Chapt16 Lecture

Chapter 16
Kinetics: Rates and Mechanisms of Chemical

Reactions
16-1
Kinetics: Rates and Mechanisms of Chemical Reactions
16.1 Factors that influence reaction rates
16.2 Expressing the reaction rate
16.3 The rate law and its components
16.4 Integrated rate laws: Concentration changes over time
16.5 Reaction mechanisms: Steps in the overall reaction
16.6 Catalysis: Speeding up a chemical reaction
16-2
Chemical Kinetics
The study of reaction rates, the changes in concentrations of

reactants (or products) as a function of time
Quantitative relationships through the derivation of a rate law
Kinetics can reveal much about the mechanism of a reaction.
16-3
Reaction rate: the central focus of chemical kinetics
Figure 16.1
16-4 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
The wide range of reaction rates
Figure 16.2
16-5
Factors Influencing Reaction Rates
Reactant Concentration: molecular collisions are required for

reactions to occur
reaction rate a collision frequency a concentration
Physical State: molecules must mix to collide
When reactants are in different phases, the more finely divided

a solid or liquid reactant, the greater the surface area per unit
volume, the more contact it makes with other reactants,
and the faster the reaction.
Temperature: molecules must collide with sufficient energy to react
Higher T translates into more collisions per unit time and

into higher-energy collisions
reaction rate a collision energy a temperature

16-6
The effect of surface area on reaction rate
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Figure 16.3 steel nail in O2 steel wool in O2

16-7
Collision energy
and reaction rate
Other factor: reaction

trajectory (not all collisions
with sufficient energy
are productive)
Figure 16.4
16-8
Expressing Reaction Rate
reaction rate = the changes in [reactants] or [products] per unit time;

[reactant] decreases, [product] increases
A B
Measure [A1] at t1, then measure [A2] at t2
Average rate of reaction = - ([A2] - [A1]) / (t2 - t1)
rate is always = - D[A] / Dt

expressed as a
positive value rate units = mol/L/s
Also, reaction rate = + D[B] / Dt
16-9
Table 16.1 Concentration of O3 at various times in its
reaction with C2H4 at 303 K
C2H4(g) + O3(g) C2H4 O(g) + O2(g)
time (s) concentration of O3 (mol/L)
0.0 3.20 x 10-5

10.0 2.42 x 10-5
20.0 1.95 x 10-5
30.0 1.63 x 10-5
40.0 1.40 x 10-5
50.0 1.23 x 10-5
60.0 1.10 x 10-5
16-10
Different Ways to Measure Reaction Rates
Reaction rate varies with time as the reaction proceeds!
C2H4(g) + O3(g) C2H4O(g) + O2(g)
average rate = - D[O3] /Dt = - (1.10 x 10-5 mol/L) - (3.20 x 10-5 mol/L)
60.0 s - 0.0 s
= 3.50 x 10-7 mol/L/s
Similar calculations over earlier and later time intervals (e.g., 0.0 -10.0 s,
50.0 - 60.0 s) reveals average rates of 7.80 x 10-7 mol/L/s and
1.30 x 10-7 mol/L/s, respectively.
Data show that the average rate decreases as the

reaction proceeds!
16-11
Concentrations of O3 vs
time during its reaction
with C2H4
Curved line indicates change

in reaction rate with time.
The slope of a tangent at any
point on the curve yields the
instantaneous rate at that point.
reaction rate = (instantaneous)

reaction rate
initial rates: measured to avoid

complications due to back
reactions
Figure 16.5
16-12
Other Plots to Determine
Reaction Rate
C2H4(g) + O3(g) C2H4O(g) + O2(g)
Plots of [C2H4] and [O2]

vs reaction time
Figure 16.6
16-13
Expressing rate in terms of changes in
[reactant] and [product]
H2(g) + I2(g) 2HI(g)
rate = - D[H2]/Dt = - D[I2]/Dt = 1/2 D[HI]/Dt
or
rate = D[HI]/Dt = -2 D[H2]/Dt = -2 D[I2]/Dt
The mathematical expression for the rate, and the numerical value of
the rate, depend on which substance is chosen as the reference.
For the general reaction: aA + bB cC + dD

