Some reactions are slow….

Oxidation of
iron
Photosynthesis
 Cellular respiration
C6H12O6(s) + 6 O2(g) ↔ 6CO2(g) + 6H2O(g)
Food Spoilage
Some reactions are fast….
NI3
Combustion of Hydrocarbons
Elephant Toothpaste
Trinitrotoluene (TNT)
1) Collision theory
a) bond forms when…
 right orientation
enough kinetic energy
wrong orientation
enough kinetic energy
 right orientation
not enough kinetic energy
1) Collision theory
a) bond forms when there is enough
kinetic energy and the molecules are
in the right orientation
Ea = Activation
Energy
b) Activation energy –
b) Activation energy –
b) Activation energy –
b) Activation energy – minimum energy
required for the reaction to occur
Energy
Barrier
i. unstable intermediate forms
i. unstable intermediate forms
“activated complex”
i. unstable intermediate forms
“activated complex”
“transition state”
ii. spark initiates reaction
Spark plug
ii. spark initiates reaction by supplying
the energy necessary to push the
“ALL reactions have activation energy”
Which reaction is faster at a given
temperature?
c) Enthalpy: energy change of a reaction
i. Exothermic ΔH = -
2NI3(s) → N2(g) + 3I2(s)
2NI3(s) → N2(g) + 3I2(s)
CH4(g) + O2(g) → CO2(g) + H2O(g)
 CH4(g) + O2(g) → CO2(g) + H2O(g)

- strong/stable bonds in product

ii. Endothermic ΔH = +
– product bonds are weak/unstable
P
O
T

Ea
E
N
T
I
A
L

E
N
E
R
G
Y Reaction coordinate
P
O
T
E Energy
N
T
I
Barrier
A
L

E
N
E
R
G
Y Reaction coordinate
P
O
T
E
N
T
I
A
L
ΔH = -
E
N
E
R
G
Y Reaction coordinate
P Stable complex = fast reaction
O
T
E
N
T
I Ea
A
L Transition State
E Intermediate
N
E Activation Complex
R
G
Y CO + NO → CO + NO
P
O
T
E
N
T Ea
I
A
L
Unstable complex
E = slow reaction
N
E
R
G
Y CO + NO → CO + NO
P
O
T
E
N
T
I
A
L

ΔH = +
E
N
E
R
G
Y Reaction coordinate
P
O
T
E
N
T
I
A Ea
L

E
N
E
R
G
Y Reaction coordinate
 IV

What represents the energy level of the

reactants?
 IV

What represents the energy level of the

products?
 IV

What represents the activation energy?

 IV

What represents the enthalpy change?

 IV

What represents the activation energy

of the reverse reaction?
Which reaction is slowest?
Which has the most unstable intermediate?
Which reaction gains energy?
Which reaction cools the environment?
Which reaction requires energy to initiate?

all
Which reaction is faster at a given temperature?
Activation energy is
A) the heat released in a reaction.
B) the energy required to start a
reaction
C) the energy given off when
reactants collide.
D) generally very high for a
reaction that takes place
rapidly.
Activation energy is
A) the heat released in a reaction.
B) the energy required to start a
reaction
C) the energy given off when
reactants collide.
D) generally very high for a
reaction that takes place
rapidly.
At what stage of an exothermic
reaction do atoms have the
highest energy?
A) reactant stage
B) product stage
C) transition state
At what stage of an exothermic
reaction do atoms have the
highest energy?
A) reactant stage
B) product stage
C) transition state
 What is another name for the
activated complex?
A) energy barrier
B) transition state
C) rate limiter
D) product
 What is another name for the
activated complex?
A) energy barrier
B) transition state
C) rate limiter
D) product
At what stage of a reaction does
the activated complex exist?

A) beginning
B) middle
C) end
At what stage of a reaction does
the activated complex exist?

A) beginning
B) middle
C) end
 What is wrong with this diagram?
P
O
T
E
N
T -ΔH
I
A
L

E
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T Ea
I
A
L

E
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L
+ΔH
E
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L
-ΔH
E
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L
-ΔH
E
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L
-ΔH
E
N
E
R
G
Y Reaction coordinate
What is the energy of the reactants?
20 kJ/mol
What is the energy of the products?
50 kJ/mol
What is the activation energy?
80 kJ/mol
What is the enthalpy?
+ 30 kJ/mol
What is the activation energy of the reverse
reaction?
50 kJ/mol
What is the enthalpy of the reverse reaction?
- 30 kJ/mol
Draw an energy diagram
which has an activation
energy of 23 kJ and ΔH
of –150 kJ.
P
O
T
E
Ea = 23 kJ
N
T
I
A
L

