CHAPTER 16

Chemical Kinetics
Chapter Goals

1. The Rate of a Reaction

Factors That Affect Reaction Rates
2. Nature of the Reactants
3. Concentrations of the Reactants: The
Rate-Law Expression
4. Concentration Versus Time: The
Integrated Rate Equation
5. Collision Theory of Reaction Rates
2
Chapter Goals

6. Transition State Theory

7. Reaction Mechanisms and the Rate-Law
Expression
8. Temperature: The Arrhenius Equation
9. Catalysts

3
The Rate of a Reaction

• Kinetics is the study of rates of chemical

reactions and the mechanisms by which
they occur.
• The reaction rate is the increase in
concentration of a product per unit time or
decrease in concentration of a reactant
per unit time.
• A reaction mechanism is the series of
molecular steps by which a reaction
occurs. 4
The Rate of a Reaction

• Thermodynamics (Chapter 15) determines if a reaction

can occur.
• Kinetics (Chapter 16) determines how quickly a reaction
occurs.
– Some reactions that are thermodynamically
feasible are kinetically so slow as to be
imperceptible.
C diamond + O 2 (g ) ® CO 2 (g ) DG 298 = -396 kJ
o

VERY SLOW
H (+aq ) + OH(-aq ) ® H 2 O (l ) DG o298 = -79 kJ
INSTANTANE OUS 5
The Rate of Reaction

• Consider the hypothetical reaction,

aA(g) + bB(g) → cC(g) + dD(g)
• equimolar amounts of reactants, A and B,
will be consumed while products, C and D,
will be formed as indicated in this graph:

6
The Rate of Reaction
1.2
Reactants & Products
1
Concentrations of

0.8
0.6 [A] & [B]
[C] & [D]
0.4
0.2
0
0
50

0
10

15

20

25

30

35
Time

• [A] is the symbol for the concentration of A in M ( mol/L).

• Note that the reaction does not go entirely to completion. 7
– The [A] and [B] > 0 plus the [C] and [D] < 1.
The Rate of Reaction
• Reaction rates are the rates at which reactants
disappear or products appear.
• This movie is an illustration of a reaction rate.

8
The Rate of Reaction

• Mathematically, the rate of a reaction can

be written as:

-D [ A ] - D [ B] +D [C] +D [ D]
Rate = = = =
a Dt b Dt c Dt d Dt

9
The Rate of Reaction

• The rate of a simple one-step reaction is directly

proportional to the concentration of the reacting
substance.

A (g) ® B(g) + C(g)

Rate µ [A ] or Rate = k[A ]
• [A] is the concentration of A in molarity or
moles/L.
• k is the specific rate constant.
10
– k is an important quantity in this chapter.
The Rate of Reaction

• For a simple expression like Rate = k[A]

– If the initial concentration of A is doubled, the
initial rate of reaction is doubled.
• If the reaction is proceeding twice as fast, the
amount of time required for the reaction to reach
equilibrium would be:
A.The same as the initial time.
B.Twice the initial time.
C.Half the initial time.
• If the initial concentration of A is halved
the initial rate of reaction is cut in half.
11
The Rate of Reaction

• If more than one reactant molecule appears

in the equation for a one-step reaction, we
can experimentally determine that the
reaction rate is proportional to the molar
concentration of the reactant raised to the
power of the number of molecules involved in
the reaction.

2 X (g ) ® Y(g ) + Z(g )
Rate µ [X ] or Rate = k[X ]
2 2 12
The Rate of Reaction

• Rate Law Expressions must be

determined experimentally.
– The rate law cannot be determined from
the balanced chemical equation.
– This is a trap for new students of kinetics.
• The balanced reactions will not work because most
chemical reactions are not one-step reactions.
• Other names for rate law expressions
are:
1. rate laws
13
2. rate equations or rate expressions
The Rate of Reaction

• Important terminology for kinetics.

