Chemical Kinetics

FOUNDATION CHEMISTRY II
CHM096
CHAPTER 2
CHEMICAL
KINETICS
1
TOPICS
2.1 Rate of Chemical Reactions
2.2 Rate Laws
2.3 Integrated Rate Laws
2.4 Collision Theory, Transition State Theory,
Activation Energy and Factors Controlling
Rates of Reactions
2.5 Arrhenius Equation
2.6 Reaction Mechanisms and Rate
Determining Step
2
TOPIC
RATE OF CHEMICAL REACTIONS
3
2.1 RATE OF CHEMICAL REACTIONS
Introduction
Rates of chemical reactions is the change in

concentration of either reactants or products as a
function of time. 4
Rates
Different reactions have different rates
- higher rate/faster reaction – the reactant concentration
decreases quickly
- lower rate/slower reaction – it decreases slowly
For reactants = -ve sign (conc. decreases)
For products = +ve sign (conc. increases)
Rate = Δ [concentration]
Δ time
Rate = Δ [products] = - Δ [reactants]
Δ time Δ time
5
at t = 0 at t = 0
[A] = 8 [X] = 8
[B] = 8 [Y] = 8
[C] = 0 [Z] = 0
at t = 16 at t = 16
[A] = 4 [X] = 7
[B] = 4 [Y] = 7
[C] = 4 [Z] = 1
6
A  A 2  A 1 Rate  

X

X2  X1
Rate    t 2  t1
t t 2  t1 t
4  8   0.25 Rate  
7  8  0.0625
Rate   16  0
16  0
C C2  C1  Z Z2  Z1 

Rate   Rate  
t t 2  t1 t t 2  t1
Rate 
4  0   0.25 Rate 
1  0   0.0625
16  0  16  0 
7
Reaction Rate Changes Over Time
• As time goes on, the rate of a reaction generally slows
down
– because the concentration of the reactants
decreases
• At some time the reaction stops, either because the
reactants run out or because the system has reached
equilibrium
Average Rate
• The average rate is the change in measured
concentrations in any particular time period
– linear approximation of a curve
8
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)
In this reaction, the concentration of butyl chloride,

C4H9Cl, was measured at various times.
Time, t (s) [C4H9Cl] (M)
0 0.100
50 0.0905
100 0.0820
150 0.0741
200 0.0671
300 0.0549
400 0.0448
500 0.0368
800 0.0200
10,000 0
9
Time, t (s) [C4H9Cl] (M) Average Rate (M/s)
0 0.100 -
50 0.0905 1.9 x 10-4
100 0.0820 1.7 x 10-4
150 0.0741 1. 6 x 10-4
200 0.0671 1.4 x 10-4
300 0.0549 1.22 x 10-4
400 0.0448 1.01 x 10-4
500 0.0368 0.8 x 10-4
800 0.0200 0.560 x 10-4
10,000 0 -
• Note that the average rate decreases as the reaction
proceeds.
• This is because as the reaction goes forward, there are
fewer collisions between reactant molecules. 10
Time, t (s) [C4H9Cl] (M) Average Rate (M/s)
0 0.100 -
50 0.0905 1.9 x 10-4
100 0.0820 1.7 x 10-4
150 0.0741 1.6 x 10-4
200 0.0671 1.4 x 10-4
300 0.0549 1.22 x 10-4
400 0.0448 1.01 x 10-4
500 0.0368 0.8 x 10-4
800 0.0200 0.560 x 10-4
10,000 0 1 x 10-5
The average rate of the reaction over each interval:
is the change in concentration divided by the
change in time: [C4H9Cl]
Average rate = t 11
• A plot of [C4H9Cl] vs.
time for this reaction
Foundations of organic chemistry from yields a curve like this.
mid-1700’s.
• The slope of a line
Compounds obtained from plants, animalstangent
hard to toisolate,
the curve
and at
purify. any point is the
instantaneous rate at
Compounds also decomposed more easily. that time.
• The instantaneous rate
Torben Bergman (1770) first to make distinction betweenthe
at the moment organic
and inorganic chemistry.
reactants are mixed
It was thought that organic compounds t = 0s)
• (must is called
contain somethe“vital
force” because they were from livinginitial rate.
sources.
12
• All reactions slow

Foundations of organic chemistry from mid-1700’s.
down over time.
Compounds obtained from plants, animals hard to isolate,
• Therefore, theand
best
purify. indicator of the rate
of a reaction is the
Compounds also decomposed more easily. instantaneous rate
near the beginning
Torben Bergman (1770) first to make distinction
of between
the organic
reaction.
It was thought that organic compounds must contain some “vital

force” because they were from living sources.
13
Stoichiometry
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)
• In this reaction, the ratio

of C4H9Cl to C4H9OH is
1:1.
• Thus, the rate of
disappearance of C4H9Cl
is the same as the rate of
appearance of C4H9OH.
-[C4H9Cl] [C4H9OH]
Rate = t = t
14
Stoichiometry
What if the ratio is not 1:1?
H2(g) + I2(g) 2HI (g)

[HI] increases twice as fast as [H2]
decreases.
Δ[H2] Δ[I2] 1 Δ[HI]
Rate = - =- =
Δt Δt 2 Δt
Δ[HI] Δ[H2] Δ[I2]

Rate = = -2 = -2
Δt Δt Δt
The expression for the rate of a reaction

and its numerical value depend on which
substance serves as the reference. 15
H2 (g) + I2 (g)  2 HI (g)
Using [H2], the
instantaneous rate
at 50 s is
Using [HI], the

instantaneous rate
at 50 s is
16
Stoichiometry
To generalize, then, for the reaction
aA + b B cC + d D
1 [A] 1 [B] 1 [C] 1 [D]

Rate = − a t = − b t = c t = d t
17
Example 1
Write the rate expressions for the following reactions in
terms of the disappearance of the reactants and the
appearance of the products:
18
Answer to Example 1
Strategy To express the rate of the reaction in terms of
the change in concentration of a reactant or product with
time, we need to use the proper sign (minus or plus) and
the reciprocal of the stoichiometric coefficient.
Solution
(a) Because each of the stoichiometric coefficients equals
1,
(b) Here the coefficients are 4, 5, 4, and 6, so
19
Example 2
For the reaction given, the [I] changes from 1.000 M to

0.868 M in the first 10 s. Calculate the average rate in the
first 10 s, and [H+]/t.
H2O2 (aq) + 3 I(aq) + 2 H+(aq)  I3(aq) + 2 H2O(l)
20
Answer to Example 2
solve the rate

equation for the
rate (in terms of
the change in
concentration of
the given quantity)
solve the rate
equation (in terms
of the change in
the concentration 2
for the quantity to
find) for the
unknown value
21
Example 3
If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a

2.0 x 102 mL flask in 5.0 minutes, find the average rate
of Br2 production in M/s.
2 NOBr(g)  2 NO(g) + Br2(l)
22
Answer to Example 3
Given: 240.0 g NOBr, 0.2000 L, 5.0 min.