E
ΔH = - 150 kJ
N
E
R
G
Y
Reaction coordinate
Draw an energy diagram
which has an activation
energy of 125 kJ and ΔH
of +80 kJ.
P
O
T
E
N
T
I Ea = 125 kJ
A
L
ΔH = +80
E
N
E
R
G
Y
Reaction coordinate
d) Catalyst

i. increases rate
without being
used up

MnO2
H2O2 H2O + O2
Catalyst
Hydrogenated Vegetable Oil
to make Shortening

Ni
C2H4 + H2 → C2H6
 Ni
C2H4 + H2 → C2H6
 Ni
C2H4 + H2 → C2H6
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L

E
Catalyzed pathway
N
E
R
G
Y Reaction coordinate
 What is wrong with this diagram?
P
O
T
E
N
T
I
A
L

E
Catalyzed pathway
N
E
R
G
Y Reaction coordinate
- enzymes
Enzymes
 KI
H2O2 H2O + O2
 KI
H2O2 H2O + O2
 KI
H2O2(l) → O2(g) + 2H2O(g)
Intermediate
H2O2 + I- → OI- + H2O

H2O2 + OI- → O2(g) + H2O + I-

H2O2(l) → O2(g) + 2H2O(g)
 KI
H2O2(l) → O2(g) + 2H2O(g)

H2O2 + I- → OI- + H2O

Catalyst
H2O2 + OI- → O2(g) + H2O + I-
H2O2(l) → O2(g) + 2H2O(g)
ii. lowers activation energy by creating
an alternative pathway with lower Ea
 IV

Which levels are affected by a catalyst?

Which of the following substances
act as a catalysts in the body?
A) carbohydrates
B) nucleic acids
C) lipids
D) enzymes
Which of the following substances
act as a catalysts in the body?
A) carbohydrates
B) nucleic acids
C) lipids
D) enzymes
A catalyst speeds up the _________
reaction.
A) forward
B) backward
C) forward and backward
equally
A catalyst speeds up the _________
reaction.
A) forward
B) backward
C) forward and backward
equally
P Stable complex = fast reaction
O
T
E
N
T
I Ea
A
L Transition State
E Intermediate
N
E Activation Complex
R
G
Y CO + NO → CO + NO
P
O
T
E
N
T Ea
I
A
L
Unstable complex
E = slow reaction
N
E
R
G
Y CO + NO → CO + NO
What is an activated complex?
The unstable species at the top of the
energy barrier comprised of the reactants
in collision.
What determines the rate of a reaction?
The instability of the activated complex
and thus the height of the energy barrier.
Why does the rate of reaction increase in
the presence of a catalyst?
The catalyst provides an alternate pathway
with a lower energy barrier.
A catalyst works by……
A) shifting the equilibrium
position toward the products.
B) lowering the activation energy
barrier.
C) changing the temperature.
D) changing the particle size of
reactants.
A catalyst works by……
A) shifting the equilibrium
position toward the products.
B) lowering the activation energy
barrier.
C) changing the temperature.
D) changing the particle size of
reactants.
2) Reaction rates
a) increased temperature
2) Reaction rates
a) increased temperature
i. more molecules pass over barrier due to
1. strike with greater force
2. increase in # of collisions
Increasing the temperature would have what
effect on each rate?

