Free Energy and Equilibrium

18.1 Spontaneous Processes

• Spontaneous: process that does occur
under a specific set of conditions
• Nonspontaneous: process that does
not occur under a specific set of
conditions

2
 Spontaneous Processes
• Often spontaneous processes are
exothermic, but not always….
• Methane gas burns spontaneously and
is exothermic
• Ice melts spontaneously but this is an
endothermic process…
• There is another quantity!

3
Spontaneous vs
Nonspontaneous

4
 18.2 Entropy
• Entropy (S): Can be thought of as a
measure of the disorder of a system

• In general, greater disorder means

greater entropy

5
Probability- what is the chance
that the order of the cards can
be restored by reshuffling?

6
 Microstates
• Number of microstates = nx
• n = possible positions
• x = number of molecules
• The distribution with the largest number
of microstates is the most probable
distribution of molecules.

7
Microstates - How many
different arrangements?

8
Microstates - Possible
distributions

9
Microstates - More possible
distributions

10
 Microstates
• 1868 - Boltzmann - entropy of a system
is related to the natural log of the
number of microstates (W)
S = k ln W

k = Boltzmann constant (1.38 x 1023J/K)

11
 Microstates
• Entropy is a state function just as
enthalpy
 S = Sfinal  Sinitial
Rewrite:
S = k ln Wfinal  k ln Winitial

• Wf > Wi then S > 0 entropy increases

12
 Standard Entropy
• Standard entropy: absolute entropy of a
substance at 1 atm (typically at 25C)
• Complete list in Appendix 2 of text
What do you notice about entropy values
for elements and compounds?
• Units: J/K·mol

13
Entropies

14
 Trends in Entropy
• Entropy for gas phase is greater than that of
liquid or solid of same substance
– I2 (g) has greater entropy than I2 (s)
• More complex structures have greater
entropy
– C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower
entropy
– Diamond has lower entropy than graphite

15
Entropy Changes in a System
Qualitative
• Ssolid < Sliquid

16
Entropy Changes in a System
Qualitative
• Sliquid < Svapor

17
Entropy Changes in a System
Qualitative
• Spure < Saqueous

18
Entropy Changes in a System
Qualitative
Slower temp < Shigher temp

19
Entropy Changes in a System
Qualitative
• Sfewer moles < Smore moles

20
Entropy Changes in a System
Qualitative
Determine the sign of S for the following
(qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a
solid yellow precipitate forms
3. Liquid water is heated from 22.5 C
to 55.8 C
21
 18.3 The Second and Third
Laws of Thermodynamics
• System: the reaction
• Surroundings: everything else

• Both undergo changes in entropy during

physical and chemical processes

22
 Second Law of
Thermodynamics
• Entropy of the universe increases in
a spontaneous process and remains
unchanged in an equilibrium process.

• Equilibrium process: caused to occur by

adding or removing energy from a
system that is at equilibrium

23
 Second Law of
Thermodynamics
• Mathematically speaking:
Spontaneous process:
Suniverse = Ssystem + Ssurroundings > 0

Equilibrium process:
Suniverse = Ssystem + Ssurroundings = 0

24
 Entropy Changes in the
System
Entropy can be calculated from the table
of standard values just as enthalpy
change was calculated.

Srxn = nS products  mS reactants

25
 Standard Entropy
• Calculate the standard entropy change
for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2NH3(g)  N2(g) + 3H2(g)

26
 Standard Entropy
2NH3(g)  N2(g) + 3H2(g)

Srxn = nS products  mS reactants

= [(1)(191.5 J/K · mol) + (3)(131.0 J/K · mol)]

- [(2)(193.0 J/K · mol)]
= 584.5 J/K · mol - 386 J/K · mol
Srxn = 198.5 J/K · mol (Entropy increases)
(2 mol gas  4 mol gas)
27
• Calculate the standard entropy change
for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2H2(g) + O2(g)  2H2O (g)

28
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
directly proportional to the enthalpy of
the system.
Ssurroundings   Hsystem

Notice: exothermic process corresponds

to positive entropy change in
surroundings
29
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
inversely proportional to temperature
Ssurroundings  1 / T

Combining the two expressions:

 Hsys
Ssurr 
T

30
 Entropy Changes
If the entropy change for a system is
known to be 187.5 J/Kmol and the
enthalpy change for a system is known
to be 35.8 kJ/mol, is the reaction
spontaneous?
Spontaneous if: Suniv= Ssys + Ssurr > 0

 Hsys
Ssurr 
T
31
 Entropy Changes
Is the reaction spontaneous?

35,800 J/mol
Ssys   120.0J/K mol
298 K

Suniv= 187.5 + 120.0 < 0 so the reaction

is non-spontaneous

32
Third Law of Thermodynamics
• Entropy of a perfect crystalline
substance is zero at absolute zero.

• Importance of this law: it allows us to

calculate absolute entropies for
substances

33
 18.4 Gibbs Free Energy
G = H – T S

• The Gibbs free energy, expressed in

terms of enthalpy and entropy, refers
only to the system, yet can be used to
predict spontaneity.

