J. Chem.

Thermodynamics 43 (2011) 15831590

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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Application of ERAS-model and PrigogineFloryPatterson theory to excess molar volumes for ternary mixtures of (2-chlorobutane + butylacetate + isobutanol) at T = 298.15 K
K. Khanlarzadeh, H. Iloukhani
Department of Physical Chemistry, Faculty of Chemistry, University of Bu-Ali Sina, Hamedan, Iran

a r t i c l e

i n f o

a b s t r a c t
Densities of the ternary mixture consisting of {2-chlorobutane (1) + butylacetate (2) + isobutanol (3)} and related binary mixtures were measured over the whole range of composition at T = 298.15 K and ambient pressure. Excess molar volumes V E for the mixtures were derived and correlated as a function of mole m fraction by using the RedlichKister and the Cibulka equations for binary and ternary mixtures, respectively. From the experimental data, partial molar volumes, V m;i excess partial molar volumes, V E partial i molar volumes at innite dilution V 0 and apparent molar volumes V u;i were also calculated. For all binm;i E ary mixtures over the entire range of mole fractions V m data are positive. The experimental results of the constituted binary mixtures have been used to test the applicability of the extended real associated solution (ERAS-model) and PrigogineFloryPaterson (PFP) theory. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 14 December 2010 Received in revised form 4 May 2011 Accepted 11 May 2011 Available online 18 May 2011 Keywords: 2-Chlorobutane Butylacetate Isobutanol Excess molar volume PFP theory ERAS-model

1. Introduction This paper is a continuation of our earlier work related to the study of thermodynamic properties of binary and ternary mixtures [14]. Study of room temperature polar liquids (RTPLs) as solvents have received an increasing attention in the last years from fundamental and applied points of view. As for thermodynamics of RTPLs in solution with other compounds, there are many experimental and theoretical studies which deal on the behavior of thermodynamic properties of mixtures of RTPL + common organic solvent. However, due to the enormous number of possible binary systems, a lot of work remains to be done. Polar compounds present good solubility with other liquids. Therefore, there are several works that study the thermodynamic properties of polar compound extensively studied due to its importance for supercritical extraction [57]. Esters are one of the best candidates that exist as dipolar associates in their pure liquid state, available with not only aliphatic, aromatic and even acrylic nature but also with a variety of general structures with molecular formulas, R(CH2)u1COOR0 where u = 1, 2, 3, 4, 5, 7, . . . , 11, 13, R = H, CnH2n +1 (n = 1, 2, 3, 4, 5, 6, . . . , 8) and R0 = CH3 or CnH2n +1 (n = 1, 2, 3, 4, . . . , 6). The excess molar enthalpies excess molar volumes, of (alkyl alkanoates + n-alkanes) were reported to study the effects due to variations in the length of R or R0 . On the other hand, much effort in
Corresponding author. Tel./fax: +98 811 8282807.
E-mail address: iloukhani@basu.ac.ir (H. Iloukhani). 0021-9614/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2011.05.017

this eld has been devoted to the study of (RTPLs + alcohol) binary mixtures, mainly motivated by their solubility with RTPLs as well as their low environmental impact. Besides, investigation of the thermo-physical properties of esters, due to their widespread use in industrial processes has increased. Esters are used in avoring, perfuming, articial essences, cosmetics, and also they are important solvents in pharmaceutical, paint, and plastic industries. The thermodynamic properties of RTPLs with other polar compounds have been studied in some extent, especially volumetric properties, but there are few works that study their thermodynamic behavior considering ERAS-model or PrigogineFloryPatterson theory. The present work analyzes the excess molar volumes, partial molar volumes V m;i excess partial molar volumes, V E partial molar i volumes at innite dilution V 0 and apparent molar volumes V u;i m;i of ternary and constituted binary mixtures of 2-chlorobutane, butylacetate, and isobutanol by means of the ERAS-model [8] and PFP theory [911]. The RTPLs were selected in order to be able to study the effect of changing the chemical structure of the cation and/or the anion on thermodynamic properties. The derived properties provide valuable information for qualitatively analyzing the molecular interactions between molecules. In fact the excess functions of binary and ternary mixtures are complex properties because they depend not only on solutesolute, solventsolvent and solutesolvent interactions, but also of the structural effects arising from interstitial accommodations. So these are very important from theoretical points of view, to understand liquid theory. Esters, haloalkanes, and alkanols, and their binary mixtures nd

