Journal of Colloid and Interface Science 253, 203–210 (2002) doi:10.1006/jcis.2002.

8505

Thermodynamic Analysis of Surface Formation of {1,4-Dioxane + 1-Alkanol} Mixtures
Encina Calvo, Mercedes Pintos, Alfredo Amigo, and Ram´ n Bravo1 o
Departamento de F´sica Aplicada, Facultad de F´sica, Universidad de Santiago de Compostela, E-15782 Santiago de Compostela, Spain ı ı Received February 4, 2002; accepted May 22, 2002

Surface tensions (σ ) for {1,4-dioxane + methanol, ethanol, or 1propanol} at the temperature 298.15 K and normal atmospheric pressure have been determined as a function of mole fractions. The experimental results have been analyzed using the ideal and Langmuir models and in the light of the well-documented bulk properties of these systems, which reflect hydrogen bonding between the alcohol and 1,4-dioxane molecules. For {1,4-dioxane + ethanol} surface tensions were also measured at other temperatures between 288.15 and 308.15 K, and these data were used to calculate the surface entropy and enthalpy per unit area. C 2002 Elsevier Science (USA) Key Words: surface tension; Langmuir model; surface entropy; surface enthalpy.

MATERIALS AND METHOD

INTRODUCTION

For most of the liquid mixtures for which surface tension data are available (1), this quantity is smaller than for an ideal mixture of the same components, although positive deviations have also been reported (e.g., for methanol + propanol (2)) and deviation from the ideal can be minimal for mixtures of components with very similar surface tensions, such as alkane + alkane mixtures (3). All three kinds of behavior are exhibited by the set of systems for which experimental surface tension data obtained at 298.15 K over the entire concentration range are reported in this paper, the binary liquid mixtures {1,4-dioxane + methanol, ethanol, or 1-propanol}. The data presented have been analyzed using the ideal and Langmuir models and in the light of the welldocumented bulk properties of these systems, which reflect hydrogen bonding between the alcohol and 1,4-dioxane molecules. For {1,4-dioxane + ethanol} surface tensions were also measured at other temperatures between 288.15 and 308.15 K, and these data were used to calculate the surface entropy and enthalpy per unit area. Consideration of these properties in relation to the corresponding bulk properties and those of water + alcohol and 1,4-dioxane + alkane mixtures throws light on the surface structure of this kind of systems.

The source and purity of the chemical compounds are shown in Table 1, together with the experimental surface tensions and values reported by other authors (4–12). Mixtures for which surface tension were measured were prepared by mass with a Mettler AT201 balance (repeatability, 1 × 10−5 g) in airtight stoppered bottles, and the error in the mole fraction was estimated to be <10−4 . Surface tension of pure liquids and mixtures at the liquid– vapor interface was determined using a Lauda drop volume tensiometer, described in a previous paper (13) as well as procedure and handling of data. The temperature of the measurement cell was controlled by a water thermostat within 0.01 K. The uncertainty obtained in σ values is less than 0.03 mN m−1 . The estimated error in the surface tension deviations, σ , defined by σ = σm − x1 σ1 − x2 σ2 , is <0.04 mN m−1 .
RESULTS AND DISCUSSION

[1]

The experimental values of σ at 298.15 K for the mixtures {1,4-dioxane + methanol or + 1-propanol} are summarized in Table 2. For each mixture the surface tensions were fitted with a Redlich–Kister function of the form
n

σ = x1 (1 − x1 )
i=1

Ai (2x1 − 1)i−1 ,

[2]

where x1 is the mole fraction of 1,4-dioxane. The coefficients Ai and standard deviations s(Ai ) listed in Table 3 were estimated by the least-squares method. Table 2 also includes the experimental values of σ for the binary mixtures {1,4-dioxane + ethanol} at different temperatures from 288.15 to 308.15 K. A function of the form
6

To whom correspondence should be addressed. Fax: 34 981 520676. E-mail: falrbq@usc.es. 203

1

σ =
i=1

i−1 {Bi,1 + Bi,2 (T − T0 ) + Bi,3 (T − T0 )2 } x1 , [3]