• The order of a reaction can be expressed in
terms of either:
1 each reactant in the reaction or
2 the overall reaction.
§ Order for the overall reaction is the sum of the orders
for each reactant in the reaction.
• For example:
2 N 2 O 5(g ) ® 4 NO2 (g ) + O 2 (g )
Rate = k[N 2 O 5 ]
This reaction is first order in N 2 O 5
14
and first order overall.
The Rate of Reaction

• A second example is:

(CH3 )3 CBr(aq ) + OH(-aq ) ® (CH3 )3 COH(aq ) + Br(-aq )

Rate = k[(CH3 )3 CBr ]
This reaction is first order in (CH3 )3 CBr,
zero order in OH- , and first order overall.

15
The Rate of Reaction

• A final example of the order of a reaction is:

2 NO ( ) + O ( ) ® 2 NO ( )
g 2 g 2 g

Rate = k[NO] [O 2
2
]
This reaction is second order in NO,
first order in O , and third order overall
2

REMEMBER, ALL RATE EXPRESSION S ARE

DETERMINED EXPERIMENTALLY

16
The Rate of Reaction

• Given the following one step reaction and its

rate-law expression.
– Remember, the rate expression would have to be
experimentally determined.
2 A ( g ) ® B( g ) + C ( g )
Rate = k[A ]
2

• Because it is a second order rate-law

expression:
– If the [A] is doubled the rate of the reaction will
increase by a factor of 4. 22 = 4
– If the [A] is halved the rate of the reaction will 17
decrease by a factor of 4. (1/2)2 = 1/4
Factors That Affect Reaction Rates

• There are several factors that can

influence the rate of a reaction:
1. The nature of the reactants.
2. The concentration of the reactants.
3. The temperature of the reaction.
4. The presence of a catalyst.
• We will look at each factor individually.

18
Nature of Reactants

• This is a very broad category that encompasses

the different reacting properties of substances.
• For example sodium reacts with water
explosively at room temperature to liberate
hydrogen and form sodium hydroxide.
2 Na (s ) + 2 H 2 O (! ) ® 2 NaOH(aq ) + H 2(g )
This is a violent and rapid reaction.
The H 2 ignites and burns.
19
Nature of Reactants

• Calcium reacts with water only slowly at

room temperature to liberate hydrogen
and form calcium hydroxide.
Ca (s ) + 2 H 2 O (! ) ® Ca (OH)2 (aq ) + H 2(g )
This is a rather slow reaction.

20
Nature of Reactants

• The reaction of magnesium with water at

room temperature is so slow that that the
evolution of hydrogen is not perceptible to
the human eye.

Mg (s ) + H 2 O (! ) ® No reaction

21
Nature of Reactants

• However, Mg reacts with steam rapidly to

liberate H2 and form magnesium oxide.

100o C
Mg (s ) + H 2O ( g ) ¾¾¾® MgO (s ) + H 2(g )
• The differences in the rate of these three
reactions can be attributed to the changing
“nature of the reactants”.

22
Concentrations of Reactants: The
Rate-Law Expression

23
 Concentrations of Reactants: The
Rate-Law Expression
• This is a simplified representation of the
effect of different numbers of molecules in
the same volume.
– The increase in the molecule numbers is
indicative of an increase in concentration.
A(g) + B (g) → Products
A B A B A B
B A B
A B A B A B
4 different possible 6 different possible 9 different possible 24
A-B collisions A-B collisions A-B collisions
 Concentrations of Reactants: The
Rate-Law Expression
Example 16-1: The following rate data were
obtained at 25oC for the following reaction. What
are the rate-law expression and the specific rate-
constant for this reaction?
2 A(g) + B(g) → 3 C(g)
Initial rate of
Experiment Initial [A] Initial [B] formation of C
Number (M) (M) (M/s)
1 0.10 0.10 2.0 x 10-4
2 0.20 0.30 4.0 x 10-4
3 0.10 0.20 2.0 x 10-4 25
Concentrations of Reactants: The
Rate-Law Expression
Initial rate of
Experiment Initial [A] Initial [B] formation of C
Number (M) (M) (M/s)
1 0.10 0.10 2.0 x 10-4
2 0.20 0.30 4.0 x 10-4
3 0.10 0.20 2.0 x 10-4

