J. Chem. Thermodynamics 35 (2003) 11291137 www.elsevier.

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Densities, viscosities, and refractive indexes for {C2H5CO2(CH2)2CH3 + C6H13OH + C6H6} at T 308:15 K
Herminio Casas, Sandra Garca-Garabal, Luisa Segade, *, Carlos Franjo, Eulogio Jimnez e Oscar Cabeza
Departamento de Fsica, Facultade de Ciencias, Universidade da Coru~a, Campus da Zapateira, n 15071 A Coru~a, Spain n Received 22 November 2002; accepted 10 March 2003

Abstract In this work we present densities, kinematic viscosities, and refractive indexes of the ternary system {C2 H5 CO2 CH2 2 CH3 C6 H13 OH C6 H6 } and the corresponding binary mixtures {C2 H5 CO2 CH2 2 CH3 C6 H6 }, {C2 H5 CO2 CH2 2 CH3 C6 H13 OH}, and {C6 H13 OHC6 H6 }. All data have been measured at T 308:15 K and atmospheric pressure over the whole composition range. The excess molar volumes, dynamic viscosity deviations, and changes of the refractive index on mixing were calculated from experimental measurements. The results for binary mixtures were tted to a polynomial relationship to estimate the coecients and standard deviations. The Cibulka equation has been used to correlate the experimental values of ternary mixtures. Also, the experimental values obtained for the ternary mixture were used to test the empirical methods of Kohler, Jacob and Fitzner, Colinet, Tsao and Smith, Toop, Scatchard et al., and Hillert. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semiempirical relations of GrunbergNissan, McAllister, Auslnder, and TejaRice. Finally, the a experimental refractive indexes were compared with the predicted results for the LorentzLorenz, GladstoneDale, Wiener, Heller, and AragoBiot equations. In all cases, we give the standard deviation between the experimental data and that calculated with the above named relations. 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Density; Refractive index; Viscosity; Excess properties; Ternary mixture

Corresponding author. Fax: +34-981-167065. E-mail address: oscabe@udc.es (O. Cabeza).

0021-9614/03/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0021-9614(03)00081-8

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1. Introduction In a previous paper [1], we have reported experimental excess molar volumes, dynamic viscosity deviations, and changes of refractive index on mixing of {C2 H5 CO2 CH2 2 CH3 C6 H13 OH C6 H6 }, and of their corresponding binary mixtures at T 298:15 K. In the present paper, we continue with the investigation of this ternary system but at T 308:15 K. This paper and the previous one complete the study of excess volumes of nonelectrolyte ternary mixtures with six carbon atoms started previously [24]. Cibulkas equation [5] has been used to correlate the experimental values of ternary mixtures. Those experimental values were used to test the empirical methods of Kohler [6], Jacob and Fitzner [7], Colinet [8], Tsao and Smith [9], Toop [10], Scatchard et al. [11], and Hillert [12]. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semiempirical relations of GrunbergNissan [13], McAllister [14], Auslnder [15], and TejaRice [16]. Finally, the experimental rea fractive indexes were compared with the predicted results for the LorentzLorenz, GladstoneDale, Wiener, Heller, and AragoBiot equations, which were compiled by Tasic et al. [17].

2. Experimental The chemicals employed were supplied by Fluka. Their mole-fraction purities were C2 H5 CO2 CH2 2 CH3 > 0:99, C6 H13 OH > 0:99, and C6 H6 > 0:995. The substances were degassed by ultrasound and dried over molecular sieves (Sigma Union Carbide, type 0.4 nm). Excess molar volumes were determined from the densities of the pure liquids and mixtures. Densities were measured with an AntonPaar DMA 60/602 densimeter thermostated at T 308:15 0:01 K in a Haake F3 circulating-water bath. The accuracy of the measured densities is around 102 kg m3 . Immediately prior to each series of measurements, distilled water and heptane were used to calibrate the densimeter. Kinematic viscosities were measured by means of SchottGerte automatic a viscometer with an accuracy of 5 1010 m2 s1 . The refractive indexes were measured with a thermostated automatic refractometer Atago RX-1000 with reproducibility in the refractive index data of 104 . Finally, mixtures were prepared in all cases by mass using a Mettler AT 201 balance. The precision of the mole fraction is estimated to be better than 104 .