0021-9797/02 $35.00
C

2002 Elsevier Science (USA) All rights reserved.

15 K Exp. h Lide and Frederikse (10).80b. . 33. b a where T0 is the reference temperature (T0 = 298. According to the Langmuir model (14. [5] 0 where β is a coefficient governing partition of the solute between the surface and the bulk.c 21. 33.4-dioxane + methanol} the experimental data were fitted to a polynomial expression: π = C1 + C2 x2 + 2 C3 x2 . 32.5 -1 0 0. 1. C3 = 4.15 K for the surface tension deviations of the mixtures {1. 15). T = 308.35 j 22. for the Pure Liquids at Different Temperatures σ/(mN m−1 ) T = 288. Purity. (7). -0.83 j 21. Papaioannou and Panayiotou (4). we also fitted the Langmuir equation to previously published data for the systems {1.204 CALVO ET AL. Figure 2 shows that the ideal model can be satisfactorily fitted to the experimental data for {1.98 22. (6). i Jim´ nez et al. 32.33g T = 303.42 21. ethanol.93e 22. is given by π= s RT x 2 .12a 23.15 K) was fitted to the results using the ordinary (unweighted) least-squares method. . π= s RT 0. 32. C2 = 6. 31. . 1. For the binary mixture {1. f Myers and Clever (8).75 21.8% Aldrich >99% Aldrich >99.m ) where x2 is the mole fraction of the solute in the bulk and s its maximum surface concentration. TABLE 1 Source.6 0.8 1 [6] x dioxane FIG.41 f 21.4-dioxane mixtures.42 21. With a view to investigating the influence of the chain length of the alcohol on the surfaces of alcohol + 1. and Surface Tension. and is negative for 1-propanol. 1-propanol.22 Lit. and the Langmuir model to those for {1.15 K Liquid 1.38 Lit.45c T = 293.4-dioxane).41 22. The parameters Bi j are listed in Table 4.15 K Exp.15 K Exp. For an ideal mixture the surface pressure π.76a 21. g Papaioannou et al.11 21. d Glinski et al.4-dioxane + 1-alkanol}: . 1-heptanol.5 1 [4] −1 ∆σ/(mN. σ.4-dioxane + ethanol}.00.30c T = 298. Acevedo et al. defined as the decrease in surface tension upon addition of a solute (in this case the alcohol) to a solvent (in this case 1. being the values of the parameters: C1 = −0. 34. Figure 1 shows that σ is positive when the alcohol is methanol.4-Dioxane Ethanol Methanol 1-Propanol Source and purity Aldrich >99% Merck >99.64 Lit. 33.036. fluctuates slightly around zero when it is ethanol.83 22.15 K Exp. (5). Plot at 298.13 23. (9).75h 32.5 ln(1 + βx2 ). methanol.4-dioxane + 1-hexanol.48c Lit.61.4-dioxane + 1-propanol}.39i 23.5% Exp.75c 22. e j Kinart et al.4 0. (12).34 j Lit. (11).2 0. c Riddick et al. e Coto et al.03 20. (2).