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K. Khanlarzadeh, H. Iloukhani / J. Chem. Thermodynamics 43 (2011) 15831590 TABLE 1 Experimental and literature values of densities, q, and refractive indices, nD of pure components at T = 298.15 K. Compound

applications as solvent in chemistry and modern technology. The excess quantities of binary mixtures have been tted to the RedlichKister equation to determine the coefcients. For correlating the ternary data, the Cibulka equation was used. As far as we know, no data are available for the mixtures investigated in the open literature. 2. Experimental

q/(g cm3)
Exp. Lit.a 0.86710 0.87636 0.79780 0.86721 0.87620 0.79784

nD Exp. 1.3999 1.3919 1.3939 Lit.a 1.4001 1.3918 1.3939

2-Chlorobutane Butylacetate Isobutanol

a

Reference [12].

2.1. Materials 2-Chlorobutane (w > 0.99), butylacetate (w > 0.99), isobutanol (w > 0.99), where w is mass fraction were purchased from Merck and used without further purications. The experimental densities and refractive indices of the pure materials are presented at T = 298.15 K in table 1 along with the corresponding literature values [12]. Compounds were stored in brown glass bottles and fractionally distilled immediately before use. 2.2. Apparatus and procedure The density of the compounds and their binary and ternary mixtures were measured with an Anton Paar digital densimeter (Model DMA-4500), operated in the static mode and the uncertainty of the density measurement was estimated to be within 1 105 g cm3. The temperature in the cell was regulated to 0.01 K with solid-state thermostat. The apparatus was calibrated once a day with dry air and double-distilled freshly degassed water. Airtight stoppered bottles were used for the preparation of the mixtures. The mass of the dry bottle was rst determined. The less volatile component of the mixture was introduced in the bottle, and the total mass was recorded. Subsequently, the other component was introduced, and the mass of bottle along with the two components was determined. Ternary mixtures were prepared by mixing of three components. A total of 40 compositions were measured at T = 298.15 K for the ternary system of {2-chlorobutane (1) + butylacetate (2) + isobutanol (3)}. Each mixtures was immediately used after it was well-mixed by shaking. All the weightings were performed on an electronic balance (AB 204-N Mettler) accurate to 0.1 mg. The uncertainty in the mole fraction is estimated to be lower than 2 104. 3. Results and discussion 3.1. Binary mixtures Excess molar volumes for all mixtures were calculated from density results at T = 298.15 K and at ambient pressure using the following equation: where x is the mole fraction of solvent, Ai are adjustable parameters obtained by tting, and N is the degree of the polynomials. The results are given in table 3 together with corresponding standard deviations. For none of the systems does the precision warrant the use of more than three parameters. In each case, the optimum number of coefcients was ascertained from an examination of the variation of the standard deviation r, with

 2 31=2 E E X V m;exp V m;cal 7 r6 4 5 ; np

VE m

N X i1

xi M i q1 q1 ; i

where q is the density of the mixture, qi, is the density of pure component, xi, is the mole fraction, Mi, is the molar mass of component i, and N stands for the number of components in the mixture. The excess molar volumes uncertainties are estimated to 1 103 cm3 mol1. The corresponding V E , values of binary mixm tures at T = 298.15 K are presented in table 2 and plotted against mole fraction x, in gure 1. The experimental results for all binary mixtures were tted by the least squares method with all points weighted equally to RedlichKister polynomial equation [13]:

E where V E m;exp and V m;cal are the experimental and calculated values of the excess molar volumes, respectively, and n and p are the number of experimental points and number of parameters retained in the respective equations. V E is the results contribution from several opposing effects. m These effects may be divided arbitrarily into three types, namely, the physical, chemical, and structural. Physical contributions, that is, nonspecic interactions between the real species present in the mixture, contributes a positive term to V E . The chemical or m specic intermolecular interactions results in a volume decrease and these effects include charge-transfer type forces and other complex-forming interactions. This effect contributes to the negative values to V E . The structural contributions are mostly the} negm ative and arise from several effects, especially from interstitial accommodation and changes of free volume}. Excess molar volume of for all binary mixtures containing (2chlorobutane + butylacetate), (2-chlorobutane + isobutanol), and (+butylacetate + isobutanol) are positive over the whole range of mole fractions. Positive values would indicate that molecular interactions between different molecules are weaker than interactions between molecules in the same pure liquid and that repulsive forces dominate the behavior of the solutions. For (2-chlorobutane + isobutanol) and (butylacetate + isobutanol), intensity attractive interactions between unlike species decrease because of breaking H-bonding and repulsive interactions predominate, leading to positive excess molar volumes values. The specic interactions of alkyl acetate with alcohols can be visualized due to presence of ion pair of electrons on the oxygen atom of alkyl acetate on account of which it can act as a strong proton-acceptor from the alkanol. Further these system are also an ideal choice to examine ideal associated solution models with Florys interaction term to predict and analyze theoretically the excess molar volume [1417]. The partial molar volumes, V m;i were evaluated using the following equation [18]:

V m;i V E V 1 xi @V E =@xi T;P m m;i m

V E x1 x m

N X k0

Ai 1 2xk ;

where V is pure molar volumes of component i. The excess partial m;i molar volumes V E V 1 V and V E V 2 V from V E and the 1 2 1 2 m molar volumes of the pure components are also calculated. The values of partial molar volumes and the excess partial molar volumes

K. Khanlarzadeh, H. Iloukhani / J. Chem. Thermodynamics 43 (2011) 15831590

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TABLE 2 Densities, q, excess molar volumes, V E , partial molar volumes, V m;i , excess partial molar volumes, V E , and apparent molar volumes, V u;i , for binary mixtures at T = 298.15 K. m i x

q/(g cm3)
0.87620 0.87555 0.87483 0.87420 0.87336 0.87280 0.87220 0.87170 0.87094 0.87027 0.86965 0.86919 0.86860 0.86819 0.86773 0.86721 0.79782 0.80182 0.80577 0.81351 0.81967 0.82701 0.83153 0.83612 0.83979 0.84508 0.84959 0.85354 0.85633 0.85977 0.86205 0.86455 0.86721 0.79782 0.80241 0.80612 0.81270 0.81903 0.82820 0.83234 0.83896 0.84514 0.85107 0.85558 0.86157 0.86579 0.87067 0.87620

V E =cm3 mol m 0.000 0.011 0.024 0.034 0.047 0.053 0.058 0.060 0.058 0.052 0.044 0.037 0.027 0.019 0.010 0.000 0.000 0.068 0.127 0.218 0.268 0.307 0.320 0.321 0.313 0.296 0.263 0.225 0.191 0.143 0.104 0.057 0.000 0.000 0.217 0.372 0.599 0.765 0.912 0.946 0.953 0.913 0.830 0.738 0.578 0.438 0.249 0.000

V m;1 /(cm3 mol1) 106.87 106.87 106.86 106.85 106.84 106.83 106.82 106.81 106.79 106.78 106.77 106.77 106.76 106.76 106.76 106.76 108.04 107.87 107.72 107.47 107.30 107.13 107.04 106.97 106.92 106.86 106.82 106.79 106.78 106.77 106.76 106.76 106.76 136.52 136.06 135.71 135.13 134.64 134.01 133.77 133.43 133.16 132.96 132.83 132.70 132.64 132.59 132.57

V m;2 /(cm3 mol1)

V E /(cm3 mol1) 1

V E /(cm3 mol1) 2 0.000 0.001 0.002 0.004 0.014 0.024 0.039 0.053 0.079 0.105 0.128 0.144 0.161 0.169 0.175 0.174 0.000 0.004 0.016 0.057 0.107 0.191 0.260 0.344 0.426 0.572 0.724 0.883 1.011 1.191 1.322 1.478 1.658 0.000 0.014 0.046 0.146 0.293 0.590 0.758 1.069 1.409 1.782 2.098 2.561 2.918 3.364 3.914

Vu,1/(cm3 mol1)

Vu,2/(cm3 mol1)

0.0000 0.0787 0.1618 0.2330 0.3250 0.3861 0.4512 0.5060 0.5902 0.6656 0.7352 0.7862 0.8516 0.8961 0.9458 1.0000 0.0000 0.0579 0.1152 0.2274 0.3166 0.4235 0.4896 0.5564 0.6097 0.6872 0.7523 0.8090 0.8487 0.8975 0.9293 0.9638 1.0000 0.0000 0.0589 0.1065 0.1907 0.2720 0.3894 0.4427 0.5277 0.6070 0.6829 0.7405 0.8166 0.8700 0.9312 1.0000

