Thermodynamic Properties of Organic Liquid Mixtures Related to Molecular Interactions between the Components

Thermodynamic Properties of Organic Liquid Mixtures Related to Molecular Interactions between the Components

Prof. (Dr) V. N. Maurya [1], Diwinder Kaur Arora [2], Er. Avadhesh Kumar Maurya [3] [1] Professor & Head, Department of Engineering Mathematics, Sanghavi College of Engineering, Nashik (University of Pune) Nashik-422202, Maharashtra, India

Abstract- In the present paper, thermodynamic properties of organic liquid mixtures related to molecular interactions between the components have been analysed intensively. In addition to that, the present paper also includes a brief discussion on comparative study between the experimental

In order to examine molecular interactions in the mixture of butylamine with alcohols through excess properties viz. excess molar volume (V E ), molar refraction deviation ( Rm ), viscosity deviation ( ) and excess Gibbs free

m

and theoretically calculated values of refractive indices at

three temperatures 293, 303 and 313K. The results have

energy of activation for viscous flow (

G* E ), this

been discussed in terms of average percentage deviation (APD).

1. INTRODUCTION

   The knowledge of the thermodynamic properties of organic liquid mixtures is of immense importance for understanding the molecular interactions between the components. This also helps to evolve theoretical models and is useful in industrial applications [1 – 4]. Excess properties of liquid systems, such as excess molar volume, deviation in molar refraction are needed for the design of separation equipment and to test the theories of the solution [5]. In addition, excess properties provide information about the molecular interactions and macroscopic behaviour of fluid mixtures and can be used to test and to improve thermodynamical models for calculating and predicting the fluid phase equilibria. The knowledge of excess Gibbs free energy of activation for viscous flow helps in understanding the molecular orientation and to study the extent of

   chapter reports here the density ( m ), refractive index ( nm ) and viscosity ( m ) for binary mixtures of butylamine with 1-butanol and tert-butanol over the entire composition range at temperatures 293, 303 and 313K. Further, seven mixing rules for refractive index proposed by Lorentz-Lorenz (L-L), Gladstone-Dale (G-D), Weiner (W), Heller (H), Arago- Biot (A-B), Newton (N) and Eykmen (Eyk) for the prediction of refractive index theoretically have been applied to these binary mixtures. A comparative study has been made between the experimental and theoretically calculated values of refractive indices at all the three temperatures. The results have been discussed in terms of average percentage deviation (APD).

2. RESULTS

   The experimental values of density ( m ), refractive index ( nm ) and viscosity ( m ) at three temperatures viz. 293,

   intermolecular interaction between component molecules of 303 and 313K along with the calculated values of excess

   m

   the liquid mixtures. In recent years, there has been considerable upsurge in the theoretical and experimental

   molar volume (V E ), molar refraction deviation (

   Rm ),

   investigation of the excess thermodynamic properties of viscosity deviation ( ) and excess Gibbs free energy

   binary liquid mixtures [6, 7].

   of activation for viscous flow (

   G* E ) are given in tables

   5.1 and 5.2 for butylamine + 1-butanol and butylamine +

   tert-butanol mixtures respectively. Adjustable parameters ai

   the strength of the interaction in mixture and is a sensitive function of wavelength, temperature and mixture

   with the standard deviations

   Y E for both the binary

   composition. Table 5.2 shows that

   Rm values are

   m

   mixtures at all the three temperatures 293, 303 and 313K are given in table 5.3. Average percentage deviations (APD) of theoretically calculated refractive indices from different semi-empirical relations are given in table 5.4. All the excess parameters viz.V E , Rm , and G* E plotted against the mole fraction of butylamine

   ( x1 ) are shown in table 5.1 to 5.4 respectively.

3. DISCUSSION

   m

   According to Fort and Moore [8], a negative excess molar volume (V E ) is an indication of strong hetero-molecular interaction in the liquid mixtures and is attributed to change-transfer, dipole-dipole interaction and hydrogen bonding between the unlike molecules, while a positive sign indicates a weak interaction and is attributed to dispersive forces. The magnitudes of the contribution will

   m

   vary with the components and composition of the mixtures. In the present investigation, both the mixtures gave negative magnitude of V E . This depicts the presence of hetero-molecular interaction, which supports the Fort and Moore [8] observation. Wen-Lu Weng [9] and Papaioannou

   negative for both the mixtures at all the temperatures. The values of V E and Rm support each other. The V E and Rm values become more negative at higher temperature for both the mixtures, suggesting an increase in interaction between unlike molecules.

   m

   m

   Table 5.3 shows that viscosity deviation ( ) values are positive for butylamine + 1-butanol and negative for butylamine + tert-butanol mixtures. The positive values of

   in butylamine + 1-butanol mixture can be explained on the basis of complex formation between unlike molecules through hydrogen bonding. The negative values

   of for butylamine + tert-butanol may be attributed to the presence of weak dipole-dipole interaction due to predominance rupture of dipolar association of tert-butanol

   and steric hindrance produced by three methyl group over

   the hydrogen bond formed between unlike molecules. Our positive values of in the case of butylamine + 1-

   butanol do not corroborate with the values of on the same mixtures reported earlier by Wen-Lu Weng [9] and Dominguez et al. [13]. However all the excess parameters