07 32.023 0.75 27.86 T = 303.6416 24.24 28.69 0. or 1-decanol} (16).5129 27.72 0.21 31.29 32.00 32.61 31.0231 0.7350 24.0 10.3614 27.8631 0.20 22.4835 27.6134 25.14 28.9830 23.3529 0.79 0.90 0.1204 0.4-dioxane + ethanol is unity.17 21.4090 28.0303 0.59 23.7883 24.36 22.71 29.1505 0. σ.64 0.0803 0. This behavior differs from that of water + alcohol mixtures.2925 0.3236 30.2182 0. Comparison with values for water + alcohol mixtures shows that alcohols are much less lyophobic in 1.43 0.0670 0.1835 0.46 31.34 0.08080 0.84 22.43 0.5610 26.7377 23.50 23.6743 25.6344 26.78 1.6696 25.9254 0.4759 28.8876 0.5115 26.82 A4 −1.68 22.8608 0.30 1.6514 25.9632 0.3979 0.9329 0.7919 0.8129 24.60 0.THERMODYNAMICS OF SURFACE FORMATION 205 TABLE 2 Experimental Surface Tensions.74 0.4-dioxane + alcohol mixtures the partition coefficient β also increases with chain length.081 0.7002 24.45 23.2268 0.7539 0.29 33.5642 25.2 −3.0474 0.1591 0. Table 5 also lists the results of a similar Langmuir analysis of 1.38 0.99 22.51 29.58 29.9434 0.9818 23.34 31.4501 28.68 0.66 30.4 24.050 −0.4-Dioxane + methanol T = 298. Table 5 lists the fitted values of s .24 T = 293.15 K 0.9761 23.1 0.9272 26.95 23.4-Dioxane + 1-propanol −0.24 0.651 −3.70 24.55 28.5650 27. These have much greater β values than the corresponding 1.3432 0.89 0.86 0.9718 0.88 .42 23.7765 24. The greater lyophobicity of the alkanes is attributable to cohesive alkane–ether interactions being much weaker than cohesive alcohol–ether interactions.4-dioxane than in water. [7] TABLE 4 Coefficients Bi j for Least-Squares Representation of σ by Eq.1172 0.68 29. which reflects the energy required to move one molecule of solute from the bulk to the surface.35 22.6961 24.45 0.51 23. and the surface area occupied by a molecule of solute.72 23.15 K.4-dioxane + n-alkane mixtures (17) at 298.83 0.13 0. the value of β for water + ethanol at 298.71 0. whereas its value for 1.67 29.39 0.8935 0.2233 0.4-Dioxane + methanol 1.2374 0. the increase in occupied surface area per CH2 unit is now no more ˚ than 30 A until nonane is reached.8330 0.61 0.52 30.0786 0.51 0.72 25.70 0.1399 0. Ethanol or 1-Propanol (2)} at Different Temperatures x2 σ/(mN m−1 ) x2 σ/(mN m−1 ) x2 σ/(mN m−1 ) TABLE 3 Redlich–Kister Coefficients of Eq.0339 0.5556 26.45 1.0004 −0.58 0.43 23. These results show that the area of the surface occupied by each alcohol molecule increases with chain length (and that from 1heptanol onwards the increment per CH2 unit is quite regular.9372 0.77 0.75 32.38 23.0798 0.6014 26.06 30.69 24.1724 0.3372 28.66 22.47 32.66 22.6083 26.6684 0.67 0.9146 0.9365 0.50 0.9677 0.67 31.8449 0. β.8542 24.7654 24.4-Dioxane + 1-propanol T = 298.9559 0.4418 26.231 0.0492 0.25 27.5564 26.08 −8.8237 0.05 31.1227 0.49 0.9504 0.49 102 · s 4. This coefficient reflects the lyophobicity of the solute.02 30.9368 0.58 32.0851 0.0600 0.4581 27.08 0.8662 0.15 21. The standard Gibbs energy of adsorption.05 0.2847 0.53 22.97 30.762 1.27 0.8248 12. ˚ 40 A).8836 0. [2] and Standard Deviations s A1 A2 A3 1.23 31.28 0.00009 −0.8923 0.3786 28.9637 0.15 K 0.07 28.4-Dioxane + ethanol T = 288.1454 0.84 0.15 K 0.74 33.6 32.7112 25.4-dioxane + alcohol mixtures. which is in keeping with the chain lying in the surface.15 30.8145 0.4998 27.61 33.04 0.30 30.85 0.50 0.7345 24.5 1.3 0.2759 33.2803 0.0389 0. [3] Bi j i =1 i =2 i =3 i =4 i =5 i =6 j =1 21.60 0.34 1.0478 0.9491 0.47 31.1356 0.11 0.31 1-octanol.53 0.0156 0.8166 23.4594 0.4-dioxane repels alkanes from the bulk much more than it does alcohols. For 1.38 0.36 30.8485 0.4406 27. for example.22 23.3471 29.15 K 0.7 j =2 −0.03 22.0542 0.9044 0.7303 0.0930 0.13 22.92 31.9231 0.97 0. showing that 1.98 0.8653 0.15 K 0.15 K 0. for the Systems {1.016 0.70 32. In keeping with this.18 0.204 0.357 0.32 29.81 30.90 21.91 22.2575 0.04 29.4581 27.22 21.43 0.6051 25.61 21.4906 26.4162 29.55 30.0154 0.2745 32.7006 25. for which the invariance of the area occupied by alcohol molecules at the surface indicates that the hydrophobic chain must project out of the surface.25 22.74 0.93 22.004 −0.57 22.8507 0.24 T = 298.15 K 0.4Dioxane (1) + Methanol.34 −0.86 21.8114 23.9893 23.2027 32.5846 27.70 1.357 0.7859 23.96 31.25 0.057 0.1101 0.9859 0.0948 0.25 0.81 33.15 K is about 209.82 0.4005 0.47 T = 308.36 j =3 0.09 0.88 22.9026 0.9350 25. can be determined for the above systems using the expression − G 0 = limx2→0 {RT ln(π/x2 )}.