2-Chlorobutane + butylacetate 132.57 0.114 132.57 0.109 132.57 0.101 132.58 0.093 132.59 0.080 132.60 0.070 132.61 0.060 132.63 0.051 132.65 0.038 132.68 0.027 132.70 0.018 132.72 0.012 132.73 0.006 132.74 0.003 132.75 0.001 132.75 0.000 2-Chlorobutane + isobutanol 92.90 1.280 92.91 1.116 92.92 0.967 92.96 0.712 93.01 0.541 93.09 0.371 93.16 0.284 93.25 0.210 93.33 0.159 93.47 0.099 93.63 0.061 93.79 0.035 93.91 0.022 94.09 0.010 94.23 0.005 94.38 0.001 94.56 0.000 Butylacetate + isobutanol 92.90 3.952 92.92 3.489 92.95 3.137 93.05 2.562 93.20 2.064 93.49 1.442 93.66 1.198 93.97 0.857 94.31 0.591 94.69 0.383 95.00 0.256 95.46 0.127 95.82 0.064 96.27 0.018 96.82 0.000

104.97 104.96 104.96 104.96 104.96 104.97 104.98 105.00 105.02 105.04 105.05 105.07 105.08 105.09 105.10

99.56 99.55 99.53 99.51 99.49 99.47 99.45 99.44 99.42 99.40 99.39 99.38 99.38 99.37 99.38

103.93 104.00 104.14 104.25 104.38 104.45 104.53 104.59 104.67 104.75 104.82 104.88 104.94 104.99 105.04 105.10

99.56 99.49 99.41 99.28 99.17 99.02 98.93 98.83 98.76 98.61 98.50 98.38 98.29 98.16 98.08 97.99

128.88 129.08 129.43 129.76 130.23 130.44 130.77 131.07 131.36 131.58 131.87 132.07 132.30 132.57

92.90 92.67 92.49 92.16 91.85 91.41 91.21 90.89 90.58 90.29 90.06 89.75 89.53 89.28

are presented in table 2 and latter were plotted against mole fraction in gures 2 and 3. The partial molar volumes, V 0 at innite dilution appear to be m;j of particular interest. In the limit of innite dilution, solutesolute interactions disappear. Thus the values of the partial molar volumes at innite dilution provide insight into solutesolvent interactions. Setting x = 0 and x = 1, respectively, in equation (4) leads to:

V u;i V 0 V E =xi ; i m

where V 0 is molar volume of the pure component. The values of i apparent molar volumes are also reported in table 2. 3.2. Ternary mixtures Excess molar volumes for ternary mixtures of {2-chlorobutane (1) + butylacetate (2) + isobutanol (3)} at T = 298.15 K were calculated using equation (1) and the results were listed in table 5 and graphically shown in gure 4. The excess molar volumes for the ternary system were correlated using the Cibulka equation [20]:

V0 j

V j

X
i0

Ai 1

{+1 for j = 1 and 1 for j = 2}. All partial molar volumes at innite dilution were calculated using the RedlichKister coefcient, Ai, in equation (5) listed in table 4. Apparent molar volumes, Vu,i which may be more convenient and accurate can be calculated as followings [19]:

DQ 123 DQ bin x1 x2 x3 D123

and

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K. Khanlarzadeh, H. Iloukhani / J. Chem. Thermodynamics 43 (2011) 15831590

vmE /(cm3 . mol-1)

vm,2E / (cm3. mol-1)

x
FIGURE 1. Excess molar volumes, V E at T = 298.15 K for the binary systems: () {2m chlorobutane (1) + butylacetate (2)}, (N) {2-chlorobutane (1) + isobutanol (3)}, () {butylacetate (2) + isobutanol (3)}. x1 is the mole fraction of the rst component in each binary. Solid line calculated with RedlichKister equation.

FIGURE 3. Excess partial molar volumes, V E m;2 at T = 298.15 K for the binary systems: () {2-chlorobutane (1) + butylacetate (2)}, (N) {2-chlorobutane (1) + isobutanol (3)}, () {butylacetate (2) + isobutanol (3)}. x1 is the mole fraction of the rst component in each binary system.

