phys 241

Thermodynamics

CH6
Thermodynamics Potentials
U, H, F, &G
Maxwell relations
 Thermodynamics potentials
The central equation of thermodynamics

d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺
• Although U is well defined (sum of particles K.E. and P.E.), it is not the most suitable potential to use for specific
thermodynamics processes [H, F, and G have direct link with experiments]
• Furthermore, U, H, F, and G provide extremely useful thermodynamic relations between P, V, T, and S [Maxwell
relations]

Internal Energy U Enthalpy H Helmholtz F Gibbs G

function U(V,S) H(P,S) F(T,V) G(T,P)
H=U+PV F=U-TS G=U+PV-TS
differential d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺 d𝑯 = 𝑽𝒅𝑷 + 𝑻𝒅𝑺 d𝑭 = −𝑷𝒅𝑽 − 𝑺𝒅𝑻 d𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻
Maxwell relations 𝜕𝑃 𝜕𝑇 𝜕𝑉 𝜕𝑇 𝜕𝑃 𝜕𝑆 𝜕𝑉 𝜕𝑆
=− = = =−
𝜕𝑆 𝑉
𝜕𝑉 𝑆
𝜕𝑆 𝑃
𝜕𝑃 𝑆
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑃 𝑇
max useful
Important results 𝝏𝑺 𝝏𝑺 W ≤ −Δ𝑭 W ≤ −Δ𝑮
𝑪𝑽 = 𝑻 𝑪𝑷 = 𝑻
𝝏𝑻 𝑽
𝝏𝑻 𝑷
QP = ΔH Δ𝑭 ≤ 𝟎 equilibrium at Δ𝑮 ≤ 𝟎 equilibrium at
constant V and T constant P andT
 Internal Energy U
Starting from the central equation of thermodynamics

d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺
𝜕𝑈 𝜕𝑈
−𝑷 = 𝑻=
𝜕𝑈 𝜕𝑈 𝜕𝑉 𝜕𝑆 𝑉
𝑆
d𝑼(𝑽, 𝑺) = 𝒅𝑽 + 𝒅𝑺
𝜕𝑉 𝑆
𝜕𝑆 𝑉

1. since dU is path independent (exact differential), then

d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺

𝜕𝑃 𝜕𝑇
− = 1st Maxwell relation
𝜕𝑆 𝑉
𝜕𝑉 𝑆

2. Heat capacity at a constant volume

ഥ 𝑽
𝒅𝑸 𝝏𝑼 𝝏𝑺
𝑪𝑽 = = from central equation  d𝑼 = 𝑻𝒅𝑺 𝑪𝑽 = 𝑻
𝒅𝑻 𝝏𝑻 𝝏𝑻 𝑽
𝑽
 Enthalpy H
H is useful for problems in which P is the important variable and is very useful in chemical reaction
Starting from the definition of enthalpy 𝑯 = 𝑼 + 𝑷𝑽
𝒅𝑯 = 𝒅𝑼 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺

𝜕𝐻 𝜕𝐻
𝒅𝑯 = 𝑽𝒅𝑷 + 𝑻𝒅𝑺 d𝑯(𝑷, 𝑺) = 𝒅𝑷 + 𝒅𝑺
𝜕𝑃 𝑆
𝜕𝑆 𝑃

1. since dH is path independent (exact differential), then:

𝜕𝑉 𝜕𝑇
= 2nd Maxwell relation
𝜕𝑆 𝑃
𝜕𝑃 𝑆

2. Heat capacity at a constant pressure

ഥ 𝑷
𝒅𝑸 𝝏𝑯 𝝏𝑺
𝑪𝑷 = = from dH equation  d𝑯 = 𝑻𝒅𝑺 𝑪𝑷 = 𝑻
𝒅𝑻 𝝏𝑻 𝑷
𝝏𝑻 𝑷

3. Chemical processes and heat of reaction (at const pressure) 𝑸𝒓𝒆𝒗

𝑷 = ΔH

𝑸𝑷 = ΔH
 Reversible an Irreversible work
During a reversible work, pressures (forces) are always in equilibrium between the
system and environment  we can use the equation of state (provides the correct path
on the P-V diagram) and calculate the work by integrating
ഥ 𝑹 = −𝑷𝒅𝑽
𝒅𝑾
If work is irreversible, pressure (forces) are not in equilibrium between the system and
environment, then work cannot be calculated by integrating the equation of state (doesn’t provide
the correct path on the P-V diagram)