rate = -1/a D[A]/Dt = -1/b D[B]/Dt = 1/c D[C]/Dt = 1/d D[D]/Dt
16-14
Sample Problem 16.1 Expressing rate in terms of changes in
concentration with time
PROBLEM: Because it generates a nonpolluting product (water vapor),

hydrogen gas is used for fuel aboard the space shuttle and may
be used by automobile 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) If [O2] decreases at 0.23 mol/L/s, at what rate is [H2O] increasing?
PLAN: Choose [O2] as the reference since its coefficient is 1. For every
molecule of O2 that disappears, two molecules of H2 disappear and two
molecules of H2O appear, so [O2] decreases at one-half the rates of
change in [H2] and [H2O].
SOLUTION: D[H2] D[O2] D[H2O]
1 1
(a) rate = - =- =+
2 Dt Dt 2 Dt
D[O2] D[H2O] D[H2O]
(b) - = 0.23 mol/L.s =+ 1 ; = 0.46 mol/L.s
Dt 2 Dt Dt
16-15
The Rate Law
The rate law expresses the reaction rate as a function of reactant

concentrations, product concentrations, and temperature. It is
experimentally determined.
The derived rate law for a reaction must be consistent

with the postulated chemical mechanism of the reaction!
For a general reaction: aA + bB + ..... cC + dD

rate law: rate = k[A]m[B]n........
k = rate constant
m and n = reaction orders (not related to a, b,...)
(for a unidirectional (one-way) reaction)!
16-16
How is the rate law determined experimentally?
The Procedure
1. Measure initial rates (from concentration measurements)
2. Use initial rates from several experiments to find the reaction orders
3. Calculate the rate constant
16-17
Reaction Order Terminology
rate = k[A] first order overall (rate a [A])

rate = k[A]2 second order overall (rate a [A]2)
rate = k[A]0 = k(1) = k zero order (rate independent of [A])
Examples
NO(g) + O3(g) NO2(g) + O2(g)
rate = k[NO][O3] second order overall
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
rate = k[NO]2[H2]1 third order overall
16-18
Properties of Reaction Orders
Reaction orders cannot be deduced from the

balanced chemical equation.
Reaction orders are usually positive integers or zero.
Reaction orders can be fractional or negative.
16-19
Sample Problem 16.2 Determining reaction order from rate laws
PROBLEM: For each of the following reactions, determine the reaction order
with respect to each reactant and the overall reaction order from
the given rate law.
(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]
(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]
PLAN: Inspect the rate law and not the coefficients in the balanced chemical
reaction.
SOLUTION:
(a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order overall.
(b) The reaction is 3/2-order in CH3CHO and 3/2-order overall.
(c) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+,
and 2nd order overall.
16-20
Determining Reaction Orders
O2(g) + 2NO(g) 2NO2
rate = k[O2]m[NO]n
To find m and n: A series of experiments is

conducted starting with different sets of reactant
concentrations. The initial reaction rate is measured
in each experiment.
16-21
Table 16.2 Initial rates in a series of experiments for the
reaction between O2 and NO
initial reactant
concentrations (mol/L) initial rate
experiment (mol/L.s)
O2 NO
1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3
2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3
3 1.10 x 10-2 2.60 x 10-2 12.8 x 10-3
4 3.30 x 10-2 1.30 x 10-2 9.60 x 10-3
5 1.10 x 10-2 3.90 x 10-2 28.8 x 10-3
16-22
Manipulating the Data
rate 2 k[O2]2m[NO]2n
= ([NO] is held constant)
rate 2 [O2]2m
= = ([O2]2 / [O1]1)m
rate 1 [O2]1m
6.40 x 10-3 mol/L/s

=
(2.20 x 10-2 mol/L/ 1.10 x 10-2 mol/L)m
3.21 x 10-3 mol/L/s
1.99 = (2.00)m
m=1
Thus, the reaction is first order with respect to O2.