Increase.
Why does an increase in temperature
increase the reaction rate?
There are more collisions, each with a greater
force. More reactants have the energy
required to pass over the energy barrier.
b) Concentration : speeds reaction
due to increased # of collisions
b) Concentration : speeds reaction
due to increased # of collisions
b) Concentration
b) Concentration : speeds reaction
due to increased # of collisions
HCl(aq) + CaCO3(s) → CO2(g) + H2O(g) + CaCl2(aq)
b) Concentration : speeds reaction
due to increased # of collisions
Steel wool in O2(g)
c) Particle Size
Powder KMnO4 Crystalline KMnO4
c) Particle Size
c) Particle Size
c) Particle Size
- increased surface area increases
# of collisions
c) Particle Size
- increased surface area increases
# of collisions
Why does rate of reaction increase with an
increased concentration?
There is an increased number of collisions
so more reactants pass over the barrier.
Why does rate of reaction increase when
reactants are powdered?
There is an increased surface area and so
and increased number of collisions so
more reactants pass over the barrier.
Why does rate of reaction increase with an
increased temperature?
There is an increased number of collisions
AND each collision has a greater force
so more reactants pass over the barrier.
Why does a small particle size
generally cause a reaction to proceed
faster?
A) There are more collisions per
second only.
B) Collisions occur with greater energy
only.
C) There are more collisions per
second and the collisions are of
greater energy.
Why does a small particle size
generally cause a reaction to proceed
faster?
A) There are more collisions per
second only.
B) Collisions occur with greater energy
only.
C) There are more collisions per
second and the collisions are of
greater energy.
Higher temperatures cause reactions to
go faster because
A) there is a greater frequency of
collisions
B) collisions occur with greater
energy sending more complexes over
the barrier.
C) both of the above.
Higher temperatures cause reactions to
go faster because
A) there is a greater frequency of
collisions
B) collisions occur with greater
energy sending more complexes over
the barrier.
C) both of the above.
How do we increase the rate of reaction?
1. Add catalyst
2. Increase temperature
3. Increase concentration
4. Decrease particle size
3) Equilibrium
H2O(l)  H2O(g)
I2(s)  I2(g)
3) Equilibrium
a) The forward and reverse reactions occur
at the same rate
NaCl(s) → NaCl(aq)
3) Equilibrium
a) The forward and reverse reactions occur
at the same rate
NaCl(s)  NaCl(aq)
b) Dynamic - the reaction has not stopped
AB
AB
AB A =0.30 M
B = 0.70 M
c) catalysts speed up forward and
reverse reactions equally
- decrease time required to reach
equilibrium
4) Equilibrium Constants
a) Relate the amounts of reactants to
products at equilibrium

Keq = [Products]coef
[Reactants] coef
Keq  1 products favored
Keq 1 reactants favored

Keq= 1 reactants = products

Do these reactions lie to toward
product or reactant?

Keq = 1.2 x 104 products

Keq = 1.2 x 10 -10

reactants
A liter of a gas mixture at some temperature
is at equilibrium and contains 0.0045 mol
N2O4 and 0.030 mol of NO2. Keq?

N2O4(g)  2 NO2(g)

Keq = [0.03]2= 0.20

[0.0045]

Reactants favored
The previous reaction is heated until
the concentrations are 0.0015 mol
N2O4 and 0.065 mol of NO2. Are
reactants or products favored?
N2O4(g)  2 NO2(g)

Keq = [0.065]2 = 2.8

[0.00150]

Products favored
0.15 mol H2, 0.25 mol N2, and 0.10 mol
NH3 are in equilibrium. Keq?
N2(g) + 3H2 (g)  2NH3 (g)

Keq = [0.10]2 = 12
[0.25][0.15]3

Products favored
Keq = 11.1 There are 4.0 mol Br2 and Cl2
equilibrium. How many moles of BrCl are
there?

2BrCl(g)  Cl2(g) + Br2(g)

11.1 = [ 4.0] [ 4.0]

[BrCl]2

[BrCl]2 = [4.0][4.0]
11.1
 Keq = 11.1 There are 4 mol Cl2 at equilibrium.
How many moles of Br2 and BrCl are there?

2BrCl(g)  Cl2(g) + Br2(g)

[BrCl]2 = [4.0][4.0]
11.1

[BrCl]2 = 1.4

[BrCl] = 1.2 mol

 Keq = 1400. If the pressures are [H2] =
1.1 atm, [H2O] =2.6 atm, and [NO] = 3.1
atm, what is the pressure for N2 at
equilibirum?
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

1400 = [N2][2.6]2
[3.1] 2[1.1]2
 1400 = [N2 ][2.6] 2

[3.1][1.1]2

[1400][3.1] 2[1.1]2 = [N2]

[2.6]2

[N2] = 2,400 atm

An equilibrium mixture contains 0.50 mol of H2
and I2.. Keq = 0.020. How many moles of HI are
there?
2HI(g)  H2(g) + I2(g)
0.020 = [0.50][0.50]
[HI]2

[HI]2 = [.50][.50]
0.02
[HI]2 = 13
[HI] = 3.6 mol
 Keq = 1400. If the pressures are [NO] =
2.3 atm, [H2O] = 4.4 atm, and [N2] = 3.1
atm, what is the pressure for H2 at
equilibirum?
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

1400 = [3.1][4.4]2
[2.3]2[H2]2
 1400 = [3.1][4.4]2
[2.3]2[H2]2

[H2]2 = [3.1][4.4]2
[2.3]21400

[H2]2 = 0.0081

[H2] = 0.090 atm

At 1065 C, Keq = 0.001100. If the
pressure of H2 is 1.1 atm, and the pressure
of S2 is 0.55 atm, what is the pressure of
H2S at equilibrium?
2H2S(g) ↔ 2H2(g) + S2(g)