3. Results and discussion The measured densities, dynamic viscosities (obtained from the measured kinematic viscosities and densities), and refractive indexes of the pure liquids at T 298:15 K are listed in reference [1] together with published values when available.

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The agreement between both sets of data indicates that the compounds used were pure and that our experimental equipment has a good accuracy. E The excess molar volumes Vm , dynamic viscosity deviations Dg, and changes in the refractive index on mixing Dn were computed using equations (1) to (3), respectively,
E Vm N X i1

xi Mi q1 q1 ; i
N X i1 N X i1

Dg g

x i gi ;

Dn g

x i ni :

In these equations q, g, and n are, respectively, the density, dynamic viscosity, and refractive index in the mixture. The qi , gi , and ni are the properties of the pure components, and N is the number of the components in the mixture (so N 2 in the case of a binary mixture and N 3 for a ternary one). The derived excess functions of the binary systems can be represented by a RedlichKister type equation [18], m X K AK xi xj ; 4 QE xi xj ij
K0

TABLE 1 Coecients AK and BK of equations (4) and (6) and standard deviations, s A0
E 106 Vm =m3 mol1 103 Dg=Pa s 103 Dn

A1

A2

A3

A4

A5

A6

s 0.0011 0.004 0.03 0.0012 0.0004 0.11 0.0012 0.007 0.15 s 0.005 0.011 0.15

fx C2 H5 CO2 CH2 2 CH3 1 x C6 H13 OHg 0.933 )0.052 0.153 )3.858 2.221 )1.776 0.9349 )4.00 )0.58 0.23 fx C2 H5 CO2 CH2 2 CH3 1 x C6 H6 g )0.217 )0.064 0.061 )0.0792 0.0209 )0.0429 )45.9 11.8 4.6 )16.7 )14.4 1.358 )3.265 )36.3 fx C6 H13 OH 1 x C6 H6 g )0.669 0.186 0.132 )0.7560 )0.1051 10.3 )2.7 B1 B2 B3

E 106 Vm =m3 mol1 3 10 Dg=Pa s 103 Dn

36.7

E 106 Vm =m3 mol1 103 Dg=Pa s 103 Dn

)0.338 )0.474 0.865

fx1 C2 H5 CO2 CH2 2 CH3 x2 C6 H13 OH 1 x1 x2 C6 H6 g E )0.545 2.392 )2.642 106 Vm;123 =m3 mol1 1.849 0.6731 2.113 103 Dg123 =Pa s 103 Dn123 18.1 8.7 )13.5

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E where QE represents any of the following properties, Vm , or Dg, or Dn; xi and xj are ij the mole fractions of components i and j, respectively; and AK denotes the polynomial coecients. The degree of the polynomial RedlichKister equation was optimised by applying the F test [19]. In table 1, we give the tted coecients AK for equation (4) and the standard deviation, s, dened by, )1=2 ( M X 2 . Ycal Yexp M 1 ; 5 s i1

where M is the number of data points, Ycal is the calculated value, and Yexp is the experimental value. E Figures 1(a) to (c) show, respectively, the experimental Vm , Dg, and Dn plotted E against x together with the tted curves. The Vm is negative for {propylpropanoate +

E FIGURE 1. (a) Excess molar volumes Vm , (b) dynamic viscosity deviations Dg, and (c) changes in the refractive index on mixing Dn at T 308:15 K plotted against mole fraction x of: s, {xC2 H5 CO2 CH2 2 CH3 1 x C6 H6 }; , {xC2 H5 CO2 CH2 2 CH3 1 x C6 H13 OH}; D, {xC6 H13 OH 1 x C6 H6 }.

