Consider the following equilibrium
\text{A} + \text{B} \rightleftharpoons \text{AB}
and the following three experiments performed at the same temperature.
Experiment 1: To an empty, rigid container with volume V_1 is added p_{\text{A},0} of molecule \text{A} and p_{\text{B},0} of molecule \text{B}. The system is allowed to go to equilibrium, p_{\text{AB},1} is measured, and K_1 is computed as
K_{p,1}=K_1=\frac{p_{\text{AB},1}p^\circ}{p_{\text{A},1}p_{\text{B},1}}
where p_{\text{A},1} = p_{\text{A},0}-p_{\text{AB},1}
Since the experiment is carried out at constant volume, equilibrium is defined as dA = 0 so the standard free energy change computed from K_1 should correspond to a standard Helmholtz free energy change, \Delta A^\circ_1.
Experiment 2: A balloon is filled with p_{\text{A},0} of molecule \text{A} and p_{\text{B},0} of molecule \text{B}. After equilibrium the volume of the balloon is V_2 and p_{\text{AB},2} is measured and K_2 computed.
Since the experiment is carried out at constant pressure, equilibrium is defined as dG = 0 so the standard free energy change computed from K_2 should correspond to a standard Gibbs free energy change, \Delta G^\circ_2.
Experiment 3: Experiment 1 is repeated using a rigid container with volume V_2.
K does not depend on the volume, so K_3 = K_1 and \Delta A^\circ_3=\Delta A^\circ_1. However, since the temperature and final volume is the same as in Experiment 2, the internal pressure and hence the partial pressures must be the same. Thus K_3 = K_2 and \Delta A^\circ_3=\Delta G^\circ_2. It follows that
\Delta A^\circ_1=\Delta G^\circ_2
So there is really only one standard free energy change associated with Eq 1, but is it \Delta G^\circ or \Delta A^\circ?
The change in standard Helmholz free energy is not the same as the change in standard chemical potential
The equilibrium constant is related to the change in standard chemical potential
K = e^{-\Delta \mu^\circ RT}
The chemical potential is defined as
\mu _X = {\left( {\frac{{\partial G}}{{\partial {n_X}}}} \right)_{p,T,n'}} = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}}
For a one-component system, G = nG_m, and the chemical potential is simply the molar Gibbs energy of the substance because
\mu = {\left( {\frac{{\partial G}}{{\partial {n_X}}}} \right)_{p,T,n'}} = {\left( {\frac{{\partial nG_m^{}}}{{\partial {n_X}}}} \right)_{p,T,n'}} = G_m
so we can write
K = e^{-\Delta G^\circ RT}
where
\Delta G^\circ = G^\circ_m(\text{AB)} -G^\circ_m(\text{A)} -G^\circ_m(\text{B)}
However, the chemical potential is not equal to the molar Helmholtz free energy
A_m = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{p,T,n'}} \ne {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}}
Notice that the middle term is for constant p and the last term is for constant V. So I can't write the equilibrium constant using \Delta A^\circ computed partial molar standard Helmholtz free energies
K = {e^{ - \Delta {\mu ^{\circ}}/RT}} \ne {e^{ - \Delta {A^{\circ}}/RT}}
Here's why. The Helmholtz free energy can be written in terms of the partition function Q=q^N/N!
A = -nRT\ln \left( {\frac{{eq}}{{n{N_A}}}} \right) = -nRT\ln \left( {\frac{{eq_0V}}{{n{N_A}}}} \right)
The chemical potential is
\mu _X = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}} = - RT\ln \left( {\frac{q}{{n{N_A}}}} \right)
To get the partial molar Helmholtz free energy we need to keep p constant, so we substitute V=nRT/p before differentiating, which cancels out the n in the parenthesis
A_m = -RT\ln \left( {\frac{{e{q_0}RT}}{{{N_A}p}}} \right) = - RT\ln \left(\frac{eq}{N_A} \right)
So from this we can see that
\mu_X = A_m + RT
In the case of G
G = A + RT =-nRT\ln \left( {\frac{{q}}{{n{N_A}}}} \right)
and we make the substitution V=nRT/p before differentiating to find \mu
\mu = - RT\ln \left(\frac{q}{N_A} \right) = G_m = A_m + RT
So measuring the equilibrium constant for the reaction in Eq 1 gives us
\Delta \mu^\circ = \Delta G^\circ = \Delta A^\circ - RT

This work is licensed under a Creative Commons Attribution 4.0
\text{A} + \text{B} \rightleftharpoons \text{AB}
and the following three experiments performed at the same temperature.