However, work can be calculated even if its is irreversible. If the environment pressure
is assumed to be constant during an irreversible process (e.g. mass (M) and vacuum as
an environment)
Work done by (or on) the system is the opposite of that of the environment (in addition
to K.E. of the mass) 𝟏
𝑾𝒆𝒏𝒗 + 𝑾𝒔𝒚𝒔 = 𝑲. 𝑬.𝒎𝒂𝒔𝒔 −𝐦 𝒈 . 𝒉 + 𝑾𝒔𝒚𝒔 = 𝑴𝒗𝟐 " − " Added for conventional
definition of system work
𝟐
If the the mass K.E. is zero, then
𝑾𝒔𝒚𝒔 = −𝑾𝒆𝒏𝒗 = −𝐦𝐠𝐡𝐦𝐚𝐱 K.E. of M is zero when the weight passes the
equilibrium point and reaches the max height
If the mass is stopped at equilibrium h, then 𝑾𝒔𝒚𝒔 = −𝑾𝒆𝒏𝒗 = −𝐦𝐠𝐡 Note that K.E. of mass M is assumed to be
returned back to the system when M is
stopped
 Enthalpy H
3. Chemical processes at const-pressure and heat of reaction (𝑸𝒓𝒆𝒗
𝑷 = ΔH)

Δ𝑼 = 𝑸𝑷 − 𝑷𝟎 Δ𝑽

𝑸𝑷 = Δ𝑼 + 𝑷𝟎 Δ𝑽 = Δ𝑼 + Δ𝑷𝑽 = Δ𝑯
pressure P = P0 at the start and end of the process (P for the system may be
different from P0 during the reaction)

𝑸𝑷 = Δ𝑯 (𝑷𝒔𝒚𝒔𝒕𝒆𝒎 = 𝑷𝟎 𝒂𝒕 𝒆𝒏𝒅 𝒑𝒐𝒊𝒏𝒕𝒔)

• ΔH is calculated and tabulated usually at T=298.15 K and P=1 bar as the formation heat of a substance from
its most stable pure elements at T=298.15 K and P=1
• The enthalpy of formation of an element in its standard state is zero at every temperature
• The heat reaction = ΔHproducts - ΔHreactants
H2(g)+ 2O2(g)2H2O(l) 4Fe(s)+ 3O2(g)2Fe2O3 (s)

ΔH=[2(-241.818)]-[0+2x0] kJ ΔH=[2(-824.2 )]-[4x0+3x0] kJ

ΔH=-241.818 kJ/mol ΔH=-824.2 kJ/mol

 Helmholtz F
F is useful for problems in which T and V are the important variables and is very useful in statistical mechanics

Starting from the definition of Helmholtz potential 𝑭 = 𝑼 − 𝑻𝑺

𝒅𝑭 = 𝒅𝑼 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻 d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺

𝜕𝐹 𝜕𝐹
𝒅𝑭 = −𝑷𝒅𝑽 − 𝑺𝒅𝑻 d𝑭(𝑽, 𝑻) = 𝒅𝑽 + 𝒅𝑻
𝜕𝑉 𝑇
𝜕𝑇 𝑉

1. since dF is path independent (exact differential), then:

𝜕𝑃 𝜕𝑆
= 3rd Maxwell relation
𝜕𝑇 𝑉
𝜕𝑉 𝑇

2. Maximum work obtainable from a system in which there is no change in temperature

W ≤ −Δ𝑭 no change in T at end points

3. Equilibrium condition for a system in thermal contact with a heat reservoir and held at constant volume
Δ𝑭 ≤ 𝟎
 Helmholtz F
2. Maximum work obtainable from a system in which there is no change in temperature
ignoring friction forces
• In classical mechanics, the work performed by the system is equal to the decrease in potential energy (falling object
w=mgh)
• In thermodynamics, the decrease in the system energy can be done as a work done by the system on the surrounding or
heat transferred from the system to the surroundings (Carnot notes)
• Consider a system which is in thermal contact with the surroundings at T0 (end points of the process are at T0, but not
necessarily the intermediate T of the system)
• Due to an additional degree of freedom (chemical energy), the system T and/or P can change during the process
• Such a system can be portrayed as in the next figure
• The total entropy change of the system and reservoir are