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benzene} and positive for the other systems, similar in shape and amplitude than for T 298:15 K [1]. The slightly negative value observed may be interpreted as proof of some weak intermolecular interactions established between the carbonyl group of propyl propanoate and the hydrogen atoms of the benzenic ring. This kind of interaction cannot be created between the OH group of 1-hexanol and benzene due to the E steric eect of the long hexanyl chain, which results in positive Vm . In a previous E work [20], there are reported Vm for {C6 H6 C6 H13 OH} at T 298:15 K and T 308:15 K. Their results are very similar to ours both in shape and absolute value. Results for Dg, given in gure 1(b), show negative curves for the three binary mixtures. The absolute value of Dg is lower in around a 30% respecting those presented before at T 298:15 K for all binary mixtures [1]. Respecting Dn, presented in gure 1(c), the data present the same shape and nearly the same amplitude for all three binary mixtures than at T 298:15 K. In conclusion, the eect of temperature is only E important for Dg, and not for Dn and Vm . Table 2 shows the parameters calculated and the standard deviations between experimental values obtained for dynamic viscosity and the predicted results using the semi-empirical relations of GrunbergNissan [13], McAllister [14], Auslnder [15], a and TejaRice [16]. The values of critical temperature and critical volume for pure components, needed for the TejaRice relationship, were obtained from reference [21]. As observed, the best accuracy is given for the Auslnder relationship. a Table 3 compares the experimental refractive indexes for binary mixtures with the predicted results for the LorentzLorenz, GladstoneDale, AragoBiot, Heller, and Wiener equations, which were compiled by Tasic et al. [17]. As in that paper, the LorentzLorenz relationship is the most suitable for our data.

TABLE 2 Parameters for the semiempirical relations of GrunbergNissan [13], McAllister [14], Auslnder [15], and a TejaRice [16] and standard deviations, s System GrunbergNissan McAllister Auslnder a TejaRice GrunbergNissan McAllister Auslnder a TejaRice GrunbergNissan McAllister Auslnder a TejaRice fx C2 H5 CO2 CH2 2 CH3 1 x C6 H13 OHg dw 1:3855 g21 1:0903 g12 0:7235 B12 3:1844 B21 0:0820 A21 0:7186 a12 0:0474 fx C2 H5 CO2 CH2 2 CH3 1 x C6 H6 g dw 0:1520 g21 0:4818 g12 0:5659 B12 1:1414 B21 7:1632 A21 0:1835 a12 0:8482 fx C6 H13 OH 1 x C6 H6 g dw 0:5121 g12 1:7373 B12 0:1523 a12 0:5029 g21 0:6530 B21 1:4048 0.05 0.012 0.009 0.04 s=mPa s 0.03 0.018 0.012 0.05 0.017 0.016 0.016 0.017

A21 1:7648

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TABLE 3 Standard deviations of the experimental refractive index results from the predicted for the LorentzLorenz (LL), GladstoneDale (GD), AragoBiot (AB), Heller (H), and Wiener (W) equations System fx C2 H5 CO2 CH2 2 CH3 1 x C6 H13 OHg fx C2 H5 CO2 CH2 2 CH3 1 x C6 H6 g fx C6 H13 OH 1 x C6 H6 g LL 0.0002 0.0003 0.0003 GD 0.0001 0.0010 0.0009 AB 0.0014 0.0013 0.0017 H 0.0004 0.0003 0.0016 W 0.0004 0.0006 0.0018

E The experimental excess molar volumes Vm;123 , dynamic viscosity deviations Dg123 , and changes of refractive index on mixing Dn123 for ternary mixtures were obtained using equations (1) to (3), respectively. The Cibulka equation [5] has been used to correlate the experimental properties of the ternary mixtures.

