Thermal Physics

Chapter 5

Free energy and Chemical thermodynamics

Chemical reactions and other transformations
- Not a closed system
: usually in contact with environment (at constant temperature, pressure)
: energy of the system is not conserved (+environement is conserved)
: volume is not fixed (rather pressure is fixed in many cases)

Thermodynamic potentials
- Internal energy U
- Enthalpy H
- Free energy F
- Gibbs free energy G
Thermodynamic identities

Free energies
Enthalpy
- State function
- Good for describing processes with constant pressure
- (Energy of a system) + (work needed to make room for it uder constant pressure)

H = U + PV
H = U + PV
U = Q + (-PV) + Wother

H
CP =

T P

H = Q + Wother
- At constant P, the chane in enthalpy is caused by heat (and other types of work)
: hence, H (heat content)
Suitable to describe a process happening at constant pressure and no other
types of work (other than compression-expansion) is done
: evaporation of water from an open tray is one example
Heat of vaporization (latent heat) is the H (between vapor and liquid phase)

Free energies
Helmholtz free energy
- State function
- Good for describing processes with constant temperature
- (Energy of a system) - (heat for free from an environment at T)

F = U - TS
- F is the energy that must be provided as work, when the system is created out
of nothing.
- F at constant temperature T,

F = U T S = Q + W - T S
Q: heat added to the system
(Q = TS only if no new entropy is created during the process)

F W

At constant T
W: all types of work done on the system

Free energies
Gibbs free energy
- State function
- Good for describing processes with constant temperature and pressure
- (Energy of a system) - (heat term in F) + (atmospheric work term in H)

G = U TS + PV
- G is the work needed to create a system at constant temperature and pressure
- G at constant temperature T, P

G = U TS + PV = Q + W - TS + PV
W: work (including one done by the environment, -PV)
(W = -PV + Wother ,Q -TS 0 )

G Wother
G = H - TS

At constant T, P

Example
- Problem 5.1. One mole of argon gas at room temperature and 1atm.
Compute the total energy (kinetic only), entropy, enthalpy, Helmholtz free energy,
and Gibbs free energy in Si units.

Electrolysis of Water
Electrolysis of water
- Liquid water into hydrogen and oxygen
- P, T are constant during process (as in many chemical reactions)

H2O H2 + O2

Electrolysis of Water
Electrolysis of water

H2O H2 + O2

Break-down of the process

- Enthalpy change of the process, H = 286kJ
: Heat which can be extracted if a mole of hydrogen is burned.
: Energy needed to from H2 and O2 from water (including work to make room for gases)
- Internal energy change of the system, U = 282kJ
H = U +PV , PV = nRT = 1.5 X 8.31 X 300 ~ 4kJ (work need to make room for gases)
- Other types of work needed to make the process possible, G = 237kJ
G = H TS = (286kJ 298K 163J/K)
(some of the energy can be entered as heat from environment for free)

Fuel cells
Fuel cell
- Energy extraction by combining hydrogen and oxygen to from water
- G = 237kJ of electrical work for every mole of hydrogen consumed
- 286kJ of heat to 237kJ of elecrtical work efficiency of 83%!

Battery
Battery
- Lead-acid cell used in car batteries

Pb + PbO2 + 4H+ + 2SO42- 2PbSO4 + 2H2O

Battery
Battery
- Lead-acid cell used in car batteries

Pb + PbO2 + 4H+ + 2SO42- 2PbSO4 + 2H2O

Break-down of the process

- Enthalpy change of the process, H = -316kJ/mol
- Gibbs free energy change, G = -394kJ
: The work produced at standard pressure, temperature, per mole of lead is 394kJ
: The work produced is actually more than the energy by 78kJ
: 78kJ comes from heat, absorbed from environment
Entropy increase S = 78 kJ / 298 K = 260 J/K (per mole)

- Work produced per electron is ~2.04eV

voltage of a cell is ~2V

Example
Prob.5.4. In a hydrogen fuel cell, the steps of the chemical reaction are
at electrode: H2 + 2OH- 2H2O + 2e- ;
at + electrode: O2 + H2O + 2e- 2OH-.
Calculate the voltage of the cell. What is the minimum voltage required for electrolysis?

Prob.5.5. Consider a fuel cell that uses methane (natural gas) as fuel.
CH4 + 2O2 2H2O + CO2.