0.0011 = [1.1]2[0.55]
[H2S]2
 2H2S(g) ↔ 2H2(g) + S2(g)

0.0011 = [1.1]2[0.55]
[H2S]2

[H2S]2 = [1.1]2[0.55]
0.0011

[H2S]2 = 605

[H2S] = 25 atm
A liter of a gas mixture at equilibrium
contains 2.0 mol of SO3, 2.5 mol of O2,
and 3.6 mol SO2. What is the
equilibrium constant? Are reactants or
products favored?

2SO2 + O2  2SO3

Keq = [2.0]2 = 0.12

[2.5][3.6]2

Reactants are favored

At a new temperature, 0.75 mol H2, 0.25
mol N2, and 0.40 mol NH3 are in
equilibrium. What is Keq?
N2(g) + 3H2 (g)  2NH3 (g)

Keq = [0.40]2
= 1.5
[0.25][0.75]3

Products favored
If a reaction is reversible, what are the
relative amounts of reactant and
product at the end of the reaction?
A) no product; all reactant
B) some product; some reactant
C) equal amounts of product
and reactant
If a reaction is reversible, what are the
relative amounts of reactant and
product at the end of the reaction?
A) no product; all reactant
B) some product; some reactant
C) equal amounts of product
and reactant
4) Le Chatelier’s Principle : a reaction
shifts to relieve stress
1.Concentration
H2CO3 CO2(g) + H2O(g)

- add H2CO3 forward

-add CO2 reverse

- decrease CO2 forward

-add H2O reverse

 2. temperature
2SO2 + O2  2SO3 + heat
(exothermic)

- cool with a fan forward

to replace heat
- add heat reverses
to remove heat
 N2O4 (g) + heat  2NO2 (g)
Clear Brown

- increase temperature forward

to remove heat
 N2O4 (g) + heat  2NO2 (g)
Clear Brown
- decrease temperature Reverse to create heat
Co(H2O)6 2+ + 4Cl- + heat  CoCl4-2
pink blue

-add heat Forward to remove heat

Co(H2O)6 2+ + 4Cl- + heat  CoCl4-2
pink blue

-cool Reverse to create heat

Why do girl scouts blow on a flame
to start a fire?

C20H42(s) + O2(g)  CO2(g) + H2O(g) + Heat

Why do firefighters hate windy days
whereas arsonists love them?
3. Pressure
- reactions with unequal number of
moles of gases shift in order to
maintain the original pressure
CO + 3H2  CH4 + H2O
CO + 3H2  CH4 + H2O
CO + 3H2  CH4 + H2O
 N2O4 (g)  2NO2 (g)

- decrease volume reverse

N2 (g) + 3H2 (g)  2NH3 (g)

- increase pressure
forward

- decrease pressure reverse

 CO2 + 2H2O → CH4 + 2O2
H = + 890 kJ
What impact does increasing pressure have
on the above reaction?

No impact!
2 SO2(g) + O2(g)  2 SO3(g) H -

- decrease volume
forward

- add oxygen
forward
- raise temperature
reverse
 NH4Cl(s)  NH3(g) + HCl(g)
H = +42.1 kcal

Temperature is increased. forward

HCl is removed. forward
NH3 is added. reverse
Pressure is decreased forward
Catalyst is added No impact
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
add CO2 reverse
cool forward
increase pressure reverse
remove H2O forward
remove C2H6 reverse
add catalyst No impact
b) Haber Process to produce (NH4)2SO4
bombs during WWI
N2(g) + 3H2(g)  2NH3(g)
H2(g)
NH3(g)
N2(g)
N2(g) + 3H2(g)  2NH3(g)
 Fritz Haber

Black
Plague
N2(g) + 3H2(g)  2NH3(g) H = -

What impact does adding H2 increase

have on the [NH3]

What impact does cooling decrease

the reaction have on N2?

What impact does a decrease

decrease
in pressure have on NH3?
 N2(g) + 3H2(g)  2NH3(g) H = -

What impact does removing decrease

NH3 have on H2?

What impact does removing increase

N2 have on H2?

What impact does adding a

No impact
catalyst have on NH3?
 2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
What impact on CO2 will decrease
removing C2H6 have?