26
Concentrations of Reactants: The
Rate-Law Expression

Example 16-2: The following data were obtained

for the following reaction at 25oC. What are the
rate-law expression and the specific rate constant
for the reaction?
2 A(g) + B(g) + 2 C(g) → 3 D(g) + 2 E(g)

27
Concentrations of Reactants: The
Rate-Law Expression

Initial [A] Initial [B] Initial [C] Initial rate

Experiment of formation
(M) (M) (M) of D (M/s)
1 0.20 0.10 0.10 2.0 x 10-4
2 0.20 0.30 0.20 6.0 x 10-4
3 0.20 0.10 0.30 2.0 x 10-4
4 0.60 0.30 0.40 1.8 x 10-3

28
Concentrations of Reactants: The
Rate-Law Expression
Example 16-3: consider a chemical reaction
between compounds A and B that is first order with
respect to A, first order with respect to B, and
second order overall. From the information given
below, fill in the blanks.
You do it!

29
Concentrations of Reactants: The
Rate-Law Expression
Initial Rate Initial [A] Initial [B]
Experiment (M/s) (M) (M)
1 4.0 x 10-3 0.20 0.050
2 1.6 x 10-2 ? 0.050
3 3.2 x 10-2 0.40 ?

30
Concentration vs. Time: The
Integrated Rate Equation
• The integrated rate equation relates time
and concentration for chemical and
nuclear reactions.
– From the integrated rate equation we can
predict the amount of product that is produced
in a given amount of time.
• Initially we will look at the integrated rate
equation for first order reactions.
These reactions are 1st order in the reactant
and 1st order overall. 31
Concentration vs. Time: The
Integrated Rate Equation
• An example of a reaction that is 1st order
in the reactant and 1st order overall is:
a A → products
This is a common reaction type for many
chemical reactions and all simple
radioactive decays.
• Two examples of this type are:
2 N2O5(g) → 2 N2O4(g) + O2(g)
238U → 234Th + 4He
32
 Concentration vs. Time: The
Integrated Rate Equation

• The integrated rate equation for first order reactions

is:

ln
[A]0
=akt
[A]
where:
[A]0= mol/L of A at time t=0. [A] = mol/L of A at time t.
k = specific rate constant. t = time elapsed since
beginning of reaction.
a = stoichiometric coefficient of A in balanced overall 33
equation.
 Concentration vs. Time: The
Integrated Rate Equation

• Solve the first order integrated rate equation for t.

1 æ [A ]0 ö
t= ln çç ÷÷
a k è [A ] ø
• Define the half-life, t1/2, of a reactant as the time
required for half of the reactant to be consumed,
or the time at which [A]=1/2[A]0.
34
Concentration vs. Time: The
Integrated Rate Equation

• At time t = t1/2, the expression becomes:

1 æ [A ]0 ö
t 1/2 = ln ç
ç 1/2[A ] ÷
÷
ak è 0 ø
1
t 1/2 = (ln 2 )
ak
0.693
t 1/2 =
ak

35
 Concentration vs. Time: The
Integrated Rate Equation
Example 16-4: Cyclopropane, an anesthetic,
decomposes to propene according to the following
equation.
CH 2 CH
H C CH H3C CH 2
2 2 (g) (g)
The reaction is first order in cyclopropane with k =
9.2 s-1 at 10000C. Calculate the half life of
cyclopropane at 10000C.

36
Concentration vs. Time: The
Integrated Rate Equation
Example 16-5: Refer to Example 16-4. How much
of a 3.0 g sample of cyclopropane remains after
0.50 seconds?
– The integrated rate laws can be used for any unit that
represents moles or concentration.
– In this example we will use grams rather than mol/L.

37
Concentration vs. Time: The
Integrated Rate Equation
Example 16-6: The half-life for the following first
order reaction is 688 hours at 10000C. Calculate
the specific rate constant, k, at 10000C and the
amount of a 3.0 g sample of CS2 that remains after
48 hours.
CS2(g) ® CS(g) + S(g)
You do it!