34
 Gibbs Free Energy
• If G < 0,negative, the forward reaction
is spontaneous.
• If G = 0, the reaction is at equilibrium.
• If G > 0, positive, the forward reaction
is nonspontaneous

35
Predicting Sign of G

36
 Predicting Temperature from
Gibbs Equation
• Set G = 0 (equilibrium condition)
0 = H – T S

Rearrange equation to solve for T- watch

for units!
This equation will also be useful to
calculate temperature of a phase
change.
37
 Example
For a reaction in which H = 125 kJ/mol
and S = 325 J/Kmol, determine the
temperature in Celsius above which the
reaction is spontaneous.
H 125 kJ/mol
T   385 K
S 0.325 kJ/K×mol

385 K  273 = 112C

38
 Standard Free Energy
Changes
Free energy can be calculated from the
table of standard values just as
enthalpy and entropy changes.

Grxn = nG products  mG reactants

39
 Standard Free Energy
Changes
Calculate the standard free-energy
change for the following reaction.
2KClO3(s)  2KCl(s) + 3O2(g)
Grxn = nG products  mG reactants
= [2(408.3 kJ/mol) + 3(0)]  [2(289.9
kJ/mol)]
= 816.6  (579.8) = 236.8 kJ/mol (spont)

40
 18.5 Free Energy and
Chemical Equilibrium
• Reactions are almost always in
something other than their standard
states.
• Free energy is needed to determine if a
reaction is spontaneous or not.
• How does free energy change with
changes in concentration?

41
 Free Energy and Equilibrium
G = G° + RT ln Q
 G = non-standard free energy
 G° = standard free energy (from
tables)
• R = 8.314 J/K·mole
• T = temp in K
• Q = reaction quotient
42
 Free Energy and Equilibrium
• Consider the reaction,
H2(g) + Cl2(g)  2 HCl(g)
How does the value of G change when
the pressures of the gases are altered
as follows at 25 C?
• H2 = 0.25 atm; Cl2 = 0.45 atm;
HCl = 0.30 atm
43
 Free Energy and Equilibrium
First, calculate standard free energy:
H2(g) + Cl2(g)  2 HCl(g)
G° = [2(95.27 kJ/mol)]  [0 + 0] =
190.54 kJ/mol
Second, find Q: (P )2 2
HCl (0.30)
QP    0.80
(P ) (P ) (0.25) (0.45)
H Cl
2 2

44
Free Energy and Equilibrium
Solve: G = G° + RT ln Q
G = 190,540 J/mol + (8.314J/K·mol)
(298 K) ln (0.80)

G =  191.09 kJ/mol (the reaction

becomes more spontaneous - free
energy is more negative)

45
• Consider the reaction,
O2(g) + 2CO(g)  2CO2(g)
How does the value of G change when
the pressures of the gases are altered
as follows at 25 C?
• O2 = 0.50 atm; CO = 0.30 atm;
CO2 = 0.45 atm

46
 Relationship Between G°
and K
• At equilibrium, G = 0 and Q = K
• The equation becomes:
0 = G° + RT ln K
or
G° = – RT ln K

47
Relationship Between G°
and K

48
 Relationship Between G°
and K
• Using the table of standard free
energies, calculate the equilibrium
constant, KP, for the following reaction
at 25 C.
2HCl(g) H2(g) + Cl2(g)

49
 Relationship Between G°
and K
First, calculate the G°:
= [0 + 0]  [2(95.27 kJ/mol)]
= 190.54 kJ/mol (non-spontaneous)
Substitute into equation:
190.54 kJ/mol =  (8.314 x 103 kJ/K·mol)(298 K)
ln KP
76.90 = ln KP = 3.98 x 1034
K < 1 reactants are favored
50
• Calculate the value of the equilibrium
constant, KP, for the following reaction
at 25 C.
2NO2(g) N2O4(g)

51
 18.6 Thermodynamics in
Living Systems
• Coupled reactions
• Thermodynamically favorable reactions
drives an unfavorable one
• Enzymes facilitate many
nonspontaneous reactions

52
 Thermodynamics in Living
Systems
• Examples:
C6H12O6 oxidation: G° = 2880 kJ/mol
ADP  ATP G° = 31 kJ/mol
Synthesis of proteins: (first step)
alanine + glycine  alanylglycine
G° = 29 kJ/mol

53
 Thermodynamics in Living
Systems
• Consider the coupling of two reactions:
ATP + H2O + alanine + glycine  ADP +
H3PO4 + alanylglycine
Overall free energy change:
G° = 31 kJ/mol + 29 kJ/mol = 2 kJ/mol
Protein synthesis is now favored.

54
ATP-ADP Interconversions

55
 Key Points
• Spontaneous vs nonspontaneous
• Relate enthalpy, entropy and free
energy
• Entropy
– Predict qualitatively
– Calculate from table of standard values
– Calculate entropy for universe

56
 Key Points
• Free energy
– Calculate from table of standard values
– Calculate from Gibbs equation
– Calculate non-standard conditions
– Calculate in relationship to equilibrium
constant

57