Thermodynamic identities
General thermodynamic identity
- A system whose energy, volume, and number of particles can change

S
dS =
U

S
S
d U +
d V +
d N
N ,V
V N ,U
N U ,V

dU = TdS PdV + dN
U

T
S N ,V

P
V N ,S

N V , S

S
P

=
V N ,U T

=
T
N V ,U

1
=
N ,V T

Thermodynamic identity
Thermodynamic identity
- for Enthalpy

dH = dU + PdV + VdP

dU = TdS PdV + dN

dH = TdS + VdP + dN
H
=T

P,N

H
=V

S ,N

H
=

S ,P

- for Helmholtz free energy

dF = dU TdS - SdT

dU = TdS PdV + dN

dF = -SdT - PdV + dN
F
= S

V , N

F
= P

T , N

F
=

T ,V

Thermodynamic identity
Thermodynamic identity
- for Gibbs free energy

dG = dU TdS SdT + PdV + VdP

dG = -SdT + VdP + dN
G
= S

P,N

G
=V

T , N

Potential

Variables

U (S,V,N)

S, V, N

H (S,P,N)

S, P, N

F (T,V,N)

V, T, N

G (T,P,N)

P, T, N

dU = TdS PdV + dN
G
=

T , P

Example
Prob.5.9. Sketch a qualitatively accurate graph of G vs. T for a pure substance as it
changes from solid to gas at fixed pressure.

Prob.5.11. Suppose that a hydrogen fuel cell is to be operated at 75oC and 1atm.
Estimate the maximum electrical work done by the cell, using only the roomtemperature data at the back of this book.

Example
Prob.5.12. Maxwell relation

Free energy as a force toward equlibrium

Open system
- When a system is in contact with its environment
: The energy of the system is not fixed (flows between the system and environment)
: Entropy of the whole system (system + environement ) increases

dStotal = dS + dSR

dS =

1
P
dU + dV dN
T
T
T

- If V, N for the reservoir are fixed (only energy can flow)

dStotal
= dS +

1
dU R
TR

1
1
1
dStotal =
dS dU =
( dU TdS ) =
dF
T
T
T
So when T, V, N are fixed, increase in entropy of the total system is same thing
as decrease in the Helmholtz free energy of the system
Maximum entropy for isolated systems (2nd law of thermodynamics) can be stated as
minimum Helmholtz free energy of systems in thermal contact with heat reservoir

Free energy as a force toward equlibrium

Open system
- When a system is in contact with its environment
: The energy of the system is not fixed (flows between the system and environment)
: Entropy of the whole system (system + environement ) increases

dStotal = dS + dSR

dS =

1
P
dU + dV dN
T
T
T

- If N for the reservoir are fixed (energy can flow and volume can changes under constant P)

dStotal =
dS +
dStotal =
dS

1
P
dU R + dVR
TR
TR

1
P
1
1
dU dV =
( dU TdS + PdV ) =
dG
T
T
T
T

So when T, P, N are fixed, increase in entropy of the total system is same thing
as decrease in the Gibbs free energy of the system
Maximum entropy for isolated systems (2nd law of thermodynamics) can be stated as
minimum Gibbs free energy of systems in thermal contact with heat reservoir

Free energy as a force toward equlibrium

Summary
- When the number of particles in the system is fixed

At constant energy and volume (U, V), S tends to increase

At constant temperature and volume (T, V), F tends to decrease
At constant temperature and pressure (T, P), G tends to decrease

F = U - TS

G = U TS + PV

Extensive and intensive quantities

Extensive quantities
- If the size of the system is doubled, the variables are also doubled
- V, N, S, U, H, F, G, mass
Intensive quantities
- The variables are unchanged even if the size of the system has changed
- T, P, , density

- If you multiply an extensive quantity by an intensive quantity, you end up with

an extensive quantity; volume density = mass
- If you divide one extensive quantity by another, you get an intensive quantity
- Adding two quantities of same types yields another quantity of same type
- Adding two quantities of different types are not allowed.
dG = -SdT + VdP + dN

G and
Gibbs free energy and chemical potential
G
= S

P,N

G
=V

T , N

G
=

T , P

G = N
- Chemical potential is just the Gibbs free energy per particle
- Ideal gas case (fixed amount of gas at a fixed temperature)

1 G V kT
=
= =
P N P N
P

(T , P ) (T , P 0 ) =
kT ln ( P P 0 )

(=
T , P ) 0 (T ) + kT ln ( P P 0 )