4-dioxane interactions must be rather weak.23 17.15 K.4-dioxane + methanol (Fig.4-Dioxane+ Hexane Heptane Octane Nonane Decane 1-Propanol 1-Hexanol 1-Heptanol 1-Octanol 1-Decanol s −1 −∆Gº/(cal.4-dioxane interactions requires.24 × 10−11 6. this was the conclusion reached by Ramadan et al.4dioxane + alcohol mixtures this rule is complied with by systems with alcohols larger than ethanol. and by Garc´a et al.63 × 10−10 1000 1 2 3 4 5 6 7 8 9 10 C-atom number FIG. [4] and [5] 1.4-dioxane + 1-alkanol} as function of alcohol concentration. showing that increased temperature favors transfer of solute from the bulk to the surface. volumetric. these latter authors’ data also suggested that the alcohol– 1. TABLE 5 Values of Γs . Surface pressure π for {1.4-dioxane + alcohol series. Standard Gibbs energy of adsorption for {1.6 80. β and the Surface Area Occupied by Each Molecule of Alcohol Obtained from Eqs.4-dioxane + ethanol mixtures to have negative excess volume and negative excess viscosity. On the basis of dielectric.42 × 10−10 1. ethanol. For example.98 10. The observed temperature dependence of the surface tensions of the 1. on average. 24) calculated that hydrogen bonding between 1.4-dioxane + ethanol mixtures allows determination of 1800 1400 (mol/cm2 ) β 58.59. at which point there is practically no free ethanol in the mixture.5 1.4-dioxane.15 K to 1435 cal/mol at 308. The transfer of alcohol molecules from the bulk to the surface depends on their interactions in the bulk.88 6. which is supported by Letcher et al.6 105.4 161.05 4. (22) finding that these mixtures have large positive excess enthalpies and hence that the rupture of alcohol–alcohol and 1.4-dioxane + alkane mixtures).206 12 CALVO ET AL. methanol.57 × 10−10 1. (21).4-dioxane + ethanol − G ◦ increases with temperature from 1390 cal/mol at 288. who studied the correlation factors of these mixtures.5 181.2 1. .17 × 10−10 9. This formation of hydrogen-bonded complexes in the bulk counteracts the tendency of the alcohol (the component with the lower surface tension) to be segregated at the surface and explains why ethanol fails to comply with Traube’s rule in the 1.24 ❛ Surface area (A2 /molecula) 116 142 172 201 242 30.4-dioxane interactions. . 2.m ) 6 4 2 0 0 0.15 K. For 1.4-dioxane + 1-alkanol} . in which these interactions partially replace alcohol–alcohol hydrogen bonding. . (19). who found 1. Similar considerations hold for methanol. 3.2 0.6 0. (23.6 236. For 1. for which − G ◦ increases by 57 cal/mol per CH2 unit (cf. but not by 1. this linear behavior is known as Traube’s rule.64 × 10−11 8. more energy than is released upon formation of alcohol–1.6 263.19 × 10−10 0. Papanastosiou et al. 1-propanol.4-dioxane + ethanol mixtures is greatest when the mole fraction of ethanol is 0.8 1 x2 FIG. However. who inferred ı negative excess volumes and negative excess Gibbs energies from measurements of viscosity and density at 298.4dioxane and ethanol in 1. 3).mol ) For water + alcohol mixtures − G ◦ increases linearly with the chain length of the alcohol (18) at the rate of 766 cal/mol per CH2 unit. and viscosimetric measurements. by Hafez et al. 10 8 −1 π/ (mN.2 151.87 × 10−11 5.4 0. (20).8 139.91 × 10−10 0.4-dioxane–1. mixtures.42 × 10−10 1.4-dioxane + ethanol or 1. Numerous authors (19–24) have provided evidence that methanol and ethanol molecules form hydrogen-bonded complexes with 1. 97 cal/mol for 1.