When [O2] doubles, the rate doubles.
16-23
= ([O2] is held constant)
via same manipulations as before:
3.99 = (2.00)n
n=2
Thus, the reaction is second order with respect to NO.

When [NO] doubles, the rate quadruples.
The rate law is: rate = k[O2][NO]2

The reaction is third order overall.
16-24
Sample Problem 16.3 Determining reaction order from initial rate data
PROBLEM: Many gaseous reactions occur in a car engine and exhaust

system. One such reaction is as follows:
NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the individual and overall reaction orders.
experiment initial rate (mol/L.s) initial [NO2] (mol/L) initial [CO] (mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20
PLAN: Solve for each reactant using the general rate law by applying the
method described previously.
SOLUTION: rate = k [NO2]m[CO]n
First, choose two experiments in which [CO] remains constant and [NO2] varies.
16-25
Sample Problem 16.3 (continued)
rate 2 k [NO2]m2[CO]n2 [NO2] 2 m

= =
rate 1 k [NO2 ]m 1 [CO]n 1 [NO2] 1
0.080 0.40 m
The reaction is
= ; 16 = 4m and m = 2
0.0050 0.10 2nd order in NO2.
rate 3 k [NO2]m3[CO]n3 [CO] 3 n

= =
rate 1 k [NO2 ]m 1 [CO]n 1 [CO] 1
0.0050 0.20 n The reaction is

= ; 1 = 2n and n = 0
0.0050 0.10 zero order in CO.
Rate Law: rate = k [NO2]2[CO]0 = k [NO2]2

The reaction is second order overall.
16-26
Determining the Rate Constant
The rate constant, k, is specific for a particular reaction

at a particular temperature.
k = rate 1 / ([O2]1[NO]12)
3.21 x 10-3 mol/L/s

= 1.73 x 103 L2/mol2/s = k
1.86 x 10-6 mol3/L3
The units for k depend on the order of the reaction

and the time unit.
16-27
Table 16.3 Units of the rate constant, k, for several overall
reaction orders
overall reaction order units of k (t in seconds)
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)
3 L2 / mol2 .s (or L2 mol-2 s-1)
16-28
Integrated Rate Laws: Change in Concentration
with Reaction Time
Consider a general first order reaction: A B
rate = - D[A]/Dt = k[A]
Upon integration over time, we obtain:
ln ([A]0/[A]t) = kt
ln = natural logarithm
[A]0 = concentration of A at t = 0
[A]t = concentration of A at any time t
ln [A]0 - ln [A]t = kt
16-29
For a simple second order reaction (one reactant only):
rate = - D[A]/Dt = k[A]2
1/[A]t - 1/[A]0 = kt
For a zero order reaction:
rate = - D[A]/Dt = k[A]0
[A]t - [A]0 = -kt
16-30
Sample Problem 16.4 Determining reaction concentration at a given time
PROBLEM: At 1000 oC, cyclobutane (C4H8) decomposes in a first-order

reaction with the very high rate constant of 87 s-1 to yield two
molecules of ethylene (C2H4).
(a) If the initial [C4H8] is 2.00 M, what is the concentration after
0.010 s of reaction?
(b) What fraction of C4H8 has decomposed in this time?
PLAN: Find [C4H8] at time t using the integrated rate law for a 1st-order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
SOLUTION: [C4H8]0 2.00 M
ln = kt ; ln = (87 s-1)(0.010 s) = 0.87
(a) [C4H8]t [C4H8]t
2.00 M / [C4H8]t = e0.87 = 2.4 [C4H8]t = 0.83 M
(b) [C4H8]0 - [C4H8]t 2.00 M - 0.83 M