Find: [Br2]/t, M/s
Conceptual
Plan:
Relationships: 2 mol NOBr:1 mol Br2,

1 mol = 109.91g, 1 mL=0.001 L
23
Exercise 1
Because it has a nonpolluting product (water vapor),
hydrogen gas is used for fuel aboard the space shuttle
and may be used by earthbound engines in the near
future.
2H2(g) + O2(g) 2H2O(g)
(a) Express the rate in terms of changes in [H2], [O2], and

[H2O] with time.
(b) When [O2] is decreasing at 0.23 mol/L.s, at what rate is

[H2O] increasing?
24
Exercise 2
Consider the reaction

4NO2 (g) + O2 (g) 2N2O5 (g)
Suppose that, at a particular moment during the

reaction, molecular oxygen is reacting at the rate of
0.024 M/s.
(a) At what rate is N2O5 being formed?
(b) At what rate is NO2 reacting?
25
Exercise 3
In a catalytic experiment involving the Haber process

N2 (g) + 3H2 (g) 2NH3 (g)
The rate of reaction was measured as

Rate = [NH3]/t = 2.0 x 10-4 mol/L.s.
(a) What was the rate of reaction expressed in terms of

N2 and H2?
26
TOPIC
RATE LAWS
27
2.2 RATE LAWS
• The rate law of a reaction is the mathematical

relationship between the rate of the reaction and
the concentrations of the reactants
 and homogeneous catalysts as well
• The rate law must be determined experimentally!!
• The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
• For the reaction aA + bB  products the rate law
would have the form given below
 n and m are called the orders for each reactant
 k is called the rate constant
28
2.2 RATE LAWS
• The exponent on each reactant in the rate law is
called the order with respect to that reactant
• The sum of the exponents on the reactants is called
the overall order of the reaction
• The rate law for the reaction given:
2 NO(g) + O2(g)  2 NO2(g)

is: Rate = k[NO]2[O2]
The reaction is:
second order with respect to [NO],
first order with respect to [O2],
and third order overall.
29
2.2 RATE LAWS
• Generally, the rate law for the respective order can

be written as below:
For example
For a reaction A  product,
If the above reaction is:
• zero order: Rate = k
• First order: Rate = k [A]
• Second order: Rate = k[A]2
30
2.2 RATE LAWS
The Order of a Reaction
A reaction has an individual order “with respect
to” or “in” each reactant, and an overall order,
the sum of the individual orders.
Lets consider only one reactant, A

A Products
Rate = k[A]n
Lets determine the order of a reaction, n by

using initial rate method
31
2.2 RATE LAWS
Finding the Rate Law: The Initial Rate Method
• The rate law must be determined

experimentally
• The rate law shows how the rate of a reaction
depends on the concentration of the reactants
• Changing the initial concentration of a reactant
will therefore affect the initial rate of the
reaction
32
2.2 RATE LAWS
if for the then doubling

reaction the initial
concentration
A → Products of A does not
change the
Rate = k[A]n initial
reaction rate.
Thus, n = 0
(Zero Order)
Rate = k 33
2.2 RATE LAWS

A → Products concentration
of A doubles
Rate = k[A]n
the initial
reaction rate.
Thus, n = 1
(First Order)
Rate = k[A]
34
2.2 RATE LAWS

A → Products
concentration
Rate = k[A]n of A
quadruples the
initial reaction
rate. Thus, n =
2 (Second
Order)
Rate = k[A]2 35
2.2 RATE LAWS
Proposed rate law: Rate = k[A]n
• If a reaction is Zero Order, the rate of the reaction is
always the same
– doubling [A] will have no effect on the reaction rate
• If a reaction is First Order, the rate is directly
proportional to the reactant concentration
– doubling [A] will double the rate of the reaction
• If a reaction is Second Order, the rate is directly
proportional to the square of the reactant
concentration
– doubling [A] will quadruple the rate of the reaction
36
Plots of reactant concentration, [A], vs. time for
first-, second-, and zero-order reactions.
37
Plots of rate vs. reactant concentration, [A],
for first-, second-, and zero-order reactions.
38
2.2 RATE LAWS
Determining the Rate Law when there are Multiple
Reactants
• Changing each reactant will effect the overall rate of
the reaction
• By changing the initial concentration of one reactant
at a time, the effect of each reactant’s concentration
on the rate can be determined
• In examining results, we compare differences in rate
for reactions that only differ in the concentration of
one reactant
39
2.2 RATE LAWS
Individual and Overall Reaction Orders
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)
If we compare Experiments 1 and 2, we see that when

[NH4+] doubles, the initial rate doubles.
40
2.2 RATE LAWS
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)
Likewise, when we compare Experiments 5 and 6, we

see that when [NO2−] doubles, the initial rate doubles.
41
2.2 RATE LAWS
First-order in [NH4+] and First order in [NO2-]
• This means
Rate  [NH4+]
Rate  [NO2−]
Rate  [NH4+] [NO2−]
which, when written as an equation, becomes
Rate = k [NH4+] [NO2−]
• The overall reaction order can be found by adding the

exponents on the reactants in the rate law.
• This reaction is second-order overall.
42
2.2 RATE LAWS
Consider the reaction between NO and O2. From the
experiment, the results showed that;-
2 NO (g) + O2 (g) 2 NO2 (g)
Rate = k[NO]2[O2]
The reaction is:
second order with respect to [NO],
first order with respect to [O2],
and third order overall.
43
2.2 RATE LAWS
The decomposition of ammonia on a platinum surface at
856oC is a zero order reaction
NH3 (g) 1/2 N2 + 3/2 H2 (g)
Rate = k[NH3]0 = k
The reaction rate is independent of NH3 concentration
44
2.2 RATE LAWS
Concentration and Rate
One can gain information about the rate of a reaction by
seeing how the rate changes with changes in
concentration (with the temperature held constant).
• The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the
concentrations of the reactants
 and homogeneous catalysts as well
• The rate law must be determined experimentally!!
• The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
45
2.2 RATE LAWS
Effect of Concentration and Reaction Rate
Consider, the decomposition of N2O5 to NO2 and O2.
N2O5 2NO2 + ½ O2
[N2O5] Rates (M.min-1)
0.17 0.00080
0.34 0.0014
0.68 0.0028
Doubling the concentration of N2O5 doubles the

reaction rate. These results showed the reaction rate
directly proportional to the reactant concentration
Rate of reaction α [N2O5] 46

2.2 RATE LAWS
Effect of Concentration and Reaction Rate
In other reactions, different relationship between
reaction rate and reactant concentration
For example - reaction rate could be independent of

concentration, or it may depend on the reactant
concentration raised to some power [reactant]n
If reaction involved several reactants, the reaction
rate may depend on the concentrations of each of
them or only one of them.
If catalyst involved, its concentration may also affect

the rate of reaction.
47
2.2 RATE LAWS
Rate Equations
The relationship between reactant concentration and
reaction rate is expressed by an equation called a rate
equation or rate law.
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
Consider, the above reaction, the rate is depend on the

concentration of Br2, but not concentration of HCOOH.
So, the above reaction can be expressed as below.
Rate of reaction = k[Br2]
48
2.2 RATE LAWS
Rate Constant
49
2.2 RATE LAWS
Rate Constant
rate α [Br2]
rate = k [Br2]
rate
k=
[Br2]
k = rate constant
= 3.50 x 10-3 s-1
Knowing the k allow you to calculate the rate at a particular
concentration. The units of k depends on the rate law or order of
reaction for a particular reaction- next slide will discussed further. 50
2.2 RATE LAWS
The Unit of Rate Constant
Reaction rates have units of mol/L.time when
concentrations are given as moles per liter.
The time in rate constant can be seconds, minutes,

hours, days, year or whatever time unit is appropriate.
Rate constants must have units consistent with the order

of a reaction
First order reactions : the units of k are 1/time

Second order reactions : the units of k are L/mol.time
Zero order reactions : the units of k are mol/L.time
51
2.2 RATE LAWS
Example 4
For the following reactions, determine the reaction order

with respect to each reactant and the overall order from
the given rate law.
H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l)

