Enthalpy and Gibbs Free Energy

Adrian Down November 21, 2005

1
1.1

Enthalpy
Review: Denition

We wrote the dierential of energy dU as a function of and V , dU (, V ) = d pdV = d d(pV ) + V dp d(U + pV ) = d + V dp This motivates the denition of enthalpy, Denition (Enthalpy). H(, p) = U + pV Note. We have eliminated in favor of p in the expression for the change in energy.

H is useful in analyzing isobaric processes (those carried out with constant pressure).

1.2

Example

Consider a vessel containing some liquid nearly at its boiling point. The vessel is capped with a piston, and there is some vapor between the piston and the liquid. Suppose an amount of heat dQ is added, which causes some of the vapor to evaporate. The increased amount of gas causes more pressure on the

piston, causing it move upwards. Work is done in moving the piston. The force exerted downwards by the the piston is F = pA. The change in energy U of the liquid and the vapor is dU = dQ d(pV ) We get an expression for H, dQ = dU + d(pV ) = dH Note. The heat of vaporization is equal to the enthalpy dierence between the gas and liquid phases. (dp = 0)

It is extremely important to remember that this derivation is carried out under conditions of constant pressure. The result can be very dierent without this assumption.

2
2.1

Gibbs Free Energy

Denition

Our goal is to get an expression for the change in energy as a function of different variables than those functions which we have already obtained. From the expression for energy U , dU = d pdV = d( ) d d(pV ) + V dp d(U + pV ) = d + V dp This motivates the denition of the Gibbs free energy, Denition (Gibbs free energy). G(, p) = U t + pV G can also be written in terms of the Helmholtz free energy. G(, ) = F + pV Note. The Gibbs free energy is a useful tool for analyzing processes carried out at constant p and . 2

2.2

Example

Consider a liquid in a vessel covered with a piston that can apply a constant pressure p. The apparatus also includes a heat source (such as a bunsen burner) that can apply heat dQ, a mechanical device (such as a paddle wheel) that can apply work dW , and a thermal reservoir at temperature . The change in energy of the system is dU = dQ d(pV ) + dW
d( )

dW = d(U + pV ) = dG Note. The work done on the system is equal to the change in the Gibbs free energy.

2.3

Connection between G and the chemical potential (K & K, Ch. 9)

All of the previous derivations assumed that the number of particles was held constant, thus the chemical potential did not appear. It is possible to generalize the derivations by allowing for diusive interaction. The dierential of the energy is then dU (, V, N ) = d pdV + dN Perform the same grouping of the dierentials, dU = d( ) d d(pV ) + V dp + dN d(U + pdV ) = d + V dp + dN = dG(, p, N ) Note. Allowing for diusive interactions introduces a term proportional to that simply carries through the derivation. G can be dierentiated holding certain parameters constant to obtain new expressions for familiar parameters. = G V =
p,N

G p

=
,N

G N

p,

The expression for can be integrated, 3

G(, p, N ) = N (p, ) Note. The chemical potential is the Gibbs free energy per particle.

The Gibbs free energy and the chemical potential will be very important in the subsequent discussion of phase transitions.

Section Summary
We introduced the notion of heat and work as inexact dierentials. Heat refers to the transfer of energy. dQ = d Work, for the particular case of a gas, is dW = pdV More generally, dW is the mechanical work that is done on a system. For a reversible process, d = 0 Carnot maximum eciencies Heat engine c = Refrigerator c = 2 1 2 1 2 1

Note. c can be greater than 1, but this is only because of our denition. We discussed the Carnot cycle 4

 Alternative energy functions Fixed N Enthalpy H(, p) = U + pV dH(, p) = d + V dp The heat of vaporization is dQ = dH. Gibbs free energy G(, p) = u + pV = F + pV dG(, p) = d + V dp dW The work done on the system at constant p and is = dG. dN = 0 dG(, p, N ) = d + V dp + dN Taking partials of G yields new expressions for quantities, = G V =
p,N

G p

=
,N

G N

p,

The chemical potential is an expression for the Gibbs free energy per particle G(, p, N ) = N (p, )

4
4.1

Phase transformations (K & K, Ch. 10)

Overview

Note. This is a very complex subject about which there is a great amount of literature. We only scratch the surface in this course. 1. Motivating examples 5

 water ice water vapor ice vapor (sublimation) paramagnet (requires an external eld to be magnetized) ferromagnet (can be spontaneously magnetized) Normal 4 He superuid 4 He. 2. Brief overview of gas/liquid/solid phase transitions pV diagrams (constant ) pT curves Coexistence curve Triple point 3. Clausius-Clapeyron equation Latent heat Vapor pressure as a function of Change in boiling point with p Latent heat of vaporization of ice (sublimation) 4. Van der Walls equation Departures from the ideal gas Prediction of p V diagrams and metastable phases Critical points