“…A more organized packing effect in longer than octane hydrocarbons is observed. The predicted molar excess enthalpies increase with increasing n-alkane carbon chain, which was observed previously for diisopropyl ether (Zhu et al, 1994a) and for TAME (Zhu et al, 1994b). The calculated molar excess enthalpy for 1-heptyne is negative, showing strong interaction with ETBE.…”
The solid−liquid equilibrium (SLE) has been measured above 280 K for eight mixtures of n-alkanes
(octadecane, eicosane, docosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane) with
methyl 1,1-dimethylethyl ether (MTBE). Experimental results of solubility are compared with values
calculated by means of the Wilson, UNIQUAC, and NRTL equations utilizing parameters taken from
the SLE. The existence of a solid−solid first-order phase transition in hydrocarbons has been taken into
consideration in the solubility calculations. The solubility of hydrocarbons in branched chain ethers is
lower than that in n-alkanes but higher than that in cycloalkanes, branched alkanes, 1-alcohols, and
tert-alcohols. The best correlation of the solubility data has been obtained by the NRTL equation, where
the average root-mean-square deviation of the solubility temperatures is 0.46 K. The liquid−liquid
equilibrium (LLE) has been measured between 300 and 360 K for binary mixtures of water with ethyl
1,1-dimethylethyl ether, methyl 1,1-dimethylpropyl ether, and ethyl 1,1-dimethylpropyl ether. The
solubility of water in branched chain ether increases with increasing temperature, whereas the solubility
of ether in water is decreasing up to 330 K and at the higher temperatures is slightly increasing. The
excess molar volumes
have been measured at the temperatures 298.15 K and 308.15 K for binary
mixtures of hexane, octane, decane, dodecane, tetradecane, hexadecane, cyclohexane, and 1-heptyne with
ethyl 1,1-dimethylpropyl ether. The excess molar volumes of all mixtures except for 1-heptyne are positive
over the whole composition range. The experimental results have been correlated with the Redlich−Kister polynomial and compared with the results predicted from Prigogine−Flory−Patterson theory. The
interchange parameter X
12, which minimized
experimental data, was adjusted and then used to
predict the heat of mixing.
“…A more organized packing effect in longer than octane hydrocarbons is observed. The predicted molar excess enthalpies increase with increasing n-alkane carbon chain, which was observed previously for diisopropyl ether (Zhu et al, 1994a) and for TAME (Zhu et al, 1994b). The calculated molar excess enthalpy for 1-heptyne is negative, showing strong interaction with ETBE.…”
The solid−liquid equilibrium (SLE) has been measured above 280 K for eight mixtures of n-alkanes
(octadecane, eicosane, docosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane) with
methyl 1,1-dimethylethyl ether (MTBE). Experimental results of solubility are compared with values
calculated by means of the Wilson, UNIQUAC, and NRTL equations utilizing parameters taken from
the SLE. The existence of a solid−solid first-order phase transition in hydrocarbons has been taken into
consideration in the solubility calculations. The solubility of hydrocarbons in branched chain ethers is
lower than that in n-alkanes but higher than that in cycloalkanes, branched alkanes, 1-alcohols, and
tert-alcohols. The best correlation of the solubility data has been obtained by the NRTL equation, where
the average root-mean-square deviation of the solubility temperatures is 0.46 K. The liquid−liquid
equilibrium (LLE) has been measured between 300 and 360 K for binary mixtures of water with ethyl
1,1-dimethylethyl ether, methyl 1,1-dimethylpropyl ether, and ethyl 1,1-dimethylpropyl ether. The
solubility of water in branched chain ether increases with increasing temperature, whereas the solubility
of ether in water is decreasing up to 330 K and at the higher temperatures is slightly increasing. The
excess molar volumes
have been measured at the temperatures 298.15 K and 308.15 K for binary
mixtures of hexane, octane, decane, dodecane, tetradecane, hexadecane, cyclohexane, and 1-heptyne with
ethyl 1,1-dimethylpropyl ether. The excess molar volumes of all mixtures except for 1-heptyne are positive
over the whole composition range. The experimental results have been correlated with the Redlich−Kister polynomial and compared with the results predicted from Prigogine−Flory−Patterson theory. The
interchange parameter X
12, which minimized
experimental data, was adjusted and then used to
predict the heat of mixing.
