7.2: Partial Molar Volume
- Page ID
- 84331
\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)
\( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)
\( \newcommand{\dsum}{\displaystyle\sum\limits} \)
\( \newcommand{\dint}{\displaystyle\int\limits} \)
\( \newcommand{\dlim}{\displaystyle\lim\limits} \)
\( \newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\)
( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\)
\( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\)
\( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\)
\( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\)
\( \newcommand{\Span}{\mathrm{span}}\)
\( \newcommand{\id}{\mathrm{id}}\)
\( \newcommand{\Span}{\mathrm{span}}\)
\( \newcommand{\kernel}{\mathrm{null}\,}\)
\( \newcommand{\range}{\mathrm{range}\,}\)
\( \newcommand{\RealPart}{\mathrm{Re}}\)
\( \newcommand{\ImaginaryPart}{\mathrm{Im}}\)
\( \newcommand{\Argument}{\mathrm{Arg}}\)
\( \newcommand{\norm}[1]{\| #1 \|}\)
\( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\)
\( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\AA}{\unicode[.8,0]{x212B}}\)
\( \newcommand{\vectorA}[1]{\vec{#1}} % arrow\)
\( \newcommand{\vectorAt}[1]{\vec{\text{#1}}} % arrow\)
\( \newcommand{\vectorB}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)
\( \newcommand{\vectorC}[1]{\textbf{#1}} \)
\( \newcommand{\vectorD}[1]{\overrightarrow{#1}} \)
\( \newcommand{\vectorDt}[1]{\overrightarrow{\text{#1}}} \)
\( \newcommand{\vectE}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash{\mathbf {#1}}}} \)
\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \)
\(\newcommand{\longvect}{\overrightarrow}\)
\( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)
\(\newcommand{\ket}[1]{\left| #1 \right>}\)
\(\newcommand{\bra}[1]{\left< #1 \right|}\)
\(\newcommand{\braket}[2]{\left< #1 \vphantom{#2} \right| \left. #2 \vphantom{#1} \right>}\)
\(\newcommand{\braopket}[3]{\left< #1 \vphantom{#2}\vphantom{#3} \right| #2 \vphantom{#1}\vphantom{#3} \left| #3 \vphantom{#1}\vphantom{#2} \right>}\)
\(\newcommand{\qmvec}[1]{\mathbf{\vec{#1}}}\)
\(\newcommand{\op}[1]{\hat{\mathbf{#1}}}\)
\(\newcommand{\expect}[1]{\langle #1 \rangle}\)
\(\newcommand{\dfn}[1]{\emph{\textbf{#1}}}\)
The partial molar volume of compound A in a mixture of A and B can be defined as
\[ V_A = \left (\dfrac{\partial V}{\partial n_A} \right)_{p,T,n_B} \nonumber \]
Using this definition, a change in volume for the mixture can be described using the total differential of \(V\):
\[ dV = \left( \dfrac{\partial V}{\partial n_A}\right)_{p,T,n_B} dn_A + \left( \dfrac{\partial V}{\partial n_B}\right)_{p,T,n_A} dn_B \nonumber \]
or
\[ dV = V_a \, dn_A + V_b\,dn_B \nonumber \]
and integration yields
\[V = \int _0^{n_A} V_a \, dn_A + \int _0^{n_B} V_b\,dn_B \nonumber \]
\[ V = V_a \, n_A + V_b\,n_B \nonumber \]
This result is important as it demonstrates an important quality of partial molar quantities. Specifically, if \(\xi_i\) represents the partial molar property \(X\) for component i of a mixture, The total property \(X \) for the mixture is given by
\[X = \sum_{i} \xi_in_i \nonumber \]
It should be noted that while the volume of a substance is never negative, the partial molar volume can be. An example of this appears in the dissolution of a strong electrolyte in water. Because the water molecules in the solvation sphere of the ions are physically closer together than they are in bulk pure water, there is a volume decrease when the electrolyte dissolves. This is easily observable at high concentrations where a larger fraction of the water in the sample is tied up in solvation of the ions.