What impact on C2H6 will

increasing the temperature
have? increase
Increasing the temperature would shift
which reaction(s) forward

A + heat  B
Decreasing the temperature would shift
which reaction(s) forward

A  B + heat
Which of the following does NOT
affect the rate of a chemical
reaction?
A) temperature
B) equilibrium position
C) concentration of reactants
D) catalyst
Which of the following does NOT
affect the rate of a chemical
reaction?
A) temperature
B) equilibrium position
C) concentration of reactants
D) catalyst
If an exothermic reaction is cooled,
the equilibrium will shift
A) forward
B) reverse
C) remain the same
If an exothermic reaction is cooled,
the equilibrium will shift
A) forward
B) reverse
C) remain the same
At equilibrium, what is the rate of
production of reactants
compared with the rate of
production of products?
A) higher
B) equal
C) lower
D) can not be determined
At equilibrium, what is the rate of
production of reactants
compared with the rate of
production of products?
A) higher
B) equal
C) lower
D) can not be determined
Practice Quiz
1. What change occurs if the pressure
is increased on the following reaction
at equilibrium.
C2H2(g) + H2(g) → C2H4(g)
A) [H2] increases
B) [C2H4] decreases
C) [C2H2] increases
D) [H2] decreases
1. What change occurs if the pressure
is increased on the following reaction
at equilibrium.
C2H2(g) + H2(g) → C2H4(g)
A) [H2] increases
B) [C2H4] decreases
C) [C2H2] increases
D) [H2] decreases
2. What change occurs if hydrogen is
removed from the chamber at
equilibrium?
C2H2(g) + H2(g) → C2H4(g)
A) [C2H2] decreases
B) [C2H4] increases
C) [C2H2] increases
D) no impact
2. What change occurs if hydrogen is
removed from the chamber at
equilibrium?
C2H2(g) + H2(g) → C2H4(g)
A) [C2H2] decreases
B) [C2H4] increases
C) [C2H2] increases
D) no impact
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
3. What effect does increasing pressure have
on the above reaction at equilibrium?

A)[O2] increases
B)[CO2] increases
C)[H2O] increases
D)[C2H6] decreases
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
3. What effect does increasing pressure have
on the above reaction at equilibrium?

A)[O2] increases
B)[CO2] increases
C)[H2O] increases
D)[C2H6] decreases
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
4. What impact does increasing the
temperature have at equilibrium?

A)[O2] decreases
B)[CO2] increases
C)[H2O] increases
D)[C2H6] increases
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
4. What impact does increasing the
temperature have at equilibrium?

A)[O2] decreases
B)[CO2] increases
C)[H2O] increases
D)[C2H6] increases
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
List methods to increase the yield of carbon
dioxide.
1. Add C2H6
2. Add O2
3. Remove H2O
4. Remove CO2
5. cool
6. Decrease pressure
Review
P Stable complex = fast reaction
O
T
E
N
T
I Ea
A
L Transition State
E Intermediate
N
E Activation Complex
R
G
Y CO + NO → CO + NO
P
O
T
E
N
T Ea
I
A
L
Unstable complex
E = slow reaction
N
E
R
G
Y CO + NO → CO + NO
 KI
H2O2 H2O + O2
 KI
H2O2(l) → O2(g) + 2H2O(g)
Intermediate
H2O2 + I- → OI- + H2O

H2O2 + OI- → O2(g) + H2O + I-

H2O2(l) → O2(g) + 2H2O(g)
 Impact of:
Temperature, concentration, particle size
Equilibrium
Keq = [products]
[reactants]
 Keq = 1400. If the pressures are [H2] =
1.1 atm, [H2O] =2.6 atm, and [NO] = 3.1
atm, what is the pressure for N2 at
equilibirum?
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

1400 = [N2][2.6]2
[3.1] 2[1.1]2
 1400 = [N2 ][2.6] 2

[3.1][1.1]2

[1400][3.1] 2[1.1]2 = [N2]

[2.6]2

[N2] = 2,400
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
What impact does increasing the temperature
have at equilibrium?

A)[O2] decreases
B)[CO2] increases
C)[H2O] increases
D)[O2] increases
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
What impact does increasing the temperature
have at equilibrium?

A)[O2] decreases
B)[CO2] increases
C)[H2O] increases
D)[O2] increases
Kinetics answers the question:
How fast will a reaction proceed.
Equilibrium answers the question:
To what extent will a reaction proceed.

Keq = 3.3 x 1024

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Keq = 1.8 x 10-5

HC2H3O2 ↔ H+ + C2H3O2-
Thermodynamics answers the question:

Why will a reaction proceed to

a particular equilibrium position.

