Excess molar volumes of mixtures containing methyl alkanoates (acetate, propanoate, and butanoate) with normal alkanols (from

ethanol to pentan-1-01)
Cdtedra de Termodindrnica y Fisicoquimica, Escuela Superior de Itlgetlieros Industriales, Po!,.rechnic University of Canarias, 35071-Las Palmas, Spain Received November 21, 1988

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J . ORTEGA P. SUSIAL. and Can. J. Chem. 67, 1 120 (1989). Measurements of uE for binary mixtures of C,,,H2,,, 1COZCH3(m = 1, 2, 3) + C,,H2,,+ I (OH) (n = 2, 3, 4, 5) are reported. + The results have been determined by using the densities obtained in a vibrating tube densimeter at 298.15 K, they are positive for all these systems. The data have also been compared with available literature values with a discussion on these mixtures. Key words: excess molar mixtures, methyl alkanoates, normal alkanols
J. ORTEGA P. SUSIAL. et Can. J. Chem. 67, 1120 (1989). (tn I(OH) (n = 2, 3, On rapporte des mesures de u" pour des melanges binaires de C,,,H2,,,+IC02CH3 = 1, 2, 3) + C,,H2n+ 4,5). On a determine les rtsultats, i 298,15 K, h I'aide d'un densimttre i tube vibrant et ils sont positifs pour tous les systemes. On a aussi compart les rtsultats ainsi obtenus avec ceux disponibles dans la litttrature et on prksente une discussion concernant ces melanges. Mots elks : mtlanges molaires en excts, alcanoates de mtthyle, alcanols normaux. [Traduit par la revue]

Introduction With a view to extending our previous study (1) of the binary systems methyl alkanoates with normal alkanols from hexan1-01 to decan-1-01, we report here the excess molar volumes of a further twelve systems formed by the same methyl esters and four other normal alkanols, from ethanol to pentan-1-01, Although the u E of the systems involving alkyl esters + methanol were presented in several reports (2-4), we later decided to undertake a separate study since these mixtures present a net effect of volume contraction, giving negative u E values. The presence of methanol causes some type of specific interaction for several reasons, two of which are singled out for mention: on the one hand, the formation of hydrogen bridges and, on the other, the better interstitial accommodation of the small molecules of methanol among the molecules of the ester. The determination of other physico-chemical magnitudes will help to verify accurately this behaviour. After the presentation of data, an analysis will be made of the effects caused by the increase in chain length of the ester and the n-alkanol on the u E , verifying the indications made in other works. Theoretical and experimental interest has increased in recent years in the thermodynamic properties of liquid mixtures containing associated compounds. The majority of the theoretical models, generally based on a rigid lattice concept, are not suitable for the prediction of volumetric properties such as u E . Thus, the model of Nitta et al. (5) permits the prediction of several properties of pure compounds and mixtures, simultaneously, including u E , and confirming that, an increase in the predictive capacity of a model causes a decrease in the capacity of representation or reproduction of experimental data. Therefore, the Nitta model does not offer a good prediction of u E for mixtures. However, in recent years, Heintz (6) and Treszczanowicz and Benson (7) in particular have developed other models with specific applications to systems involving alkanols + alkanes that allow g E , h E , and u E to be calculated simultaneously. Their extension to another type of systems requires previous knowledge of a large number of experimental
Printed in Canada 1 ImprimC au Canada

data that confirm the models developed. This necessity arises when applying any of the models chosen.

Experimental
All the products employed were of the best quality commercially available (Fluka AG). The characteristics of the methyl esters have been reported previously (1). The normal alkanols, and likewise the esters, were used without further purification; however, prior to use, they were degassed with ultrasound and dried with a molecular sieve, type 4A by Fluka. After this treatment and to verify the purity of components used, the physical properties n~ and p were determined at 298.15 K, with comparable literature values shown in Table 1. Refractive indices of pure components were measured with a Bausch and Lomb refractometer with an accuracy of :0.0001 unit. All measurements were made for a wavelength of 5893 A for the sodium-D line, having been checked with pure water at 298.15 K. Measurements of densities for pure components and their mixtures were made with a DMA-55 densimeter (Anton Paar, Graz, Austria) with a reproductibility of 20.01 kg m-3 and calibrated with doubly distilled and degassed wter, p(298.15 K) = 997.04 kg m-3, and n-nonane (Fluka 74252 purum), p(298.15 K) = 71 3.85 kg m-3. The densities of water and n-nonane offer a wide interval and are much closer to those of the majority of organic products, which recommends their joint use as substances for calibration purposes. Both the digital densimeter and the refractometer were thermostated by a Heto Birdkerod ultrathermostat which controlled the temperature within 2 0.01 K using a precision thermometer Anton Paar DT-100, whose performance was checked in accordance with the IPTS-68 norms. All the mixtures were prepared by weighing in hermetically sealed 2.5 cm3 glass vials, injecting the products with a hypodermic syringe to avoid evaporation. The mole fractions were calculated with an imprecision smaller than 5 x From the densities, pi, and molar masses, M i , of the pure liquids ( i = 1 for methyl alkanoates, 2 for n-alkanols) and the density p of the mixture, the molar excess volumes are given by