TABLE 3 Coefcients of RedlichKister equation, Ai and standard deviations, r for binary mixtures at T = 298.15 K. System A0 (cm mol 2-Chlorobutane + butylacetate 2-Chlorobutane + isobutanol Butylacetate + isobutanol 0.236 1.276 3.827
3

TABLE 4 The partial molar volumes at innite dilution V 0 of the binary mixtures at m;i T = 298.15 K. System 2-Chlorobutane + butylacetate 2-Chlorobutane + isobutanol Butylacetate + isobutanol
1  V 0 =cm3 mol m;1 1  V 0 =cm3 mol m;2

A1
1

A2

) 0.092 0.193 0.106 0.0005 0.0015 0.0004

106.87 108.04 136.52

132.75 94.56 96.82

0.03 0.189 0.019

D123 B0 B1 x1 B2 x2 :

vm,1E /(cm3. mol-1)

The ternary parameters, B0, B1, and B2, were determined with the optimization algorithm similar to that for the binary parameters. The tting parameters and the corresponding standard deviations are given in table 6. Excess molar volumes for studied ternary system were also predicted using four geometrical solution models [2124]. These models use binary contributions evaluated by RedlichKister equation. 1. JacobFitzner Model [21]

V E V E x1 x2 =x1 x3 =2x2 x3 =2V E x1 x3 = 123 12 13 x1 x2 =2x3 x2 =2 V E x1 x3 = 23 x2 x1 =2x3 x1 =2:

2. Kohler Model [22]

10

V E V E x1 x2 2 V E x1 x3 2 V E x2 x3 2 : 123 12 13 23
x
FIGURE 2. Excess partial molar volumes, V E m;1 at T = 298.15 K for the binary systems: () {2-chlorobutane (1) + butylacetate (2)}, (N) {2-chlorobutane (1) + isobutanol (3)}, () {butylacetate (2) + isobutanol (3)}. x1 is the mole fraction of the rst component in each binary system.
3 3 XX i1 j>i

11

3. Rastogi Model [23]

V E V E x1 x2 V E x1 x3 V E x2 x3 =2: 123 12 13 23
4. Radojkovic Model [24]

12

DQ bin

DQ ij ;

VE VE VE VE : 123 12 13 23

13

where DQ123 refers to V E for the ternary system and m x3 = 1 x1 x2. DQij in equation (8) is the binary contribution of each ij pair to the V E given by equation (2) with the parameters m of Ai, reported in table 3. The ternary contribution term D123 was correlated using the expression suggested by Cibulka:

Standard deviations presented in table 7, were determined for all models as:

v u n 1 uX E S t V 123 expi V E cali 2 : 123 n i1

14

K. Khanlarzadeh, H. Iloukhani / J. Chem. Thermodynamics 43 (2011) 15831590 TABLE 5 Experimental densities, q and excess molar volumes, V E for the ternary mixture of {2m chlorobutane (1) + butylacetate (2) + isobutanol (3)} at T = 298.15 K. x1 0.0506 0.0577 0.0628 0.0751 0.0756 0.0699 0.0601 0.0584 0.0547 0.1028 0.1115 0.1260 0.1313 0.1434 0.2218 0.2412 0.2612 0.2770 0.2495 0.2293 0.5385 0.7449 0.5630 0.5164 0.4555 0.4002 0.4558 0.4431 0.4784 0.5051 0.4624 0.4390 0.5525 0.6282 0.6605 0.6900 0.7740 0.8649 0.9176 x2 0.0526 0.1739 0.3414 0.5398 0.8665 0.6048 0.3798 0.2121 0.0658 0.0327 0.1775 0.3440 0.5533 0.7953 0.1750 0.3457 0.5462 0.6672 0.4439 0.2587 0.2722 0.0721 0.2974 0.3852 0.4357 0.5463 0.0291 0.1752 0.3456 0.4407 0.2556 0.1004 0.1758 0.3219 0.1782 0.2565 0.1755 0.0316 0.0329

1587

q/(g cm3)
0.80556 0.81574 0.82938 0.84588 0.87160 0.85058 0.83219 0.81883 0.80691 0.80767 0.82003 0.83437 0.85113 0.87069 0.82787 0.84297 0.85981 0.86987 0.85120 0.83520 0.85773 0.85531 0.86125 0.86469 0.86447 0.86890 0.83165 0.84345 0.85932 0.86792 0.85130 0.83682 0.85100 0.86713 0.85851 0.86634 0.86580 0.86014 0.86419

V E /(cm3 mol1) m 0.224 0.529 0.755 0.733 0.110 0.686 0.783 0.600 0.264 0.196 0.508 0.659 0.590 0.129 0.445 0.491 0.330 0.124 0.443 0.493 0.183 0.196 0.144 0.133 0.158 0.118 0.340 0.315 0.197 0.107 0.266 0.333 0.236 0.081 0.142 0.067 0.045 0.141 0.0492