= = 0.58
[C4H8]0 2.00 M
16-31
Reaction Order from the Integrated Rate Law
Graphical methods to determine reaction orders
(when you don’t have initial rate data!)
Rearranged integrated rate laws:
ln [A]t = -kt + ln [A]0 first order reaction
1/[A]t = kt + 1/[A]0 simple second order reaction
[A]t = -kt + [A]0 zero order reaction
All take the form: y = mx + b
16-32
Graphical method to determine reaction order
[A]t = -kt + [A]0
ln[A]t = -kt + ln[A]0
1/[A]t = kt + 1/[A]0
Figure 16.7
16-33
Graphical determination of the reaction order for the
decomposition of N2O5
nonlinear
linear!
nonlinear
Figure 16.8
16-34
Conclusion
For the decomposition of N2O5......
the reaction must be first order in N2O5.
Graphical approach can likewise be applied to reactions

involving multiple reactants.
16-35
Reaction Half-Life
Just another way to express the speed of a reaction
half-life (t1/2) = the time required for the reactant concentration

to reach one-half of its initial value
For a first order reaction at fixed conditions: t1/2 is a constant,

independent of reactant concentration
16-36
A plot of [N2O5] vs time for three half-lives
A first order
reaction
Figure 16.9
16-37
Why is t1/2 independent of reactant concentration
for a first order reaction?
ln ([A]0/[A]t) = kt
After one half-life, t = t1/2 and [A]t = 0.5[A]0. Substituting.....
ln ([A]0/0.5([A]0) = kt1/2
or
ln 2 = kt1/2
t1/2 = (ln 2)/k = 0.693/k

first order reaction: A B
16-38
Sample Problem 16.5 Determining the half-life of a first-order reaction
PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its

60o bond angles allow poor orbital overlap, its bonds are weak.
As a result, it is thermally unstable and rearranges to propene at
1000 oC via the following first-order reaction:
CH2
D
H2 C CH2 (g) H3C CH CH2 (g)
The rate constant is 9.2 s-1. (a) What is the half-life of the reaction? (b) How
long does it take for [cyclopropane] to reach one-quarter of its initial value?
0.693
PLAN: Use the half-life equation, t1/2 = , to find the half-life.
k
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 t1/2 = 2 (0.075 s) = 0.15 s
16-39
Half-Life for Zero and Second Order Reactions
t1/2 = 1/k [A]0 simple second order (rate = k[A]2)
As a second order reaction proceeds, the half-life increases.
t1/2 = [A]0/2k zero order (rate = k)
For zero order reactions, higher initial reactant concentrations

translate into longer half-lives.
16-40
Table 16.4 An overview of zero-order, first-order and
simple second-order reactions
zero order first order second order
rate law rate = k rate = k[A] rate = k[A]2
units for k mol/L.s 1/s L/mol.s
integrated rate law in [A]t = ln[A]t = 1/[A]t =

straight-line form kt + [A]0 -kt + ln[A]0 kt + 1/[A]0
plot for straight line [A]t vs t ln[A]t vs t 1/[A]t = t
slope, y-intercept -k, [A]0 -k, ln[A]0 k, 1/[A]0
half-life [A]0/2k (ln 2)/k 1/k[A]0
16-41
Temperature and Reaction Rate
Consider the rate law for a first order reaction:

rate = k[A]
Where is the temperature dependence?

Answer: It is embodied in the rate constant, k, that is,
k depends on the temperature at which the
reaction is conducted.
What does the T-dependence of k look like?
test R-COOR’ + H2O R-COOH + R’OH

reaction ester acid alcohol
organic ester hydrolysis
16-42
Dependence of k on temperature for the
hydrolysis of an organic ester
Note that both

reactant
concentrations are
held constant
k increases
exponentially!
Figure 16.10
16-43
Quantitative treatment of the effect of
temperature on k
The Arrhenius equation
k = the kinetic rate constant at T

k = Ae -Ea/RT Ea = the activation energy
R = the universal gas constant

ln k = ln A - Ea/R (1/T) T = Kelvin temperature
y = b + mx A = collision frequency factor
e = base of natural logarithms
k2 Ea 1 1
ln = - -
k1 R T2 T1
16-44
Graphical determination of the activation energy, Ea
ln k = -Ea/R (1/T) + ln A
An Arrhenius plot
Figure 16.11 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
16-45
More about the Arrhenius Equation
The activation energy = the minimum energy that the molecules

