concept
Ultrasonic Studies of Binary Liquid Mixtures of Benzonitrile with Amyl Alcohol At 298.15k, 303.15k, 308.15k
Paper Id :  16923   Submission Date :  05/12/2022   Acceptance Date :  22/12/2022   Publication Date :  25/12/2022
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Deepali Singhal
Associate Professor
Chemistry
SGRR (PG) College
Dehradun,Uttrakhand, India,
Sandeep Negi
(Corresponding Author) Associate Professor Chemistry
SGRR (PG) College
Dehradun, Uttrakhand, India
Rakesh Dhaundiyal
Associate Professor
Chemistry
SGRR (PG) College
Dehradun, Uttrakhand, India
H V Pant, Harish Chandra
Associate Professor
Chemistry
SGRR (PG) College
Dehradun, Uttrakhand, India
Abstract Ultrasonic velocity (u) and density (ρ) has been measured for binary liquid mixture of Benzonitrile with Amyl alcohol at 298.15K, 303.15K, 308.15K over the entire range. Isentropic compressibility (βs), intermolecular free length (Lf), molar sound velocity (Rm), specific acoustic independence (Z) and molar volume (Vm) and their excess values has been calculated using experimental data of ultrasonic velocity and density. The variation of these properties helps us to understand the strength of intermolecular interaction in the liquid mixture.
Keywords Ultrasonic Velocity, Density, Binary Liquid Mixture, Intermolecular Free Length, Intermolecular Interaction.
Introduction
The studies of thermodynamical properties of binary liquid mixtures have found wide applications in chemical, textile, leather, and nuclear industries. For a better understanding of the Physico-chemical properties and the molecular interaction between the participating components of these mixtures, Ultrasonic velocity and density are measured at different temperatures for different concentration of the components in the mixture. These data furnish information about the interaction. In order to understand the nature of molecular interactions between the components of the liquid mixtures, it is to discuss the same in terms of excess parameters. Ultrasonic velocity and density in fourteen binary liquid mixtures representing different types and degree of interaction studied by Fort and Moore[1].
Aim of study The study of thermodynamic properties of binary liquid mixtures has proved to be a useful tool in elucidating the interactions that are operating between component molecules[2]. Excess thermodynamic functions, which depend on the composition, temperature, and pressure of the system, are of great importance to a chemical engineer in the design of industrial separation process and to a chemist for arriving at theories of liquid mixtures. The primary objective is to measure the speeds of sound and densities of liquid systems in order to estimate the value of isentropic compressibility, intermolecular free length and molar volume which in turn is widely used to study the molecular interactions through its excess value.
Review of Literature

The physical and chemical properties of liquid mixtures are influenced by intermolecular forces[3-7]. Study of the ultrasonic velocity in liquids and liquid mixtures and its influence on the molecular structure was studied by several researchers [8-17]. Ultrasonic investigations of liquid mixtures consisting of polar and non-polar components enable us to understand the molecular interactions and structural behavior of molecules and their mixtures 18-20. Dipole-dipole, dipole–induced dipole, charge transfer interaction, and hydrogen bonding between unlike molecules are responsible for possessing negative excess values [21-23].
Main Text

Experimental Details

The ultrasonic velocities is measured by using a single crystal ultrasonic interferometer (M/S Mittal Enterprises, New Delhi) operating at 2 MHz frequency with an accuracy of ±0.05% (Model F-81), which is calibrated with water and benzene.  The temperature stability is maintained within 0.1K by circulating thermostat water around interferometer cell that contains the liquid with a circulating pump. In order to minimize the error of measurements several maxima of ultrasonic velocity are allowed to pass and their number n is counted. All maxima are recorded with highest swing of the needle on the micrometer scale of the interferometer.  The total distance d moved by the reflector of the interferometer cell is given by

d = n λ/2 ----------------------------(1)

Where λ is wavelength of ultrasonic wave. The frequency ν of the interferometer crystal is accurately known (2 MHz) and using λ from eq 1, the ultrasonic velocity v m/s is calculated by the relation

v = ν λ------------------------------ (2)

Employing the measurement values of velocity (v) and density (ρ) some thermodynamic properties such as isentropic compressibility (βs), intermolecular free length (Lf) and molar volume (Vm) have been computed through the following expressions[24-25]. 

Molar volume                     ...… (1)                      

Vm = [M-/e]

Isentropic compressibility               …… (2)                      

βs = 1/V2ρ

Intermolecular free length              …… (3)

Lf = [K √βs]

High purity chemicals (E. Merck and S.D. fine) are used and purified by the standard methods[26].

Excess values of various parameters are computed using the following relation: -

AE = (A) exp – (X1A1 + X2A2) where AE is excess function (A) exp is experimental value of the mixture, A1 and A2 are the values for the pure components 1 and 2 whose mole fractions are X1 and X2.

