Study of Excess Properties of Binary and Ternary Mixtures of Trichloroethene, Ethanoic Acid, and N,N-Dimethylformamide at Different Temperatures

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1 Regular Article PHYSICAL CHMISTRY RSARCH Published by the Iranian Cheical Society Phys. Che. Res., Vol. 7, No. 2, , June 2019 OI: /pcr Study of xcess Properties of Binary and Ternary Mixtures of Trichloroethene, thanoic Acid, and N,N-iethylforaide at ifferent Teperatures H. Zarei a, *, M. Oidi a and M. Behroozi b a epartent of Physical Cheistry, Faculty of Cheistry, Bu-Ali Sina University, Haedan, Iran b epartent of Cheistry, Faculty of Science, University of Zanjan, Zanjan, Iran (Received 7 January 2019, Accepted 22 February 2019) ensity, viscosity, and refractive index easureents were perfored for a ternary ixture of trichloroethene + ethanoic acid + N,Ndiethylforaide and their binary ixtures in the whole coposition range. ensity data were obtained within the teperature range K and viscosity and refractive index data were easured at K. xcess olar volues, viscosity deviations, and refractive index deviations were calculated fro the experiental data. The V values for the ternary ixture and also for the two binary ixtures of trichloroethene (1) + N,N-diethylforaide (3), and ethanoic acid (2) + N,N-diethylforaide (3) were negative and becae ore negative by increasing the teperature. For the trichloroethene (1) + ethanoic acid (2) ixture, the values were positive and becae ore positive with rising teperature. An inverse trend was observed for viscosity deviations of the ixtures. The refractive index deviations were positive for all the ixtures. The experiental data for the binary and ternary ixtures were correlated with Redlich- Kister, and Cibulka equations, respectively. Keywords: ensity, Viscosity, Refractive index, Ternary ixture INTROUCTION Molecular interactions between the liquid ixture constituents lead to special behavior in real solutions. These solutions have attracted the attention of any researchers fro therodynaic point of view. The study of excess properties can offer helpful inforation about the particular interactions and acroscopic behavior of fluid ixtures. In fact, the nature of olecular interactions can be understood fro the data. In addition, these data are iportant in industrial process designing and also to test theories of solution. Many studies have been done in this field on the binary and ternary ixtures [1-10]. Soe studies have been reported for excess properties of binary and ternary ixtures containing trichloroethene or N,N-diethylforaide (MF) with polar and non-polar solvents [1,9,11-18]. In this paper, ternary ixture of *Corresponding author. -ail: zareih@basu.ac.ir (trichloroethene + ethanoic acid + N,N-diethylforaide) and their binary ixtures have been selected in order to study the excess properties. The selected cheicals are very iportant industrially. N,N-diethylforaide and trichloroethene are coon industrial solvents and ethanoic acid is an iportant cheical reagent, so, their ixture and the study of their interactions can be helpful in order to use the ost adequate solvent in the industrial process. The densities ρ, for the ixtures have been easured over a wide range of coposition at teperatures fro K. Viscosities, η, and refractive index, n, easureents were carried out for the ixtures at K. The excess olar volues and deviation properties (viscosity and refractive index deviations) were calculated fro the experiental data. xcess olar volues and deviations of viscosity for ethanoic acid + MF binary ixture were copared with the obtained values at K in the literature [18]. The agreeents between the experiental data and their