38
Concentration vs. Time: The
Integrated Rate Equation

ln
[A]
= k t \ ln [A ] - ln [A ] = k t
0

[A] 0

ln(3.0) - ln [A ] = (0.00101 hr )(48 hr)

-1

1.10 - ln [A ] = 0.048
ln [A ] = -(0.048 - 1.10) = 1.052
[A] = e
1.052
= 2.86 g » 2.9 g or 97% unreacted

39
Concentration vs. Time: The
Integrated Rate Equation
• For reactions that are second order with respect
to a particular reactant and second order
overall, the rate equation is:
1 1
- =akt
[A] [A]0
• Where:
[A]0= mol/L of A at time t=0. [A] = mol/L of A at time t.
k = specific rate constant. t = time elapsed since
beginning of reaction.
a = stoichiometric coefficient of A in balanced overall equation.
40
Concentration vs. Time: The
Integrated Rate Equation

• Second order reactions also have a half-life.

– Using the second order integrated rate-law as a
starting point.
• At the half-life, t1/2 [A] = 1/2[A]0.

1 1
- = a k t1/2
1 / 2[A ]0 [A ]0
which has a common denominato r of [A ]0

41
Continued…

2 1
- = a k t1/2 or
[A]0 [A]0
1
= a k t1/2
[A]0
42
Concentration vs. Time: The
Integrated Rate Equation
• If we solve for t1/2:

1
t1/2 =
a k [A ]0
• Note that the half-life of a second order
reaction depends on the initial
concentration of A.
43
Concentration vs. Time: The
Integrated Rate Equation

Example 16-7: Acetaldehyde, CH3CHO, undergoes

gas phase thermal decomposition to methane and
carbon monoxide.
D
CH 3CHO( g ) ¾¾® CH 4( g ) + CO( g )
The rate-law expression is Rate = k[CH3CHO]2, and k
= 2.0 x 10-2 L/(mol.hr) at 527oC. (a) What is the half-
life of CH3CHO if 0.10 mole is injected into a 1.0 L
vessel at 527oC?
44
Concentration vs. Time: The
Integrated Rate Equation

Example 16-7:
D
CH 3CHO( g ) ¾¾® CH 4( g ) + CO( g )
The rate-law expression is Rate = k[CH3CHO]2, and k
= 2.0 x 10-2 L/(mol.hr) at 527oC. (a) What is the half-
life of CH3CHO if 0.10 mole is injected into a 1.0 L
vessel at 527oC?

45
Concentration vs. Time: The
Integrated Rate Equation

(b) How many moles of CH3CHO remain after 200

hours?

46
Concentration vs. Time: The
Integrated Rate Equation
(c) What percent of the CH3CHO remains
after 200 hours?

47
Concentration vs. Time: The
Integrated Rate Equation
Example 16-8: Refer to Example 16-7. (a) What is
the half-life of CH3CHO if 0.10 mole is injected into
a 10.0 L vessel at 527oC?
– Note that the vessel size is increased by a factor of 10
which decreases the concentration by a factor of 10!
You do it!

48
Concentration vs. Time: The
Integrated Rate Equation
• (b) How many moles of CH3CHO remain
after 200 hours?
You do it!

49
Concentration vs. Time: The
Integrated Rate Equation
• (c) What percent of the CH3CHO remains
after 200 hours?
You do it!

50
Collision Theory of
Reaction Rates
• Three basic events must occur for a
reaction to occur the atoms, molecules or
ions must:
1. Collide.
2. Collide with enough energy to break and form
bonds.
3. Collide with the proper orientation for a
reaction to occur.