rate = k[H2O2][I-]
52
2.2 RATE LAWS
Answer to Example 4
PLAN:
Look at the rate law and not the coefficients of the
chemical reaction.
SOLUTION:
The reaction is 1st order in H2O2, 1st order in I- and zero
order in H+, while being 2nd order overall.
53
2.2 RATE LAWS
Example 5
The rate equation for the reaction of NO with

ozone is Rate = k[NO][O3].
If the rate is 6.60 x 10−5 M/sec when [NO] = 1.00 x

10−6 M and [O3] = 3.00 x 10−6 M, calculate the rate
constant k
54
2.2 RATE LAWS
Answer to Example 5
Given: [NO] = 1.00 x 10 −6 M, [O3] = 3.00 x 10−6 M,
Rate = 6.60 x 10−6 M/s
Find: k, M−1s−1
Conceptual Rate, [NO], [O3]

k
Plan:
Relationships: Rate = k[NO][O3]
55
2.2 RATE LAWS
Example 6
The rate law for the decomposition of

acetaldehyde, CH3CHO, is Rate = k[CH3CHO]2.
What is the rate of the reaction when the
[CH3CHO] = 1.75 x 10−3 M and the rate constant
is 6.73 x 10−6 M−1•s−1?
56
2.2 RATE LAWS
Answer to Example 6
Given: [CH3CHO] = 1.75 x 10

−3 M, k= 6.73 x 10−6
M−1•s−1
Find: Rate, M/s
Conceptual
Plan: k, [acetaldehyde] Rate
Relationships: Rate = k[acetaldehyde]2
57
2.2 RATE LAWS
Example 7
Determine the rate law and rate constant for the reaction
NO2(g) + CO(g)  NO(g) + CO2(g)
given the data below
58
2.2 RATE LAWS
Answer to Example 7
Comparing Expt #1 and Expt #2, the

[NO2] changes but the [CO] does not
59
2.2 RATE LAWS
Answer to Example 7
60
2.2 RATE LAWS
Answer to Example 7
61
2.2 RATE LAWS
Answer to Example 7
62
2.2 RATE LAWS
Origins of Organic Chemistry
Answer to Example 7
Compounds obtained from plants, animals hard to isolate, and

purify.
Compounds also decomposed more easily.
Torben Bergman (1770) first to make distinction between organic


63
2.2 RATE LAWS
Answer to Example 7

purify.

andminorganic
n = 2, =0 chemistry.

64
2.2 RATE LAWS
Answer to Example 7
Foundations
Substitute theof organic chemistry from mid-1700’s.
Expt. Initial Initial Rate
Initial
concentrations Number [NO2], (M) [CO], (M) (M/s)
Compounds
and rate for obtained from plants, animals hard to isolate, and
any purify.
experiment 1. 0.10 0.10 0.0021
into the rate 2. 0.20 0.10 0.0082
Compounds
law and solvealso decomposed more easily.
3. 0.20 0.20 0.0083
for k
Torben Bergman (1770) 4. first to make
0.40 distinction
0.10between0.033
organic
Rateand k[NO
inorganic
2
]2
chemistry.
for expt 1
k 0.10 they
M were from living sources.
2
M because
force”
0.0021 s
0.0021 Ms 1 1
k  0.21 M  s
0.01 M2 65
2.2 RATE LAWS
Example 8
Foundations
Determine of organic
the chemistry
rate law from
and rate mid-1700’s.
constant for the reaction
NH4+ + NO2− N2 + 2 H2O
purify. given the data below


66
2.2 RATE LAWS
Answer to Example 8

purify.


67
2.2 RATE LAWS
Answer to Example 8

purify.


68
2.2 RATE LAWS
Answer to Example 8
Rate = k[NH4+]n[NO2]m

purify.


69
2.2 RATE LAWS
Exercise 4
Ammonia decomposes to nitrogen and hydrogen gases
at ToC. The rate of decomposition is first order with
respect to ammonia.
a) Write the rate law for the decomposition of ammonia

b) The rate of the above reaction is found to be 0.0216
mol dm-3s-1 when the concentration of NH3 is 0.67 mol
dm-3. Calculate the rate constant for the
decomposition of ammonia at ToC
70
2.2 RATE LAWS
Exercise 5
The dimerization of a compound A in ethanol at 40oC

can be illustrate as a follow reaction
2A A2
The above reaction showed a second order reaction
a) Write a rate law for the reaction

b) Calculate the initial concentration of A when k is
0.137 L.mol-1.s-1 and initial rate is found to be
3.4 x 10-4 mol L-1.s-1
71
2.2 RATE LAWS
Exercise 6
The reaction 2NO (g) + Cl2 (g) ⇋ 2NOCl (g) was

studied at -10oC and the following data were obtained.
Initial Concentration, mol/L
Run NO Cl2 Initial rate of formation
of NOCl, mol/L.min
1 0.10 0.10 0.18
2 0.10 0.20 0.35
3 0.20 0.20 1.45
a) What is the order of reaction with respect to NO and

with respect to Cl2
b) What is the numerical value of the rate constant at
-10oC 72
2.2 RATE LAWS
Origins of Organic
Exercise 7
Chemistry
When methyl
Foundations of bromide reacts from
organic chemistry withmid-1700’s.
hydroxide ion in
solution, methyl alcohol and bromide ion form.
Compounds obtained from plants, animals hard- to isolate, and
CHpurify.
3Br + OH
- CH3OH + Br
Determine
Compounds the
also rate law andmore
decomposed evaluate
easily. the rate constant
from the experimental data.
Torben BergmanInitial
Experiment
(1770) first to make
[CH3Br]
distinction between
Initial [OH-]
organic
Initial Rate
(M) (M) (M/s)
1 0.050 0.010 2.4 x 10-3
It was thought that organic compounds must contain some -3“vital
2 because they
force” 0.080 0.020
were from living sources. 7.7 x 10
3 0.080 0.010 3.8 x 10-3
73
2.2 RATE LAWS
Origins of Organic
Exercise 8
Chemistry
Consider the reaction X + Y Z
These data are obtained are 360 K
Exp
purify. Initial Rate (M/s) [X] [Y]
1 0.147 0.10 0.50
Compounds
2 also decomposed
0.127 more easily. 0.20 0.30
3 4.064 0.40 0.60
Torben 4Bergman (1770)1.016
first to make distinction
0.20 between organic
0.60
5 0.508 0.40 0.30
a) Determine thethey
force” because order of from
were the reaction
living sources.
b) Determine the initial rate of disappearance of X when
the concentration of X is 0.30 M and Y is 0.40 M
74
2.2 RATE LAWS
Exercise 9
The rate of reaction between bromate ions and bromide ions in acidic
aqueous solution in terms of changes in concentration of reactants and
products is given below
Rate = - ∆[BrO-3] = -1/5 ∆[Br-] = -1/6∆[H+] = 1/3∆[Br2] = 1/3 ∆[H2O]
∆t ∆t ∆t ∆t ∆t
The data from 4 experiments are listed in table below
Exp [BrO3-] [Br-] [H+] Rate

