Transport Properties of Binary Liquid Mixtures of γ – butyrolactone + aliphatic Alcohols Studied in the Temperature Range of (303.15 to 313.15) K

Transport Properties of Binary Liquid Mixtures of – butyrolactone + aliphatic Alcohols Studied in the Temperature Range of (303.15 to 313.15) K

butyrolactone + aliphatic Alcohols Studied in the Temperature Range of (303.15 to 313.15) K

Amara Jyothi Koppula

Department of Chemistry, Kakatiya University Warangal, Telangana, India

Murali Krishna Patwari

Department of Chemistry, Kakatiya University Warangal, Telangana, India

Satyanarayana Nallani

Department of Chemistry, Kakatiya University

* Sathyanarayana Boodida

Department of Chemistry, JNTUH College of Engineering Jagtial, Jagtial, Telangana, India

Abstract Densities () and viscosities () have been measured as a function of mole fraction for the mixtures of

butyrolactone (GBL) with 1-propanol (1-pro), 2-propanol (2- pro), 1-butanol (1-but) and 2-butanol (2-but) at the temperatures of 303.15, 308.15, and 313.15 K. From these measurements, deviation in viscosity ) was calculated. The computed property has been fitted to a Redlich-Kister type polynomial equation to derive binary coefficients and standard deviations.

Keywords butyrolactone; aliphatic alcohol; deviation in viscosity;binary mixture; binary coefficient.

1. INTRODUCTION

   butyrolactone is an important industrial solvent which has several advantageous physico-chemical properties such as a broad liquid range (45 oC to 205 oC), medium relative permittivity (41.65 at 25 oC) and high viscosity (1.76 m. Pas at 25 oC) [1]. It is an excellent electrolytic solvent used in lithium batteries [2, 3] Generally, alcohols are self-associated liquids and exist in a three-dimensional network of H-bonding in the liquid state. Hence the study of binary mixtures of GBL with alcohols have been made to understand how the solution structure has been varying due to H-bonding interactions between hydroxyl groups of alcohol in presence of external polar solvent.

   As part of our current research programme, to determine the different thermodynamic properties of binary liquid mixtures [4-10], we report here with the deviation in viscosity () of the binary systems: butyrolactone (GBL) with homologous series of aliphatic alcohols (1-propanol, 2- propanol, 1-butanol and 2-butanol). The experimental results have been fitted to Redlich-Kister type polynomial equation using multi parametric non-linear regression analysis [11] to derive the binary coefficients and to estimate the standard deviation between experimental and calculated data.

2. EXPERIMENTAL

   1. Material and Methods

      butyrolactone (Aldrich, >99 mol %) was purified by doing distillation under reduced pressure as reported by Aurbach and Gottlieb [12] 1-propanol, 2-propanol, 1-butanol and 2-butanol were obtained from Merk (>99%) India and used after single distillation. The isomeric alcohols were stored over type 3A x 1.5 nm molecular sieves. The purities of the samples were confirmed by comparing their physical properties with the reported data. The densities and viscosities of pure substances and their comparison with literature values are listed in table 1.

   2. General Procedure

   Binary mixtures were prepared by mass in air tight bottles and the mass measurements were performed on a Dhona 100 DS, India, single pan analytical balance with a resolution of ± 0.01.10 kg. The required properties of the mixture were measured on the same day. The uncertainty in mole fraction was estimated to be less than ± 1.10. Density of pure liquids and their mixtures were determined by using a 1.10 m3 double arm pycnometer [10]. The uncertainty in density values was found to be ± 4.10 g.cm and 1.10 cm3 .mol.

   Ubbelohde viscometer [13] having a capacity of about 15ml and the capillary having a length of about 90 mm and 0.5 mm internal diameter has been used to measure the flow times of pure liquids and liquid mixtures and it was calibrated with benzene and doubly distilled water (water conductivity less than 1.10 ohm.cm) as their density 0.87381 and 0.87341 g.cm at 298.15 and 308.15 K and

   0.9970 and 0.9940 g.cm at 298.15 and 308.15 K respectively. The detailed experimental procedure of viscometer was discussed earlier [8]. Viscosity values () of pure liquids and mixtures are calculated using the relation:

   * Corresponding Author

   IJERTV6IS070246 www.ijert.org

   = (atb/t) .(1)

   where a and b are the characteristic constants of the viscometer, is the density and t represents the flow time. The flow time of pure liquids and liquid mixtures were repeated for 5 times. The uncertainty of viscosity was ±0.005×10 m Pas.