51
Collision Theory of
Reaction Rates

• One method to increase the number of collisions

and the energy necessary to break and reform
bonds is to heat the molecules.
• As an example, look at the reaction of methane
and oxygen:
CH 4(g) + O 2(g) ® CO 2(g) + H 2 O (g) + 891 kJ
• We must start the reaction with a match.
– This provides the initial energy necessary to break
the first few bonds.
– Afterwards the reaction is self-sustaining.
52
Collision Theory of
Reaction Rates
• Illustrate the proper orientation of
molecules that is necessary for this
reaction.
X2(g) + Y2(g) → 2 XY(g)
• Some possible ineffective collisions are :
X Y
Y Y X X X X Y Y
X Y

53
Collision Theory of
Reaction Rates
• An example of an effective collision is:

X Y X Y X Y
+

X Y X Y X Y

54
Collision Theory of
Reaction Rates
• This picture illustrates
effective and
ineffective molecular
collisions.

55
 Transition State Theory

• Transition state theory postulates that

reactants form a high energy intermediate,
the transition state, which then falls apart into
the products.
• For a reaction to occur, the reactants must
acquire sufficient energy to form the
transition state.
– This energy is called the activation energy or Ea.
• Look at a mechanical analog for activation
energy 56
 Transition State Theory

Boulder
Eactivation
Epot=mgh2 h2 DEpot = mgDh
Height

Cross section Dh
of mountain

h1

Epot=mgh1 57
 Transition State Theory

Representation of a chemical reaction.

Eactivation - a kinetic quantity

Potential
Energy X2 + Y2 DE »DH
a thermodynamic
quantity

2 XY
Reaction Coordinate 58
Transition State Theory

59
Transition State Theory

• The relationship between the activation

energy for forward and reverse reactions
is
– Forward reaction = Ea
– Reverse reaction = Ea + DE
– difference = DE

60
Transition State Theory

• The distribution of molecules possessing

different energies at
a given temperature
is represented in this
figure.

61
Reaction Mechanisms and the
Rate-Law Expression
• Use the experimental rate-law to postulate a
molecular mechanism.
• The slowest step in a reaction mechanism is the
rate determining step.

62
Reaction Mechanisms and the
Rate-Law Expression

63
Reaction Mechanisms and the
Rate-Law Expression
• Use the experimental rate-law to
postulate a mechanism.
• The slowest step in a reaction mechanism
is the rate determining step.
• Consider the iodide ion catalyzed
decomposition of hydrogen peroxide to
water and oxygen.
I-
2 H 2 O 2(! ) ¾¾® 2 H 2 O (! ) + O 2(g )
64
Reaction Mechanisms and the
Rate-Law Expression
• This reaction is known to be first order in H2O2 ,
first order in I- , and second order overall.
• The mechanism for this reaction is thought to be:
Slow step H 2 O 2 + I ® IO + H 2 O
- -

Fast step IO - + H 2 O 2 ® H 2 O + O 2 + I -
Overall reaction 2 H 2 O 2 ® 2 H 2 O + O 2
Experiment al rate law []
R = k[H 2 O 2 ] I -

65
Reaction Mechanisms and the
Rate-Law Expression
• Important notes about this reaction:
1. One hydrogen peroxide molecule and
one iodide ion are involved in the rate
determining step.
2. The iodide ion catalyst is consumed in
step 1 and produced in step 2 in equal
amounts.
3. Hypoiodite ion has been detected in the
reaction mixture as a short-lived reaction
intermediate.
66
Reaction Mechanisms and the
Rate-Law Expression
• Ozone, O3, reacts very rapidly with nitrogen
oxide, NO, in a reaction that is first order in each
reactant and second order overall.
O3(g ) + NO(g ) ® NO2(g ) + O 2(g )
Experiment al rate - law is Rate = k[O3 ][NO]

67
Reaction Mechanisms and the
Rate-Law Expression
• One possible mechanism is:

Slow step O3 + NO ® NO3 + O

Fast step O + NO3 ® NO2 + O 2
Overall reaction O3 + NO ® NO2 + O 2

68
Reaction Mechanisms and the
Rate-Law Expression

• A mechanism that is inconsistent with the

rate-law expression is:
Slow step O3 ® O 2 + O
Fast step O + NO ® NO2
Overall reaction O3 + NO ® NO2 + O 2
The rate - law from this mechanism is Rate = k[O3 ]
which proves this mechanism cannot be correct.
69
Reaction Mechanisms and the
Rate-Law Expression
• Experimentally determined reaction
orders indicate the number of molecules
involved in:
1. the slow step only, or
2. the slow step and the equilibrium steps
preceding the slow step.