…DOES NOT address the rate at all.

6) Thermodynamics
a) driving forces determine if a reaction
is spontaneous
1. Entropy
 1. Entropy
Second Law of Thermodynamics:
for all spontaneous processes, the
entropy of the universe must
increase

Δ Suniverse = Δ Ssystem + Δ Ssurroundings

= +
Diffusion
ΔS= - ΔS= +
ΔS= - ΔS= +
ΔS= -
ΔS= +
ΔS= -
ΔS= +
ΔS= -
ΔS= +
Order Disorder

S=- S=+
1. Increases when a salt dissociates
NaCl(s) → Na+ + Cl -
2. Increases if # products is greater than
# reactants

2H2O(g) → 2H2(g) + O2(g)

4Fe(s) + 3O2(g) → 2Fe2O3(s)

Entropy decreases
3. Entropy increases with
Kinetic energy (temperature)
- Third Law of Thermodynamics:
Entropy of a crystal at
absolute zero is zero
4. Solids Liquids Gases

S=- S=+
5. Increase number of bonds.
HF CH4

S=- S=+
 2H2O (l) ↔ 2H2 (g) + O2 (g)
Increase ΔS = +

CO2 (g) + H2O (g) ↔ H2CO3(s)

Decrease ΔS = -

CaCO3(s) ↔ CaO(s)+ CO2 (g)

Increase ΔS = +

C6H12O6 (s) +6O2(g)↔ 6CO2(g)+ 6H2O(g)

Increase ΔS = +
N2 (g) + 3H2 (g) ↔ 2NH3 (g)

Decrease ΔS = -
4Fe(s) + 3O2 (g) ↔ 2 Fe2O3 (s)
Decrease ΔS = -
cooling nitrogen gas from 20 °C to -50 °C

Decrease ΔS = -
Which has more entropy:

1 mol NaCl(s) 1 mol HCl(g)

2 mol HCl(g) 1 mol HCl(g)

H2O(l) H2O(g)
 Entropy…

Popped Balloon Increase ΔS = +

 Entropy…
Dissolving salt Increase ΔS = +

Dissolving gas Decrease ΔS = -

disorder
order
Order Disorder
2. Enthalpy
- exothermic reactions are favored:
products have strong stable bonds

ΔH= -
The universe tends toward low enthalpy.
Nitroglycerin
 Nitroglycerin
4C3H5N3O9(l) →

12CO2(g) + 6N2(g) + O2(g) + 10H2O(g)

+ heat + kinetic energy

Ultimate chaos!!!
Trinitrotoluene (TNT or dynamite)
2C7H5N3O6(l) → 12CO(g) + 2 C2(s) + 5 H2(g) + 3N2(g)
+ heat
Trinitrotoluene (TNT or dynamite)
7) Spontaneous Reactions
Spontaneous →
Spontaneous →
Nonspontaneous →
Nonspontaneous →
Nonspontaneous (above 0 °C) →
7) Spontaneous Reactions
a) naturally favor the formation
of products

b) determined by driving forces:

entropy and enthalpy
c) spontaneous reactions release free
energy to do work
Gibbs Free Energy = -
Keq > 1
d) nonspontaneous reactions requires
energy (work) to proceed forward
Keq < 1
Gibbs Free Energy = +
e) Analysis of Reactions
1. ΔH = - ΔS = +
exothermic and chaotic

Driving forces: enthalpy and entropy

C6H12O6(s) + 6O2(g) ↔ 6CO2(g) + 6H2O(g) + heat

- highly spontaneous
Methylhydrazine (rocket fuel)
2CH6N2(l) + 5O2(g) →
2N2(g) + 2CO2(g) + 6H2O(g)
H = - 2600 kJ
- capable of doing a lot of work
2C8H18(l)+ 25O2(g) ↔ 18H2O(g) + 16CO2(g)
+ heat
2. ΔH = + ΔS = +
endothermic and chaotic
H2O(s) + heat  H2O (l)

heat
 H2O(s) + heat H2O (l)

Driving forces: entropy

-weakly spontaneous

heat
Ba(OH)2(s) + 2NH2SCN(s) + heat

→ Ba2++ 2 SCN- + 2 NH3(g) + 10H2O(l)

- all endothermic reactions must create an
overall greater disorder in the universe

CaCO3(s)+ heat → CaO(s)+ CO2 (g)

 3. ΔH = - ΔS = -
exothermic and ordered

Driving forces: enthalpy

N2 (g) + 3H2(g) → 2NH3 (g) + heat

-Crystallization/Freezing
H2O(l) → H2O(s) heat
- Condensation heat
H2O(g) → H2O(l)
- Deposition heat
I2(g) → I2(s)
4 Fe(s) + 3 O2 (g) → 2 Fe2O3 (s) + heat

-weakly spontaneous
- all reactions that create order must be
exothermic
- plants and animals are ordered…
but create an overall disorder in the
universe through cellular respiration

C6H12O6(s) + 6O2(g) → 6CO2(g) +6H2O(g) + heat

4. ΔH + ΔS = -
endothermic and ordered

Driving forces: none

- Nonspontaneous
ΔG = +
 1000 points extra credit!