must possess in order for reaction to occur
The negative exponent suggests that, as T increases, the

negative exponent becomes smaller (less negative), the value of k increases,
and thus the reaction rate increases.
higher T larger k increased rate
16-46
Sample Problem 16.6 Determining the energy of activation
PROBLEM: The decomposition reaction of hydrogen iodide,
2HI(g) H2(g) + I2(g)
has rate constants of 9.51 x 10-9 L/mol.s at 500. K and 1.10

x 10-5 L/mol.s at 600. K. Find Ea.
PLAN: Use a modification of the Arrhenius equation to find Ea.
SOLUTION: -1
k2 Ea 1 1 k2 1 1
ln = - - Ea = - R ln -
k1 R T2 T1 k1 T2 T1
1.10 x 10 -5 L/mol.s 1 1 -1
Ea = - (8.314 J/mol . K) ln -
9.51 x 10 -9 L/mol.s 600. K 500. K
Ea = 1.76 x 105 J/mol = 176 kJ/mol

16-47
Information Sequence to Determine the
Kinetic Parameters of a Reaction
series of plots
of [ ] vs time initial
rates reaction rate constant
orders (k) and actual
Determine slope
Compare initial
rate law
of tangent at t0 of
each plot rates when [A] Substitute initial rates,
changes and [B] orders, and Find k at
is held constant concentrations into varied T
and vice versa general rate law: rate = k
A + B C + D [A]m[B]n
activation
rate constant energy, Ea
integrated
and reaction Find k at
rate law
order varied T
(half-life,
t1/2)
Rearrange to
Figure 16.12 linear form
16-48 and graph
Using Collision Theory to Explain the Effects
of [ ] and T on Reaction Rate
Model: A + B products
Why are [A] and [B] multiplied in the rate law?
Consider several cases where there are a finite number

of particles each of A and B and determine the
number of possible A-B collisions.
16-49
The dependence of possible collisions on the
product of reactant concentrations
A B 4 collisions
2x2=4
A B
Add another A
molecule of A 6 collisions
B
A 3x2=6
B
A
A B
Add another 9 collisions
molecule of B A B 3x3=9
A B
Figure 16.13
16-50
Temperature and Reaction Rate
increased T increased average speed of particles

increased collision frequency increased reaction rate
But,
most collisions fail to yield products!
Significance of activation energy: only those collisions with

energy equal to, or greater than, Ea can yield products.
Increasing T enhances the fraction of productive collisions, f.
f = e-Ea/RT
From this equation, we can see that both Ea and T
affect f, which in turn influences reaction rate.
16-51
Table 16.5 Effect of Ea and T on the fraction (f) of collisions
with sufficient energy to allow reaction
Ea (kJ/mol) f (at 298 K)
50 1.70 x 10-9
75 7.03 x 10-14
100 2.90 x 10-18
T f (Ea = 50 kJ/mol)
25 oC (298 K) 1.70 x 10-9 DT = 10o; f

~ doubles; reaction
35 oC (308 K) rate ~ doubles!
3.29 x 10-9
45 oC (318 K) 6.12 x 10-9
16-52
The effect of temperature on the distribution of collision energies
Figure 16.14
16-53
Energy-Level Diagram for an Equilibrium Reaction
A + B C + D
ACTIVATED STATE
Ea (forward)
Collision Energy
Collision Energy
Ea (reverse)
reactants
A + B
products
C + D
The forward reaction is exothermic because the
reactants have more energy than the products.
Figure 16.15
16-54
An energy-level diagram of the fraction of
collisions exceeding Ea
A + B C + D
Figure 16.16
16-55
Effective Collisions
Not all collisions that occur with energy equal to, or exceeding,
the activation energy lead to products.
Molecular orientation is critical!
k = Ae -Ea/RT
the frequency factor = product of collision

frequency Z and an orientation probability
factor p (A = Zp)
16-56
Molecular orientation and effective collisions
NO + NO3 2 NO2
Figure 16.17
16-57
Transition State Theory
Addresses the limitations of collision theory in explaining

chemical reactivity
Key principle: During the transformation of reactant into

product, one or more very short-lived chemical species
form that resemble (but are different from) reactant or product;
these transitional species contain partial bonds; they are called
transition states (TS) or activated complexes.
The activation energy is used to stretch/deform specific bonds

in the reactant(s) in order to reach the transition state.
Example reaction:
CH3Br + OH- CH3OH + Br-