QE QE x1 x2 1 x1 x2 B1 B2 x1 B3 x2 ; 123 bin

E FIGURE 2. Curves of constant (a) 106 Vm;123 =m3 mol1 ), (b) 103 Dg123 =Pa s, and (c) Dn123 , for {x1 C2 H5 CO2 CH2 2 CH3 x2 C6 H13 OH 1 x1 x2 C6 H6 } at T 308:15 K.

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where QE QE QE QE : bin 12 13 23 7
E The symbol QE represents Vm;123 , Dg123 or Dn123 , and QE is given by equation (4). 123 ij The parameters BK for equation (6) and the corresponding standard deviations, s, dened by equation (5), are given in table 1. The lines of constant ternary excess properties, calculated by equations (6) and (7), are shown in gures 2(a) to (c) for E Vm;123 , Dg123 , or Dn123 , respectively. Figures 3(a)(c) shows lines of constant ternary contribution, which represent the dierence between the experimental value and that predicted from the binary mixtures (QE QE ). Inside the triangular diagrams 123 bin exist maxima and/or minima, whose coordinates are presented in table 4.

E E FIGURE 3. Curves of ternary contribution (a) 106 Vm;123 Vm;bin =m3 mol1 ), (b) 103 Dg123 Dgbin =Pa s, and (c) (Dn123 Dnbin ) for {x1 C2 H5 CO2 CH2 2 CH3 x2 C6 H13 OH 1 x1 x2 C6 H6 } at T 308:15 K.

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TABLE 4 Maxima and minima for ternary contributions of the mixture: {x1 C2 H5 CO2 (CH2 )2 CH3 + x2 C6 H13 OH + (1 ) x1 ) x2 ) C6 H6 } Value 10
6

Coordinates x1 x1 x1 x1 0:67 0:19 0:32 0:40 x2 x2 x2 x2 0:12 0:53 0:38 0:27

E Vm;123

VE =m3 bin

mol

103 Dg123 Dgbin =Pa s Dn123 Dnbin

Maximum 0.0125 Minimum )0.0420 Maximum 0.105 Maximum 0.0006

E Finally, values of Vm;123 , Dg123 , and Dn123 have been also calculated using the empirical equations proposed by Kohler [6], Jacob and Fitzner [7], Colinet [8], Tsao Smith [9], Toop [10], Scatchard et al. [11], and Hillert [12], which take only the binary contribution into account. For the asymmetric methods (TsaoSmith, Toop, Scatchard, and Hillert), we must indicate the order of components in the mixtures. Table 5 shows the standard deviations, s, between experimental and predicted values. The most accurate predictions correspond to those of Toop, Scatchard, and Hillert.

TABLE 5 Standard deviations s of dierent models for: (a) {x1 C2 H5 CO2 (CH2 )2 CH3 + x2 C6 H13 OH + (1 ) x1 ) x2 ) C6 H6 }; (b) {x1 C6 H13 OH + x2 C6 H6 + (1 ) x1 ) x2 ) C2 H5 CO2 (CH2 )2 CH3 }; (c) {x1 C6 H6 + x2 C2 H5 CO2 (CH2 )2 CH3 + (1 ) x1 ) x2 ) C6 H13 OH} a Jacob and Fitzner Kohler Colinet Tsao and Smith Toop Scatchard Hillert Jacob and Fitzner Kohler Colinet Tsao and Smith Toop Scatchard Hillert Jacob and Fitzner Kohler Colinet Tsao and Smith Toop Scatchard Hillert 10 0.012 0.018 0.015 0.057 0.021 0.016 0.017
6

b
E Vm;123 ,

c
1

s=m mol

0.024 0.028 0.027 0.027

0.033 0.007 0.008 0.007

103 Dg123 , s=Pa s 0.0620 0.0790 0.0758 0.2484 0.0159 0.1342 0.0158 0.1339 0.0157 0.1339 0.0157 Dn123 , s 0.0004 0.0005 0.0004 0.0017 0.0007 0.0006 0.0006

0.2432 0.0924 0.0782 0.0916

0.0020 0.0006 0.0005 0.0006

0.0002 0.0002 0.0002 0.0002

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