The results obtained from these investigations have been incorporated in Table (1-3) and in Graph (1-4).
Result and Discussion

The measured values of ultrasonic velocity (u), density (ρ) and computed values of molar volume (Vm), excess molar volume (VmE), isentropic compressibility (βs), excess isentropic compressibility(βsE), intermolecular free length (Lf), excess value of intermolecular free length (LfE) for the binary liquid mixture of Benzonitrile with Amyl alcohol at different temperature are presented in table 1,2 and 3.

The variation of ultrasonic velocity, excess isentropic compressibility(βsE), excess value of intermolecular free length (LfE) and excess molar volume (VmE) are shown in figure 1,2,3 and 4.

Table 1‒Experimentally determined ultrasonic velocity, density, calculated excess values of isentropic compressibility, intermolecular free length and molar volume for Benzonitrile with Amyl alcohol at 298.15K

Mole fraction

X1

Ultrasonic velocity (u) ms-1

Density (ρ)

gml-1

Excess isentropic

Compressibility (BSE)

cm2 dyne-1

X1012

Excess intermolecular freelength (LfE)

Ao

Excess molar volume (VmE)

ml mole-1

 

1.0000

1416

1.0012

0.0000

0.0000

0.0000

0.9048

1400

0.9844

-0.5478

-0.0013

-0.2377

0.8086

1386

0.9674

-1.1562

-0.0030

-0.4649

0.7113

1374

0.9509

-1.8866

-0.0054

-0.7572

0.6129

1360

0.9324

-2.2453

-0.0064

-0.8396

0.5136

1346

0.9140

-2.5159

-0.0072

-0.9376

0.4131

1334

0.8949

-2.8164

-0.0083

-0.9580

0.3115

1320

0.8755

-2.7601

-0.0082

-0.8947

0.2088

1304

0.8546

-2.2928

-0.0068

-0.7400

0.1050

1288

0.8335

-1.5815

-0.0048

-0.4982

0.0000

1268

0.8106

  0.0000

 0.0000

 0.0000

Table 2‒Experimentally determined ultrasonic velocity, density, calculated excess values of isentropic compressibility, intermolecular free length and molar volume for Benzonitrile with Amyl alcohol at 303.15K

Mole fraction

X1

Ultrasonic velocity (u)  ms-1

Density (ρ)

gml-1

Excess isentropic

Compressibility (BSE)

cm2 dyne-1

X1012

Excess intermolecular freelength (LfE)

Ao

Excess molar volume (VmE)

ml mole-1

 

1.0000

1400

0.8864

0.0000

0.0000

0.0000

0.9047

1388

0.9804

-0.8159

-0.0025

-0.3088

0.8084

1376

0.9649

-1.6051

-0.0050

-0.6850

0.7111

1362

0.9476

-2.0636

-0.0062

-0.8799

0.6128

1352

0.9292

-2.7132

-0.0083

-0.9601

0.5134

1338

0.9114

-2.9662

-0.0090

-1.1135

0.4129

1326

0.8922

-3.2034

-0.0099

-1.1089

0.3113

1312

0.8728

-3.1120

-0.0096

-1.0793

0.2087

1296

0.8525

-2.5872

-0.0080

-0.9350

0.1049

1284

0.8313

-2.2446

-0.0073

-0.6649

0.0000

1260

0.8073

0.0000

-0.0000

0.0000

Table 3‒Experimentally determined ultrasonic velocity, density, calculated excess values of isentropic compressibility, intermolecular free length and molar volume for Benzonitrile with Amyl alcohol at 308.15K

Mole fraction

X1

Ultrasonic velocity (u)  ms-1

Density (ρ)

gml-1

Excess isentropic

Compressibility (BSE)

cm2 dyne-1

X1012

Excess intermolecular freelength (LfE)

Ao

Excess molar volume (VmE)

ml mole-1

 

1.0000

1382

0.9918

 0.0000

 0.0000

 0.0000

0.9047

1374

0.9771

-1.1614

-0.0040

-0.4386

0.8084

1362

0.9621

-1.9502

-0.0046

-0.8627

0.7111

1352

0.9452

-2.7376

-0.0090

-1.0951

0.6127

1340

0.9266

-3.1775

-0.0102

-1.1459

0.5133

1328

0.9090

-3.5939

-0.0115

-1.3152

0.4129

1316

0.8897

-3.7943

-0.0122

-1.2906

0.3113

1304

0.8708

-3.9103

-0.0127

-1.3134

0.2087

1290

0.8515

-3.6526

-0.0120

-1.2867

0.1050

1274

0.8299

-2.7962

-0.0093

-0.9594

0.0000

1248

0.8038

 0.0000

 0.0000

 0.0000


Conclusion In the present study, the data of Ultrasonic velocity, density, and related thermodynamic parameters with their excess values suggest the existence of a strong intermolecular interaction. The negative values indicate a strong intermolecular interaction in the component of a binary liquid mixture of Benzonitrile with Amyl alcohol over the entire range.
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