(L/mol.s)
1 0.1 0.1 0.1 8.0 x 10-4
2 0.2 0.1 0.1 1.6 x 10-3
3 0.2 0.2 0.1 3.2 x 10-3
4 0.1 0.1 0.2 3.2 x 10-3
a) Write a balanced equation for the reaction
b) If the rate of the above reaction is first order with respect to BrO-3 and
Br-, calculate the order of the reaction with respect to H+ and write the
rate law of the reaction 75
TOPIC
INTEGRATED RATE LAWS
76
2.3 INTEGRATED RATE LAWS
Origins of OrganicRelationships:
Concentration-Time Chemistry
Integrated Rate Laws
The rate laws only tell us the rate or concentration at a
given instant
Compounds allowing
obtained from us to find
plants, the hard
animals “How to fast”
isolate,isand
the
purify. proceeding at the moment [reactants] are
reaction
mixed.
It is important
Torben to know
Bergman (1770) first “how
to makelong” a reaction
distinction must
between organic
proceed to reach
and inorganic a predetermined concentration of
chemistry.
some reactant of product, or what the reactant and
Itproduct concentrations
was thought will be after
that organic compounds mustsome time
contain has
some “vital
elapsed- therefore
force” because integrated
they were ratesources.
from living laws will employ
77
Zero Order Reactions
Using calculus
Foundations to integrate
of organic the rate
chemistry from law for a zero-order
mid-1700’s.
process gives us
purify.
[A]t = −kt + [A]0
Where also decomposed more easily.
Compounds
[A]0 is the initial concentration of A, and
[A]tand inorganic
is the chemistry. of A at some time, t, during the
concentration
course of the reaction.
78
• Rate = k[A]0 = k
• Compounds
Integrated
purify.
obtained
rate from
law: plants,
[A] = − k
animalst hard
+ [A]to isolate, and
initial
• Graph of [A] vs. time is straight line with slope
= −k andalso
Compounds y–intercept
decomposed = [A]easily.
more initial


79
[A]initial obtained from plants, animals hard to isolate, and

Compounds
purify.

[A]

time
80
Half Life for Zero Order Reactions
• Integrated rate law: [A]t = −kt + [A]0
• Compounds
= [A]t obtained
t ½purify. = ½ [A]from
0
plants, animals hard to isolate, and
½[A]0 = -k
• Compounds alsot ½ + [A]0 more easily.
decomposed
t ½ = [A
• Torben ]/2k
Bergman = [A
(1770)0 firstkto make distinction between organic
]/2
0
• ItWhen Ratethat
was thought = M/sec, k = M/sec
organic compounds must contain some “vital
81
Integrated Rate Laws : First-Order Reactions
Using calculus to integrate the rate law for a first-order
process gives us
purify. [A] t
ln = −k t
[A] 0
TorbenWhere
Bergman (1770) first to make distinction between organic
[A]t force”
is the because
concentration
they wereoffrom
A atliving
some time, t, during the
sources.
82
Foundations ofthis
Manipulating organic chemistry
equation from mid-1700’s.
produces…
[A]
t
purify. ln = −k t
[A]0
ln [A]t − ln [A]0 = − kt
ln [A]t = − kt + ln [A]0
…which is in thethey
force” because formwere from living sources.
y = mx + b
83
• Rate = k[A]1 = k[A]
• ln[A] t = −kt + ln[A]0
purify.
• Graph ln[A] vs. time gives straight line with
slope = −k and y–intercept = ln[A]0
– used
Torben to determine
Bergman (1770) first tothe rate
make constant
distinction between organic

84
ln[A]0
purify.

ln[A]

time 85
Half-Life
•Foundations of organic
The half-life, t1/2chemistry from mid-1700’s.
, of a reaction is the time it
takes for the concentration of the reactant
to
fall to ½ its initial value
purify.
• The half-life of the reaction depends on the
order of the reaction

86
Half Life for First- Order
• Integrated rate law : ln[A]t = −kt + ln[A]0
purify.
• t ½ = [A]t = ½ [A]0
• ln ½ [A]0 = −k t½ + ln[A]0
• ln and
½ [A] 0 = −k chemistry.
inorganic t½
[A]0
• t½ force”
= 0.693/ k. The
because half-life
they of aliving
were from first sources.
order reaction is
constant
• When Rate = M/sec, k = s–1
87
The Half-Life of a First Order Reaction
is Constant

purify.


88
Rate Data for:
C4H9Cl +ofHorganic
Foundations 2O chemistryC 4H9mid-1700’s.
from OH + HCl

purify.


89
is Constant

purify.


90
is Constant

purify.


91
Origins of of
The Half-Life Organic Chemistry
a First Order Reaction
is Constant
Compounds obtained from plants, animals hard slope

to isolate,
= and
purify. −2.01 x 10−3
k=
Compounds also decomposed more easily. 2.01 x 10−3 s-1


92
Second Order Reactions
Using calculus to integrate the rate law for a Second-
order process
Compounds gives
obtained fromusplants, animals hard to isolate, and
purify.
1 1
= ktmore
Compounds also decomposed + easily.
[A]t [A]0
TorbenWhere
Bergman (1770) first to make distinction between organic
[A]t force”
is the because
concentration
they wereoffrom
A atliving
some time, t, during the
sources.
93
• Rate = k[A] 2
1/[A]t = kobtained
• Compounds t + 1/[A]from
0 plants, animals hard to isolate, and
purify.
• Graph 1/[A] vs. time gives straight line with
slope = kalso
Compounds and y–intercept
decomposed = 1/[A]initial
more easily.
– used to determine the rate constant

94

purify.

1/[A]

1/[A]initial
time 95
Half Life for Second Order Reactions
• Integrated Law: 1/[A] = kt + 1/[A]0
purify.
• t ½ = [A]t = ½ [A]0
• 1/ ½ [A]0 = k t½ + 1/[A]0
• t½ = 1/(k[A0])
• When Rate = M/sec, k = M−1s−1
96

purify.


97
Table 1 Units of the Rate Constant k
Overall Reaction Order Units of k (t in seconds)
purify.
0 mol/L*s (or mol L-1 s-1)
1 1/s (or s-1)
2 L/mol*s (or L mol -1 s-1)
force” because they were from2living sources.
3 L / mol2 *s (or L2 mol-2 s-1)
98
Origins of Organic
Example 9
Chemistry
Determining
Foundations the Half-Life
of organic of a First-Order
chemistry from mid-1700’s. Reaction
Cyclopropane is the smallest cyclic hydrocarbon. It is thermally
Compounds
unstable obtained from
and rearranges plants, at
to propene animals
1000oChard to isolate,
via the andfirst-
following
orderpurify.
reaction:
CH2

Compounds alsoHdecomposed
2C CH2 (g) more easily.
H3C CH CH2 (g)
The rate constant is 9.2 s-1,

(a) What is the half-life
and inorganic of the reaction?
chemistry.
(b) How long does it take for the concentration of cyclopropane to
It was
reach thought that
one-quarter organic
of the compounds
initial value? must contain some “vital
Use the half-life equation, t1/2 = 0.693
k
99
Answer to Example 9
0.693
Use the half-life equation, t1/2 = k
purify.
One-quarter of the initial value means two half-lives have passed.
SOLUTION:
(a) t1/2 = 0.693/9.2 s-1 = 0.075 s
(b) 2 t = 2(0.075 s) = 0.150 s
1/2

100
Example 10
The reaction SO2Cl2(g)  SO2(g) + Cl2(g) is first order with a
rate constant of 2.90 x 10 −4 s−1 at a given set of
conditions.
purify. Find the [SO2Cl2] at 865 s when [SO2Cl2]initial =
0.0225 M
Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4 s−1
Torben Bergman
Find: [SO(1770)
2Cl2]
first to make distinction between organic
Conceptual Plan:
[SO2Cl2]init, t, k [SO2Cl2]
ItRelationships:
was thought that organic compounds must contain some “vital
101
Answer to Example 10
Compounds
Solution:obtained from plants, animals hard to isolate, and
purify.

