The Gibbs-Helmholtz equation relates the change in Gibbs free energy (ΔG) of a system to temperature and enthalpy (H). It can be derived by taking the derivative of the Gibbs free energy equation (G = H - TS) with respect to temperature. The equation shows that ΔG/T is equal to -ΔH/T2. This allows ΔG to be determined from measurements of H at different temperatures. The Gibbs-Helmholtz equation is useful for analyzing phase transitions and determining thermodynamic properties as a function of temperature.
The Gibbs-Helmholtz equation relates the change in Gibbs free energy (ΔG) of a system to temperature and enthalpy (H). It can be derived by taking the derivative of the Gibbs free energy equation (G = H - TS) with respect to temperature. The equation shows that ΔG/T is equal to -ΔH/T2. This allows ΔG to be determined from measurements of H at different temperatures. The Gibbs-Helmholtz equation is useful for analyzing phase transitions and determining thermodynamic properties as a function of temperature.
The Gibbs-Helmholtz equation relates the change in Gibbs free energy (ΔG) of a system to temperature and enthalpy (H). It can be derived by taking the derivative of the Gibbs free energy equation (G = H - TS) with respect to temperature. The equation shows that ΔG/T is equal to -ΔH/T2. This allows ΔG to be determined from measurements of H at different temperatures. The Gibbs-Helmholtz equation is useful for analyzing phase transitions and determining thermodynamic properties as a function of temperature.
The Gibbs-Helmholtz equation relates the change in Gibbs free energy (ΔG) of a system to temperature and enthalpy (H). It can be derived by taking the derivative of the Gibbs free energy equation (G = H - TS) with respect to temperature. The equation shows that ΔG/T is equal to -ΔH/T2. This allows ΔG to be determined from measurements of H at different temperatures. The Gibbs-Helmholtz equation is useful for analyzing phase transitions and determining thermodynamic properties as a function of temperature.
7: The Gibbs-Helmholtz Equation - Chemistry LibreTexts
22.7: The Gibbs-Helmholtz Equation
22.7.0.1: Ideal gas For a mole of ideal gas we can use the gas law to integrate volume over pressure and we get
P2 ΔG molar = RT ln( ) P1
It is customary to identify one of the pressures (P1} with the standard state of 1 bar and use the plimsoll to indicate the fact that we are referring to a standard state by writing:
P o o G molar (P ) = G + RT ln( ) = G + RT ln[P ] molar molar 1
The fact that we are making the function intensive (per mole) is usually indicated by putting a bar over the G symbol, although this is often omitted for Gomolar
22.7.0.1: Solids For solids the volume does not change very much with pressure (the isothermal compressibility κ is small), so can assume it more or less constant:
G(Pf inal ) = G(Pinitial ) + ∫ V dP (from init to final) ≈ G(Pinitial ) + V ∫ dP (from init to final) = G(Pinitial ) + V ΔP
22.7.1: The Gibbs-Helmholtz Expression
G H = −S T T
Take the derivative under constant pressure of each side to get
∂ G/T H 1 ∂H ∂S ( ) = − + ( ) −( ) 2 ∂T T T ∂T ∂T P P P
We make use of the relationship between C and H and C and S
p p
∂ G/T H CP CP ( ) = − + − (22.7.1) 2 ∂T T T T P
H = − (22.7.2) 2 T
We said before that S is a first order derivative of G . As you can see from this derivation the enthalpy H is also a first order derivative, albeit not of G itself, but of G/T .
∂ ΔG/T △H ( ) = − 2 ∂T T P
The last step in the derivation simply takes the step before twice -say for the G and H at the begin and end of a process- and subtracts the two identical equations leading to a Δ symbol. In this differential form the Gibbs-Helmholtz equation can be applied to any process.
22.7.2: Gibbs Energy as a Function of Temperature
If heat capacities are know from 0 K we could determine both enthalpy and entropy by integration: T Cp S (T ) = S (0) + ∫ dT 0 T
H (T ) = H (0) + ∫ Cp dT 0
As we have seen we must be careful at phase transitions such as melting or vaporization. At these points the curves are discontinuous and the derivative C is undefined. p
T f us T boil
H (T ) = H (0) + ∫ Cp (T )solid dT + ΔH f us + ∫ Cp (T )liquid dT + ΔH vap + etc. (22.7.3)
0 T f us
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Physical_Chemistry_(LibreTexts)/22%3A_Helmhol… 1/2 8/10/22, 11:39 AM 22.7: The Gibbs-Helmholtz Equation - Chemistry LibreTexts f
T f us T boil Cp (T )solid Cp (T )liquid S (T ) = S (0) + ∫ dT + ΔS f us + ∫ dT + ΔS vap + etc. (22.7.4) 0 T T f us T
T f us T boil Cp (T )solid ΔH f us Cp (T )liquid ΔH vap = S (0) + ∫ dT + +∫ dT + + etc. (22.7.5) 0 T Tf us T f us T Tboil
with H (T = 0) = undefined and S (T = 0) = 0 from the third law of thermodynamics.
We also discussed the fact that the third law allows us to define S (0) as zero in most cases. For the enthalpy we cannot do that so that our curve is with respect to an undefined zero point. We really should plot H (T ) − H (0) and leave H (0) undefined.
Because the Gibbs free energy G = H − T S we can also construct a curve for G as a function of temperature, simply by combining the H and the S curves (Equations 22.7.3 and 22.7.5):
G(T ) = H (T ) − T S (T )
Interestingly, if we do so, the discontinuties at the phase transition points will drop out for G because at these points Δ H = T trs Δ trs S . Therefore, G is always continuous. trs
The H (0) problem does not disappear so that once again our curve is subject to an arbitrary offset in the y-direction. The best thing we can do is plot the quantity G(T ) − H (0) and leave the offset H (0) undefined. We have seen above that the derivative of G with temperature is −S . As entropy is always positive, this means that the G- curve is always descending with temperature. It also means that although the curve is continuous even at the phase transitions, the slope of the G curve is not, because the derivative −S makes a jump there. Fig. 22.7 in the book shows an example of such a curve for benzene. Note the kinks in the curve at the mp and the boiling point.
22.7: The Gibbs-Helmholtz Equation is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