Ternary predictions using the JacobFitzner [21], Kohler [22] Rastogi [23], and Radojkovic [24] models show good agreement with experimental data for this system. Although this standard deviation is beyond to experimental error, both models present the advantage of using exclusively binary data, which are easily available in the literature. 4. The theoretical models 4.1. PFP theory The PrigogineFloryPatterson (PFP) theory [911] has been commonly employed to analyze excess thermodynamic properties. This theory has been used to interpreting the results of measurements of the excess properties of a number of binary systems formed by molecular species which differ in size and shape. Although in the development of the theory hydrogen bonds and interactions of strong electrostatic nature are specically excluded, a purely empirical application of the Flory formalism can still provide an interesting correlation between the excess molar volumes of more complex mixtures. In fact, and despite the ionic character of the PL systems, the use of Flory-type theories has proven successful in predicting and modeling both the excess properties and uid-phase behavior of PL-containing mixtures [25,26].The PFP theory considers a molecule to be made up of equal segments (isomeric portions), specied by the effective number. Each segment has intermolecular contact sites capable of interacting with neighboring sites. According to the PFP theory, V E calculations inm clude three contributions: (i) interactional, which is proportional to the (v12) parameters; (ii) the free volume contribution which arises from the dependence of the reduced volume upon the reduced temperature as a result of the difference between the degree of expansion of the two components, and (iii) the (P) contribution, which depends both on the differences of internal pressures and differences of reduced volumes of the components. The V E was calm culated by means of the PFP theory using the following equation with the three contributions.

butylacetate
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.2 0.1 0.1 0.3 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.8 0.7 0.6 0.5 0.4 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.08 0.3 0.2 0.05 0.1 0.0 1.0

isobutanol

0.0

2-chlorobutane

FIGURE 4. Isolines at constant excess molar volume V E for ternary mixtures of {2-chlorobutane (1) + butylacetate (2) + isobutanol (3)} correlated by Cibulka equation. m

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TABLE 6 Ternary coefcients of Cibulka equation, Bi for V E and standard deviations, r, at T = 298.15 K. m System 2-Chlorobutane + butylacetate + isobutanol B0 4.7443 B1 1.9767 B2 2.2710

r/(cm3 mol1)
0.018

TABLE 7 Standard deviation, S=V E in the prediction of V E with m m different models for the ternary mixture at T = 298.15 K. Model JacobFitzner Kohler Rastogi Radojkovic S (V E /(cm3 mol1) m 0.03 0.04 0.02 0.02

TABLE 8 Parameters of pure components used in Flory theory. Reduction parameters for pressure, P molar hard core volumes, V reduction parameters for temperature, T at T = 298.15 K. Component 2-Chlorobutane Butylacetate Isobutanol P/(J cm3) 494.694 513.001 436.253 V/(cm3 mol1) 81.583 105.313 70.997 T/K 4450.39 5045.43 5296.04

V E =x1 V x2 V m 1 2

~ ~ V 1=3 1V 2=3 W1 h2 v12 ~ 1=3 1=P 4=3V

1

~ ~ ~ V 1 V 2 2 14=9V 1=3 1W1 W2 ~ 1=3 1V ~ 4=3V 15

VmE/(cm 3.mol -1)

~ ~ V 1 V 2 P P W1 W2 1 2 : P W2 P W1 1 2

~ The V of the solution is obtained through the Florys theory. The characteristic parameters Vand P are obtained from thermal expansion coefcient ai, and isothermal compressibility, bT. The thermal expansion coefcient ai, is used to calculate the reduced volume by equation:

e V i 1 4=3ai T=1 ai T3 :
Here, the molecular contact energy fraction is calculated by:

16
x

W1 u1 P =u1 P u2 P 1 1 2
with the hard-core volume fractions dened by:

17

u1 x1 V =x1 V x2 V : 1 1 2

18

FIGURE 5. Excess molar volumes V E at T = 298.15 K for the binary systems: () m {2-chlorobutane (1) + butylacetate (2)}, (N) {2-chlorobutane (1) + isobutanol (3)}, () {butylacetate (2) + isobutanol (3)}. x1 is the mole fraction of the rst component in each binary. Solid line calculated with PFP theory.