   V E , R and reported here, are in conformity

   et al. [10] have also observed negative values of V E in m m

   m

   m

   the case of butylamine + 1-butanol mixture. The negative V E values of butylamine +1- butanol observed in the present investigation have been found to be in good

   agreement with the values of V E reported earlier by Wen-

   with each other. values are found to decrease with increasing temperature in the positive and negative directions in the case of butylamine + 1-butanol and

   butylamine + tert-butanol mixtures respectively.

   m

   Lu Weng [9] and Papaioannou et al. [10]. The negative

   Table 5.4 shows that,

   G* E

   values are positive for

   m

   values of V E

   indicate that volume contraction takes place

   butylamine + 1-butanol and negative for butylamine + tert- butanol mixtures respectively. However, a smaller positive

   upon mixing of butylamine with 1-butanol/tert-butanol due

   trend has been observed at temperature 313K in butylamine

   to cross association between these dissimilar molecules

   rich region. The positive values of

   G* E

   indicates the

   [11]. The magnitude of the volume contraction follows the sequence of 1-butanol > tert-butanol. This is in agreement

   presence of strong interaction in butylamine + 1-

   G* E

   with the results eported by Ali and Nain [11] on binary

   butanol mixture, whereas a negative

   values for

   mixtures of THF with 1-butanol and tert-butanol which suggests that the excess values follow the same sequence, due to the steric hindrance produced by the presence of three methyl groups at 30 carbon atom in tert-butanol, as compared to one butyl group in 1-butanol. Molar refraction

   butylamine + tert-butanol mixture may be assigned to the predominance of dispersive forces. This is due to the fact that C-O bond is weaker in the case of tertiary alcohols due to +I (electron repelling) effect of alkyl groups while O-H bond is weaker in primary alcohols as electron density

   deviation ( Rm ) represents the electronic perturbation

   increases between O-H bond and hydrogen tends to

   separate as a proton. During O-H cleavage, proton is given

   due to orbital mixing of two components [12].

   Rm gives

   out showing that alcohols are acidic in nature. Acidic nature increases from tertiary to secondary and from secondary to

   primary as +I effect decreases [14]. Gupta et al. [15] and Mialkowski et al. [16] have also reported similar variations

   in the

   G* E

   values for binary mixtures of ether

   +alcohols and -butyrolactone + dimethylcarbonate.

   Further, Seven empirical relations were used for the prediction of refractive indices. The refractive index data correlated with these semi-empirical equations for both the binary mixtures show an excellent agreement with the respective experimental values of refractive index. It can be seen from table 5.4 that the correlation of these equations showed the suitability of all the seven relations for representing the mixing refractive indices of the binary mixtures of butylamine + 1-butanol/tert-butanol. The applicability of these semi-empirical relations for predicting refractive index has also been emphasized by others [17, 18].

4. CONCLUSION

The measured values of refractive index and viscosity along with the estimated values of various developed parameters suggest the existence of hetero-molecular association through hydrogen bonding in butylamine + 1-butanol mixture while behaviour of butylamine + tert-butanol mixture indicates the presence of long range dispersive forces among the components. The behaviour of all the excess parameters studied here supports each other. The various semi-empirical relations for representing the refractive index data theoretically give reasonably good results.

Table 5.1

m

Density ( m ), refractive index ( nm ), viscosity ( m ), excess molar volume (V E ), molar refraction deviation

( Rm ), viscosity deviation ( ) and excess Gibbs free energy of activation for viscous flow ( G* E ) for

butylamine + 1-butanol mixture with mole fraction of butylamine (x1) at T= 293, 303 and 313K.

V

E

m

m

x n m R

G* E

1 m

(mPa.s)

m (mPa.s)

T=313K

m

Density ( m ), refractive index ( nm ), viscosity ( m ), excess molar volume (V E ), molar refraction deviation

( Rm ), viscosity deviation ( ) and excess Gibbs free energy of activation for viscous flow ( G* E ) for

butylamine + tert-butanol mixture with mole fraction of butylamine (x1) at T= 293, 303 and 313K.

m

x1

(g.cm-3)

nm m

(mPa.s)

E (cm3.mol-

V

m

1)

Rm

(mPa.s)

G* E

(kJ.mol-1)

T=293K

Table 5.3

Adjustable parameters ai with the standard deviations

( Y E )

for excess molar volume (V E ), molar

m

refraction deviation (

Rm ), viscosity deviation ( ) and excess Gibbs free energy of activation for viscous

flow (

G* E ) for both the binary mixtures at varying temperatures.

a

Parameters Temp.

1 a2

(K)

a 3 a4 a5 Y

E

butylamine +1-butanol

m

Table 5.4

Average percentage deviation (APD) of theoretically calculated refractive index from different semi- empirical relations at all the three temperatures.

