Showing posts with label Chemical Potential. Show all posts
Showing posts with label Chemical Potential. Show all posts

Friday, May 15, 2015

Osmotic Pressure Calculation

By thermodynamics, the chemical potential of solvent (water) in a solution containing pure solvent and solute is expressed as,

\[ \mu_{w}\left(l,x_{w},p+\pi\right)=\mu_{w}^{0}\left(l,p+\pi\right)+\nu RT\ln a_{w}
\]

where, $\mu_w$ is the chemical potential of solvent, which is a function of solvent, $l$, mole fraction of solvent $x_w$, external pressure, $p$, and additional osmotic pressure exerted by solutes, $\pi$ (whereas, for the pure solvent, $x_w$ goes away); $\nu$ is the dissociation coefficient (a solute dissociates into $\nu$ ions); $R$ is the gas constant; $T$ is temperature in consistent with $R$; $a_w$ is water activity.

The addition to the pressure is expressed through the expression for the energy of expansion:

\[ \mu_{w}^{o}(l,p+\pi)=\mu_{w}^{0}(l,p)+\int_{p}^{p+\pi}V\mathrm{d}p
\]


where, $V$ is the molar volume of solvent.

To balance the chemical potentials of solvent for two solutions with and without solute separated by semipermeable membrane, $\mu_{w}\left(l,x_{w},p+\pi\right)$ and $\mu_{w}\left(l,p\right)$,

\[ -\nu RT\ln a_{w}=\int_{p}^{p+\pi}V\mathrm{d}p

\]

Thus, osmotic pressure is expressed as opposed to pure solvent (water), in which water activity is 1,

\[ \pi=-\nu RT/V\ln a_{w}

\]

Conventionally, the gradient of osmotic pressure is approximated using the concentration or the mass fraction of solute (salt). The derivation is shown as follows.

A definition of water activity is,

\[ a_{w}=l_{w}x_{w}=l_w(1-x_s)
\]


where, $l_w$ is activity coefficient; and $x_w$ is the mole fraction of water in aqueous fraction ($x_s=1-x_w$ is the mole fraction of solute). By Raoult's law, $l_w$ is usually approximated as unity in dilute solution.

Using Taylor series, $\ln l_w(1-x_s) \approx -x_s$.

Thus, the osmotic pressure becomes ($C$ is the molar concentration of solute),

\[ \pi=-\nu RT/V\ln a_{w} = \nu RT/V x_s = \nu RT C

\]


Also, the relation between the gradients of osmotic pressure and chemical potential is,

\[ \nabla\pi=-\frac{1}{V}\cdot\nabla\mu_{w}

\]

The relation between the gradient of osmotic pressure and the concentration or the mass fraction of solute (salt) becomes,

\[  \nabla\pi\approx\nu RT\nabla C=\nu RT\frac{\rho}{M_{s}}\nabla X
\]


where, $\rho$ is the solution density; $M_s$ is molar mass of solute; and $X$ is the mass fraction of solute.