(a) Entropy of surface formation per unit area for {1. For 2 .4 0. The results displayed in Fig. 4. Assuming that the surface is a monolayer in which the surface concentrations of the components are the surface concentrations . [12] x ethanol b 80 70 −1 ∆h/(mN.4dioxane + ethanol} mixtures. In other words.15 K 0. the enthalpy of surface formation per unit area.2 0. Above 298.2 0.4 0.15 [8] The reason for the name of this quantity can be seen by considering the Gibbs adsorption equation.4-dioxane. and at higher ethanol concentrations it decreases with temperature. and are therefore given by dµi = −Sib dT + vib d P + ∂µi ∂ x2 d x2 . defined by (25) s = −(∂σ /∂ T ) p. allow calculation of the surface excess 1 2 1 concentrations 2 and 1 . can be calculated from the expression h = σ + T s.8 1 x ethanol FIG. respectively. but as temperature falls the plot of s against x2 begins to feature a minimum at the same mole fraction as was found by Papanastosiou et al.P [10] 288. h.THERMODYNAMICS OF SURFACE FORMATION 207 the entropy of surface formation per unit area. [11] 0 0. while that of 1.15 K it decreases steadily with increasing ethanol concentration.6 0.6 0.10 where the superscript s indicates surface quantities and the subscripts 1 and 2 properties of the solvent and solute. The enthalpy of surface formation per unit area behaves similarly (Fig.8 1 where A is the area of the surface and is = n is /A. 1 2 308.4-dioxane + ethanol mixtures.m ) Figure 4a shows that for ethanol in 1. together with data published in the vapor–liquid equilibrium literature (26).4-dioxane is positive and peaks at a mole fraction of 0. s. (23) to afford maximum interaction between 1.15 K 40 0 0. (b) Enthalpy of surface formation per unit area for {1. 5 for 308.15 K (VLE data are not available for other temperatures) show that at this temperature the surface excess of ethanol relative to 1. 1 1 2 2 [9] -1 -1 ∆s/(mN.k ) 308.15 K 0.76. T [13] 2 with an analogous expression for 1 . 4b). Adσ = −S s dT + v s d P − n s dµs − n s dµs . for at equilibrium the chemical potentials µi are the same as in the bulk. The measured surface tensions of the 1. which is a 0.05 where the superscript b indicates bulk quantities. which highlights the influence of bulk interactions on surface properties.9 it increases with temperature.4-dioxane + ethanol} mixtures. s is the difference between the surface excess entropy per unit area and the entropy of a bulk system with the same components as are “in” the surface corresponding to one unit area of the surface.28.4-dioxane relative to ethanol is negative.4-dioxane and ethanol in the bulk. s is positive at all the temperatures considered.x2 . T. Given the surface tension σ and s. so that s= Ss − A s b 1 S1 − s b 2 S2 .m . with a negative peak at x2 = 0. ∂σ /∂ x2 = −(∂σ /∂µ2 )T = − ∂µ2 /∂ x2 . At mole fractions of ethanol below 0.15 K 60 50 288.