3. RESULTS AND DISCUSSION

   Before The values of density (), viscosity () and deviation in viscosity () for the binary mixtures of

   butyrolactone (1) with 1-propanol (2), 2-propanol (2), 1-

   butanol (2) and 2-butanol (2) at temperatures T= 303.15, 308.15, and 313.15 K along with the mole fraction are listed in table 2.

   The deviation in viscosity is calculated using the relation

   m (x11 + x2 2) .(2)

   where m, 1, 2, x1, and x2 are viscosity of the liquid mixture, viscosity and mole fractions of pure liquids respectively.

   The deviation in viscosity Y was fitted by the method of non linear least squares to a Redlich-Kister type polynomial[14]

   Y = x1x2 Ai( x1x2)i ….(3)

   In each case, the optimum number of coefficients Ai was determined from an examination of the variation of standard deviation as calculated by:

   (Y) = [ (Yobs Ycal ) / ( n m )] ½ .(4) where n represents the number of experimental points and

   m is the number of coefficients. It is found that for the solution of the fifth degree polynomial, the agreement between the experimental values and the calculated ones is satisfactory. The derived parameters (Ai) and the estimated standard deviation ( for are given in table 3.

   A perusal of table 2 shows that the value of viscosity deviation, are negative over the entire composition range for all the binary liquid mixtures at T=303.15 to 313.15 K and falls in the order and the same has been depicted in the figures 1-3.

   2-But > 1-But > 2-Pro > 1-Pro > 0

   It is well known that alkanols are strongly self associated and the degree of association depending on the factors such as chain length, the position of the OH group, temperature and dilution by other solvents. The strength of H-bonding in alkanols is expected to decrease with increase in their chain length and with the addition of dissimilar molecules which disrupt the H-bonding network. GBL structure is stabilized by dipolar-dipole interactions. Thus, both GBL and alkanols are self-associated liquids; mixing of these solvents leads to

   negative molar volumes VE as reported earlier [15] and positive

   values for the binary mixtures. However, it is observed that

   values are negative for all the systems and become more negative with an increase in chain length. This indicates the presence of dispersion forces [16] which are dominating than dipolar interactions between the mixing components in these mixtures to be more negative.

   It is noticed that many binary liquid mixtures have no simple correlation between the strength of the interactions and the observed properties. Rastogi [17] has suggested that the observed excess property is a combination of an interaction part and a non interaction part. An inter comparison of VE and

   supports the contention of Kaulgud [18] that two properties are determined by different factors ma lead to anomaly in the observed properties.

   The temperature dependence of deviation in viscosity for the binary mixtures of butyrolactone with four alcohols was studied in the temperature interval 303.15 to 313.15 K. The values of are in decreasing trend with increase in temperature indicating that the molecular interactions decreasing with temperature between dissimilar molecules.

4. CONCLUSIONS

This paper reports experimental data for deviation in viscosity () at T = 303.15, 308.15 and 313.15 K for four systems of GBL+1-pro, +2-pro, +1-but, +2-but. The results were analyzed to explain the intermolecular interactions between mixing components. Position of hydroxyl group with alkyl chain length has shown significant effect on thermodynamic properties of the investigated systems. Fair correlations were obtained from calculated deviation in viscosity () using the Redlich-Kister type polynomial equation.

ACKNOWLEDGMENT

We acknowledge the help rendered by Dr. K. Sampath Kumar, Assistant Professor, Department of Applied Statistics, Telangana University, Nizamabad (Telangana, India) in calculating the binary coefficients of polynomial equation of various degrees through non-linear regression analysis.