“…The experimental values of from Tables and are plotted in Figures and , respectively. Also shown in these figures are the results for DIPE (1) + 3MP (2) given in Table and the results for DIPE (1) + nC8 (3) and DIPE (1) + nC10 (3) reported by Zhu et al In both figures, it can be seen that the results for the three ternary mixtures fall between those for the two constituent binaries.…”
Section: Resultsmentioning
confidence: 62%
“…Curves: , calculated from the representation of the results by eqs 1−4, using the ternary term given in the footnote of Table ; - - -, estimated by means of the Liebermann−Fried model. 2 Excess molar enthalpies, , for DIPE (1) + 3MP (2) + nC10 (3) at 298.15 K. Experimental results: ▵, x 2 / x 3 = 0.3333; ○, x 2 / x 3 = 0.9994; ▿, x 2 / x 3 = 3.0013; ◇, x 2 = 0, Zhu et al; □, x 3 = 0. Curves: , calculated from the representation of the results by eqs 1−4, using the ternary term given in the footnote of Table ; - - -, estimated by means of the Liebermann−Fried model.…”
Section: Resultsmentioning
confidence: 99%
“…For both systems at constant x 1 , the enthalpies decrease as x 2 / x 3 increases. 1 Excess molar enthalpies, , for DIPE (1) + 3MP (2) + nC8 (3) at 298.15 K. Experimental results: ▵, x 2 / x 3 = 0.3332; ○, x 2 / x 3 = 1.0002; ▿, x 2 / x 3 = 2.9995; ◇, x 2 = 0, Zhu et al; □, x 3 = 0. Curves: , calculated from the representation of the results by eqs 1−4, using the ternary term given in the footnote of Table ; - - -, estimated by means of the Liebermann−Fried model.…”
Section: Resultsmentioning
confidence: 99%
“…The equations used in this application have been outlined by Wang et al Values of the Liebermann−Fried interaction parameters, A ij and A ji , for each of the binary mixtures are given in Table . These were obtained by fitting the Liebermann−Fried formula for to the primary experimental results in Table and those reported for the other relevant binaries by Zhu et al, Hamam et al., and Hamam and Benson . Also included in Table are values of the standard deviations s achieved in the fitting process and values ,, of the isobaric thermal expansivities α p of the components, used in evaluating the contributions due to different molecular sizes.…”
Excess molar enthalpies, measured at 298.15 K in a flow microcalorimeter, are reported for diisopropyl
ether + 3-methylpentane + octane and for diisopropyl ether + 3-methylpentane + decane. Smooth
representations of the results are described and used to construct constant excess molar enthalpy contours
on Roozeboom diagrams. The latter are compared with diagrams obtained when the model of Liebermann
and Fried is used to estimate the excess molar enthalpies of the ternary mixtures from the physical
properties of the components and the excess molar enthalpies of their constituent binary mixtures.
Microcalorimetric measurements of excess molar enthalpies at 298.15 K are reported for the two ternary mixtures, methyl tert-butyl ether (MTBE) or di-isopropyl ether (DIPE) + n-octane + 2-methylpentane (2-MP). The excess enthalpies for DIPE + 2-MP are also reported. Smooth representations of the ternary enthalpies results are presented and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. It is shown that good estimates of the ternary enthalpies can be obtained from the Liebermann and Fried model, using only the physical properties of the components and their binary mixtures.Des mesures microcalorimétriques des enthalpies molaires excédentairesà 298,15 K sont fournies pour les deux mélanges ternaires, l'éther méthyltertiobutylique ou l'éther isopropylique + n-octane + 2-méthylpentane (2-MP). Un compte rendu des enthalpies excédentaires pour l'éther isopropylique + 2-MP estégalement fourni. Des représentations aplanies des résultats des enthalpies ternaires sont présentées et serventà construire des contours d'enthalpie molaire excédentaire constante sur des diagrammes de Roozeboom. Il est montré que l'on peut obtenir de bonnes estimations des enthalpies ternairesà partir du modèle de Liebermann et Fried en n'utilisant que les propriétés physiques deséléments et de leurs mélanges binaires.
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