8 1 x ethanol FIG. s E . [15] allows more detailed analysis of the energy and entropy of surface formation.208 60 CALVO ET AL. in the range 0.4-dioxaneophobic: at the water + ethanol surface the ethanol 1 + s 1 . Figure 7a shows that s E is positive at all concentrations.15 K. the concentration of 1. It should also be borne in mind that the 1. the vapor being richer in ethanol than the liquid at lower mole fractions and vice versa at higher.ideal ). 2 falls slightly s with increasing x2 and x2 > x2 > y2 . Γ2 .m− ) 20 0 be summarized by considering three x2 ranges.8 1 x ethanol FIG.8 = xi 1 − i 3−i s a3−i s x 1 a1 + s x 2 a2 . and s 1 x2 > x2 .778 < x2 < 1. (1).2 0. over the region centered on the composition of maximum interaction between 1. s i [14] is related to i 3−i This formula can be evaluated because the bulk mole fractions xi by s i and 0.M − s s. 1 falls with increasing x2 .4 0. by sE = where sm − ideal sm = s s.6 where the partial molar areas ais are calculated (27) as [N A (νi0 )2 ]1/3 (νi0 being the molar volume of component i and N A Avogadro’s number).. up to x2 = 0. Plot of ethanol mole fraction at the surface versus bulk for the system {1.2 0. the reduced number of free ethanol molecules in the bulk at this composition hinders the adsorption of ethanol at the surface. [17] -60 0 0. 6.. 10 /(mol.4-dioxane + ethanol system has an azeotrope at x2 = 0. Figure 6 shows that the mole fraction of ethanol at the surface. 308. (1) found that s is negative for water + ethanol.E = s s. with a maximum at x2 = 0. If this composition is identified with the maximum 1 i s of 2 .E − s E . i.e. as follows. that the excess entropy is always greater at the surface than in the bulk.4 0.E being the surface excess entropy per mol (s s. the change from a rapid to a more gradual increase with increasing x2 occurring over the range x2 = 0. Plot of 2 1 and 1 2 for the system {1.4-dioxane + ethanol} at 308. we define and excess entropy of surface formation per mol.e.M.4-dioxane–ethanol complex formation) and 2 a local minimum at the minimum of 1 . calculated in this way.778. this difference is due to ethanol being more hydrophobic than 1. both 1 and 2 increase with x2 . and comparing the ELV data (26) with s s the calculated values for x2 we obtain the relation x2 < y2 < x2 . where y2 is the concentration of ethanol in the vapor phase.4 0.4–0. By contrast. In 2 the low-ethanol range. [15] 0. The is obtained from Eq.6 0.ideal ) and s E the bulk excess entropy per mol (s E = s M − s M. s i.4-dioxane is lower in the vapor phase than in the liquid phase.778. 40 Γ2 1 2 1 2 7 Γ1 .28. -20 Γ1 2 [16] -40 sm = s s 1 + s 2 . the behavior of the 3−i and x2 as functions of x2 may x2 s 0.6 (the point of greatest 1. is given by s x2 = s 2 s 2 s s.7.15 K. is greater than its mole fraction in the bulk at all concentrations. In the 2 1 range 0. 5.4-dioxane and ethanol in the bulk. Clearly. Following Aratono et al. Finally. x2 . Again.6 0. i.28 < x2 < 0.4-dioxane + ethanol} at s the mole fraction of ethanol in this monolayer. Aratono E et al.2 0 0 0. .

and this ordering reduces the entropy of the surface. Papaioannou.6 0.mol ) 1 0. A. 7.2 0. Colloid Interface Sci.6 0. A. L. T. Motomura. 6. x ethanol FIG. H. M. this linear behavior is known as Traube’s rule. A. is positive for {1.e.4 0.4-dioxane and ethanol molecules in the bulk counteracts the tendency of the alcohol to be segregated at the surface and explains why ethanol fails to comply with Traube’s rule in the 1. Magopoulou. Talilidou. surface formation is energetically disfavored. and Panayiotou. 68.mol hm = h s 1 + s 2 . Toyomasu. ı 25 (1999). B. Riddick. G. PGIDT01PXI20601PR.. D.THERMODYNAMICS OF SURFACE FORMATION 209 hm − h ideal = h s. N.15 This work was supported by Xunta de Galicia. Coto..4-dioxane + ethanol or 1. G. “Techniques of Chemistry.4-dioxane + alcohol series. C. L. Bunger. for which − G ◦ increases by 57 cal/mol per CH2 unit. For water + alcohol mixtures the standard Gibbs energy of adsorption.4 0. 949 (1974).-K. 87. R.8 0.4 0 0 0.. M. Mendui˜ a.. and Clever. J.4-dioxane + ethanol mixtures allows determination of the entropy and enthalpy of surface formation. An.3 E Surface tension deviation... and Ikeda.4-dioxane+ ethanol} at 308. and Platten. (b) Excess enthalpy of surface formation for the system {1. Colloid Interface Sci.45 − ∆h /(kJ.4-dioxane + alcohol mixtures this rule is complied with by systems with alcohols larger than ethanol.4-dioxane + methanol. 9.8 1 x ethanol b 0. 104.6 0.4-dioxane + methanol}. Argent. J. Qu´m..K . − G ◦ . Rubio. Y. Myers. h E . 5. Evans.15 K. M.. and Sakano. J. J. 3433 (1964).. defining the excess enthalpy of surface formation per mol.15 K..4-dioxane + ethanol h E is positive at all concentrations (Fig. S.. New York. (a) Excess entropy of surface formation for the system {1.. T. SUMMARY 0. and Clever. Using the experimental σ values together with published VLE data we can also obtain the surface excess concentration for this binary mixture. Formation of hydrogen-bonded complexes between 1. The obtained results show clearly the relation between bulk and surface properties for these liquid systems. Pedrosa. Data 39.. A. Chem. Acevedo..8 1 1. R. 7.4dioxane + ethanol} at 308.. Aratono. I. C. 1986.. 3. D. Wiley-Interscience. J... 2. increases linearly with the chain length of the alcohol at the rate of 766 cal/mol per CH2 unit. J. ACKNOWLEDGMENTS 0. m [18] a 2 hE = where 1. J. Eng. Chavepeyer. and Katz. 156. J. Papaioannou. i. Chem.6 Ε −1 −1 ∆s /J. E. Asoc. Faraday Trans.. K. 7b).M − h M . R. 8. Similar considerations hold for methanol. J. o REFERENCES 0 0 0. L... Villeneuve. Phys. K.. Chem.. B.. molecules project upward.. 457 (1994).. by . 8816 (1996). fluctuates slightly around zero when the alcohol it is ethanol.. Glinski. and Renuncio. H.. Pando. G. 2779 (1995).” 4th ed. Secretar´a Xeral de Investiı gaci´ n e Desenvolvemento.. 4. [19] 1.. C. 146 (1997).. Chem.. A similar treatment can be given to the enthalpy. but not by 1. and is negative for 1-propanol. The temperature dependence of the surface tensions of the 1. For 1. M. Caba˜ as. and Panayiotou. Organic Solvents. B.2 h s. 91. G. H. σ . T. J. 6. Soc. 52 (1993). n n J. G. Uchizono. 191. Takieu. For 1.. Thermodyn.M and h M being the mixing molar enthalpy in the surface and in the bulk respectively. Chem.2 0.. Phys.