The values of pure parameters for the pure liquid components and the mixture are obtained by Flory theory. The pure compounds and the mixtures parameters values obtained by Flory theory are showed in table 8. The values of thermal expansion coefcient ai, and isothermal compressibility bT, for the pure components were obtained from the literature. In order to obtain V E it is necessary to nd the interm actional parameter, v12, which was obtained by tting the theory E to experimental values of V m for each one of the binary system. Table 9 presents the calculated equimolar values of the three contributions to V E according to equation, together with the interm actional parameter, v12. An analysis of each of the three contributions to V E shows that, the interactional contribution is always m positive in all binary mixtures; this contribution seems important to explain the V E behavior for system studied. The free volume efm fect is negative and it seems to have little signicance for the system studied. Figure 5 shows the excess molar values predicted by PFP theory for binary systems.

4.2. ERAS-model The ERAS-model [8] has been utilized to interpret quantitatively the thermodynamic properties of mixtures and combines the linear-chain association model with Florys equation of state. The ERAS model was successfully applied to describe simultaneously HE, GE, and VE of (alkanol + alkane) mixtures as well as activity coefcients and apparent molar volumes. The ERAS model, originally developed for (alkanol + alkane) mixtures, has been extended to binary (alkanol + amine/ester) mixtures [27]. The ERAS model has subsequently being successfully applied by many investigators to describe the excess properties of (alkanol + ester) mixtures. The procedure for calculation of reduction parameters and their corresponding values for associated liquids are different than that for non-associated components as originally adopted by Flory and co-workers [5,28]. We have also examined the ERAS-model to analyze the present volumetric properties of three introduced binary

TABLE 9 Calculated values of contributions of the PFP theory. Interactional parameters, System 2-Chlorobutane + butylacetate 2-Chlorobutane + isobutanol Butylacetate + isobutanol

v12 reduction parameters for pressure, P for binary mixtures at T = 298.15 K.

Interactional 0.1689 0.2523 0.9115 Free volume 0.0733 0.1192 0.0105 P 502.895 464.819 472.134

v12 =J cm3
8.5 14.5 52.5

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TABLE 10 Properties and parameters of pure components used in the ERAS-model, thermal expansion coefcients, a, isothermal compressibility, bT self-association constants, KA reduction parameters for volume, V reduction parameters for pressure, P self-association enthalpies, Dh and self-association volume, Dv at T = 298.15 K. Component 2-Chlorobutane Butylacetate Isobutanol 104a/(K1) 13.13 10.69 9.78 104 bT =MPa1 13.55 9.89 10.33 KA 0 0 16.46 V/(cm3 mol1) 81.62 105.07 77.88 P/(J cm3) 495.39 513.13 310.39

Dh/(kJ mol1)
0 0 25.6

Dv/(cm3 mol1)
0 0 5.6

TABLE 11 ERAS-model binary mixture parameters, van der Waals interaction parameters, T = 298.15 K. System 2-Chlorobutane + butylacetate 2-Chlorobutane + isobutanol Butylacetate + isobutanol

v12 cross association constant, KAB cross association volume, Dv and standard deviations, r at
KAB 0 35.05 12.52

v12/(J cm3)
8.52 1.79 2.73

Dv/(cm3 mol1)
0 4.78 2.95

r
0.004 0.005 0.003

systems at T = 298.15 K. The assumption made in frame of the ERAS model includes the self-association of isobutanol and polarity of chloroalkane and butylacetate according to the following reaction scheme:

Am A ! Am1 ; Bn B ! Bn1 ;
KA

KA

Here uA and uB are the stoichiometric hard-core volume fractions of components. The physical contribution V E in ERAS-model is derived from Flop rys equation of state which is assumed to be valid not only for pure components but also for the mixture

19 20

~ 1=3 ~~ V Pi V i 1 1=3i ; ~i ~~ ~ 1 V iTi T Vi

28

where m or n are the degree of self-association, ranging from 1 to 1. The cross-association between A and B molecules are represented by:

Am Bn ! Am Bn :

KAB

21

The association constants Ki (i = A, B, AB) are assumed to be independent of the chain length. Their temperature dependence is given by

~ ~ ~ where i = A, B. In equation (28), V i V i =V ; Pi Pi =P ; T i T i =T i i i are the reduced volume, pressure, and temperature, respectively. All the reduction parameters V i ; P i ; T i of pure components can be determined knowing the experimental data for molar volume V, thermal expansion coefcient a, isothermal compressibility bT , provided suitable association parameters Ki, Dv ; Dhi are known. i The reduction parameters for the mixture PM ; T M and V are calcuM lated from mixing rules [30,31].