Temp.(K) L-L G-D W H A-B N Eyk

butylamine +1-butanol

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FIRST AUTHOR

Dr. V. N. Maurya, currently the Professor & Head, Department of Applied Mathematics, Sanghavi College of Engineering, Nashik (University of Pune, Maharashtra), is one of the leading experts in Applied Mathematics and

Operations Research in India and has made significant contributions to many mathematical, statistical, computer science and industrial engineering relatedareas basic as well as application oriented. Formerly Prof. V. N. Maurya has worked as Founder Director at Vision Institute of Technology, Aligarh (U.P. Technical University,

Lucknow) and as Principal/Director at Shekhawati College of Engineering, Dundlod, Rajasthan (Rajasthan Technical University, Kota) and also as Selected Professor & Dean Academics at Institute of Engineering & Technology, Sitapur, UP, India. He obtained M.Sc. and Ph.D. Degree in Mathematics & Statistics with specialization in Operations Research from Dr. Ram Manohar Lohia Avadh University, Faizabad, UP, India in the year 1996 and 2000 respectively and thereafter he accomplished another Masters Degree-MBA with specialization in Computer Science from NU, California, USA in 2003. He started his teaching career as Lecturer in 1996 to teach post-graduate courses MBA/MCA and M.Sc. and was appointed as Reader/Assistant Professor at LIET Alwar, Rajasthan in the year 2002. Since 2004 he has spent his entire scientific and professional career in teaching as Professor & Head/Dean as well as keen Researcher for Post-Doctoral research at various premier technical institutions of the country such as at Singhania University, Rajasthan; Haryana College of Technology & Management, Kaithal; United College of Engineering & Research, Allahabad. On the basis of significant research work carried out by him in the last few years of his professional career, Prof. V. N. Maurya has published more than 45 scientific research papers including his Ph.D. and D.Sc. Thesis in reputed refereed National and International Journals and Seminars of Mathematical and Management Sciences, Engineering & Technology in India, USA, Malaysia, Algeria and other countries. Some of his published research papers in India, USA, Algeria and Malaysia are regarded as landmark contributions in the field of Mathematical Sciences, Engineering & Technology. Since last 7 years Prof. Maurya is actively engaged as Research Supervisor of M. Phil. & Ph.D. Scholars in wide fields of Operations Research, Optimization Techniques, Statistical Inference, Applied Mathematics and Operations Management & Computer Science. He is an approved Supervisor for Research Programmes leading to M. Phil. & Ph.D. Degree of UGC recognized various Indian Universities such as Shridhar University, Pilani (Rajasthan), Singhania University, Rajasthan and CMJ University, Sillong, Meghalaya and JJTU Jhunjhunu, Rajasthan etc.

In the course of his distinguished professional career, Dr. Maurya has been appointed as Head Examiner for UG and PG Programs from leading Indian Universities – U.P. Technical University, Lucknow during 2005-06 and Chhatrapati Shahu Ji Maharaj University, Kanpur for three terms during 2000-2004. On the basis and recognition of his knowledge and significant research contributions in diversified fields of Mathematical and

Management Sciences as well as Engineering & Technology, Prof. Maurya has been the recipient of Editorial Member and Reviewer of many International Journals of India, USA and Italy and also Fellow/Senior/Life Member of various reputed National and International professional bodies including Operations Research Society of India, Kolkata; Indian Society for Technical Education, New Delhi; Indian Association for Productivity, Quality & Reliability, Kolkata; Indian Society for Congress Association, Kolkata; International Indian Statistical Association, Kolkata; All India Management Association, New Delhi; Rajasthan Ganita Parishad, Ajmer and International Association of Computer Science & Information Technology, Singapore etc.

SECOND AUTHOR

Diwinder Kaur Arora is MBA with specialization in Human Resources from Pondicherry Central University, Pondicherry and she accomplished her B.Sc. (Medical) Degree from Kanpur University, Kanpur, UP and did

Diploma Programme also from Government Polytechnic College, Amethi, Uttar Pradesh throughout in First Division. She has vast experience of more than 21 years as Police Officer of Central Reserve Police Force, Ministry of Home Affairs, Govt. of India. She was selected as Assistant Sub-Inspector in 1991 by Central Reserve Police Force, Ministry of Home Affairs, Govt. of India and thereafter successful completion of her services she was promoted as Sub-Inspector in 2004 and subsequently in the grade of Inspector of Police in 2012. Apart from this, she has published few research papers in both her field of Chemical Sciences and Management & Administration in the International Journals of repute.

THIRD AUTHOR

Er. Avadhesh Kumar Maurya is M. Tech. in Branch of Digital Communication Engineering from Uttarakhand

Technical University, Dehradun, UK and accomplished B. Tech. in Electronics &

Communication Engineering from Rajasthan Technical University, Kota (Rajasthan). He has been recipient of Four First Divisions during his Student career. Since last two years Er. A. K. Maurya is working as Network Engineer at Joint Venture of HCL & National Informatics Centre, Nainital, UK, India. He has worked on some projects such as Movable Target Shooter using Ultrasonic Radar and Hartley Oscillator. Apart from this, he has got industrial training in Door Darshan Kendra, Lucknow, UP in the field of TV Program Generation and Broadcasting of different channels for partial fulfilment of his Degree and also published several research papers in refereed International Journal of India and abroad.