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THERMODYNAMICS
Entropy, Free Energy,
and Equilibrium
nonspontaneous
spontaneous
nonspontaneous
Spontaneous reactions
H2O (s)
NH4NO3 (s)
disorder
S = Sf - Si
If the change from initial to final results in an increase in randomness
Sf > Si
S > 0
For any substance, the solid state is more ordered than the
liquid state and the liquid state is more ordered than gas state
Ssolid < Sliquid << Sgas
H2O (s)
H2O (l)
S > 0
Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, enthalpy, pressure, volume, temperature, entropy
It is independent of
pathway
Processes that
lead to an
increase in
entropy (S > 0)
Equilibrium process:
10
cC + dD
11
Exothermic Process
Ssurr > 0
Endothermic Process
Ssurr < 0
13
14
Equilibrium process:
G = Hsys -TSsys
G < 0
G > 0
G = 0
18.4
The standard free-energy of reaction ( G0rxn) is the freeenergy change for a reaction when it occurs under standardstate conditions.
aA + bB
cC + dD
0
Grxn
= [ cG0f (C) + dG0f (D) ] - [ aG0f (A) + bG0f (B) ]
0
Grxn
= nG0f (products) - mG0f (reactants)
0
Grxn
= nG0f (products) - mG0f (reactants)
0
Grxn
= [ 12Gf0 (CO2) + 6Gf0 (H2O)] - [ 2Gf0 (C6H6)]
0
Grxn
= [ 12x394.4 + 6x237.2 ] [ 2x124.5 ] = -6405 kJ
G = H - TS
18
H0 = 177.8 kJ
S0 = 160.5 J/K
G0 = H0 TS0
At 25 0C, G0 = 130.0 kJ
G0 = 0 at 835 0C
19
G0 = 0 = H0 TS0
H2O (l)
S =
H2O (g)
H
40.79 kJ
=
T
373 K
= 109 J/K
20
Q=K
0 = G0 + RT lnK
G0 = RT lnK
21
G0 < 0
G0 > 0
22
G0 = RT lnK
At equilibrium, Q = K, and G = 0.
The equation becomes
0 = G + RT lnK
Rearranging, this becomes
G = RT lnK
or,
K = eG/RT
23
EXTRA Examples
24
4. Dissolution of a gas
Agasbecomesmoreorderedwhenitdissolvesinaliquidorsolid .
5. Atomic size or molecular complexity
Insimilarsubstances,increasesinmassrelatedirectlytoentropy.
Inallotropicsubstances,increasesincomplexity(e.g.bond
flexibility)relatedirectlytoentropy.
Ssurroundings = -
Hsystem
T
3CO2(g) + 4H2O(l)
S = [(3 mol)(S0 CO2) + (4 mol)(S0 H2O)] - [(1 mol)(S0 C3H8) + (5 mol)(S0 O2)]
S = [(3 mol)(213.7J/mol*K) + (4 mol)(69.9J/mol*K)] - [(1 mol)(269.9J/mol*K) +
(5 mol)(205.0J/mol*K)]
S = - 374 J/K
Sample Problem 2
PROBLEM:
PLAN:
4KClO3(s)
3KClO4(s) + KCl(s)
Sample Problem 2
continued
S0rxn = mS0products - nS0reactants
S0rxn = (3 mol)(151 J/mol*K) + (1 mol)(82.6 J/mol*K) (4 mol)(143.1 J/mol*K)
S0rxn = -36.8 J/K
G0rxn = H0rxn - T S0rxn
G0rxn = -144 kJ - (298K)(-36.8 J/K)(kJ/103 J)
G0rxn = -133 kJ
Sample Problem 3
PROBLEM:
2SO3(g)
Sample Problem 3
continued
(b) G0rxn = H0rxn - T S0rxn
G0rxn = -198.4kJ - (1173K)(-187.9J/mol*K)(kJ/103J)
G0rxn = 22.0 kJ; the reaction will be nonspontaneous at 900.0C
G0 = - RT lnK
Sample Problem 4
2SO3(g)
Sample Problem 4
continued
SOLUTION: (a) Calculating K at the two temperatures:
(G /RT )
G = -RTlnK so K e
0
/RT )
=-
/RT )
(8.314J/mol*K)(298K)
= 57.2
= e57.2 = 7x1024
(-141.6kJ/mol)(103J/kJ)
= e1.50 = 4.5
(-12.12kJ/mol)(103J/kJ)
(8.314J/mol*K)(973K)
= 1.50
Sample Problem 4
continued
pSO32
(pSO2)2(pO2)
(0.100)2
(0.500) (0.0100)
2
= 4.00
Since Q is < K at both temperatures the reaction will shift right; for 298K
there will be a dramatic shift while at 973K the shift will be slight.
(c) The nonstandard G is calculated using G = G0 + RTlnQ
G298 = -141.6kJ/mol + (8.314J/mol*K)(kJ/103J)(298K)(ln4.00)
G298 = -138.2kJ/mol
G973 = -12.12kJ/mol + (8.314J/mol*K)(kJ/103J)(973K)(ln4.00)
G298 = -0.9kJ/mol