17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

DENSITY AND VISCOSITY OF BINARY 1,4-DIOXANE+ 1-HEXANOL SYSTEM AT 298.15 K

Anca Fedeles1, Oana Ciocirlan1, Olga Iulian1
The densities and dynamic viscosities for the binary 1,4-dioxane+1-hexanol system have been determined at 298.15 K over the whole composition range at atmospheric pressure. The excess molar volumes (V E), viscosity deviations () and excess Gibbs energy of activation of viscous flow (G *E) were calculated from the experimental data and were fitted to the Redlich-Kister type polynomial equation to derive the parameters and estimate the standard deviation values. The experimental results of VE have been used to test the applicability of the Prigogine-FloryPatterson theory of solutions. The resulting excess functions were analyzed in terms of molecular interactions between the components of the mixture.

Keywords: density, viscosity, 1,4-dioxane, 1-hexanol, Prigogine-Flory-Patterson 1. Introduction Mixed solvents, rather than single pure liquids, are of great practical importance in most chemical, industrial and biological processes, as they provide a wide range of mixtures with desired properties. Liquid mixtures frequently appear in chemical research. Most of the mixtures are non-ideal and show peculiar behavior. The interpretation of non-ideality is a fascinating area and a large number of contributions were made over the last decade on this topic. Solution theory is still far from enough to account for solution non-idealities in terms of the constituent molecules properties [1]. The volumetric properties of mixed solvent systems and their dependence on composition find different applications in many important chemical, industrial, and biological processes. The study of functions such as excess molar volume of binary liquid mixtures is useful in understanding the nature and strength of molecular interactions between the component molecules. 1,4-Dioxane is a cyclic ether that has electron-donor ability due to two ion pairs of electrons on each oxygen atom. It is an excellent aprotic solvent having a zero dipole moment and is commercially used in polymerization and other chemical reactions in the cleaning of polymer surfaces and electronic materials
1 Dept. of Applied Physical Chemistry and Electrochemistry, University POLITEHNICA of Bucharest, Romania, e-mail: ancafedeles@yahoo.com

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

[1]. Alcohols are organic liquids that are widely used as the basic organic compound for the syntheses of other chemicals. 1-hexanol is a protic and strongly associated solvent due to H-bonding ability of the OH group, as the hydroxyl group in 1-alkanols possesses one hydrogen bond donor (the H atom) and two acceptors (the two lone pairs of electrons on the oxygen atom) [1]. The study of binary mixtures containing alcohol as one of the components has paid great attention due to a number of factors like (i) self-association of alcohol and (ii) change in the extent and strength of H-bonding in the mixture, which affect the values of their thermodynamic properties, among others, the systematic measurement of volumetric and transport properties of different liquid mixtures [1]. This work represents a continuation of our studies concerning the behavior of binary systems with alkanols [2, 3] and report density and viscosity data for the binary 1,4-dioxane + 1-hexanol system at 298.15 K and atmospheric pressure. To our best knowledge, for this system at temperature of 298.15 K only experimental density data are reported [4] and no viscosity data are available in literature. The excess molar volume (VE), viscosity deviation () and excess Gibbs energy of activation of viscous flow (G*E) were calculated from experimental data. The computed quantities were fitted to the Redlich-Kister type polynomial equation to derive the binary coefficients and estimate the standard deviations between experimental and calculated results. The experimental results of VE have been used to test the applicability of the Prigogine-Flory-Patterson theory of solutions. 2. Experimental 1,4-Dioxane and 1-hexanol (Merck, mole fraction > 0.995) were used without further purification. Experimental density and viscosity of the pure components are in agreement with the literature values, as Table 1 shows.
Table 1 Densities and viscosities of pure components at 298.15 K

Compound 1,4-dioxane 1-hexanol

(g cm-3) experimental literature 1.0279 [1] 1.02793 1.02772 [4] 0.81491 [4] 0.81534 0.81523 [6]

(mPa s) experimental literature 1.187 [1] 1.1988 1.1902 [5] 4.4869 4.4029 [6]

The binary mixtures were prepared by mass on a HR-120 (A&D Japan)

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

electronic balance with a precision of 10-4 g. The experimental uncertainty in mole fraction was estimated to be less than 0.0002. Densities of pure liquid and of mixtures were measured using an Anton Paar DMA 4500 densitometer with precision of 0.00005 g cm-3. The thermostatted sample was controlled to 0.01 K. The dynamic viscosities of mixtures were measured using an Anton Paar automated micro viscosimeter (AMVn), which is based on the rolling ball principle. The temperature is controlled by means of a built-in Peltier thermostat within 0.01 K. Measurements were made with constant angle of 70 using a calibrated capillary with d = 1.6 mm. 3. Results and Discussions On the basis of experimental density and viscosity data, the corresponding excess properties were calculated as follows: Excess molar volumes (VE): V E = X i M i 1 i1