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   0.3852	0.9424	1.3561	-0.2627
   0.4913	0.9746	1.3054	-0.2875
   0.6003	1.0064	1.2896	-0.2767
   0.7242	1.0418	1.2642	-0.2719
   0.8512	1.0766	1.3084	-0.1967
   0.9776	1.1095	1.4492	-0.0251
   1.0000	1.1141	1.4688	0.0000
   T = 313.15 K
   0.0000	0.8144	1.5120	0.0000
   0.0207	0.8226	1.4995	-0.0096
   0.1409	0.8628	1.3931	-0.0988
   0.2623	0.9015	1.2880	-0.1865
   0.3852	0.9395	1.2354	-0.2215
   0.4913	0.9715	1.2030	-0.2387
   0.6003	1.0033	1.2116	-0.2145
   0.7242	1.0383	1.2080	-0.2003
   0.8512	1.0727	1.2605	-0.1296
   0.9776	1.1054	1.3621	-0.0099
   1.0000	1.1096	1.3688	0.0000
   Butyrolactone (1) + 1-Butanol (2)
   T = 303.15 K
   0.0000	0.8038	2.2973	0.0000
   0.0214	0.8111	2.2053	-0.0770
   0.1441	0.8509	1.8610	-0.3354
   0.2658	0.8914	1.6584	-0.4527
   0.3914	0.9326	1.5190	-0.5041
   0.4966	0.9670	1.4449	-0.5045
   0.6264	1.0085	1.4320	-0.4265
   0.7621	1.0522	1.4582	-0.3052
   0.8728	1.0865	1.4930	-0.1928
   0.9824	1.1152	1.5761	-0.0329
   1.0000	1.1203	1.5967	0.0000
   T = 308.15 K
   0.0000	0.7991	2.0147	0.0000
   0.0214	0.8070	1.9230	-0.0800
   0.1441	0.8464	1.6487	-0.2873
   0.2658	0.8866	1.4701	-0.3995
   0.3914	0.9276	1.3627	-0.4383
   0.4966	0.9622	1.3031	-0.4405
   0.6264	1.0026	1.2857	-0.3871
   0.7621	1.0455	1.3373	-0.2614
   0.8728	1.0785	1.3912	-0.1471
   0.9824	1.1095	1.4446	-0.0338
   1.0000	1.1141	1.4688	0.0000
   T = 313.15 K
   0.0000	0.7959	1.7924	0.0000
   0.0214	0.8026	1.7267	-0.0566
   0.1441	0.8420	1.5054	-0.2259
   0.2658	0.8837	1.3851	-0.2947
   0.3914	0.9256	1.2746	-0.3520
   0.4966	0.9596	1.2313	-0.3508
   0.6264	0.9984	1.2487	-0.2784
   0.7621	1.0364	1.2663	-0.2033
   0.8728	1.0699	1.3268	-0.0959
   0.9824	1.1043	1.3596	-0.0167
   1.0000	1.1096	1.3688	0.0000
   Butyrolactone (1) + 2-Propanol (2)
   T = 303.15 K
   0.0000	0.7913	1.8492	0.0000
   0.0222	0.7988	1.7758	-0.0678
   0.1463	0.8412	1.5588	-0.2534
   0.2695	0.8829	1.4318	-0.3493
   0.3947	0.9251	1.3518	-0.3978
   0.4999	0.9600	1.3147	-0.4083
   0.6003	0.9930	1.3049	-0.3928
   0.7253	1.0335/p>	1.3277	-0.3384
   0.8510	1.0735	1.4170	-0.2174
   0.9758	1.1128	1.5504	-0.0525
   1.0000	1.1203	1.5967	0.0000
   T = 308.15 K
   0.0000	0.7857	1.5831	0.0000

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TABLE I

# values at T=298.15 K

TABLE II

TABLE III

Figure 1: Variation of deviation in viscosity () vs mole fraction for the binary mixtures of butyrolactone (1) + ; 1-propanol (2), ; 2-propanol (2),

; 1-butanol (2) and ; 2-butanol (2) at 303.15 K.

Figure 2: Variation of deviation in viscosity () vs mole fraction for the binary mixtures of butyrolactone (1) + ; 1-propanol (2), ; 2-propanol (2),

; 1-butanol (2) and ; 2-butanol (2) at 308.15 K.

Figure 3: Variation of deviation in viscosity () vs mole fraction for the binary mixtures of butyrolactone (1) + ; 1-propanol (2), ; 2-propanol (2),

; 1-butanol (2) and ; 2-butanol (2) at 313.15 K.