2 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Table 1. Nae, Purity Grade, Supplier, CAS Nuber, ensity ρ, and Refractive Index n 25, of the Pure Coponents at K. Coponent Purity CAS ρ n (ass fraction) Supplier nuber (kg -3 ) xpt. Lit. xpt. Lit. Trichloroethene > Merck a d N,N-diethylforaide > 99.5 Merck b e thanoic acid > 99.8 Merck c c Standard uncertainties u are u(ρ) = 0.05 kg -3 and u(n ) = a Ref. [14]. b Ref. [21]. c Ref. [22]. d Ref. [23]. e Ref. [24]. corresponding literature values were good. For correlation of the experiental data for the binary and ternary ixtures Redlich-Kister [19] and Cibulka [20] equations were eployed, respectively. XPRIMNTAL Materials High-purity grade organic liquids, trichloroethene (> ass%), ethanoic acid (> 99.8 ass%) and MF (> 99.5 ass%), were supplied fro Merck. The sources of the substances and their purity grades are given in Table 1. The cheicals were used without further purification. The densities and refractive indices of the pure substances were easured and copared with the corresponding literature values [14,21-24]. Good agreeent was observed between the experiental and literature values as reported in Table 1. Apparatus and Procedure The binary and ternary ixtures were prepared in dark airtight stopper bottles gravietrically by a Mettler AB 204- N balance with an uncertainty of kg. The uncertainty in the ole fraction was estiated to be less than The density of the saples was easured with an Anton Paar digital vibrating u-tube densieter (odel MA 4500) with an uncertainty of 0.05 kg -3 whose cell teperature was controlled with an uncertainty of 0.01 K, with a solid-state therostat. The density easureents were perfored at T = (293.15, and ) K. The viscosity of pure coponents and ixtures was easured by Ubbelohde viscoeter with an uncertainty of Pa s at K. Water and 1-butanol were used for calibration of the viscoeter and an electronic digital stopwatch was used for flow tie easureents with readability of 0.01 s. Refractive index easureents were perfored at K with an Abbé refractoeter with an uncertainty of RSULTS AN ISCUSSION xperients The densities, ρ, viscosities, η, and refractive index, n, easureents were done for the binary and ternary ixtures of trichloroethene, ethanoic acid and N,Ndiethylforaide. The following equations were applied to calculate the excess olar volues, V, viscosity deviations,, and deviation of refractive index, n, fro the experiental data. Uncertainty in deterination of was ol -1. V / 3 n ol x M ( ), i 1 i i i V (1) n Y Y Y i x ), (2) i ( i where is the density of the ixture and x i, M i, i are ole 348

3 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June fraction, olecular ass, and the density of coponent i, respectively. Y in the second equation represents η or n. The results are given in Tables 2-5 and represented graphically in Figs The values of V and η, for the binary ixture of ethanoic acid (2) + diethylforaide (3) were copared with the literature values [18] at K and represented in Figs. 1c and 3a. The agreeent between the was good. The values of the excess olar volues, V, are positive for trichloroethene (1) + ethanoic acid (2) binary ixture (Fig. 1a) with a axiu around x and becoe ore positive with increasing teperature over the entire range of coposition and at T = (293.15, and ) K. Negative trend was observed for trichloroethene (1) + MF (3) and ethanoic acid (2) + MF (3) ixtures with a iniu around x over the whole coposition range and teperatures and becae ore negative by increasing the teperature (Figs. 1b, c). Ternary ixture of trichloroethene (1) + ethanoic acid (2) + MF (3) show negative values for V (Fig. 2) and becoe ore negative with rising teperature. As can be seen fro Tables 3 and 5, the values of η are positive for trichloroethene (1) + ethanoic acid (2) + MF (3) ternary ixture and also for binary ixtures of trichloroethene and ethanoic acid with MF. Negative values are observed for viscosity deviations ixture trichloroethene (1) + ethanoic acide (2) over the entire range of ole fractions at K. Graphical representations of the binary and ternary ixtures are given in Fig. 3a and Fig. 4, respectively. The viscosity deviations are functions of interactions as well as size and shape of olecules [7]. Refractive index deviation, Δn, was positive for ternary ixture of trichloroethene (1) + ethanoic acid (2) + MF (3) and the three binary ixtures (Tables 3 and 5). Graphical representations of Δn for the binary and ternary ixtures are given in Figs. 3b and Fig. 5, respectively. The observed V values are resultant fro the Table 2. ensities, ρ, and xcess Molar Volues, V, for Binary Mixtures at Teperature Range ( ) K x 1 ρ 10-3 V 10 6 ρ 10-3 V 10 6 ρ 10-3 V 10 6 (kg -3 ) ( 3 ol -1 ) (kg -3 ) ( 3 ol -1 ) (kg -3 ) ( 3 ol -1 ) Trichloroethene (1) + ethanoic acid (2) T = K T = K T = K

4 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Table 2. Continued Trichloroethene (1) + diethylforaide (3) T = K T = K T = K thanoic acid (2) + diethylforaide (3) T = K T = K T = K Standard uncertainties ( u) are u(ρ) = 0.05 kg -3 and u(t) = 0.01 K and the cobined expanded uncertainty (U c ) are U c (x) = and U c ( V ) = ol -1 (0.95 level of confidence). 350