Find an example of a
spontaneous reaction which is
both endothermic and creates
order in the universe!!!!
The more order mankind creates
in his environment…
… the greater the chaos in the world.
 Entropy…

Dissolving salt Increase ΔS = +

 Entropy…
Decrease ΔS = -
Crystalizing salt
 Entropy…

Expanding gas Increase ΔS = +

 Entropy…
A solid cools from 25 °C to 15 °C
Decrease ΔS = -
125 Sublimation
100 Evaporization →
Condensation ←

0 Melting → Deposition
Freezing ←
-25
0 5 10 15 20 25 30 35 40 45 50
You should begin to question all
examples of order around you:
You should begin to question all
examples of endothermic reactions:
 ΔH ΔS
Burning gasoline - +

Melting + +

Freezing - -

Nonspontaneous + -
What is the driving force of evaporation?

Entropy
What is the driving force of condensation?

Enthalpy
What is the driving force of freezing?
Enthalpy
What is the driving force of melting?

Entropy
What is the driving force of sublimation?
CO2(s) → CO2(g) Entropy
What is the driving force of precipitation of
a salt?
Enthalpy
 What are the driving forces?

NH4NO3(s) + heat ↔ NH4+ + NO3-

Entropy
NH4Cl(s)  NH3(g) + HCl(g)
H = +42.1 kcal
Entropy
Ca(s) + H2O (l) → CaO(s) + H2(g) + heat

Entropy and Enthalpy

What are the signs for ΔH, ΔS, and ΔG for
the melting of ice at -273 °C?

ΔH ΔS ΔG
A + - +
B + + +
C + + -
D - - -
What are the signs for ΔH, ΔS, and ΔG for
the freezing of liquid water at -10 °C?

ΔH ΔS ΔG
A + - +
B - - 0
C - + -
D - - -
What are the signs for ΔH, ΔS, and ΔG for
the melting of ice at 25 °C?

ΔH ΔS ΔG
A + - +
B - - 0
C + + -
D - - -
What are the signs for ΔH, ΔS, and ΔG for
the sublimation of dry ice at 25 °C?

ΔH ΔS ΔG
A + + +
B + - +
C - + -
D + + -
 BCl3(g) + NH3(g) → Cl3BNH3(s)

The above reaction is spontaneous.

Is it endothermic or exothermic.
Exothermic
The reaction must have a driving force.
Because the reaction creates order,
enthalpy MUST be the driving force.
BCl3(g) + NH3(g) → Cl3BNH3(s)

Keq = 2.3 x 104

What can you say about ΔG?

- The reaction is spontaneous:

- ΔG is negative
- Free energy is released and is
available to do work.
 HC2H3O2 → H+ + C2H3O2-

Keq = 1.8 x 10-5.

What can you say about ΔG?

- The reaction is nonspontaneous:

- ΔG is positive.
- Work must be done to make the reaction
go.
The melting of ice at absolute zero is
_____.
a. spontaneous
b. exothermic
c. nonspontaneous
d. ectothermic
The melting of ice at absolute zero is
_____.
a. spontaneous
b. exothermic
c. nonspontaneous ΔG = +
d. ectothermic
 Which of the following processes would ΔS° be
expected to be most positive?
a. C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(g)
b. Na+(aq) + Cl-(aq) → NaCl(s)
c. H+(aq) + OH-(aq) → H2O(l)
d. CO2(g) → CO2(s)
e. Cl2(g) + H2(g) → 2 HCl(g)
or which of the following processes would ΔS° be
expected to be most positive?
a. C6H12O6(s) + 6 O2(g) → 6 CO2(g) + 6 H2O(g)
b. Na+(aq) + Cl-(aq) → NaCl(s)
c. H+(aq) + OH-(aq) → H2O(l)
d. CO2(g) → CO2(s)
e. Cl2(g) + H2(g) → 2 HCl(g)
Which of the following samples of oxygen has
the greatest positional entropy?
a. 1 mole of O2(g) at 2.0 atm and 200 K
b. 1 mole of O2(g) at 1.0 atm and 273 K
c. 1 mole of O2(g) at 0.5 atm and 273 K
d. 1 mole of O2(g) at 2.0 atm and 273 K
e. 1 mole of O2(s) at 15 K
Which of the following samples of oxygen has
the greatest positional entropy?