Check: the new concentration is less than the original, as
expected
102
Example 11
The reactionof
Foundations  2 R chemistry
Q organic is secondfromorder in Q. If the initial [Q]
mid-1700’s.
= 0.010 M and after 5.0 x 102 seconds the [Q] = 0.0010 M,
Compounds obtainedfind
fromthe rate animals
plants, constant
hard to isolate, and
purify.


103
Foundations
Given:of[Q]
organic= chemistry
0.010 M, t from
= 5.0 mid-1700’s.
x 102 s, [Q]t = 0.0010 M
init
Find:obtained
Compounds k from plants, animals hard to isolate, and
purify.
Conceptual
[Q]init, t, [Q]t k
Plan:also decomposed more easily.
Compounds
Relationships:
Solution:
104
Graphical Determination of the
Rate Law for A Product
• Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs. time
Compounds obtained fromofplants,
allow determination animals
whether hard to isolate,
a reaction and
is zero,
purify.
first, or second order
Whichever
• Compounds plot
also gives a straight
decomposed line determines the
more easily.
order with respect to [A]
– if linear
Torben is (1770)
Bergman [A] vs.first
time, = k[A]0 between organic
Ratedistinction
to make
–and
if inorganic
linear is chemistry.
ln[A] vs. time, Rate = k[A]1
– if linear is 1/[A] vs. time, Rate = k[A]2
105
Example 12
Complete
Foundations of organicthe Table and
chemistry fromDetermine
mid-1700’s. the
Rate Equation for the Reaction A 2 Product
purify.


What will the rate be when the [A] = 0.010 M?

106

purify.


107

purify.


108

purify.


109

purify.


110
Conclusion for the determination of the
rate equation
Compounds obtainedfor
fromtheplants,
reaction A hard to2isolate,
animals Product and
purify.
Because the graph 1/[A] vs. time is linear, the
reaction is second order,
Rate  k[A]2
k  Bergman
Torben slope of(1770) firstto0.10
the line make –1 s –1
Mdistinction between organic

111
Relationship Between Order and Half-Life
• For a zero order reaction, the half-life is directly
proportional
Compounds to the
obtained initial
from concentration.
plants, animals hard toThe lower
isolate, andthe
initial
purify.concentration of the reactants, the shorter the
half-life
– t1/2 = [A]init
Compounds /2kdecomposed more easily.
also
• For a first order reaction, the half-life is independent of
the concentration.
Torben Bergman (1770) (t first = constant)
1/2 to make distinction between organic
= ln(2)/k chemistry.
t1/2inorganic
–and
• For a second order reaction, the half-life is inversely
It proportional
was thought that to organic
the initial concentration
compounds – increasing
must contain some “vital
the initial
force” concentration
because they were from shortens the half-life
living sources.
– t1/2 = 1/(k[A]init)
112
Exercise 10
The reaction of decomposition Exp [N2O5] (M) Time (s)

as follow
1 0.1000 0
N2O5 (g) 4NO 2 (g) + O2 (g) 2 0.0707 50
3 0.0500 100
The following data were obtained
4 0.0250 200
a) What is the order of reaction? 5 0.0125 300
b) What is the rate constant? 6 0.00625 400
c) Calculate the [N2O5] at 150 s.
d) Find the half life
113
Exercise 11
The pesticide fenvalerate, C25H22ClO3N, is insect

repellent to combat the mosquitoes that spread West
Nile virus. It degrades in the environment with first order
at a rate constant 3.9 x 10-7 s-1. An accidental discharge
of 100kg fenvalerate into a holding pond results in a
fenvalerate concentration of 1.3 x 10-5 M. Calculate the
concentration after 1 month (2.6 x 106 s) after the spill.
114
Exercise 12
Substance A reacts according to a first order rate law
with k = 5.0 x 10-5 s-1
a) If the initial concentration of A is 1.00M what is the

initial rate?
b) What is the rate after 1.00 hr?
115
Exercise 13
The age of Otzi, the Ice Man was determined by carbon-

14. Carbon-14 is a radioisotope with a half life of 5730
years. A sample of carbon containing material was found
to have 52.7% of its original amount of carbon -14.
Calculate how long ago Otzi lived.
116
Try this- Test 1 Nov-Mac 2012
The reaction between A2 and B2 at 277oC is 2nd order overall
Foundations of organic2A + B2 from mid-1700’s.
chemistry
2 2A2B
For a mixture containing 0.5 M each of A and B at 227oC, it was

found that doubling the concentration of B has no effect on the
purify.
rate of the reaction, and the concentration of A decreases by
50% in 129s
a) Write the rate law for the reaction
b) Write
Torben the integrated
Bergman (1770) rate
first law for the
to make reaction between organic
distinction
c) and
What is the rate
inorganic in A2B if A decreasing at 0.78Ms-1
chemistry.
d) Calculate the rate constant, k at 277oC
e) Calculate the initial rate at 277oC
Itf)was
Howthought that
long will organic
it take for compounds must contain
the concentration of A to some “vitalby
decrease
force”
another because
50% they were from living sources.
117
2.4 THEORIES OF CHEMICAL KINETICS
118
• For most reactions, for a reaction to take place, the

reacting molecules must collide with each other
– on average about 109 collisions per second
• Once molecules collide they may react together or
they may not, depending on two factors –
1. whether the collision has enough energy to "break
the bonds holding reactant molecules together";
and
2. whether the reacting molecules collide in the
proper orientation for new bonds to form
119
OriginsThe
of Collision
OrganicTheory
Chemistry
• Foundations
Moleculesofor organic
atoms chemistry
or ions from mid-1700’s.
can only react if they collide
Compounds
with eachobtained
other. from plants, animals hard to isolate, and
purify.
• In a chemical reaction,
bonds arealso
Compounds broken and new
decomposed more easily.
bonds are formed.
For aBergman
• Torben collision(1770)
to befirst to make distinction between organic
effective, thechemistry.
and inorganic reacting
molecules must have
It sufficient
was thoughtkinetic energy
that organic to
compounds must contain some “vital
force” because
overcome the they were from living sources.
energy
barrier.
120
The Collision Theory
The collision
Foundations theorychemistry
of organic developed
fromfrom kinetic theory to
mid-1700’s.
account for the effects of concentrations and
temperature
Compounds on reaction
obtained rates.
from plants, animals hard to isolate, and
purify.
The reaction
Compounds alsorate is measured
decomposed on effective collision.
more easily.
Any factor that increases the rate of effective collision
will also
Torben increase
Bergman the
(1770) rate
first of the
to make reaction.
distinction between organic
The effective collision = (total collision frequency) X
(fraction of
It was thought that organic compounds molecules
must with“vital
contain some
force” because they weresufficient
from living sources.
energy)
121
Activation Energy
• The activation energy, Ea is a minimum amount of
energy required to initiate reaction:
• Molecules
purify. must possess a certain minimum kinetic
energy called the activation energy for a reaction to
occur
 energy needed to break the bonds of the reacting molecules
 reaction
Torben with(1770)
Bergman low activation energy
first to make is easier between
distinction to take place, and
organic
isand
faster
inorganic chemistry.

122
The Collision Theory
Furthermore,
Foundations molecules
of organic must
chemistry collide
from with the correct
mid-1700’s.
orientation and with enough energy to cause bond
breakage obtained
Compounds and formation.
from plants, animals hard to isolate, and
purify.


123
Activation Energy
Just as a ball
• Foundations cannot
of organic get over
chemistry a hill
from if it does not roll up
mid-1700’s.
the hill with enough energy, a reaction cannot occur
unless theobtained
Compounds molecules
frompossess sufficient
plants, animals energy
hard to isolate,to get
and
purify.
over the activation energy barrier.