5 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Table 3. Viscosities, η, Refractive Index, n, eviation of Viscosities Δη, and eviation of Refractive Index, n, of Binary Mixtures at Teperature K x η n Δη n (Pa s) (Pa s) Trichloroethene (1) + ethanoic acid (2) Trichloroethene (1) + N,N-diethyl foraide (3)

6 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Table 3. Continued thanoic acid (2) + N,N-diethyl foraide (3) Standard uncertainties ( u) are u(ρ) = 0.05 kg -3, u(t) = 0.01 K and u(n ) = and the cobined expanded uncertainties (U c ) are U c (x) = and U c (η) = Pa s (0.95 level of confidence). Table 4. ensities, ρ, and xcess Molar Volue, (3)} Ternary Mixture at ifferent Teperatures ( ) V, of {Trichloroethene (1) + thanoic Acid (2)+ iethylforaide ρ 10-3 V 10 6 ρ 10-3 V 10 6 ρ 10-3 V 10 6 x 1 x 2 (kg -3 ) ( 3 ol -1 ) (kg -3 ) ( 3 ol -1 ) (kg -3 ) ( 3 ol -1 ) T = K T = K T = K

7 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Table 4. Continued Standard uncertainties ( u) are u(ρ) = 0.05 kg -3 and u(t) = 0.01 K and the cobined expanded uncertainties (U c ) are U c (x) = and U c ( V ) = ol -1 (0.95 level of confidence). 353

8 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Table 5. Viscosities, η, eviation of Viscosities, Δη, Refractive Index, Refractive Index, n, of Ternary Mixture at K n, and eviation of x 1 x 2 η Δη n n (Pa s) (Pa s) Trichloroethene (1) + ethanoic acid (2) + N,N-diethylforaide (3)

9 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Table 5. Continued Standard uncertainties (u) are u(ρ) = 0.05 kg -3, u(t) = 0.01 K and u(n ) = and the cobined expanded uncertainties (U c ) are U c (x) = and U c (η) = Pa s (0.95 level of confidence). copetition between the two positive and negative contributions to V. Trichloroethene is an unassociated and polar liquid having a dipole oent of µ= 0.8 [13], and ethanoic acid is self-associated through hydrogen bonding because of the presence of electron donor and electron acceptor sites [25]. MF is also highly polar solvent having a dipole oent of µ = 3.24 [21]. uring the ixing of trichloroethene, MF and ethanoic acid with each other, the dissociation of self-associated ethanoic acid occurs and provides a positive contribution to V. In addition, disruption of the dipolar order in the coponents has a positive effect. The polar interactions between unlike olecules, donor-acceptor interactions, or the foration a new H-bonded olecular coplex in the binary ixtures have a negative contribution to V. The ixing of trichloroethene with ethanoic acid leads to positive V values. In this process, dissociation of self-associated ethanoic acid by trichloroethene olecules is a doinant contribution. The ixing of trichloroethene and ethanoic acid with MF leads to contraction in volue and provides a negative contribution tov. The study results show that polar interactions between unlike olecules are doinant contributions for the systes except for trichloroethene (1) + ethanoic acid (2) binary ixture where is in an agreeent with the η values. The negative η values are attributed to the predoinance of the dispersion forces [7]. Correlations Redlich-Kister polynoial [19] was applied to correlate the experiental data of excess olar volues, viscosity deviations, and refractive index deviation for the binary ixtures: k i Y x (1 x ) A i (1 2x ), (3) 1 1 i 0 1 where Y = (V, Δη or Δn ), x 1 is the ole fraction of coponent 1, and k is the degree of the polynoial expansion. Teperature dependence of the fitting paraeters for the excess olar volues is expressed by the following equation. 355

10 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Fig. 1. xcess olar volues, V, of binary ixtures at different teperatures:, K;, K;, K;, ref. 18 at K, for: (a) trichloroethylene (1) + ethanoic acid (2); (b) trichloroethene (1) + diethylforaide (3); (c) ethanoic acid (2) + diethylforaide (3). The solid lines represent the values calculated fro teperature dependent Redlich-Kister equation. 356