More
chaotic
Which of the following samples of oxygen has
the greatest positional entropy?
a. 1 mole of O2(g) at 2.0 atm and 200 K
b. 1 mole of O2(g) at 1.0 atm and 273 K
c. 1 mole of O2(g) at 0.5 atm and 273 K
d. 1 mole of O2(g) at 2.0 atm and 273 K
e. 1 mole of O2(s) at 15 K
Which of the following liquids is likely to
have the highest value for S°?
a. H2
b. N2
c. O2
d. Cl2
e. F2
Which of the following liquids is likely to
have the highest value for S°?
a. H2
b. N2
c. O2
d. Cl2
e. F2
Which of the following statements are true for the
reaction I2(g) → I2(s)
I. ΔH is positive
II. ΔH is negative
III. ΔS is positive
IV. ΔS is negative
V. The reaction is spontaneous at any temperature
a. IV only
b. V only
c. II and IV
d. I and III
e. I only
Which of the following statements are true for the
reaction I2(g) → I2(s)
I. ΔH is positive
II. ΔH is negative
III. ΔS is positive
IV. ΔS is negative
V. The reaction is spontaneous at any temperature
a. IV only
b. V only
c. II and IV
d. I and III
e. I only
Which of the following statements is true?
a. For a process to be spontaneous, the number of
moles of product must exceed the number of
moles of reactant
b. A system at constant temperature cannot
experience entropy change
c. Exothermic reactions are always spontaneous
d. In a spontaneous process, ΔG has a positive
value
e. The entropy of the universe must increase.
Which of the following statements is true?
a. For a process to be spontaneous, the number of
moles of product must exceed the number of
moles of reactant
b. A system at constant temperature cannot
experience entropy change
c. Exothermic reactions are always spontaneous
d. In a spontaneous process, ΔG has a positive
value
e. The entropy of the universe must increase.
Is the following reaction highly, weakly or
nonspontaneous?
4C3H5N3O9(l) →

12CO2(g) + 6N2(g) + O2(g) + 10H2O(g) + heat

Highly Spontaneous
Is the following reaction highly, weakly or
nonspontaneous?
NH4Cl(s)  NH3(g) + HCl(g)
H = +42.1 kcal

Weakly Spontaneous
Is the following reaction highly, weakly or
nonspontaneous?

N2 (g) + 3H2 (g)  2NH3 (g) + heat

Weakly Spontaneous
Is the following reaction highly, weakly or
nonspontaneous?

CaCO3(s) + heat ↔ CaO(s)+ CO2 (g)

Weakly Spontaneous
Spontaneous reactions…..

A) are always exothermic

B) always take place at a rapid rate
C) always result in more disorder of
the system
D) always give off free energy
Spontaneous reactions…..

A) are always exothermic

B) always take place at a rapid rate
C) always result in more disorder of
the system
D) always give off free energy
Review
 CH4(g) + O2(g) → CO2(g) + H2O(g)
Exothermic: strong/stable bonds in product
 How do you increase reaction rates?
1. Increased temperature
2. Increase concentration
3. Decrease particle size
4. Add a catalyst
 KI
H2O2(l) → O2(g) + 2H2O(g)
Intermediate
H2O2 + I- → OI- + H2O

H2O2 + OI- → O2(g) + H2O + I-

H2O2(l) → O2(g) + 2H2O(g)
 KI
H2O2(l) → O2(g) + 2H2O(g)
Catalyst
H2O2 + I- → OI- + H2O

H2O2 + OI- → O2(g) + H2O + I-

H2O2(l) → O2(g) + 2H2O(g)
A liter of a gas mixture at some temperature
is at equilibrium and contains 0.0045 mol
N2O4 and 0.030 mol of NO2. Keq?

N2O4(g)  2 NO2(g)

Keq = [0.03]2= 0.20

[0.0045]

Reactants favored
2C2H6(g) + 5O2(g)  4CO2(g) + 6H2O(g)
H = -
What impact does increasing the temperature
have at equilibrium?

A)[O2] decreases
B)[CO2] increases
C)[H2O] increases
D)[O2] increases