• Reaction quotient Q is same mathematical expression as

Kc or KP but with non-equilibrium [ ] or pressures

• Q used to qualitatively predict direction of shift in
equilibria due to non-equilibrium [products], [reactants]
without using ICE table
TIP Q5
H2 (g) + I2 (g) 2HI (g) Kc = 54.3 at 430°C
[H2]0 = 0.243 M, [I2] 0 = 0.146 M, [HI] 0 = 1.98M
Direction of equilibrium shift?
TIP Q5
H2 (g) + I2 (g) 2HI (g) Kc = 54.3 at 430°C
[H2]0 = 0.243 M, [I2] 0 = 0.146 M, [HI] 0 = 1.98M
Direction of equilibrium shift?

 54.3
 2
[HI] [HI]2o
KC  eq
QC 
[H 2 ]eq [I2 ]eq [H 2 ]o [I2 ]o

 54.3

Qc > Kc
therefore equilibrium shifts towards reactants
H2 (g) + I2 (g) 2HI (g)
 Summary
Factors that affect Equilibrium
• Catalysts do not affect equilibria
• Catalysts enhance rate of a reaction by lowering the
reaction’s Ea. But catalysts lower the Ea of both
forward and reverse reactions
• Increase in temperature favours endothermic reaction
• Decrease in temperature favours exothermic reaction
• Increase in pressure (decrease in volume) favours net
reaction that decreases the total number of moles of
gases
• Change in concentration, pressure and volume do not
change K, at fixed temperature
Chapter 17: Gibbs Energy and Thermodynamics

Entropy is a measure of DISORDER

The disorder of Figure 17.3

a system
increases
with ability of
constituents
to move
freely

Entropy solid < Entropy liquid < Entropy gas

Chapter 17: Gibbs Energy and Thermodynamics

Entropy is a measure of DISORDER

Symbol for Figure 17.3

entropy: S
Units of
entropy:
J
K mol

Entropy solid < Entropy liquid < Entropy gas

Free rotation about C-C
No rotation about C-C
bonds in linear alkanes
bonds in cyclic alkanes

Flexible molecules
have more entropy
than rigid molecules
S° Standard pressure of 1 atm or 1 bar
Tabulated values of entropy at 298K:

S°(gas) is at least 2 - 3
times larger than that of
its corresponding solid or
liquid

S° increases with
molecular complexity
(more degrees of freedom
along the many different
bonds)
 Entropy of many salts
dissociated in aqueous
solution greater than
entropy of salt in
crystalline state
Standard concentration 1M
Figure 17.7 Third Law of
Thermodynamics
Entropy is zero for a perfect
monatomic crystal at zero
Kelvin

Standard entropy of
carbon(s) at 298K
depends on its crystalline
form : diamond or
graphite
Which of the following processes has a ΔS > 0?
A) CH3OH(l) → CH3OH(s)

B) N2(g) + 3H2(g) → 2NH3(g)

C) CH4(g) + H2O (g) → CO(g) + 3H2(g)

D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)

E) H2O(g) → H2O(l)
 ΔS > 0 means an entropy increase
Which of the following processes has a ΔS > 0?

✗ A) CH3OH(l) → CH3OH(s) Solids have lower

entropy than liquids
B) N2(g) + 3H2(g) → 2NH3(g)

C) CH4(g) + H2O (g) → CO(g) + 3H2(g)

D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)

E) H2O(g) → H2O(l)
 ΔS > 0 means an entropy increase
Which of the following processes has a ΔS > 0?

✗ A) CH3OH(l) → CH3OH(s) 2 moles gas have less

✗ B) N2(g) + 3H2(g) → 2NH3(g) entropy than 4 moles
gas
C) CH4(g) + H2O (g) → CO(g) + 3H2(g)

D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)

E) H2O(g) → H2O(l)
 ΔS > 0 means an entropy increase
Which of the following processes has a ΔS > 0?