Δ𝑆 + Δ𝑆0 ≥ 0
−𝑄
𝑄 Δ𝑆0 =
𝑇0
Δ𝑆 − ≥0
𝑇0
𝑄 − 𝑇0 Δ𝑆 ≤ 0
Δ𝑈 = Q − W
Δ𝑈 + 𝑊 − 𝑇0 Δ𝑆 ≤ 0
Δ 𝑈 − 𝑇𝑆 + W ≤ 0 in a process in which the end point temperatures are the
same as the surroundings, the maximum work obtainable
The equality sign holds
for a reversible process
W ≤ −Δ𝐹 no change in T at end points is equal to the decrease in the Helmholtz function
 Helmholtz F
3. Equilibrium condition for a system in thermal contact with a heat reservoir and held at constant volume

Δ𝑆 + Δ𝑆0 ≥ 0 −𝑄
Δ𝑆0 =
𝑄 𝑇0
Δ𝑆 − ≥ 0
𝑇0
𝑄 − 𝑇0 Δ𝑆 ≤ 0
Δ𝑈 = Q
Δ𝑈 − 𝑇0 Δ𝑆 ≤ 0
Δ𝑈 − Δ𝑇𝑆 ≤ 0

Δ(𝑈 − 𝑇𝑆) ≤ 0 Due to an additional degree of freedom (chemical

energy), the system T changes during the process
but the system temperature is T0 at end points

Δ𝑭 ≤ 𝟎
The condition for thermodynamic equilibrium in a system in
thermal contact with a heat reservoir and maintained at
constant volume is that the Helmholtz function is a minimum
 Gibbs G
G is useful for problems in which P and T are the important variables and is very useful in chemistry and in the study of systems
with two phases mixture of a substance (e.g. ice and water)
Starting from the definition of Gibbs potential G= 𝑼 + 𝑷𝑽 − 𝑻𝑺 d𝑼 = −𝑷𝒅𝑽 + 𝑻𝒅𝑺
𝒅𝑮 = 𝒅𝑼 + 𝑷𝒅𝑽 + 𝑽𝒅𝑷 − 𝑻𝒅𝑺 − 𝑺𝒅𝑻
𝜕𝐺 𝜕𝐺
𝒅𝑮 = 𝑽𝒅𝑷 − 𝑺𝒅𝑻 d𝑮(𝑷, 𝑻) = 𝒅𝑷 + 𝒅𝑻
𝜕𝑃 𝑇
𝜕𝑇 𝑃

1. since dG is path independent (exact differential), then:

𝜕𝑉 𝜕𝑆
=− 4th Maxwell relation
𝜕𝑇 𝑃
𝜕𝑃 𝑇

2. Maximum useful work obtainable from a system in which there is no change in temperature or pressure
W 𝑢𝑠𝑒𝑓𝑢𝑙 ≤ −Δ𝐆 no change in T and P at end points

3. Equilibrium condition for a system in thermal and mechanical contact with a heat and pressure reservoir
Δ𝐆 ≤ 𝟎
 Gibbs G
2. Maximum useful work obtainable from a system in which there is no change in temperature or pressure

• Let’s start from the maximum work obtained from a system in which there is no change in temperature

W ≤ −Δ𝐹 no change in T

• Since there is always a wasteful work done on the surrounding W 𝑤𝑎𝑠𝑡𝑒 = 𝑃0 Δ𝑉

W useful + P0 Δ𝑉 ≤ −Δ𝐹
W useful ≤ −(Δ𝐹 + P0 Δ𝑉)

W useful ≤ −Δ(𝐹 + 𝑃𝑉)

The equality sign holds
for a reversible process W useful ≤ −Δ𝐺 no change in T and P at end points

For a simple system fixing P and T  fixing V and no

in a process in which the end point temperatures and pressure are work is done
the same as the surroundings, the maximum useful work obtainable For a change in volume to occur under these
is equal to the decrease in the Gibbs function conditions, there must be additional degree of
freedom within the system (e.g. internal chemical
reaction)
 Gibbs G
3. Equilibrium condition for a system in thermal and mechanical contact with a heat and pressure reservoir