where x is the mole fraction of methyl alkanoate. The results for uE are estimated to be accurate to better than

ORTEGA AND SUSIAL

TABLE Physical properties p and n, of pure normal alkanols obtained experimentally 1. at 298.15 K and their comparison with literature data m-3) Compound Ethanol, C2HS(OH) This work 785.05 Literature 785.09 (8) 784.93 (9) 785.1 (10) 799.75 (8) 799.60 (9) 799.5 (10) 806.0 (8) 805.75 (9) 805.9 (10) 811.2 (8) 810.8 (9) 810.9 (10) This work nu Literature

Propan-1-01, C3H7(OH)

799.65

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Butan-1-01, C4H9(OH)

805.97

Pentan- 1-01, CSH1(OH) I

810.84

I
I

+0.001 cm3 mol-I. The accuracy of the technique described was checked by measuring the uEdata for the test binary mixture benzene + cyclohexane at 298.15 K and the results agree satisfactorily with those of other authors.

Results and discussion

The excess molar volumes of the twelve systems studied are summarized in Table 2. The said results can be satisfactorily represented by a fitting equation, such as

where x is the mole fraction of the methyl ester. Table 3 shows the A, coefficients determined by a least-squares method and the standard deviations, s(uE), of the fits. With these values and those of k, the curves in Fig. 1 could be plotted for all the systems studied. The best values of k were achieved upon optimizing the corresponding correlation of the set of values of each system, bearing in mind that k will always have positive values since, if k < 0 , the term between brackets in eq. [2] will present a discontinuity in x = k/(l + k). Of the twelve systems studied, data have only been found in the literature for methyl propanoate + ethanol (1 1). Although the representation of these data are qualitatively rather similar, quantitatively there exists a difference, at x = 0.5, between our data and those reported in ref. 11 of -0.02 cm3 mol-'. We attribute this to the major imprecision of their picnometric technique in measurements of small excess volumes. The same effects on the volumetric behaviour of these systems, already described in earlier papers (1-4), can be observed in the curves plotted in Fig. 1. On the one hand, the negative effect on uE due to the increase in the chain of the methyl ester and, on the other, the quasi-linear increase of uE with the increase in length of the n-alkanol chain, when interacting with any one ester. This latter effect can be noted perfectly upon plotting uE, at x = 0.5, for the binary systems methyl alkanoate + C,H2,+ ,(OH) as a function of n. However, the proportionality indicated is clear for values of n > 4,

FIG. 1. Representation of the oE curves using eq. [I] for the binary systems indicated by the pair (m, n): {xHZm+ ICmC02CH3 = 1, 2, (m 3) + (1 - x)C,H2,+ ,(OH) (n = 2, 3 , 4 , 5)). The dash line indicates the curve obtained by Polak and Lu ( I I ) for the system (2,2).

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ORTEGA A N D SUSIAL

xH7C3C02CH3 ( 1 + 0.18787 0.0433 0.22619 0.0499 0.25509 0.0542 0.28302 0.0585 0.32556 0.0635 0.35422 0.0667

x)C2H5(OH) 0.39000 0.0704 0.43279 0.0726 0.48455 0.0750 0.52167 0.0761 0.56486 0.0758 0.62215 0.0739

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xH7C3C02CH3+ (1 - x)C3H7(0H) 0.17160 0.0952 0.38310 0.1511 0.19786 0.1071 0.41368 0.1545 0.22768 0.1168 0.51115 0.1579 0.27002 0.1285 0.521 19 0.1578 0.30497 0.1368 0.63730 0.1485 0.1455 0.34919 0.72277 0.1301 xH7C3C02CH3+ (1 - x)C4H9(OH) 0.23954 0.1521 0.46678 0.2016 0.27228 0.1661 0.50757 0.2048 0.30130 0.1750 0.54929 0.2039 0.34732 0.1869 0.57957 0.1996 0.38454 0.195 1 0.63429 0.1898 0.41933 0.1991 0.67853 0.1808 xH7C3C02CH3 (1 - x)C5HII (OH) + 0.26410 0.1955 0.50350 0.2403 0.31713 0.2150 0.54109 0.2399 0.35078 0.2230 0.59384 0.2295 0.37928 0.2316 0.62939 0.2261 0.43127 0.2394 0.67197 0.2140 0.46750 0.2392 0.70658 0.1985

