Chapter 5: Free Energy and Chemical Thermodynamics
Outline
Free Energy as Available Work
Free Energy as Force toward Equilibrium
Chapter 5: Free Energy and Chemical Thermodynamics
Applications of the laws of thermodynamics Part 1: Chemical reactions
X Bai
SDSMT, Physics
Fall 2014
X Bai
Chapter 5: Free Energy and Chemical Thermodynamics
Outline
Free Energy as Available Work
Free Energy as Force toward Equilibrium
1 Free Energy as Available Work Basic tools Electrolysis, Fuel Cells, Batteries Thermodynamic Identities revisit: In chemical reactions
2 Free Energy as Force toward Equilibrium Non-isolated system
X Bai
Chapter 5: Free Energy and Chemical Thermodynamics
Outline
Basic tools
Free Energy as Available Work
Free Energy as Force toward Equilibrium
What are the typical thermal conditions for chemical reactions and
other transformations of matter?
Electrolysis:
H2O
H2
+
1 2
O2
Energy: may vary (reactions may release or absorb heat),
chemical reactions happen in non-isolated system
Volume: often not fixed, new substances can be created
Number of particles: often change in reactions
Pressure: often fixed, equal to the environment
Temperature: equal to the environment, approximately fixed
We are looking for Tools for fixed T and P !!!
X Bai
Chapter 5: Free Energy and Chemical Thermodynamics
Outline
Basic tools
Free Energy as Available Work
Free Energy as Force toward Equilibrium
To describe the energy budget:
1. Enthalpy :
H U + PV
(1)
H: The total energy to create the system AND let it stay
in the environment with pressure P - Need the work.
2. Helmholtz Free Energy :
F U - TS
(2)
U: The total energy to create the system;
TS = Q: The heat from the environment, with T fixed.
F : energy needed in the format of work if the
system is created from nothing.
3. Gibbs Free Energy :
G U - TS + PV = F + PV = H - TS
(3)
PV is the work done under the constant pressure P.
X Bai
Chapter 5: Free Energy and Chemical Thermodynamics
Outline
Free Energy as Available Work
H, G, Q=TS, W=PV: An example
Free Energy as Force toward Equilibrium
Nothing Rabbit
Left: in an environment with pressure P (without heat exchange with the environment)
W = PV : push out a volume for the rabbit H = Urabbit + PV : Required entire energy, the Enthalpy.
Right: in chemical reactions that can have heat exchange with the environment. Q = TS: can flow in as heat from the environment. G = H - TS: Energy the magician needs to provide.
X Bai
Chapter 5: Free Energy and Chemical Thermodynamics
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