Δ𝑆 + Δ𝑆0 ≥ 0
−𝑄
Δ𝑆0 =
𝑄 𝑇0
Δ𝑆 − ≥0
𝑇0
𝑄 − 𝑇0 Δ𝑆 ≤ 0
Δ𝑈 = Q − P0 ΔV
Δ𝑈 + P0 ΔV − 𝑇0 Δ𝑆 ≤ 0

Δ𝑈 + Δ(𝑃V) − Δ(𝑇𝑆) ≤ 0

Δ(𝑈 + 𝑃𝑉 − 𝑇𝑆) ≤ 0

Δ𝐆 ≤ 𝟎
The condition for thermodynamic equilibrium in a system in
thermal and mechanical contact with a heat and pressure
reservoir is that the Gibbs function is a minimum
 Gibbs G
3. Equilibrium condition for a system in thermal and mechanical contact with a heat and pressure reservoir
G = 𝑼 + 𝑷𝑽 − 𝑻𝑺 Δ𝐆 ≤ 𝟎
G = 𝑯 − 𝑻𝑺 → Δ𝑮 = Δ𝑯 − 𝑺Δ𝑻 − TΔ𝑺 Δ𝐇 − 𝐓𝟎 ΔS ≤ 𝟎
This result for the minimization of G is of enormous importance because the conditions at which this result is true, are
encountered in many natural processes where the surrounding atmosphere at P0 and T0 acts as a pressure and heat reservoir
For 1 mol at T=0 oC:
H2O(solid)H2O(liquid)
ΔH=6 kJ
ΔS=(6/273) kJ/K Δ𝐇 − 𝐓𝟎 ΔS =?
Assume ΔH and ΔS don’t change much at
1oC and -1oC

1 oC 0 oC -1 oC
Δ𝐆 6000 6000 6000
6000 − 𝟏 + 𝟐𝟕𝟑 = −ve 6000 − (𝟎 + 𝟐𝟕𝟑) =0 6000 − −𝟏 + 𝟐𝟕𝟑 = +ve
If H2O is 273 273 273
water
Δ𝐆 6000 6000 6000
−6000 + 𝟏 + 𝟐𝟕𝟑 = +ve 6000 − (𝟎 + 𝟐𝟕𝟑) =0 −6000 + −𝟏 + 𝟐𝟕𝟑 = −ve
If H2O is 273 273 273
ice
(note that the use of Δ𝐆 ≤ 𝟎 requires H2O to be at the same T before and after the change for each case. This means water is super cooled at -
1oC and ice is super heated at 1oC)
 Energy needed to create the system is 𝑼

𝐓𝟎 ≈ 0 K
𝑷𝟎 ≈ 0 bar

Energy needed to create the system is

𝑼 + 𝑷𝑽 − 𝑻𝑺

𝐓𝟎 = 300 K
𝑷𝟎 = 1 bar

http://hyperphysics.phy-astr.gsu.edu/
Availability Function A

Independent reading
Maxwell Relations & Example of their Use
Society for the Prevention
of Teaching Vectors

Note that (-) appears when you have 𝜕P/𝜕S or 𝜕S/𝜕P

𝜕𝑃 𝜕𝑇 𝜕𝑉 𝜕𝑇 𝜕𝑃 𝜕𝑆 𝜕𝑉 𝜕𝑆
=− = = =−
𝜕𝑆 𝑉
𝜕𝑉 𝑆
𝜕𝑆 𝑃
𝜕𝑃 𝑆
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑃 𝑇
 Maxwell Relations & Example of their Use
A block of metal was squashed reversibly and isothermally (at T0) from a pressure Pi to Pf
Heat will flow out o f the metal. Let us calculate how much heat flows out of the block
The crucial step is knowing where to start by using the appropriate basic equation
Here, we want to calculate Q and it is reversible process:
ҧ 𝑹 = 𝑇 𝑑𝑆
𝑑𝑄
Now we need to find dS to find QR and in the question T is constant and the change is given in P
𝑆 = 𝑆(𝑇, 𝑃)

𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑃 + 𝑑𝑇
𝜕𝑃 𝜕𝑇 1 𝜕𝑉
𝑇 𝑃 β=
𝑉 𝜕𝑇 𝑃
𝑃𝑓
𝜕𝑆
𝑄𝑅 = 𝑇0 න 𝑑𝑃
𝑃𝑖 𝜕𝑃 𝑇
𝑃𝑓 𝑃𝑓
𝜕𝑉 Assuming:
𝑄𝑅 = 𝑇0 න − 𝑑𝑃 = −𝑇0 න 𝑉β 𝑑𝑃 ≈ −𝑇0 𝑉β (𝑃𝑓 − 𝑃𝑖 ) 1. small change of V with
𝑃𝑖 𝜕𝑇 𝑃 𝑃𝑖 respect to change in P
(reasonable in solid)
2. β is constant