K i K 0 expDhi =R1=T 1=T 0 ;

22

P uA P uB P X AB uA hB ; M A B T M
A P A =T M

29 30 31

where K0 is the equilibrium constant at the standard temperature T0 = 298.15 K, R the gas constant and Dhi , enthalpy for the reactions given by equations (26)(30), which corresponds to the hydrogen bonding energy. These reactions are also characterized by the volume change Dv , related to the formation of the linear chains. i The essential property of the ERAS-model is that the excess E function V m is split into a chemical and a physical contribution. The expression for V E of the ERAS-model extended to the twom block approach of cross-association are given by [27,29]

P M ; uB P =T B M

V xA V x B V : M A B

e e e V E xA v xB v V M uA V A uB V B ; p A B V E V E V E; p c

24 25

wherein KA and KB are the equilibrium constants of chain self-asso ciation of alkanol and/or ester, respectively. KAB, and DhAB , are the association constants and hydrogen bond energy from the crossassociation. uA1 and uB1 are the hard core volume fraction of the butylacetate and isobutanol in the mixture, respectively. They have to be calculated numerically from the solution of the following coupled equations.

vmE / (cm3. mol-1)

~ V E V M xA K A Dv uA1 u0 xB K B Dv uB1 u0 xA K AB Dv A A1 B B1 AB c ' uB1 1 K A uA1 ; 23 V B =V A 1 K B uB1 K AB uB1

x
FIGURE 6. Excess molar volumes V E at T = 298.15 K for the binary systems: () m {2-chlorobutane (1) + butylacetate (2)}, (N) {2-chlorobutane (1) + isobutanol (3)}, () {butylacetate (2) + isobutanol (3)}. x1 is the mole fraction of the rst component in each binary. Solid line calculated with ERAS-model.

uA uA1 =1 K AuA1 2 1 V A K ABuB1 =V B 1 K BuB1 ; uB uB1 1 K BuB1 2 1 K ABuA1 =1 K AuA1 :

26 27

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K. Khanlarzadeh, H. Iloukhani / J. Chem. Thermodynamics 43 (2011) 15831590

XAB is an interaction parameter characterizing the difference of dispersive intermolecular interaction between A and B, ui and hi are hard-core volume fraction and the surface fraction of the component i [32]. The mixture parameters appearing in the theoretical expression of excess molar volume are: X AB ; K A ; K B ; K AB ; DhA ; DhB ; DhAB ; Dv A ; Dv B ; Dv AB . All the parameters can be obtained by adjusting them to V E of binary systems. m The properties and parameters as equilibrium constant K, thermal expansion coefcient a, isothermal compressibility bT molar volume Vm characteristic volume V and characteristic pressure P for pure component are listed in table 10 and the ERAS-model parameters for binary mixture are listed in table 11. The results of tting experimental data with ERAS-model are shown in gure 6. The values of calculated V E for all binary mixtures are in good m agreement with experimental data.

Acknowledgments The authors thank the University authorities for providing the necessary facilities to carry out the work. References
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5. Conclusions Excess molar volumes V E of binary and ternary mixtures of {2m chlorobutane (1) + butylacetate (2) + isobutanol (3)} were calculated by using measured densities at T = 298.15 K. The experimental V E of binary systems were tted by RedlichKister polynomial m equation and ternary system results were tted by Cibulka equation. V E for ternary mixtures were also predicted by many empirm ical expressions using data for the corresponding binary mixtures. Excess molar volume of for all binary mixtures containing (2-chlorobutane + butylacetate), (2-chlorobutane + isobutanol), and (+butylacetate + isobutanol) are positive over the whole range of mole fractions. Positive values would indicate that molecular interactions between different molecules are weaker than interactions between molecules in the same pure liquid and that repulsive forces dominate the behavior of the solutions. Excess molar volumes for binary mixtures are described qualitatively for all ranges of mole fractions by the PFP and ERAS-models. The standard deviations between experiment and models are satisfactory for mixtures under study. The ERAS-model parameter calculation is more complex, although suitable for the property representation, as can be observed in gure 6 which show that the ERAS-model is better to reproduce the experimental data rather than PFP theory.

[13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25]

[26] [27] [28] [29] [30] [31] [32]

JCT 10-425