Isobaric vapor-liquid equilibria for acetone + chloroform + benzene and the three constituent binary systems

Abstract

Vapor-llquld equlllbrlum data for acetone + chloroform + benzene and for the three constltuent binary systems acetone + chloroform, chloroform + benzene, and benzene + acetone have been measured at 101.3 kPa by using a dynamlc equlllbrlum still. The experlmental data have been correlated and predlcted to appreciable accuracy urlng the Wilson equation. I ntroductlonThis paper deals with the measurement of vapor-liquid equilibria (VLE) at 101.3 kPa for the ternary system acetone + chloroform + benzene and the three constituent binary systems. I t also discusses correlation and prediction of experimental VLE data using the Wilson equation (7). Moreover, it compares our binary data with the predictions of evaluated Wilson parameters (2) and Reinders' data (3) with the predictions of our parameters. Experimental SectionAmaratus and Procedure. A liquid-vapor ebullition type equilibrium stili, described in detail in ref 4, was used for measuring VLE. The still has two ebuiliometers connected in series. Two electric heaters were wed, one in the liquklphase and the other in the vapor-phase boiling vessels.Vapor and liquid equilibrium compositions were determined by using a Shimazu gas chromatograph type GC3BT equipped with a thermal conductMty cell. PEG 1500 was used as column packing and helium as the carrier gas at a flow rate of 33 cm3 min-'. The column temperature was maintained at 338 K. Compositions were determined to better than 1 % by the relative area method (5). The equilibrium temperature was measured with an accuracy of 0.01 K by using a Hewlett-Packard quartz thermometer Model 2804A, calibrated at the triple point of water. The pressure in the still was measured by a Fortin type mercury barometer. Since the barometric pressure changed slightly, the experimental temperatures were corrected to 101.3 kPa.Matdab. Acetone, chloroform, and benzene were special grade pure reagents, supplied by Wako Pure Chemicals Co. Acetone was used after its minute water content was removed with calcium sulfate, using molecular sieves 3A. Chloroform was treated with sulfwic acid, neutralized with sodium hydroxide, washed with water, dried overnight on potassium carbonate, and then distilled. The purities of the materials were checked by gas chromatographic analysis and found to be better than 99.9 mol %. The densities and normal boiling points of the purified reagents are shown in Table I. -1 0 -0 0 0.5 1 X1 Flguro 1. Vapor-phase mole fraction y l and activity coefficients y, for the binary system acetone (1) + chloroform (2) at 101.3 kPa as a function of llqukl-phase mole fraction x 1: (e) experimental values.The curves are calculated by using Wilson equation. Experlmental ResultsBhary Systems. Table I1 and Figures 1-3 show the experimental VLE data at a pressure P = 10 1.3 kPa for the three systems acetone + chloroform, chloroform + benzene, and 002 1-956819 1 I 1 736-0343$02.50/0 I 0 0 0 5 1 0 X 1 Flguro 2. Vapor-phase mole fraction y 1 and actlvity coefflcknts y, for the blnary system chloroform (1) + benzene (2) at 101.3 kPa ...

Microstructures of negative and positive azeotropes

“…[1][2][3] The acetone-chloroform azeotrope is a popular text book example of a negative or maximumboiling azeotrope displaying negative deviations from Raoult's law, as shown in Figure 1(a), as well as an exothermic enthalpy of mixing. 7,8,[10][11][12][13][14][15][16][17][18] The non-ideality of acetone-chloroform mixtures is often attributed to the formation of C-H···O hydrogen bonds between chloroform and acetone. In fact, this system was one of the first for which a hydrogen bond with a C-H donor was proposed.…”

“…2,23 Despite the general importance of azeotropes relatively little is known about their microstructures. Acetone-chloroform mixtures have been studied, although not always at the azeotropic composition, by analysis of thermodynamic excess functions, 7,8,[10][11][12][13][14][15][16][17][18] NMR, [24][25][26][27] Raman, 28,29 FT-IR, 27,28,30 NIR, 31 terahertz time-domain 32 and inelastic neutron spectroscopy 29 as well as Monte Carlo simulations. 22 There is general consensus that hydrogen bonding interactions are likely to be present.…”

The development of unlike induced association-site models to study the phase behaviour of aqueous mixtures comprising acetone, alkanes and alkyl carboxylic acids with the SAFT-γ Mie group contribution methodology

“…Binary mixtures of acetone and chloroform exhibit high-boiling azeotropes, reflecting the strong interaction between the two components (see, e.g., refs. [25,26]). The formation of hydrogen bonds between water and acetone has been confirmed by ab initio simulation [27], and is observed experimentally in the ultraviolet (UV) absorption spectra of acetone in water [28].…”

Structural, single-particle and pair dynamical properties of acetone–chloroform mixtures with dissolved solutes

“…Acetone-chloroform mixtures constitute an interesting mixed liquid that attracted a rather large number of investigation in the past using both experimental [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] and theoretical [18][19][20] methods. Many of these studies have looked at the ideality of these mixtures as originally defined by Raoult's law for vapor pressures [21] or its generalizations to other properties of liquid mixtures.…”

“…Many of these studies have looked at the ideality of these mixtures as originally defined by Raoult's law for vapor pressures [21] or its generalizations to other properties of liquid mixtures. The acetone-chloroform mixtures have been found to possess nonideal behavior in excess thermodynamic [1][2][3][4][5][6], dynamical [16,17], dielectric and optical [19] properties with variation of composition. The observed nonideal behavior of this system has generally been attributed to formation of hydrogen bonded complexes between unlike molecules.…”