✗A) CH3OH(l) → CH3OH(s)

✗B) N2(g) + 3H2(g) → 2NH3(g)
C) CH4(g) + H2O (g) → CO(g) + 3H2(g) Solid has
less
✗D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)
E) H2O(g) → H2O(l) entropy
than gas
 ΔS > 0 means an entropy increase
Which of the following processes has a ΔS > 0?
✗ A) CH3OH(l) → CH3OH(s)

✗ B) N2(g) + 3H2(g) → 2NH3(g)

C) CH4(g) + H2O (g) → CO(g) + 3H2(g)

✗ D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)

✗ E) H2O(g) → H2O(l)
Liquid has less entropy
than gas
 ΔS > 0 means an entropy increase
Which of the following processes has a ΔS > 0?
✗ A) CH3OH(l) → CH3OH(s)
4 moles gas
✗ B) N2(g) + 3H2(g) → 2NH3(g) have more
entropy than
✓ C) CH4(g) + H2O (g) → CO(g) + 3H2(g)
2 moles gas
✗ D) Na2CO3(s) + H2O(g) + CO2(g) → 2NaHCO3(s)
✗E) H2O(g) → H2O(l)
Identify the statement that is TRUE.
A) The entropy of a gas is lower than the entropy of a
liquid.
B) Entropy generally decreases with increasing
molecular complexity.
C) Free atoms have lower entropy than molecules.
D) Entropy usually decreases with dissolution.
E) Entropy has no absolute zero value.
 Identify the statement that is TRUE.
A) The entropy of a gas is lower than the entropy of a
liquid.
B) Entropy generally decreases with increasing
molecular complexity.
✓ C) Atoms have lower entropy than molecules.
D) Entropy usually decreases with dissolution.
E) Entropy has no absolute zero value.

Increasing molecular complexity

increases entropy
 Calculating S for chemical reactions:

aA + bB  cC + dD

S° = c Sf°(C ) + d Sf°(D) – a Sf° (A) – b Sf° (B)

Standard entropies of
formation of products - Standard entropies of
formation of reactants

Standard pressure of 1 atm or 1 bar

TIP Q2, 3
Calculate S° at 25°C for:
2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)
 TIP Q2, 3
Calculate S° at 25°C for:
2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)

S°298K = -12.5 J K—1 S° < 0

Decrease in entropy
Calculating S for phase changes:

q Heat absorbed or given off

S  during phase change
T
Temperature (K) at which
phase change occurs

q  mH
Calculate ∆S
Calculating S for phase changes:

q  mH melting

q mH melting
S  
T T

1g333.4Jg1  J Disorder
S   1.22 increases
273.15K K upon melting
a solid
Calculating S for phase changes:

q  mH melting

q mH melting q mH melting

S   S  
T T T T

This image cannot currently be display ed.

Disorder
increases
upon melting
a solid
 Gibbs Free Energy:
G = H - TS

enthalpy entropy
“Spontaneous” does not mean “how fast” but rather
whether a process or reaction is possible under current
pressure and temperature conditions

G < 0 reaction is spontaneous

G > 0 reaction is not spontaneous
G = 0 reaction is at equilibrium
TIP Q 3
Calculate H°, S°, G° at 25°C for:
2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)

S 298
o
K
 (1mol ) S o
f
( Al 2
O3
)  (3mol ) S o
f
( Zn)
 (2mol ) S of ( Al )  (3mol ) S of ( ZnO )
 TIP Q 3
Calculate H°, S°, G° at 25°C for:
2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)

Note that reaction creates 4 moles of solid products

from 5 moles of solid reactants:
We would predict a decrease in entropy
We would predict ΔS < 0
 TIP Q 3
Calculate H°, S°, G° at 25°C for:
2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)

kJ
H 298 K  (1mol )(1669.8
o
)  (3mol )(0)
mol
kJ
 (2mol )(0)  (3mol )(348.0 )  625.8kJ
mol
 G298K
o
 H o  TS o
 J  1kJ 
G298K
o
 625.8kJ   298.15K 12.5  3 
 K 10 J 
T(K) = T(°C) + 273.15

G298K
o
 622.1kJ Do not forget to convert J to kJ!

G°298K < 0 spontaneous

Reaction is possible at 1atm and 25°C
Alternative Method:

G o
298K  (1mol)G (Al2O3 )  (3mol)G (Zn)
o
f
o
f

 (2mol)G of (Al)  (3mol)G of (ZnO)

kJ kJ
Go
298 K  (1mol )(1576.4 )  (3mol )(0 )
mol mol
kJ kJ
 (2mol )(0 )  (3mol )(318.2 )
mol mol
G298K
o
 621.8kJ G°298K = -622 kJ
same value as obtained from
(H°-TS°) to 3 sig fig
A particular reaction has a positive ΔH and a positive ΔS.
Which of the following statements is TRUE?
A) This reaction will be spontaneous only at high
temperatures.
B) This reaction will be spontaneous at all temperatures.
C) This reaction will be nonspontaneous at all
temperatures.
D) This reaction will be nonspontaneous only at high
temperatures.
E) This reaction will be spontaneous only at very low
temperatures.
A particular reaction has a positive ΔH and a positive ΔS.
Which of the following statements is TRUE?
A) This reaction will be spontaneous only at high
temperatures.
B) This reaction will be spontaneous at all temperatures.
C) This reaction will be nonspontaneous at all
temperatures.
D) This reaction will be nonspontaneous only at high
temperatures.
E) This reaction will be spontaneous only at very low
temperatures.
A particular reaction has a and a .
Which of the following statements is TRUE?
A) This reaction will be spontaneous only at high
temperatures.
B) This reaction will be spontaneous at all temperatures.
C) This reaction will be nonspontaneous at all
temperatures.
D) This reaction will be nonspontaneous only at high
temperatures.
E) This reaction will be spontaneous only at very low
temperatures.
 G o
298K  H o
298K  TS o
298K
Sign of ΔH and ΔS Effect on ΔG at different T

when H° < 0 and S° > 0, G°< 0 for all temperatures
 G o
298K  H o
298K  TS o
298K
Sign of ΔH and ΔS Effect on ΔG at different T

when H° > 0 and S° < 0, G°> 0 for all temperatures
 G o
298K  H o
298K  TS o
298K
Sign of ΔH and ΔS Effect on ΔG at different T

when H° < 0 and S° < 0, G°< 0 at low temperatures

Recall that LeChatelier’s Principle predicts that exothermic
reactions are favoured at lower temperatures
 G o
298K  H o
298K  TS o
298K
Sign of ΔH and ΔS Effect on ΔG at different T

when H° > 0 and S° > 0, G°< 0 at high temperatures

Recall that LeChatelier’s Principle predicts that endothermic
reactions are favoured at higher temperatures
 A particular reaction has a positive ΔH and a positive ΔS.
Which of the following statements is TRUE?
✓A) This reaction will be spontaneous only at high
temperatures.
B) This reaction will be spontaneous at all temperatures.
C) This reaction will be nonspontaneous at all
temperatures.
D) This reaction will be nonspontaneous only at high
temperatures.
E) This reaction will be spontaneous only at very low
temperatures.
For the following example, what is true about ΔH and
ΔS?
H2O(l) → H2O(s)
A) negative ΔH and negative ΔS
B) positive ΔH and negative ΔS
C) negative ΔH and positive ΔS
D) positive ΔH and positive ΔS
E) ΔH = 0 and positive ΔS
 For the following example, what is true about ΔH and
ΔS?
H2O(l) → H2O(s) Freezing water:
energy
✓ A) negative ΔH and negative ΔS removed/lost by
B) positive ΔH and negative ΔS system
C) negative ΔH and positive ΔS ΔH < 0
D) positive ΔH and positive ΔS Liquids have
E) ΔH = 0 and positive ΔS more disorder
than solids:
decrease in
entropy
ΔS < 0
 TIP Q3, 4

2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)

H 298K
o
 625.8kJ mol-1 mol-1

This reaction is spontaneous (G° < 0) at 298K.

Over what range of temperatures will this
reaction no longer be spontaneous?
For what T is G° > 0?
 2 Al (s) + 3 ZnO (s)  Al2O3 (s) + 3 Zn (s)
H 298K
o
 625.8kJ mol-1 mol-1

G = H – TS
For G to change from negative to positive it has to go through zero.

0 = H – TS
0 = -6.258 X 105 J - T(-12.5 JK-1)
6.258 X 105 J/-12.5 JK-1 = -T
T = 50,100 K
Make sure your change kJ to J!
To determine RANGE of temperature over which
reaction is spontaneous: DRAW 2 NUMBER LINES
T
T=298K T=50100 K
G
G = -622kJ G = 0 kJ

G < 0, Reaction will be spontaneous for T < 50100K

G > 0, Reaction will be not spontaneous for T > 50,100K

Relationship between Keq and G°:

G o  RT lnK c Solutions:

Keq in
concentration
G o  RT lnK P units

Gases:
Keq in pressure
units
TIP Q3
Calculate KP for the following at 25°C:

H2 (g) + I2 (g) 2 HI (g)

For which ΔG° = 2.60 kJ mol-1

TIP Q3
TIP Q3
TIP Q3
Calculate KP for the following at 25°C:

H2 (g) + I2 (g) 2 HI (g)

For which ΔG° = 2.60 kJ mol-1 ΔG° > 0

Nonspontaneous
at 25°C

KP < 1
Reactants
favoured at 25°C
At 25°C, Kc = 6.25 × 1013 for:

Fe2+ (aq) + 2 OH- (aq) Fe(OH)2 (s)

Find ΔG°. Precipitation of Fe(OH)2 should be

VERY spontaneous!

