Chemical Kinetics PDF

FOUNDATION CHEMISTRY II
CHM096
CHAPTER 2
CHEMICAL
KINETICS
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
red-brown
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
time
From left to right, the decrease in bromine concentration as time

elapses shows up as a loss of colour.
[Br2]
Rate = -
t
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
9
2.1 Rate of Reaction
Average Rate, Instantaneous Rate & Initial Rate
D[Br2] [Br2]final – [Br2]initial
Average rate = - =-
Dt tfinal - tinitial
Instantaneous rate = Rate for specific instance in time

= Can be obtained by computing the
slope of line tangent to the curve at
that point.
Initial rate = Rate at the beginning of reaction,

computed from the slope of line tangent to the curve at
t = 0s.
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 0.100
50.0 0.0905
100.0 0.0820
150.0 0.0741
200.0 0.0671
300.0 0.0549
400.0 0.0448
500.0 0.0368
800.0 0.0200
10,000 0
11
Time, t (s) [C4H9Cl] (M) Average Rate (M/s)
0.0 0.100 -
50.0 0.0905 1.9 x 10-4
100.0 0.0820 1.7 x 10-4
150.0 0.0741 1. 6x 10-4
200.0 0.0671 1.4x 10-4
300.0 0.0549 1.22 x 10-4
400.0 0.0448 1.01x 10-4
500.0 0.0368 0.8x 10-4
800.0 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. 12
Time, t (s) [C4H9Cl] (M) Average Rate (M/s)
0.0 0.100 -
50.0 0.0905 1.9 x 10-4
100.0 0.0820 1.7 x 10-4
150.0 0.0741 1. 6x 10-4
200.0 0.0671 1.4x 10-4
300.0 0.0549 1.22 x 10-4
400.0 0.0448 1.01x 10-4
500.0 0.0368 0.8x 10-4
800.0 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 13
• 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 toisolate,
hard to 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 (t =
0s) is called the initial
It was thought that organic compounds must contain some “vital
force” because they were from livingrate.
sources.
14
• 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.

force” because they were from living sources.
15
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
16
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. 17
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
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
19
Example 1
Write the rate expressions for the following reactions in
terms of the disappearance of the reactants and the
appearance of the products:
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

Example 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?

Answer to Example 2 Rate Law and Stoichiometry
Strategy To calculate the rate of formation of N2O5 and

disappearance of NO2, we need to express the rate of the
reaction in terms of the stoichiometric coefficients as in
Example 2.1.1:
We are given
where the minus sign shows that the concentration of O2 is

decreasing with time.
23
Answer to Example 2 Rate of Reactions and Stoichiometry
Solution
(a)From the preceding rate expression we have
Therefore
b) Here we have
So,
24
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)
25
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
26
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?
27
Exercise 2
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?
TOPIC
RATE LAWS
29
2.2 RATE LAWS
• The rate law expresses the relationship of the rate of
a reaction to the rate constant and the
concentrations of the reactants raised to some
powers.
 It is directly proportional
• The rate law must be determined experimentally!!
• It may not be equal to the coefficients (mole ratios) in
the balanced equation
• 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
2.2 RATE LAWS
aA + bB cC + dD
Rate α [A]n[B]m
Rate = k [A]n[B]m
Reaction is nth order in A

Reaction is mth order in B
Reaction is (n +m)th order overall
k is the rate constant
The values of n and m are not necessarily related in any

way to the coefficients a and b.
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 respective order:

A  product,
If the above reaction is:
• zero order: Rate = k
• First order: Rate = k [A]
• Second order: Rate = k[A]2
2.2 RATE LAWS
In other reactions, there are 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.
2.2 RATE LAWS
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
Consider, the above reaction, by experiment, the rate

depends on the concentration of Br2, but not
concentration of HCOOH.
So, the above reaction can be expressed as below.
Rate of reaction = k[Br2]

EXAMPLE (REACTION RATE IS NOT DEPEND ON THE
CONCENTRATION OF REACTANT):
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
35
2.2 RATE LAWS
Determination of order of reaction
Method 1 • Initial rate method
Method 2 • Units of rate constant, k
Method 3 • Half-life method
• Linear plots based on the

