1.14.74: Vaporization
- Page ID
- 391455
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\(\newcommand{\avec}{\mathbf a}\) \(\newcommand{\bvec}{\mathbf b}\) \(\newcommand{\cvec}{\mathbf c}\) \(\newcommand{\dvec}{\mathbf d}\) \(\newcommand{\dtil}{\widetilde{\mathbf d}}\) \(\newcommand{\evec}{\mathbf e}\) \(\newcommand{\fvec}{\mathbf f}\) \(\newcommand{\nvec}{\mathbf n}\) \(\newcommand{\pvec}{\mathbf p}\) \(\newcommand{\qvec}{\mathbf q}\) \(\newcommand{\svec}{\mathbf s}\) \(\newcommand{\tvec}{\mathbf t}\) \(\newcommand{\uvec}{\mathbf u}\) \(\newcommand{\vvec}{\mathbf v}\) \(\newcommand{\wvec}{\mathbf w}\) \(\newcommand{\xvec}{\mathbf x}\) \(\newcommand{\yvec}{\mathbf y}\) \(\newcommand{\zvec}{\mathbf z}\) \(\newcommand{\rvec}{\mathbf r}\) \(\newcommand{\mvec}{\mathbf m}\) \(\newcommand{\zerovec}{\mathbf 0}\) \(\newcommand{\onevec}{\mathbf 1}\) \(\newcommand{\real}{\mathbb R}\) \(\newcommand{\twovec}[2]{\left[\begin{array}{r}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\ctwovec}[2]{\left[\begin{array}{c}#1 \\ #2 \end{array}\right]}\) \(\newcommand{\threevec}[3]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\cthreevec}[3]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \end{array}\right]}\) \(\newcommand{\fourvec}[4]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\cfourvec}[4]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \end{array}\right]}\) \(\newcommand{\fivevec}[5]{\left[\begin{array}{r}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\cfivevec}[5]{\left[\begin{array}{c}#1 \\ #2 \\ #3 \\ #4 \\ #5 \\ \end{array}\right]}\) \(\newcommand{\mattwo}[4]{\left[\begin{array}{rr}#1 \amp #2 \\ #3 \amp #4 \\ \end{array}\right]}\) \(\newcommand{\laspan}[1]{\text{Span}\{#1\}}\) \(\newcommand{\bcal}{\cal B}\) \(\newcommand{\ccal}{\cal C}\) \(\newcommand{\scal}{\cal S}\) \(\newcommand{\wcal}{\cal W}\) \(\newcommand{\ecal}{\cal E}\) \(\newcommand{\coords}[2]{\left\{#1\right\}_{#2}}\) \(\newcommand{\gray}[1]{\color{gray}{#1}}\) \(\newcommand{\lgray}[1]{\color{lightgray}{#1}}\) \(\newcommand{\rank}{\operatorname{rank}}\) \(\newcommand{\row}{\text{Row}}\) \(\newcommand{\col}{\text{Col}}\) \(\renewcommand{\row}{\text{Row}}\) \(\newcommand{\nul}{\text{Nul}}\) \(\newcommand{\var}{\text{Var}}\) \(\newcommand{\corr}{\text{corr}}\) \(\newcommand{\len}[1]{\left|#1\right|}\) \(\newcommand{\bbar}{\overline{\bvec}}\) \(\newcommand{\bhat}{\widehat{\bvec}}\) \(\newcommand{\bperp}{\bvec^\perp}\) \(\newcommand{\xhat}{\widehat{\xvec}}\) \(\newcommand{\vhat}{\widehat{\vvec}}\) \(\newcommand{\uhat}{\widehat{\uvec}}\) \(\newcommand{\what}{\widehat{\wvec}}\) \(\newcommand{\Sighat}{\widehat{\Sigma}}\) \(\newcommand{\lt}{<}\) \(\newcommand{\gt}{>}\) \(\newcommand{\amp}{&}\) \(\definecolor{fillinmathshade}{gray}{0.9}\)A given chemical substance \(j\) can exist in phases I and II. For phase I,
\[\mathrm{U}_{\mathrm{j}}^{*}(\mathrm{I})=\mathrm{H}_{\mathrm{j}}^{*}(\mathrm{I})-\mathrm{p} \, \mathrm{V}_{\mathrm{j}}^{*}(\mathrm{I}) \label{a} \]
\(\mathrm{U}_{\mathrm{j}}^{*}(\mathrm{I}), \mathrm{~H}_{\mathrm{j}}^{*}(\mathrm{I}) \text { and } \mathrm{V}_{\mathrm{j}}^{*}(\mathrm{I})\) are the molar thermodynamic energy, enthalpy and volume respectively of chemical substance \(j\) in phase I at pressure \(\mathrm{p}\). Chemical substance \(j\) can also exist in phase II at the same pressure \(\mathrm{p}\).
\[\mathrm{U}_{\mathrm{j}}^{*}(\mathrm{II})=\mathrm{H}_{\mathrm{j}}^{*}(\mathrm{II})-\mathrm{p} \, \mathrm{V}_{\mathrm{j}}^{*}(\mathrm{II}) \label{b} \]
Equations \ref{a} and \ref{b} are quite general. In an important application we identify phase II as the vapor phase which we assume to have the properties of a perfect gas. Phase I is the liquid state. For the process `liquid → vapor' ( i.e. vaporization) at temperature \(\mathrm{T}\),
\[\Delta_{\text {vap }} \mathrm{U}_{\mathrm{j}}^{*}(\mathrm{~T})=\Delta_{\mathrm{vap}} \mathrm{H}_{\mathrm{j}}^{*}(\mathrm{~T})-\mathrm{p} \,\left[\mathrm{V}_{\mathrm{j}}^{*}(\mathrm{~g})-\mathrm{V}_{\mathrm{j}}^{*}(\ell)\right] \nonumber \]
But at temperature \(\mathrm{T}\), \(\mathrm{V}_{\mathrm{j}}^{*}(\mathrm{~g})-\mathrm{V}_{\mathrm{j}}^{*}(\ell) \gg 0\) Also for one mole of a perfect gas, \(\mathrm{p} \, \mathrm{V}_{\mathrm{j}}^{*}(\mathrm{~g})=\mathrm{R} \, \mathrm{T}\).
Hence,
\[\Delta_{\text {vap }} \mathrm{U}_{\mathrm{j}}^{*}(\mathrm{~T})=\Delta_{\text {vap }} \mathrm{H}_{\mathrm{j}}^{*}(\mathrm{~T})-\mathrm{R} \, \mathrm{T} \nonumber \]
\(\Delta_{\text {vap }} \mathrm{H}_{\mathrm{j}}^{\mathrm{N}}(\mathrm{T})\) is obtained from the dependence of vapour pressure on temperature; see Clausius - Clapeyron Equation. Hence we obtain the molar thermodynamic energy of vaporisation.