“Hydroxides …
are generally
insoluble”
At 25°C, Kc = 6.25 × 1013 for:

Fe2+ (aq) + 2 OH- (aq) Fe(OH)2 (s)

Find ΔG°. Precipitation of Fe(OH)2 should be

VERY spontaneous!
At 25°C, Kc = 6.25 × 1013 for:

Fe2+ (aq) + 2 OH- (aq) Fe(OH)2 (s)

Find ΔG°. Precipitation of Fe(OH)2 should be

VERY spontaneous!
ΔG° << 0
Spontaneous at
25°C

Kc >> 1
Products
favoured at 25°C
 The Difference between and

Under nonstandard conditions, the spontaneity of a

chemical process can be predicted by:

Reaction quotient
• Consider the following reaction at 298 K
2 NO(g) + O2(g) 2 NO2(g) Go = -71.2 kJmol-1

Calculate G when PNO = 0.100 bar; PO2 = 0.100 bar; PNO2 = 2.00 bar

= (2.00)2 /(0.100)2(0.100) = 4.00 X 103

So
G = -71.2 X 103 Jmol-1 + 8.314 Jmol-1K(298 K)ln(4.00 X 103)

G = -50.7 X 103 Jmol-1

Relationship between equilibrium constant K and
free energy ΔG:
 van’t Hoff equation:

By measuring the equilibrium constant K at

different T, it is possible to find the enthalpy
ΔH and entropy ΔS
Which of the following statements is TRUE:
A) If K > 1, ΔG for forward reaction is positive
B) If K < 1, ΔG for forward reaction is negative
C) If K > 1, ΔG for forward reaction is negative
D) If K < 1, ΔG for reverse reaction is positive
 Which of the following statements is TRUE:
A) If K > 1, ΔG for forward reaction is positive
B) If K < 1, ΔG for forward reaction is negative
✔ C) If K > 1, ΔG for forward reaction is negative
D) If K < 1, ΔG for reverse reaction is positive
• products favoured
• forward reaction is
spontaneous
• ΔG < 0 for forward
reaction
Predict which of the following reactions will have the largest
equilibrium constant:
A) CaCO3 (s)  CaO (s) + CO2 (g) ΔG° = +131.1 kJ mol-1
B) 2 Hg (g) + O2 (g)  2 HgO (s) ΔG° = -180.8 kJ mol-1
C) 3 O2 (g)  2 O3 (g) ΔG° = +326 kJ mol-1
D) Fe2O3 (s) + 3 CO (g)  2 Fe (s) + 3 CO2 (g) ΔG° = -28.0 kJ mol-1
 Predict which of the following reactions will have the largest
equilibrium constant:
A) CaCO3 (s)  CaO (s) + CO2 (g) ΔG° = +131.1 kJ mol-1
B) 2 Hg (g) + O2 (g)  2 HgO (s) ΔG° = -180.8 kJ mol-1
C) 3 O2 (g)  2 O3 (g) ΔG° = +326 kJ mol-1
D) Fe2O3 (s) + 3 CO (g)  2 Fe (s) + 3 CO2 (g) ΔG° = -28.0 kJ mol-1

ΔG° < 0:
Forward reaction spontaneous
[products] > [reactants]
K>1
 Predict which of the following reactions will have the largest
equilibrium constant:
A) CaCO3 (s)  CaO (s) + CO2 (g) ΔG° = +131.1 kJ mol-1
✔ B) 2 Hg (g) + O2 (g)  2 HgO (s) ΔG° = -180.8 kJ mol-1
C) 3 O2 (g)  2 O3 (g) ΔG° = +326 kJ mol-1
D) Fe2O3 (s) + 3 CO (g)  2 Fe (s) + 3 CO2 (g) ΔG° = -28.0 kJ mol-1

ΔG° < 0:
Forward reaction spontaneous
[products] > [reactants] The most negative ΔG° will
K>1 have the largest K …