11 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Fig. 2. xcess olar volues, V, of ternary ixture of {trichloroethene (1) + ethanoic acid (2) + N,N diethylforaide (3)} at K. represents the experiental points. Curves represent the values calculated fro Cibulka equation. The unit in the triangle plot is ole fraction. A i 2 j 0 B T ij j, (4) nuber of adjustable paraeters in q. (3). Cibulka equation [20] was applied to correlate the experiental data (V, Δη and Δn ) of the ternary ixture. The adjustable teperature and independent paraeters, B ij, are derived by the least squares ethod and are reported in Tables 6 and 7 along with the standard deviations defined as: 1/ 2 n 2 ( Yexp Ycal ) /( n p), (5) i 1 where n is the nuber of experiental points, and p is the Y Y Y Y x x x B B x B (6) x2 For excess olar volue, every B p ternary paraeter is a function of teperature as expressed in q. (4). Tables 6 and 7 report the adjustable paraeters along with the standard deviation, σ. 357

12 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Fig. 3. (a) Viscosity deviations, η, and (b) deviation of refractive index, η, of binary ixtures at K; for:, trichloroethene (1) + ethanoic acid (2);, trichloroethene (1) + diethylforaide (3);, ref. 18 at K,,ethanoic acid (2) + diethylforaide (3). CONCLUSIONS xcess olar volues of trichloroethene (1) + ethanoic acid (2) + MF (3) ternary ixture and their binary ixtures were deterined fro density easureents over the entire range of coposition at different teperatures. Viscosity and refractive index deviations were obtained fro the viscosity and refractive index easureents at K. All the experiental data were fitted to the Redlich Kister and Cibulka equations for binary and ternary ixtures, respectively. The values of the ternary and binary ixtures of trichloroethene and ethanoic acid with MF were negative and becae ore negative with increasing teperature. Positive values were observed for trichloroethene (1) + ethanoic acid (2) ixture and becae ore positive with increasing teperature. The results interpreted in ters of copetition between two positive and negative effects. Positive effect is due to dissociation of self-associated coponent and also disruption of the dipolar order in the coponents. Negative effect is due to polar interactions between unlike olecules, donor-acceptor interactions, or the foration of a new H-bonded olecular coplex in the ixtures. Viscosity deviation values were positive for the ternary ixture and their binary ixtures except for trichloroethene (1) + ethanoic acide (2) ixture over the entire range of ole fractions. Positive trend was observed for deviation in refractive index of the ixtures. The trends are in agreeent with the values. ACKNOWLGMNTS The authors would like to thank Bu-Ali Sina University for providing the necessary facilities to carry out the research. 358

13 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Fig. 4. Viscosity deviations, η, of ternary ixture of {trichloroethene (1) + ethanoic acid (2) + N,N-diethylforaide (3)} at K. represents the experiental points. Curves represent the values calculated fro Cibulka equation. The unit in the triangle plot is ole fraction. Table 6. Coefficients, A ij, of quations (3)-(6) for the Binary and Ternary Systes along with the Standard eviations,, for the Fits of the xcess Molar Volues over the Teperature Range ( ) K j i σ (c 3 ol -1 ) Trichloroethene (1) + ethanoic acid (2)

14 Zarei et al./phys. Che. Res., Vol. 7, No. 2, , June Table 6. Continued Trichloroethene (1) + N,N-diethylforaide (3) thanoic acid (2) + N,N-diethylforaide (3) Trichloroethene (1) + ethanoic acid (2) + N,N-diethylforaide (3) Table 7. The Paraeters of quations (3)-(6) and Standard eviation for the Fits of Viscosity and Refractive Index eviations for the Binary and Ternary Mixtures at K B 0 B 1 B 2 B 3 B 4 σ Trichloroethene (1) + ethanoic acid (2) Δη (Pa s) n Trichloroethene (1) + N,N-diethylforaide (3) Δη (Pa s)

15 Study of xcess Properties of Binary and Ternary Mixtures/Phys. Che. Res., Vol. 7, No. 2, , June Table 7. Continued n thanoic acid (2) +N,N-diethylforaide (3) Δη (Pa s) n Trichloroethene (1) + ethanoic acid (2) + N,N-diethylforaide (3) Δη (Pa s) n x Acetic acid Trichloroethylene MF n Fig. 5. Refractive index deviations, n, of ternary ixture of {trichloroethene (1) + ethanoic acid (2) + N,N-diethyl- foraide (3)} at K. represents the experiental points. Curves represent the values calculated fro Cibulka equation. The unit in the triangle plot is ole fraction. 361

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