Chapter 17 - Chemical Thermodynamics
Chapter 17 - Chemical Thermodynamics
• FLoT: E = q + w;
Entropy
The Expansion of An Ideal Gas
Into an Evacuated Bulb
Entropy
• Thermodynamic function that describes the
number of arrangements that are available to a
system existing in a given state.
What is Entropy?
• A thermodynamic (energy) function that
describes the degree of randomness or
probability of existence.
• As a state function – entropy change depends
only on the initial and final states, but not on
how the change occurs.
Entropy
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H S T G Comments Examples
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• - + high - spontaneous at 2H2O2(l) 2H2O(l) + O2(g)
• or low all temperature
• + + high - spontaneous at CaCO3(s) CaO(s) +
CO2(g)
• high temperature
• - - low - spontaneous at N2(g) + 3H2(g) 2NH3(g)
• low temperature
• + - high + nonspontaneous at 2H2O(l) + O2(g)
2H2O2(l)
• or low all temperature
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Free Energy (G)
G
Suniv = (at constant T and P )
T
• In Thermodynamic System:
ΔG = ΔH – TΔS (at constant T and P)
Gibb’s Free Energy
• For spontaneous reactions,
Suniv = Ssys + Ssurr > 0
Ssurr = -Hsys/T
Suniv = Ssys - Hsys/T
-TSuniv = Gsys = Hsys - TSsys < 0
Gsys is called Gibb’s free energy
• Another criteria for spontaneous process is Gsys < 0
Concept Check
S = 132 J/K·mol
Ssurr = -132 J/K·mol
G = 0 kJ/mol
Spontaneous Reactions
Effect of H and S on Spontaneity
H S Result
+ spontaneous at all temps
+ + spontaneous at high temps
spontaneous at low temps
+ not spontaneous at any temp
Concept Check
Gas A2 reacts with gas B2 to form gas AB at
constant temperature and pressure. The bond
energy of AB is much greater than that of either
reactant.
Explain.
Third Law of Thermodynamics
G = G° + RT ln(P)
or
ΔG = ΔG° + RT ln(Q)
The Meaning of ΔG for a Chemical Reaction
ΔG = 0 = ΔG° + RT ln(K)
ΔG° = –RT ln(K)
Change in Free Energy to Reach Equilibrium
Qualitative Relationship Between the
Change in Standard Free Energy and the
Equilibrium Constant for a Given Reaction
Free Energy and Work
• Example-1:
• C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g), (np > nr)
Sorxn = {(3 x SoCO ) + (4 x SoH O)} – {(SoC H ) + (5 x SoO )}
2 2 3 8 2
S o
rxn < 0 if np < nr
• Example-2:
• CO(g) + 2H2(g) CH3OH(g), (np < nr)
Sorxn = (SoCH OH) – {(SoCO) + (2 x SoH )}
3 2
Example:
• Fe2O3(s) 2Fe(s) + 3/2 O2(g); Go = 740 kJ (eq-1)
• CO(g) + ½ O2(g) CO2(g); Go = -283 kJ
• 3CO(g) + 3/2 O2(g) 3CO2(g); Go = -849 kJ (eq-2)
Combining eq-1 and eq-2,
• Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g); Go = -109 kJ
Coupling Reactions in Biological System