Chapter 19

Overview
Spontaneous Processes
Entropy
Second Law of Thermo.
Standard Molar Entropy
Gibbs Free Energy
Free Energy & Temp. & Equil. Const.

Thermodynamics and Entropy
Gibbs Free Energy DG = DH - TDS
Thermo. and the Equilibrium Constant
DG = -RT ln K
eq

Thermodynamics and Time
Spontaneous Processes
Energy is conserved in all processes
Some processes are spontaneous
occur with no outside intervention
Some reactions are reversible
In an irreversible rxn the forward reaction is
spontaneous, its reverse reaction will be non-
spontaneous
Dependent on temp, energy & rxn direction
Thermo. and Entropy:
Thermodynamics: Energy Transfer
Difference btw product/reactant energy
Spontaneous product favored
Nonspontaneous reactant favored
Kinetics: Speed of Reactions
Can be spontaneous (prod. favored) but slow
Entropy: Measure of Disorder
Disorder is more probable than order
Increase in entropy increase in disorder
Is a state function independent of pathway
The more molecules, the smaller the probability of an
ordered system
A B
A
A
A B
B
B
In General, Entropy (DS = q
rev
/ T) of
gases > liquids > solids
more complex molecules > simpler ones
ionic solids > as ionic attractions weaken
dissolved substances > pure substances
evolved gas > dissolved gas
small entropy large entropy
DS = q
rev
/ T where q is heat transferred in a
reversible reaction to the system at constant T
DE = q + w q = heat absorbed by system
w = work done on the system
(review Ch. 5, 1
st
Law & Enthalpy)
Problem: Calculate the DS for the vaporization of
benzene. DH
vap
= 30.9 kJ/mol at 80.1C
DS = q / T
= 30.9 x 10
3
J/mol
353.1 K
= 87.5 J/mol K
liquid to vapor + 87.5 J/molK
vapor to liquid - 87.5 J/molK
Problem: Predict if entropy will increase or decrease
with each process
CO
2(g)
CO
2(s)

KCl
(s)
KCl
(aq)

MgCO
3(s)
MgO
(s)
+ CO
2(g)

decrease
increase
increase
Second Law of Thermodynamics:
The total entropy of the universe continually
increases for an irreversible process
For any product-favored reaction, DS
universe
is +
D S
universe
= D S
system
+ D S
surroundings

D S
surroundings
= q
surr.
/ T = -DH
system
/ T
For an individual system
DS
system
= S S
products
- S S
reactants

Problem: Calculate DS
system
, DS
surroundings
and
DS
universe
to determine if H
2(g)
+ Cl
2(g)
2HCl
(g)
is
product-favored.
DS
system
= +20.05 J/mol K = S S
products
- S S
reactants

DS
surroundings
= 619.5 J/mol K = -DH
system
/ T
DS
universe
= +639.6 J/mol K = D S
system
+ D S
surroundings

Since D S
universe
is positive, product-favored
Standard Molar Entropy
Denoted as S
Defined at 1 atm and 298 K
SMEs of elements not zero
S S
products
- S S
reactants

Calculate the SME of N
2(g)
+ 3H
2(g)

3(g)

Gibbs Free Energy:
D S
universe
= DS
surroundings
+ DS
system

D S
universe
= -DH
system
/ T + DS
system

-T DS
universe
= DH
system
- T DS
system

D G = -T D S
universe
= Gibbs Free Energy
D G
system
= DH
system
- T DS
system

Prediction of Spontaneous Rxn:
DH
system
DS
system


Spontaneous
- + yes, always
- - at low temperature
+ + at high temperature
+ - no, never
D G
system
= DH
system
- T DS
system
Standard Free Energy of Formation
D G
rxn
= S DG
f

prod
- S DG
f

react

D H
rxn
= S DH
f

prod
- S DH
f

react
Standard Enthalpy of Formation
DS
rxn
= S S
prod
- S S
react
Standard Molar Entropy of Rxn
Free Energy & Eq. Constant
Free energy is related to equil. constant
DG = DG + RT ln Q for rxn not at equil.
0 = DG + RT ln K for a rxn at equil.
DG free energy, non-standard conditions
DG free energy, standard conditions
DG negative K > 1
DG zero K = 1
DG positive K < 1