)
(1)

where Xi is the mole fraction of component i of the mixture; is the density of the mixture; Mi, i are the molar mass and density of the pure compounds, respectively. The viscosity deviation ():

= X i i

(2)

where and i are the dynamic viscosity of the mixture, and of the pure component i, respectively. Excess Gibbs energy of activation of viscous flow (G*E): G * E = RT ln( V ) xi ln( Vi i )

]
(3)

where V and Vi are the molar volume of the mixture and of the pure components, respectively. R is the gas constant and T, the absolute temperature. The excess properties data, YE, were correlated with Redlich Kister equation:

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

(4) where Ak are the fitting parameters and p is the degree of polynomial expansion. The standard deviation was defined:
k =0

Y E = X i X j Ak ( X i X j )
p

( Yi exp Yi calc ) 2 = N exp N par (5) where Nexp is the number of experimental data and Npar is the number of parameters. The fitting parameters Ak (Eq. 4) together with the standard deviations (Eq. 5) are gathered in Table 2. It should be noted that for studied system three parameters were necessary for correlation to obtain optimum standard deviation.
0.5

Table 2 Parameters Ak of the fitting equation 4 and standard deviations for 1,4-dioxane + 1-hexanol system at 298.15 K

A0 VE, (cm3mol-1) 1.8954 , (mPa s) -2.7206 G*E, (J mol-1) -2.9513 3 -1 -6 3 (1 cm mol = 10 m mol-1)

A1 -0.1640 6.4704 0.3963

A2 0.1894 -1.8977 -0.6209

0.0033 0.0057 0.0042

As is indicated in Figure 1, the excess molar volume values are positive for 1,4-dioxane + 1-hexanol system at 298.15 K, in agreement with literature data [4]. This behavior indicates that the positive contributions from the breaking up of alcohol agglomerates and ether-ether interaction dominate over the negative contribution resulting from intermolecular interaction. The obtained negative values of the viscosity deviations for this system (Figure 2) probably indicate the prevailing of dispersion forces in this mixture, with compounds of different molecular size. Also, the excess Gibbs energy for viscous flow is negative over the whole composition range (Figure 3). This suggests that breaking up of self-associated structures of the pure compounds is dominant over the interactions between unlike molecules. The VE behavior of 1,4-dioxane + 1-hexanol system can be correlated using the Prigogine-Flory-Patterson (PFP) theory of solutions, which has been widely used to analyze the excess thermodynamic properties for different kinds of liquid mixtures. The PFP theory considers the VE of binary mixtures to be the sum of three contributions: (i) the interactional contribution, which is proportional to the interaction parameter, 12; (ii) the free volume contribution, which arises from

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

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 internal pressure contribution, which depends both on the differences of internal pressures and on the differences of reduced volumes of the components and can be related to the structure-breaking effect on mixing.
0.5 0.4
-1

0 -0.2 -0.4

V E , cm 3 mol

, (mPa s) 0 0.2 0.4 x1 0.6 0.8 1

0.3 0.2 0.1 0

-0.6 -0.8 -1 -1.2 -1.4 0 0.2 0.4 0.6 0.8 1

x1

Fig. 1 Excess molar volume, VE, for 1,4-dioxane(1) +1-hexanol (2) at 298.15 K (); correlation with Redlich Kister equation ()
0 -0.1 -0.2 G*E, kj mol-1 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8 0 0.2 0.4

Fig. 2 Deviation of viscosity, , for 1,4-dioxane(1)+1-hexanol (2) at 298.15 K (); correlation with Redlich Kister equation ()

0.6 x1

0.8

Fig. 3 Excess Gibbs energy of activation of viscous flow, G*E, for 1,4-dioxane(1) + 1-hexanol (2) at 298.15 K (); correlation with Redlich Kister equation ()

In the present study, the following form of the PFP model has been used to correlate VE values:

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

E PFP

(6) ~ vi and ~ are the reduced volume of pure components and mixtures, v where * * respectively, Vi is the characteristic volume, and Pi is the characteristic pressure of pure components; they are obtained from thermal expansion coefficient, , and isothermal compressibility, kT. In Eq. 6, i is the molecular contact energy fraction and 2, the molecular surface fraction. The various characteristic and reduced parameters of pure liquids needed for the VE estimation were calculated by using the expressions given in literature [7-10] and are listed in Table 3. The experimental and calculated VE values using PFP model and three PFP contributions for near equimolar composition at 298.15 K are summarized in Table 4 and suggestively reflected in Figure 4 at 298.15 K. The interactional parameter, 12 , was evaluated by fitting the experimental VE values to Eq. 6 and using the least-squares method over the whole composition range; the obtained values are indicated also in Table 4, together with standard deviation, , calculated using type 5 equation. A perusal of the Table 4 and Figure 4 reveals that the internal pressure contribution is the most significant term, playing a dominant role in deciding the E E sign and magnitude of V values. Free volume contributes negatively to the V PFP values and does not seem to play a dominant role in deciding the sign and magnitude of the excess molar volume. The interactional contribution has positive values; also the interactional parameter, 12 , is positive. In the original PFP
E model, the Vint values are generally positive in the absence of H-bond and other specific interactions. This is indeed the case for 1,4-dioxane + 1-hexanol mixture, as was stated above to the VE analysis.