124
Activation Energy
The activation
• Foundations energy
of organic may be
chemistry shown
from on diagrams called
mid-1700’s.
energy profiles. The energy barrier, Ea is the activation
energy forobtained
Compounds forwardfrom
reaction
plants, animals hard to isolate, and
purify.
E
n E
n
Compounds also
e
r
Ea decomposed more easily.
e products
g r
g Ea
y
y
Torbenreactants
Bergman (1770) first
∆H = -veto make distinction between organic
∆H = +ve
products
reactants
It was thought
Progressthat organic compounds must contain
of reaction some “vital
Progress of reaction
(a) Energy profile for an (b) Energy profile for an
exothermic reaction endothermic reaction
125
Origins of Organic
Activation Chemistry
Energy
Activated state Activated state
Foundations
E
of organic chemistry from mid-1700’s.
n E Ea (reversed)
Ea (forward) Ea (reversed) n
e Ea (forward)
r e
g r
g
ypurify.
reactants
products
y
products
Compounds also decomposed more easily.reactants

Progress of reaction Progress of reaction
∆H = E (forward) – E (reversed) ∆H = E (forward) – E (reversed)
a a a a
∆H = -ve ∆H = +ve
•AItreversible
was thought thathas
reaction organic compounds
two activation must contain some “vital
energies:-
activation
•Theforce” energythey
because ,Ea (forward) , is the
were from energy
living difference between the
sources.
activated state and the reactants
•The activation energy ,Ea (reverse) is the energy difference between the
activated state and the products.
126
The Transition State Theory
The transition
•Foundations state
of organic theory from
chemistry is concerned
mid-1700’s.with what
actually happens during a collision.
This theory
•Compounds explains
obtained fromhow the
plants, energy
animals hardof to
collisions
isolate, andis
used
purify.to form a high-energy activated complex when
reactants particles collide with each other.
•Compounds
There existsalso decomposed
an intermediate more easily.
stage before reactant
molecules change into products.
•Torben
The Bergman (1770)
activated first toormake
complex
distinction
transition between
state is a organic
chemical species with partially broken and partially
formed
It was bonds
thought that organic compounds must contain some “vital
– has highest
force” becauseenergy
they and
were extremely unstable
from living – exists at instant
sources.
– has more potential energy than either the reactants or the products
– the bonds in the reactant molecules are in the process of breaking
while the new bonds in the products molecules are start to form. 127
The Transition State Theory
Reaction
Foundations of energy diagrams
organic chemistry andmid-1700’s.
from possible transition
states.
purify.


128
Origins of Organic
Exercise
Chemistry
The gas phase
Foundations reaction
of organic chemistry from mid-1700’s.
NO (g) + F2 (g)  NOF (g) + F (g) has an overall
enthalpy
Compounds change
obtainedoffrom
-60 kJ. Theanimals
plants, activation energy
hard to isolate,the
and
reaction
purify. is 16.3 kJ
a)Compounds
Sketch the alsoenergy profile
decomposed for easily.
more the reaction and label Ea
∆H and draw the activated complex.
b)Torben
WhatBergman
is the activation energy
(1770) first to for reverse
make distinction reaction?
between organic

129
Origins of Organic
Exercise
Chemistry
Based on their
Foundations activation
of organic energies
chemistry and energy changes
from mid-1700’s.
and assuming that all collision factors are the same,
which of theobtained
Compounds following
fromreactions would
plants, animals beto
hard fastest
isolate,and
and
which would be slowest?
purify.
I)Compounds
Ea = 45 kJ/mol ; ∆H = -25
also decomposed kJ/mol
more easily.
I)Torben
Ea =Bergman
35 kJ/mol ; ∆H
(1770) = -15
first kJ/mol
to make distinction between organic
I) Ea = 55 kJ/mol ; ∆H = 10 kJ/mol
Whichforce”
of because they were
the reactions from
will be living
fastestsources.
and will be slowest
in reverse direction?
130
FACTORS CONTROLLING
RATES
Foundations of organic OF REACTIONS
chemistry from mid-1700’s.
1 CONCENTRATIONS OF REACTANTS
purify.
2 CHEMICAL NATURE OF REACTANTS
3 TEMPERATURE
and4inorganic chemistry.
THE USE OF A CATALYST
131
FACTORS CONTROLLING
RATES
Concentrations of Reactants
purify.– As the concentration of reactants
increases, so does the likelihood that
Compoundsreactant
also decomposed morewill
molecules easily.
collide.


132
FACTORS CONTROLLING
RATES
The Effect
Compounds of Concentration
obtained onhard
from plants, animals Collision Theory
to isolate, and
purify.
When the concentration increases, the frequency of
collision also increases
The more
and particles
inorganic present in the same volume, so
chemistry.
they are more likely to collide more frequently, thus
increase the that
It was thought reactions
organic rate.
compounds must contain some “vital
133
FACTORS CONTROLLING
RATES OF REACTIONS
Chemical Nature of Reactants
– In order to react, molecules must come in
contact with each other.
– The more homogeneous the mixture of
reactants, the faster the molecules can
react.
134
FACTORS CONTROLLING
RATES OF REACTIONS
Temperature
– At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
135
FACTORS CONTROLLING
RATES
The Effect
Compounds of Temperature
obtained on Collision
from plants, animals Theory
hard to isolate, and
purify.
When the temperature of the reaction is increased ,
the frequency
Compounds alsoofdecomposed
collision also
moreincreases
easily.
According to the
Torben Bergman kinetic-molecular
(1770) theorybetween
first to make distinction of gases,
organic
increasing the temperature
and inorganic chemistry. increases molecular
speeds.
As molecules move
force” because theyfaster,
were fromthey collide
living more forcefully
sources.
(more energy), and more frequently, increasing
reaction rates. 136
FACTORS CONTROLLING
RATES OF REACTIONS
The Use of A Catalyst
– Catalysts speed up reactions by

changing the mechanism of the reaction.
– Catalysts are not consumed during the
137
Effect of Temperature on Reaction Rate:
FoundationsMaxwell-Boltzmann
of organic chemistry fromDistributions
mid-1700’s.
• Temperature is defined as a measure of the average
kinetic energy
Compounds of the
obtained frommolecules in ahard
plants, animals sample.
to isolate, and
purify.
• Some molecules are moving at different speeds, at any
Compounds
given time.also decomposed
Some more easily.
have higher energies, some medium
or some molecules have lower energies.
• At any temperature there is a wide distribution of
kinetic energies.- Use Maxwell-Boltzman Distribution
138
Maxwell-Boltzmann
Foundations of organic chemistry fromDistributions
mid-1700’s.
The area under distribution curve is proportional to total
number of molecules
purify. Most of molecules have
values somewhere in the
Fraction of molecules
middle