Chem. A. Eng. 10. “An Introduction to the Principles of Surface Chemistry. 167 (1992). Papanastasiaou.. Data 37.. J. and El-Zyadi. A.. 20. A. Data 32. Chem. Phys. 55 (1991). and Gast.. and Bald. Pintos.. I.” 6th ed. W. 17. M. Chem. Data 44.. J. M. I. Pak.. 19.. E. and Ziogas. M. D. Velasco. and Kokkinidis. Cambridge. and Franjo. 22. 1361 (1918). Bassiouni. J.. H.. Chem.. Wiley Interscience. 931 (1999). E. Lide. “The Properties of Gases & Liquids. S.. J. Data 46. J. M. 37.. R.. A. Chem. 15. Chem. A. A.. 3279 (1999). SH. Langmuir. Chem. 16. M. M.. Bravo. Sci. Adamson. 40.. M. Liq.. A. 378 (1987). and Bravo. Soc. Chem. Amigo. and Ramadan. Chem.. Chem.. 13. . J. H. 27. R.. R. 25. 12. A. F. R. Aveyard. Ramadan. New York. Casas. M... M. Data 45. 1097 (1995). Calvo. Hafez. 11.. G. J. “CRC Handbook of Chemistry and Physics. 1973. J. Chem..” 4th ed.. and Postigo.. L. J.. Phys. R. M. and Haydon. 23. “Physical Chemistry of Surfaces. G. Data 40. 1997. Papoutsis... and Frederikse.. 26. R. 317 (1999). Artal. Am.. Prausnitz. M. C. J. Langmuir 15. Papanastasiaou.. n Thermodyn. M. 91 (1985). and Poiling. D. McGraw-Hill..... and Govender. Penas.. B. Kinart. A. Anales de la Asociaci´ n Qu´mica Argentina ı o ı 85. 193 (1999). Reid. Letcher. Eng. P.. W. A. A. J. Sh. New York. R.. Eng. 1987. Res. A. T. J. 37. 31.. 10. 14.. C.. M. E. G. Amigo. J. Eng.. Pintos. I.. P.. and Bravo. Hafez. 682 (2000).. E.. n ı Eng. C. J. Eng.” Cambridge University Press. A. e 862 (2000). A.. P.. Data 45. P. Garc´a. Eng. Pi˜ eiro. Brocos. 692 (2001). Jim´ nez. Mu˜ oz-Embid. 1996. M. Gracia-Fadrique. Calvo.. 18. Kinart. and Ot´n.. and Amigo. Segade. FL... 209 (1997). Pintos.210 CALVO ET AL. Calvo.” CRC Press.. Penas. A. J. 21. 24. E.

Sign up to vote on this title
UsefulNot useful