TABLE Coefficients A i of eq. [I] and standard deviations, s(uE),in cm3 mol-I for binary systems methyl 3. alkanoate + alkan- 1-01 Mixture .rH3CC02CH3+ (1 + (1 + (1 + (1
- x)C2Hs(OH) - x)C~H~(OH) - x)C4H9(OH) - x ) C ~ H (OH) II

Ao

AI

Ar

A3

s(uE)

xH5C2C02CH3 ( 1 - x)C2H5(0H) + + (1 - x)C3H7(0H) + (1 - x)C4H9(OH) + (1 - *)C5HII(OH) .rH7C3C02CH3 (1 - x)C2H5(0H) + + (1 - x)C3H7(OH) + (1 - x)C4H9(OH) + (1 - .r)C5HI (OH)

1124

CAN. I.

CHEM. VOL. 67. 1989 with the data of the previous paper for the remaining normal alkanols (from hexan- l-ol to decan- l-ol). A general qualitative interpretation of the results of the excess molar volumes of the mixtures of esters + n-alkanols is that they are the result of different factors which may be resumed as follows. First, a positive effect on the uE due to the destruction of polymers and to the steric effect of the molecular groups of the pure compounds. However, added to these effects are others having opposite consequences on uE, such as interstitial accommodation and especially the appearance of specific interactions with the formation of new polymers ester + n-alkanol. These act negatively in mixtures of ester with alkanols in addition to the effect of changes in the free volume. These negative effects may even predominate over the first ones, with the uE taking on negative values as the number of carbon atoms of the n-alkanol decreases.

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Acknowledgements
Financial support for this work was provided by the Canarias Government, under a research project 52/86. 1. J. ORTEGA J. D. GARCIA. J. Chem. 66, 1520 (1988). and Can. and 2. J. ORTEGA, BRAVO, JIMENEZ, M. I. PAZ-ANDRADE. R. E. J. Chem. Thermodyn. 18,403 (1986). 3. J. ORTEGA, I. PAZ-ANDRADE, RODRIGUEZ, L. M. E. and ROMANI. Aust. J. Chem. 38, 1435 (1985). 4. J. ORTEGA. Chem. Eng. Data, 30, 465 (1985). J. 5. T. NITTA, A. TUREK, R. A. GREENKORN.I. Ch. E. J. E. and A. 23, 144 (1977). 6. A. HEINTZ. Bunsenges. Phys. Chem. 89, 172 (1985). Ber. 7. A. J. TRE~ZCZANOWICZG. C. BENSON. and Fluid Phase Equilibria, 23, 117 (1985). 8. R. C. WILHOIT B. J. ZWOLINSKI.Phys Chem. Ref. Data. and J. Vol. 11. 1973. Supplement no. 1. 9. J. A. RIDDICK, B. BUNGER, T. K. SAKANO. W. and Organic solvents. Techniques of chemistry. Vol. 11. 4th ed. Wiley Interscience, New York. 1986. 10. J. ORTEGA. Chem. Eng. Data. 27, 312 (1982). J. 11. J. POLAK B. C-Y. Lu. J. Chem. Eng. Data. 17,456 (1972). and

FIG. 2. Representation of uZE" for normal alkanols C,,H2,+ ,(OH) diluted in methyl alkanoates, Hz,,,+ ,C,,,COZCH3 = 1 , 2, 3), as a (m functionof m; x , n = 2; n = 8; 0, n = 4; a, n = 5. Theother points correspond to the values derived from ref. 1 for n-alkanols, from hexan- 1-01to decan- l-ol.

+,

falling abruptly for n < 4, to produce contractions of volume in the case of methanol. To complete the earlier paper ( I ) , the curves of the partial molar volumes were also determined by means of eq. [2]. In particular, the values at infinite dilution were determined by means of u~~~ = CAI (i = 0, 1 , 2 , ...) for the four n-alkanols, being represented in Fig. 2 as a function of the number of carbon atoms, m , of the methyl ester C,,HZm+ ,COOCH3, and together