70
Temperature:
The Arrhenius Equation
• Svante Arrhenius developed this
relationship among (1) the temperature
(T), (2) the activation energy (Ea), and (3)
the specific rate constant (k).
Ea
-
k = Ae RT

or
Ea
ln k = ln A -
RT 71
Temperature:
The Arrhenius Equation

72
Temperature:
The Arrhenius Equation
• If the Arrhenius equation is written for two
temperatures, T2 and T1 with T2 >T1.

Ea
ln k1 = ln A -
RT1
and
Ea
ln k 2 = ln A -
RT2
73
Temperature:
The Arrhenius Equation
1. Subtract one equation from the other.
Ea æ Ea ö
ln k 2 - ln k1 = ln A - ln A - - ç- ÷
RT2 è RT1 ø
Ea Ea
ln k 2 - ln k1 = -
RT1 RT2

74
Temperature:
The Arrhenius Equation
2. Rearrange and solve for ln k2/k1.

k 2 Ea æ 1 1 ö
ln = ç - ÷
k1 R è T1 T2 ø
or
k 2 E a æ T2 - T1 ö
ln = ç ÷
k1 R è T2T1 ø
75
Temperature:
The Arrhenius Equation
• Consider the rate of a reaction for which Ea=50
kJ/mol, at 20oC (293 K) and at 30oC (303 K).
– How much do the two rates differ?
k 2 E a æ T2 - T1 ö
ln = ç ÷
k1 R è T2T1 ø
k 2 50,000 J mol æ 303 - 293 ö
ln = ç ÷K
k1 8.314 K mol è (303)(293)ø
J

k2
ln = 0.677
k1
k2
= e0.677 = 197
. »2 76
k1
Temperature:
The Arrhenius Equation
• For reactions that have an Ea»50 kJ/mol, the
rate approximately doubles for a 100C rise in
temperature, near room temperature.
• Consider:
2 ICl(g) + H2(g) ® I2(g) + 2 HCl(g)
• The rate-law expression is known to be
R=k[ICl][H2].
0 -1 -1
At 230 C, k = 0.163 M s
0 -1 -1
At 240 C, k = 0.348 M s
k approximately doubles 77
Catalysts

• Catalysts change reaction rates by providing an

alternative reaction pathway with a different
activation energy.

78
Catalysts

• Homogeneous catalysts exist in same phase as

the reactants.
• Heterogeneous catalysts exist in different
phases than the reactants.
– Catalysts are often solids.

79
Catalysts

80
Catalysts

• Examples of commercial catalyst systems

include:
2 C8 H18( g ) +25 O 2( g ) ¾¾¾¾®16 CO 2( g ) + 18 H 2O( g )
NiO and Pt

2 CO( g ) +O 2( g ) ¾¾¾¾
NiO and Pt
® 2 CO 2( g )
2 NO( g ) ¾¾¾¾
NiO and Pt
® N 2( g ) + O 2( g )
Automobile catalytic converter system

81
Catalysts

82
Catalysts

• A second example of a catalytic system is:

2 SO 2(g ) + O 2(g ) ¾¾ ¾ ¾¾® 2 SO3(g )

V2 O 5 or NiO/Pt

Sulfuric acid preparatio n

83
Catalysts

• A third examples of a catalytic system is:

N 2(g ) + 3 H 2(g ) ¾¾ ¾¾® 2 NH3(g )

Fe or Fe 2 O 3

Haber Process

84
Catalysts

• Look at the catalytic oxidation of CO to CO2

• Overall reaction
2 CO(g)+ O2(g) ® 2CO2(g)
• Absorption
CO(g) ® CO(surface) + O2(g)
O2(g) ® O2(surface)
• Activation
O2(surface) ® 2 O(surface)
• Reaction
CO(surface) +O(surface) ® CO2(surface)
• Desorption 85
CO2(surface) ® CO2(g)
Catalysts

86