Method 4
integrated rate law
Method 1 • Initial rate method
Order Rate of reaction
If doubling the concentration of reactant

0 has no effect on the rate, the reaction is
zero-order with respect to A (rate = k[A]0 = k)
If doubling the concentration of reactant,

1 doubles the rate of reaction, the reaction is
first-order with respect to A (rate = k[A])
If doubling the concentration of reactant
increase the rate by a factor 4, the reaction
2 is second-order with respect to A (rate =
k[A]2)
For the reaction
A → product
The 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
Plots of reactant concentration, [A], vs. time for
first-, second-, and zero-order reactions.
Plots of rate vs. reactant concentration, [A],
for first-, second-, and zero-order reactions.
Individual and Overall Reaction Orders
Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
Likewise, compare Experiments 5 and 6:

when [NO2-] doubles, the initial rate doubles.
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.
43
 A rate law shows the relationship between the rate
of reaction and the concentrations of reactants.
 k is a constant that has a specific value for each

reaction.
 The value of k is determined experimentally.
 “Constant” is relative here-

k is unique for each reaction
k changes with temperature
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-]
45
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.
46
Initial Rate Method
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
47
Example 5
Table : Initial Rates for the Reaction between A and B
Initial Rate Initial [A] Initial [B]

Experiment (mol/L·s) (mol/L) (mol/L)
1 1.75x10-3 2.50x10-2 3.00x10-2
2 3.50x10-3 5.00x10-2 3.00x10-2
3 3.50x10-3 2.50x10-2 6.00x10-2
4 7.00x10-3 5.00x10-2 6.00x10-2
[B] is kept constant for experiments 1 and 2, while [A] is doubled.

Then [A] is kept constant while [B] is doubled.
Answer to Example 5
Finding m, the order with respect to A:
We compare experiments 1 and 2, where [B] is kept constant but [A] doubles:
Rate 2 k[A] m [B] n m

[A] 2 [A]2 m
2 2 = =
=
Rate 1 k[A] m
1
[B] n1 m
[A]1
[A]1
m
3.50x10-3 mol/L·s 5.00x10-2 mol/L
=
1.75x10-3mol/L·s 2.50x10-2 mol/L
Dividing, we get 2.00 = (2.00)m so m = 1

Finding n, the order with respect to B:
We compare experiments 3 and 1, where [A] is kept constant but [B] doubles:
Rate 3 k[A] m [B] n n

[B] 3 [B]3 n
3 3 = =
=
Rate 1 k[A] m
1
[B] n1 n
[B]1
[B]1
m
3.50x10-3 mol/L·s 6.00x10-2 mol/L
=
1.75x10-3mol/L·s 3.00x10-2 mol/L
Dividing, we get 2.00 = (2.00)n so n = 1

Thus, Rate = k[A][B]
Example 6
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
51
Answer to Example 6
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]
52
Example 7
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?
53
Answer to Example 7
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
54
Exercise 4
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 -10 oC?
Exercise 5
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 56
Method 2 • Units of the rate constant, k
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
Overall Reaction Order Units of k (t in seconds)
0 mol/L*s (or Ms-1)
1 1/s (or s-1)
2 L/mol*s (or M-1s-1)

Method 3 • Half-life method
 The half-life, t1/2, of a reaction is the time it takes

for the concentration of the reactant to fall to ½
its initial value
 The half-life of the reaction depends on the

order of the reaction
Order Half-Life
[A]0
0 t½ =
2k
1 t½ = ln 2
k
1
2 t½ =
k[A]0
• Linear graph method
Method 4 (Integrated Rate Law)
• Differential Rate Law (rate law) – describes the

change in concentration of reactant(s) per
change in time.
• Integrated Rate Law – using calculus, the rate law

