1.10.33: Gibbs Energies- Liquid Mixtures- Typically Non-Aqueous Positive; TNAP
- Page ID
- 386450
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)For this sub-group of binary aqueous liquid mixtures, \({\mathrm{G}_{\mathrm{m}}}^{\mathrm{E}}\) is positive. An example of such a mixture is ‘water + ethanenitrile’. The positive \({\mathrm{G}_{\mathrm{m}}}^{\mathrm{E}}\) reflects endothermic mixing across nearly all the mole fraction range. These mixtures have a tendency to be partially miscible with an Upper Critical Solution Temperature, UCST. For aqueous mixtures the composition at the UCST is often ‘water-rich’. For ethanenitrile + water, the UCST is \(272 \mathrm{~K}\). The positive \({\mathrm{G}_{\mathrm{m}}}^{\mathrm{E}}\) and endothermic mixing are attributed to disruption of water-water hydrogen bonding by added mathrm{MeCN}; cf. \(\mathrm{CCl}_{4} + \mathrm{~MeOH}\) [1,2].
Footnotes
[1] MeCN + water.
- \({\mathrm{G}_{\mathrm{m}}}^{\mathrm{E}}\); H. T. French, J.Chem.Thermodyn.,1987, 19,1155.
- \({\mathrm{H}_{\mathrm{m}}}^{\mathrm{E}}\);
- R. H. Stokes, J.Chem.Thermodyn.,1987,19,977;
- K. W. Morcom and R. W. Smith, J. Chem. Thermodyn., 1969,1,503.
- Volumes
- A. J. Easteal and L. A. Woolf, J.Chem.Thermodyn.,1988,20,693,701.
- D. A. Armitage, M. J. Blandamer, M. J. Foster, N. J. Hidden, K. W. Morcom, M. C. R. Symons and M. J. Wootten, Trans. Faraday Soc.,1968,64,1193.
- Sound Absorption M. J. Blandamer, M. J. Foster and D. Waddington, Trans. Faraday Soc.,1970,66,1369.
- Miscibility; M. Hurth and D. Woermann, Ber. Bunsenges. Phys. Chem., 1987, 91, 614.
- Excess thermodynamic properties; G. Douheret, C. Moreau and A. Viallard, Fluid Phase Equilib., 1986,26,221
- Analysis of TD properties; M. J. Blandamer, N. J. Blundell, J. Burgess, H. J. Cowles and I. M. Horn, J. Chem. Soc. Faraday Trans.,1990, 86,277.
[2] Propylene Carbonate Miscibility; N. F. Catherall and A. G. Williamson, J. Chem. Eng. Data, 1971, 16, 335.