( ~1 ~2 ) 2 ((14 / 9) ~ 1 / 3 1) 1 2 ( ~1 v2 ) ( P1* P2* ) 1 2 v v v v ~ + ~ P2* 1 + P1* 2 [( 4 / 3) ~ 1 / 3 1] v v

X 1V1* + X 2V2*

= V +V +V
E int E fv

E ip

~ (v 1) ~ v = [( 4 / 3) ~ v
1/ 3

2/3

1 2 12

1 / 3

1 P1*

Table 3 Physico-chemical data of pure components used in PFP theory at 298.15K

K-1
1,40.001095a dioxane 1-hexanol 0.000895a

kT cm3 J-1
0.0007431b 0.000839c

~ vi
1.2653 1.2232

Vi Vi * cm3 mol-1 cm3 mol-1

85.59a 125.32a 67.64 102.45

Pi * J cm-3
698.21 469.50

~ Ti
0.05962 0.05310

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania
a

this work. b ref. 11. c ref. 12.

Table 4 Experimental and calculated VE and three PFP contributions for near equimolar composition at 298.15K
E E E E V fv Vip Vint V PFP cm3 mol-1 cm3 mol-1 cm3 mol-1 cm3 mol-1 cm3 mol-1 0.4800 0.4802 0.1990 -0.0538 0.3350 E Vexp

12 J cm-3
15.77

cm3 mol-1
0.013

0.5 0.4 V E , cm 3mol -1 0.3 0.2 0.1 0.0 -0.1 0.0 0.2 0.4 X1 0.6 0.8 1.0

Fig. 4 Excess molar volumes for 1,4-dioxane (1) + 1-hexanol (2) system at 298.15 K calculated with the PFP theory: interactional contribution (---); free volume contribution ( ); internal pressure contribution ( total excess molar volume predicted by PFP theory ( ); ); experimental results ()

The Prigogine-Flory-Patterson model provide a good description of the excess molar volume in the mixtures where are not presented H-bonds and associations between components, like the studied system in this work. 4. Conclusions Experimental data of densities and dynamic viscosities for the binary systems 1,4-dioxane + 1-hexanol at 298.15 K have been reported. The obtained excess molar volumes are positive, and the viscosity deviations and excess Gibbs energy for viscous flow are negative. This suggests that breaking up of selfassociated structures of the pure compounds is dominant over the interactions between unlike molecules.

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17th Romanian International Conference on Chemistry and Chemical Engineering September 7 10, 2011, Sinaia Romania

In accordance with structural information is the theoretically analysis of excess molar volume. The interactional contribution has positive values, indicating the absence of H-bond and other specific interactions on mixing. E Internal pressure contributes positively to the V PFP values and represents the most significant term in the VE values. The PFP theory has a good performance in correlating the excess molar volumes of mixtures of 1,4-dioxane + 1-hexanol. REFERENCES 1. A. Omrani, A.A. Rostami, M. Mokharty, J. Molec Liquids, 2010, 157, 1824. 2. A. Fedeles, O. Ciocirlan, O.Iulian, UPB Sci. Bull. series B, 2009, 71 (4), 100-106 3. O. Ciocirlan, A. Fedeles, O.Iulian, Rev. Roum. Chim., 2010, 55 (9), 579-584. 4. E. Calvo, P. Brocos, A.l Pineiro, M. Pintos, A. Amigo, R. Bravo, A. H. Roux, G. Roux-Desgranges, J. Chem. Eng. Data 1999, 44, 948-954. 5. O. Iulian, C. Stoicescu, O. Ciocirlan, Rev. Roum. Chim., 2006, 51(7-8), 811817. 6. A.S. Al-Jimaz, J.A. Al-Kandary, A.-H. M. Abdul-Latif, Fluid Phase Equilibria, 2004, 218, 247-260. 7. P.J. Flory, J. Am. Chem. Soc., 1965, 87, 1833 1838. 8. A. Abe, P.J. Flory, J. Am. Chem. Soc., 1965, 87, 1838 1846. 9. D. Paterson, G. Delmas, Disc. Faraday Soc., 1970, 49, 1970, 98-105. 10. I. Prigogine, A. Ballemans, V. Mathot, Molecular Theory of Solutions, North-Holland, Amsterdam, 1957 11. C.M. Romero, C. Guzman, I. Gascon, P. Cea, M.C. Lopez, Int. J. Thermophys., 2006, 27 (3), 760-776. 12. A. Ali, A.K. Nain, Abida, J. Chinese Chem Soc., 2004, 51, 477-485.

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