A few molecules
It was thought havesome
that organic compounds must contain high energy
“vital
A few molecules
have low energy
Kinetic Energy
139
Foundations Maxwell-Boltzmann
of organic chemistry fromDistributions
mid-1700’s.
• Figure shows the
T1
Compounds obtained from T2 plants, animalsdistribution of and
hard to isolate, kinetic
purify. energy for gaseous
molecules at T1 and
Compounds also decomposed more easily.T
2
• The area under each
and inorganic chemistry. curve is the same, so
This fraction of molecules can
total number of
be found
It was through
thought theorganic
that expression
compounds must molecules used“vital
contain some for T1
force” because-Ethey and T2 are the same.
were from living sources.
a
RT
f=e
Where R is the gas constant and T is the Kelvin temperature. 140
Maxwell-Boltzmann
Foundations of organic chemistry fromDistributions
mid-1700’s.
T1 • As the temperature
Compounds obtained from increases, the curve
T2 plants, animals hard to isolate, and
purify. move towards the right to
a higher kinetic energy
thus shape become
Compounds also decomposed more easily.flattens and broadens.
• If the dotted line
Torben Bergman (1770) first to make distinction between
represents organic
the activation
and inorganic chemistry. energy, then as
Thus at higher temperatures, a larger temperature increases,
population of molecules
It was thought hascompounds
that organic higher the contain
must fraction some
of molecules
“vital
energy. Asbecause
force” a result,they
the reaction rate
were from that can overcome the
living sources.
increases. activation energy barriers
also increases
141
The Effect of a Change of Temperature
Let ‘s assume Ea = 50 kJ/mol
and T1 = 293 K so the value
of fraction is
purify.
-50000
8.314 x 293
f=
Compounds also decomposed more easily. e
= 1.21 x 10-9
and inorganic chemistry. By raising the temperature
just 10oC and T2 = 303 K so
the value of fraction is
So force”
the fraction of thethey
because molecules able toliving sources. -50000
were from
react has almost double by increasing
the temperature by 10oC. That causes
f = e 8.314 x 303
the rate of reaction to almost double = 2.38 x 10-9 142
The Effect of a Catalyst
AFoundations
catalyst will of organic
provide chemistry from mid-1700’s. mechanism
a new route/different
for the reaction with lower total activation energy
purify.
Without catalyst Ea = 50 Let’s assume in the presence of
kJ/mol and T1 = 293 K so the catalyst Ea = 25 kJ/mol at same
value of fractionalso
is decomposed temperature so the value of
Compounds more fraction
easily. is
-50000 -25000
Torben8.314
Bergman
x 293 (1770) first to make distinction between
8.314 x 293 organic
f =and
e inorganic chemistry. f = e
= 1.21 x 10-9 = 3.47 x 10-5
So the fraction of the molecules able to react has almost 30000 times more
molecules which can react in the presence of the catalyst compared to
without catalyst. The catalyst speed up the reactions rate.
143
The Effect of a Catalyst

purify.

It was thought
-50000 that organic compounds must contain some
-25000“vital
force”
8.314 xbecause
293 they were from living sources. 8.314 x 293
f=e f=e
= 1.21 x 10-9 = 3.47 x 10-5
144
Exercise
The activation energy for isomerization of methyl
isonitrile is 160 kJ/mol. Calculate the fraction of methyl
isonitrile
purify. molecules that has an energy of 160 kJ at 500 K
IfCompounds
the abovealso
reactions using
decomposed a catalyst
more easily. to speed up the
reaction rate and found that the new activation energy is
lower
Torbenabout three-quarter
Bergman (1770) first tofrom
makethe original
distinction values.
between organic
Determine the ratio
and inorganic of the fraction of molecules
chemistry.

145
TOPIC
2.5 ARRHENIUS EQUATION
146
Svante Arrhenius found that the most reactions the increase in rate
with increasing temperature is nonlinear but exponential.
Reaction rate obeyed on three factors

• the fraction of molecules possessing an energy of Ea or greater
• the number of collisions occurring per second and
• the fraction of collisions that have the appropriate orientation
Therefore, the three factors are incorporated into Arrhenius

equation
This Arrhenius equation quantitatively describes the relationship

between the rate constant k, temperature and the activation energy.
147
where A is the Arrhenius constant , is related to the

frequency collision or the frequency factor, (a number
that represents the likelihood that collisions would
occur with the proper orientation for reaction).
where T is the temperature in kelvins
R is the gas constant in energy units, 8.314 J/(mol•K)
Ea is the activation energy, the minimum energy
needed for the molecules to react
148
• This equation is very useful to analyse the effect of temperature

on the rate constant and to determine the Ea if the values of the
rate constant are known at different temperatures.
• Notice from the equation, the larger the activation energy, Ea,
the fewer molecules that have sufficient energy to overcome the
energy barrier, the smaller the rate constant k.
Increase in temperature, T, (-Ea/RT) is a smaller number,

therefore, Ae(-Ea/RT) is a larger number. This means the
rate constant will be larger and the rate faster.
for activation energy: If you decrease Ea, (-Ea/RT) is a

smaller number, therefore Ae(-Ea/RT) is a larger number.
This means the rate constant will be larger and the rate
faster. 149
Exercise 15
a) If the activation energy for a given compound is found
to be 42.0 kJ/mol, with a frequency factor of 8.0 × 1010 s-
1, what is the rate constant for this reaction at 298 K?
b) The rate constant for the reaction is 1.60 × 102 M-1s-1

at 249 K, Calculate the activation energy for this reaction
with a frequency factor of 4.0 × 1013 s-1,
c) The decomposition of N2O into N2 and O in the

presence of gaseous argon follows second order
kinetics, with k = (5.0 x 1011 L.mol-1.s-1)e -29000K/T .Calculate
the activation energy for this reaction
150
The Effect of Temperature on the Rate Constant
At different temperature, thus, rate constant is changed, the rate
constant k, is plotted against the temperature T an exponential
curve is obtained
K1 = Ae-Ea/RT1 K2 = Ae-Ea/RT2
K2 = Ae-Ea/RT2 K2 = e-Ea/RT2
K1 = Ae-Ea/RT1 K1 = e-Ea/RT1
K2
= e-(Ea/RT2)-(Ea/RT1)
K1
K2
= eEa/R(1/T1)-(1/T2)
K1 151
Taking the natural

logarithm of both sides,
the equation becomes
K = Ae-Ea/RT
Ea 1
ln k = -
R
( T
) + ln A
y = m x + b
Therefore, if k is determined experimentally at several
temperatures, Ea can be calculated from the slope of a
plot of ln k vs. 1T .
152
Example 13
Determine the activation energy and frequency factor
for the reaction O3(g)  O2(g) + O(g) given the following
data:
153
154
slope, m = 1.12 x 104 K

y–intercept, b = 26.8
155
Arrhenius Equation: Two-Point Form
• If you only have two (T,k) data points, the following
forms of the Arrhenius Equation can be used:
K2
= eEa/R(1/T1)-(1/T2)
K1
156
Example 14
The reaction NO2(g) + CO(g)  CO2(g) + NO(g) has a rate

constant of 2.57 M−1∙s−1 at 701 K and 567 M−1∙s−1 at
895 K. Find the activation energy in kJ/mol
157
T = 701 K, k = 2.57 M−1∙s−1, T = 895 K, k = 567

Given: 1 1 2 2
M−1∙s−1
Find:
Ea, kJ/mol
Conceptual T1, k1, T2, k2 Ea

Plan:
Relationships:
Solution:
158
Exercise 14
Determine the Activation Energy (Ea ) and (A) in the hydrolysis of an

ester if one set of data points given to you as follow:
Exp T (K) K
(L/mol.s)
1 288 0.0521
2 298 0.101
3 308 0.142
4 318 0.332
159
Exercise 15
Determine the Activation Energy (Ea ) in the reaction

between:
CH4 (g) + 2S2 (g) CS2 (g) + 2H2S (g)
At 550oC rate constant for the reaction is 1.1 L/mol.s

and 625oC the rate constant is 6.4 L/mol.s. Calculate Ea
160
Exercise 16
Biochemists often define Q10 for a reaction as the ratio

of the rate constant at 37oC to the rate constant at
27oC. Determine the activation energy for a reaction
that has a Q10 of 2.5
161
TOPIC
REACTION MECHANISMS AND RATE
DETERMINING STEP
162
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is
called the reaction mechanism.
• Reactions may occur all at once or through several

discrete steps.
• Each of these processes is known as an elementary
reaction or elementary process.
163
Multistep Mechanisms
The molecularity of a process tells how many molecules

are involved in the process.
164
• In a multistep process, one of the steps will be

slower than all others.
• The overall reaction cannot occur faster than this
slowest, rate-determining step.
165
Slow Initial Step
NO2 (g) + CO (g)  NO (g) + CO2 (g)
• The rate law for this reaction is found experimentally

to be
Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the rate
of the reaction does not depend on its concentration.
• This suggests the reaction occurs in two steps.
166
Slow Initial Step
• A proposed mechanism for this reaction is

Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.
• Rate = k1[NO2][NO2] = k1[NO2]2 and Rate = k2[NO3][CO]
• K1 = k, the rate law for the rate-determining step (slow)
is identical to the experimental rate law
167
Slow Initial Step
NO2(g) + CO(g)  NO(g) + CO2(g) Rateobs = k[NO2]2
1. NO2(g) + NO2(g)  NO3(g) + NO(g) Rate = k1[NO2]2 Slow
2. NO3(g) + CO(g)  NO2(g) + CO2(g) Rate = k2[NO3][CO] Fast
The first step is slower than the

second step because its
activation energy is larger.
The first step in this mechanism is

the rate determining step.
The rate law of the first step is the

same as the rate law of the overall
reaction. 168
Validating a Mechanism
• To validate (not prove) a mechanism, two
conditions must be met:
1. The elementary steps must sum to the overall
reaction
2. The rate law predicted by the mechanism must be
consistent with the experimentally observed rate
law
169
Mechanisms with a Fast Initial Step
• When a mechanism contains a fast initial step, the rate

limiting step may contain intermediates
• When a previous step is rapid and reaches equilibrium,
the forward and reverse reaction rates are equal – so
the concentrations of reactants and products of the
step are related
– and the product is an intermediate
• Substituting into the rate law of the RDS will produce a
rate law in terms of just reactants
170
Fast Initial Step
2 NO (g) + Br2 (g)  2 NOBr (g)
• The rate law for this reaction is found to be

Rate = k [NO]2 [Br2]
• Because termolecular processes are rare, this rate law
suggests a two-step mechanism.
171
Fast Initial Step
• A proposed mechanism is
Step 1: NO + Br2 ⇋ NOBr2 (fast)
Step 2: NOBr2 + NO  2 NOBr (slow)
Step 1 includes the forward and reverse reactions.
172
Fast Initial Step
• The rate of the overall reaction depends upon

the rate of the slow step.
• The rate law for that step would be
Rate = k2 [NOBr2] [NO]
• But how can we find [NOBr2]?
173
Fast Initial Step
• NOBr2 can react two ways:

– With NO to form NOBr
– By decomposition to reform NO and Br2
• The reactants and products of the first
step are in equilibrium with each other.
• Therefore,
Ratefoward = Ratereverse
174
Fast Initial Step
• Because Ratefoward = Ratereverse ,
k1 [NO] [Br2] = k−1 [NOBr2]
• Solving for [NOBr2] gives us
k1
k−1 [NO] [Br2] = [NOBr2]
175
Fast Initial Step
Substituting this expression for [NOBr2] in

the rate law for the rate-determining step
gives
k2k1
Rate = k [NO] [Br2] [NO]
−1
= k [NO]2 [Br2]
176
Example 15
Show that the proposed mechanism for the reaction

2 O3(g)  3 O2(g) matches the observed rate law
Rate = k[O3]2[O2]−1
1. O3(g) ⇋ O2(g) + O(g) Fast
2. O3(g) + O(g)  2 O2(g) Slow Rate = k2[O3][O]
177
1. O3(g) ⇋ O2(g) + O(g) Fast
2. O3(g) + O(g)  2 O2(g) Slow Rate = k2[O3][O]
178
Exercise 17
Mechanisms with a slow Initial Step
2NO2 (g) + F2 (g) 2NO2F (g)
Experimental rate law is first order for NO2 and F2.
Rate = k [NO2] [F2].
Proposed mechanism
1. NO2 (g) + F2 (g) NO2F (g) + F (g) (slow, rate determining step)
2. NO2 (g) + F (g) NO2F (g) (fast)
179
Exercise 18
Mechanisms with a Fast Initial Step
2NO (g) + O2 (g) 2NO2 (g)
Experimental rate law is first order for NO2 and F2.
Rate = k [NO]2 [O2].
Proposed mechanism
1. NO (g) + O2 (g) ⇋ NO3 (g) (fast, reversible)

2. NO3 (g) + NO (g) → 2NO2 (g) (slow, rate determining step)
180
End of Chapter 2
Please Read Chapter 3
Thank You
181

Chemical Kinetics

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Chemical Kinetics

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FOUNDATION CHEMISTRY II

Rates of chemical reactions is the change in

A  A 2  A 1 Rate  

C C2  C1  Z Z2  Z1 

In this reaction, the concentration of butyl chloride,

• All reactions slow

It was thought that organic compounds must contain some “vital

• In this reaction, the ratio

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

Δ[HI] Δ[H2] Δ[I2]

The expression for the rate of a reaction

Using [HI], the

To generalize, then, for the reaction

1 [A] 1 [B] 1 [C] 1 [D]

(b) Here the coefficients are 4, 5, 4, and 6, so

For the reaction given, the [I] changes from 1.000 M to

H2O2 (aq) + 3 I(aq) + 2 H+(aq)  I3(aq) + 2 H2O(l)

solve the rate

If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a

2 NOBr(g)  2 NO(g) + Br2(l)

Given: 240.0 g NOBr, 0.2000 L, 5.0 min.

Relationships: 2 mol NOBr:1 mol Br2,

(a) Express the rate in terms of changes in [H2], [O2], and

(b) When [O2] is decreasing at 0.23 mol/L.s, at what rate is

Consider the reaction

Suppose that, at a particular moment during the

(a) At what rate is N2O5 being formed?

(b) At what rate is NO2 reacting?

In a catalytic experiment involving the Haber process

The rate of reaction was measured as

(a) What was the rate of reaction expressed in terms of

• The rate law of a reaction is the mathematical

2 NO(g) + O2(g)  2 NO2(g)

• Generally, the rate law for the respective order can

Lets consider only one reactant, A

Lets determine the order of a reaction, n by

Finding the Rate Law: The Initial Rate Method

• The rate law must be determined

if for the then doubling

if for the then doubling

Finding the Rate Law: The Initial Rate Method

if for the then doubling

If we compare Experiments 1 and 2, we see that when

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Likewise, when we compare Experiments 5 and 6, we

• The overall reaction order can be found by adding the

Doubling the concentration of N2O5 doubles the

Rate of reaction α [N2O5] 46

For example - reaction rate could be independent of

If catalyst involved, its concentration may also affect

Consider, the above reaction, the rate is depend on the

So, the above reaction can be expressed as below.

Rate of reaction = k[Br2]

The time in rate constant can be seconds, minutes,

Rate constants must have units consistent with the order

First order reactions : the units of k are 1/time

For the following reactions, determine the reaction order

H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l)

The rate equation for the reaction of NO with

If the rate is 6.60 x 10−5 M/sec when [NO] = 1.00 x

Rate = 6.60 x 10−6 M/s

Conceptual Rate, [NO], [O3]

Relationships: Rate = k[NO][O3]

The rate law for the decomposition of