Experiment 1: To an empty, rigid container with volume V_1 is added p_{\text{A},0} of molecule \text{A} and p_{\text{B},0} of molecule \text{B}. The system is allowed to go to equilibrium, p_{\text{AB},1} is measured, and K_1 is computed as
K_{p,1}=K_1=\frac{p_{\text{AB},1}p^\circ}{p_{\text{A},1}p_{\text{B},1}}
where p_{\text{A},1} = p_{\text{A},0}-p_{\text{AB},1}
Since the experiment is carried out at constant volume, equilibrium is defined as dA = 0 so the standard free energy change computed from K_1 should correspond to a standard Helmholtz free energy change, \Delta A^\circ_1.
Experiment 2: A balloon is filled with p_{\text{A},0} of molecule \text{A} and p_{\text{B},0} of molecule \text{B}. After equilibrium the volume of the balloon is V_2 and p_{\text{AB},2} is measured and K_2 computed.
Since the experiment is carried out at constant pressure, equilibrium is defined as dG = 0 so the standard free energy change computed from K_2 should correspond to a standard Gibbs free energy change, \Delta G^\circ_2.
Experiment 3: Experiment 1 is repeated using a rigid container with volume V_2.
K does not depend on the volume, so K_3 = K_1 and \Delta A^\circ_3=\Delta A^\circ_1. However, since the temperature and final volume is the same as in Experiment 2, the internal pressure and hence the partial pressures must be the same. Thus K_3 = K_2 and \Delta A^\circ_3=\Delta G^\circ_2. It follows that
\Delta A^\circ_1=\Delta G^\circ_2
So there is really only one standard free energy change associated with Eq 1, but is it \Delta G^\circ or \Delta A^\circ?
The change in standard Helmholz free energy is not the same as the change in standard chemical potential
The equilibrium constant is related to the change in standard chemical potential
K = e^{-\Delta \mu^\circ RT}
The chemical potential is defined as
\mu _X = {\left( {\frac{{\partial G}}{{\partial {n_X}}}} \right)_{p,T,n'}} = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}}
For a one-component system, G = nG_m, and the chemical potential is simply the molar Gibbs energy of the substance because
\mu = {\left( {\frac{{\partial G}}{{\partial {n_X}}}} \right)_{p,T,n'}} = {\left( {\frac{{\partial nG_m^{}}}{{\partial {n_X}}}} \right)_{p,T,n'}} = G_m
so we can write
K = e^{-\Delta G^\circ RT}
where
\Delta G^\circ = G^\circ_m(\text{AB)} -G^\circ_m(\text{A)} -G^\circ_m(\text{B)}
However, the chemical potential is not equal to the molar Helmholtz free energy
A_m = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{p,T,n'}} \ne {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}}
Notice that the middle term is for constant p and the last term is for constant V. So I can't write the equilibrium constant using \Delta A^\circ computed partial molar standard Helmholtz free energies
K = {e^{ - \Delta {\mu ^{\circ}}/RT}} \ne {e^{ - \Delta {A^{\circ}}/RT}}
Here's why. The Helmholtz free energy can be written in terms of the partition function Q=q^N/N!
A = -nRT\ln \left( {\frac{{eq}}{{n{N_A}}}} \right) = -nRT\ln \left( {\frac{{eq_0V}}{{n{N_A}}}} \right)
The chemical potential is
\mu _X = {\left( {\frac{{\partial A}}{{\partial {n_X}}}} \right)_{V,T,n'}} = - RT\ln \left( {\frac{q}{{n{N_A}}}} \right)
To get the partial molar Helmholtz free energy we need to keep p constant, so we substitute V=nRT/p before differentiating, which cancels out the n in the parenthesis
A_m = -RT\ln \left( {\frac{{e{q_0}RT}}{{{N_A}p}}} \right) = - RT\ln \left(\frac{eq}{N_A} \right)
So from this we can see that
\mu_X = A_m + RT
In the case of G
G = A + RT =-nRT\ln \left( {\frac{{q}}{{n{N_A}}}} \right)
and we make the substitution V=nRT/p before differentiating to find \mu
\mu = - RT\ln \left(\frac{q}{N_A} \right) = G_m = A_m + RT
So measuring the equilibrium constant for the reaction in Eq 1 gives us
\Delta \mu^\circ = \Delta G^\circ = \Delta A^\circ - RT
This work is licensed under a Creative Commons Attribution 4.0
No comments:
Post a Comment