can be integrated to obtain an integrated rate
equation that links concentration of reactants or
products with time directly.
Graphical
Origins of Determination
Organic of the
Chemistry
Rate Law for A Product
• Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs. time
Compounds obtained fromofplants,
allow determination whetheranimals 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]
Torben Bergman
– if linear is (1770)
[A] vs.first to make
time, Ratedistinction
= k[A]0 between organic
– if linear is ln[A] vs. time, Rate = k[A]1
– if thought
It was linear is 1/[A]
that vs. compounds
organic = k[A]
time, Rate must 2
contain some “vital
62
1/[A]t = kt + 1/[A]0
ln[A]t = -kt + ln[A]0 [A]t = -kt + [A]0
Zero-Order Reaction
(I) For zero-order reaction : A → products
By the rate law (differential); Rate = - d[A] = k[A]0 = k

dt
Integrating the differential rate law, we obtained the

integrated rate law
[A]t = -kt + [A ]o where [A]o = initial

concentration of A
A plot of [A]t versus t gives a straight line, slope = -k
and y-intercept = [A]o
The Half-Life of Zero-Order Reaction
The half- life of a reaction, t1/2 is the time required for

the concentration of a reactant to decrease to half its
original concentration
½ [A]o = -kt½ + [A]o
kt½ = ½ [A]o
t½ = [A]o ; ** the half life of a zero

2k order reaction is directly
proportional to [A]o
First-Order Reaction
(II) For first-order reaction A → products
By the rate law , Rate = - d[A] = k[A]

dt
Integrated first-order rate law gives
ln[A]t = -kt + ln[A]o
ln [A]o = kt
[A]t
A plot of ln [A]t versus t will give a straight line.
slope = –k and y-intercept = ln [A]o.
[A]t = [A]0e−kt ln[A]t = ln[A]0 - kt
ln [A]t = - kt
[A]0
(a) (b)
First order reaction characteristic, (a) decrease of

reactant concentration with time; (b) A plot of In [A]t
versus t. The slope = -k
[A]t is the concentration of A at any time t

[A]0 is the concentration of A at time t=0
The Half-Life of First-Order Reaction
The half-life is derived by rewriting the integrated

rate law as
ln{ [A]o / [A] } = kt
At t = t½ , [A] = ½ [A]o ; ln 2 = kt½
0.693 = kt½ and t½ = 0.693/ k
** the half life of a first order reaction is independent

of the initial concentration of reactant. i.e 1st half-life
(t‟½) = 2nd half-life (t‟‟½)
The Half-Life of First-Order Reaction
Second-Order Reaction
(III) For second-order reaction A → products
By the rate law, Rate = -d[A] = k[A]2

dt
Integration of the rate law will give the
integrated second order rate law as
1 = kt + 1
[A]t [A]o
A plot of 1/[A]t versus t give a straight line with a
slope = k and the y-intercept = 1/[A]o
The Half-Life of Second-Order Reaction
At half-life , t½ , where [A] = ½ [A]o
1 = kt½ + 1
½[A]o [A]o
kt½ = 2 - 1 = 1
[A]o [A]o [A]o
t½ = 1
k[A]o
** The half life of a second order reaction is inversely proportional to

the initial concentration of the reactant
Thus , the second half-life (t‟‟½) = 2(t‟½)
Origins ofBetween
Relationship Organic Chemistry
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)
76
EXAMPLE: graphical determination of k
2N2O5 4NO2 (g) + O2 (g)
t (s) [N2O5] (M) ln [N2O5] 1/[N2O5]

0 0.91 -0.094 1.099
300 0.75 -0.29 1.333
600 0.64 -0.45 1.563
1200 0.44 -0.82 2.273
3000 0.16 -1.83 6.250
Plot In [N2O5] is straight line, therefore, the rate is
first order
ln[A] = ln[A]0 - kt
What is the half-life of N2O5 if it decomposes with a
rate constant of 5.7 x 10-4 s-1?
t½ = ln 2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
-4 -1
How do you know decomposition is first order?

units of k (s-1)
Origins of Organic
Example 8 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,

Torben Bergman (1770) first to make distinction between organic
(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
80
OriginsAnswer
of Organic Chemistry
to Example 8

0.693
Use the half-life equation, t1/2 = k
Compounds obtained from plants, animals hard to isolate, and
purify.
One-quarter of the initial value means two half-lives have passed.
SOLUTION:
Compounds also decomposed more easily.
(a) t1/2 = 0.693/9.2 s-1 = 0.075 s
(b) 2 t = 2(0.075 s) = 0.150 s
1/2

81
Origins of Organic
Example 9 Chemistry
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
82
OriginsAnswer
to Example 9
Compounds
Solution:obtained from plants, animals hard to isolate, and
purify.

Check: the new concentration is less than the original, as
expected
83
Origins of Example
Organic10Chemistry
The reaction of
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.


84
Answer to Example 10
Origins of Organic Chemistry
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:
85
Origins Example 11
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?

86
OriginsAnswer to Example
of Organic 11
Chemistry

purify.


87
OriginsAnswer
to Example 11

purify.


88
OriginsAnswer
to Example 11

purify.


89

purify.


90
OriginsAnswer to Example
of Organic 11
Chemistry
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

91
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.
92
2.3 FACTORS THAT AFFECT THE RATE
OF REACTION
93
2.3 Factors that affect The Rate of Reaction
• In a chemical reaction, bonds are broken and new

bonds are formed
• For a reaction to take place, the reacting molecules
must collide with each other
• 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
• Physical nature of the reactants:

– Homogeneous reaction: all of
the reactants are in the same
phase.
– Heterogeneous reaction: the
reactants are present in different
phases, the area of contact
between the phases determines
the reaction rate.
• Concentrations of the reactants:
– The rates of both homogeneous and heterogeneous
reactions are affected by the concentrations of the
reactants.
• Temperature of the system:
– Almost all chemical reactions occur faster at higher
temperatures.
• Presence of catalysts:
– Catalysts are substances that increase the rate of
chemical reactions without being used up.
2.4 THEORIES OF CHEMICAL KINETICS
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.
• For a collision to be
effective,also
Compounds thedecomposed
reacting more easily.
molecules must have
sufficient
Torben kinetic
Bergman energy
(1770) first to to
make distinction between organic
overcome thechemistry.
and inorganic energy
barrier.
97
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 were sufficient
from living sources.
energy)
98
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.

99
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.


100
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.


101
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
102
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.
103
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.
state 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. 104
The Transition State Theory
Reaction
Foundations of energy diagrams
organic chemistry andmid-1700’s.
from possible transition
states.
purify.


105
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
(1770) first energy for reverse
to make distinction reaction?
between organic

106
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 sources.
fastest and will be slowest
in reverse direction?
107
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
108
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.


109
FACTORS CONTROLLING
RATES
The Effect
Compounds of Concentration
obtained on hard
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
110
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.
111
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.
112
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. 113
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
course of the reaction.
114
Effect of Temperature on Reaction Rate:
Maxwell-Boltzmann
Foundations 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
115
Maxwell-Boltzmann
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 that organic compounds havesome
must contain high energy
“vital
A few molecules
have low energy
Kinetic Energy
116
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. 117
Maxwell-Boltzmann
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
118
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
Compounds also decomposed more easily.f = 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 10-9 119
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.
120
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
121
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.

122
TOPIC
2.5 ARRHENIUS EQUATION
Svante Arrhenius found that in most reactions the increase in rate
with increasing temperature is nonlinear but exponential.
Exponential curve graph

124
Reaction rate obeyed on three factors

• the fraction of molecules with sufficient kinetic energy to react
• 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.
125
where A is the Arrhenius constant , is related to the

frequency collision or the frequency factor (z) and
proper orientation for reaction (p).
where T is the temperature in Kelvin
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
k = pze-Ea/RT
126
• 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. 127
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
128
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
129
Graphical determination of the activation energy
ln k = (-Ea/R )(1/T) + ln A
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.
131
Example 13
Determine the activation energy and frequency factor
for the reaction O3(g)  O2(g) + O(g) given the following
data:
132
133
slope, m = 1.12 x 104 K

y–intercept, b = 26.8
134
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
135
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
136
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:
137
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
138
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
139
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
140
TOPIC
REACTION MECHANISMS AND RATE
DETERMINING STEP
141
2.6 REACTION MECHANISMS AND RATE DETERMINING
STEP
Reaction Mechanisms
Most reactions do not occur in a single step. The net overall reaction
is the result of a series of simple reactions.
The overall progress of a chemical reaction can be represented at the
molecular level by a series of simple elementary steps or
elementary reactions.
The sequence of elementary steps that leads to product formation
is the reaction mechanism.
2NO (g) + O2 (g) 2NO2 (g)
Elementary step: NO + NO N2O2
N2O2 is
+ Elementary step: detected during
N2O2 + O2 2NO2
the reaction!
Overall reaction: 2NO + O2 2NO2
142
2.6 Reaction Mechanism & Rate Determining Step
Reaction Mechanisms
• The rate law of an elementary reaction can be

written from its chemical equation.
• This rule only applies to elementary reactions.
• The overall rate law derived from the mechanism
must agree with the observed rate law for the
overall reaction.
N.H.Seth 143
2.6 REACTION MECHANISMS AND
RATE DETERMINING STEP
Multistep Mechanisms
The molecularity of a process tells how many reactant

molecules are involved in the process.
144
Intermediates
Overall: H2(g) + 2 ICl(g)  2 HCl(g) + I2(g)
Step (1): H2(g) + ICl(g)  HCl(g) + HI(g)
Step (2): HI(g) + ICl(g)  HCl(g) + I2(g)
• Notice that the HI is a product in Step 1, but then a

reactant in Step 2
• Because HI is made but then consumed, HI does
not show up in the overall reaction
• Materials that are products in an early mechanism
step, but then a reactant in a later step, are called
intermediates
• In a multistep process, one of the steps will be

slower than all others, rate-determining step.
• The overall reaction cannot occur faster than this
slowest step, rate-determining step.
146
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
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.
148
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
149
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.
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
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.
152
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.
153
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]?
154
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
155
Fast Initial Step
• Because Ratefoward = Ratereverse ,
k1 [NO] [Br2] = k−1 [NOBr2]
• Solving for [NOBr2] gives us
k1
k−1 [NO] [Br2] = [NOBr2]
156
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]
157
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]
158
1. O3(g) ⇋ O2(g) + O(g) Fast
2. O3(g) + O(g)  2 O2(g) Slow Rate = k2[O3][O]
159
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)
160
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)
161
End of Chapter 2
Please Read Chapter 3
Thank You
Question!
162

Chemical Kinetics PDF

Hochgeladen von

Dokumentinformationen

Originalbeschreibung:

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Chemical Kinetics PDF

Hochgeladen von

Copyright:

Verfügbare Formate

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

From left to right, the decrease in bromine concentration as time

Instantaneous rate = Rate for specific instance in time

Initial rate = Rate at the beginning of reaction,

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]

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

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?

Strategy To calculate the rate of formation of N2O5 and

where the minus sign shows that the concentration of O2 is

If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a 2.0

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

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

Reaction is nth order in A

The values of n and m are not necessarily related in any

• The exponent on each reactant in the rate law is

• The rate law for the respective order:

In other reactions, there are different relationship

For example - reaction rate could be independent of

If reaction involved several reactants, the reaction

If catalyst involved, its concentration may also affect

Consider, the above reaction, by experiment, the rate

So, the above reaction can be expressed as below.

Rate of reaction = k[Br2]

The decomposition of ammonia on a platinum surface at

The reaction rate is independent of NH3 concentration

Determination of order of reaction

Method 1 • Initial rate method

Method 2 • Units of rate constant, k

Method 3 • Half-life method

• Linear plots based on the

Order Rate of reaction

If doubling the concentration of reactant

If doubling the concentration of reactant,

• If a reaction is Zero Order, the rate of the reaction is

Compare Experiments 1 and 2:

Likewise, compare Experiments 5 and 6:

• The overall reaction order can be found by adding the

 k is a constant that has a specific value for each

 The value of k is determined experimentally.

 “Constant” is relative here-

For the following reactions, determine the reaction order

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