What might the TS look like for this substitution reaction?
16-58
The proposed transition state in the reaction
between CH3Br and OH-
The TS is trigonal bipyramidal; note the elongated C-Br

and C-O bonds
Figure 16.18
16-59
Reaction Energy Diagrams
Shows the potential energy of the system during a

chemical reaction
(a plot of potential energy vs reaction progress)
16-60
Reaction energy diagram for the reaction between CH3Br and OH-
Figure 16.19
16-61
General Principles of TS Theory
Every reaction (and each step in an overall reaction) goes

through its own TS.
All reactions are reversible.
Transition states are identical for the individual forward and reverse
reactions in an equilibrium reaction.
16-62
Sample Problem 16.7 Drawing reaction energy diagrams
and transition states
PROBLEM: A key reaction in the upper atmosphere is
O3(g) + O(g) 2O2(g)
The Ea(fwd) is 19 kJ, and DHrxn for the reaction is -392 kJ. Draw a reaction
energy diagram for this reaction, postulate a transition state, and calculate
Ea(rev).
PLAN: Consider relationships between reactants, products and transition state.
The reactants are at a higher energy level than the products, and the
transition state is slightly higher in energy than the reactants.
SOLUTION: Ea= 19 kJ
Potential Energy
O3+O transition state Ea(rev) = (392 + 19) kJ =

DHrxn = -392 kJ 411 kJ
breaking
O bond
2O2 O O
forming O
Reaction progress bond
16-63
Reaction energy diagrams and possible
transition states for three reactions
endothermic exothermic
exothermic
Figure 16.20
16-64
Reaction Mechanisms
The Specific Steps in an Overall Reaction
How a reaction works at the molecular level
2A + B E + F
A + B C
possible
C + A D steps
D E + F
C and D are reaction intermediates.
All postulated steps must sum to yield the chemical equation for the overall reaction.
Mechanisms of reactions are proposed and then tested.
16-65
Elementary Reactions and Molecularity
individual steps = elementary reactions (or steps)
Elementary steps are characterized by their molecularity.

molecularity = number of reactant particles involved in the step
2O3(g) 3O2(g)
O3(g) O2(g) + O(g) unimolecular

O3(g) + O(g) 2O2(g) bimolecular
Termolecular elementary steps are rare!
The rate law for an elementary reaction can be deduced

from the reaction stoichiometry; equation coefficients are
used as the reaction orders.
16-66
Table 16.6 Rate Laws for General Elementary Steps
elementary step molecularity rate law
A product unimolecular rate = k [A]
2A product bimolecular rate = k [A]2
A+B product bimolecular rate = k [A][B]
2A + B product termolecular rate = k [A]2[B]
16-67
Sample Problem 16.8 Determining molecularity and rate laws for
elementary steps
PROBLEM: The following two reactions are proposed as elementary steps in

the mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl (g)
(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(c) Write the rate law for each step.
PLAN: (a) The overall equation is the sum of the steps.

(b) The molecularity is the sum of the reactant particles in the step.
SOLUTION: (b) Step (1) is unimolecular.

(a) (1) NO2Cl(g) NO2(g) + Cl (g) Step (2) is bimolecular.
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g) (c) rate1 = k1 [NO2Cl]

rate2 = k2 [NO2Cl][Cl]
2NO2Cl(g) 2NO2(g) + Cl2(g)
16-68
The Rate-Determining Step of a Reaction Mechanism
All of the elementary steps of a mechanism do

not occur at the same rate. Usually one step is
much slower than the others. This step is called the
rate-determining (or rate-limiting) step.
The overall rate of a reaction is related to the rate of

the rate-determining step. That is, the rate law for
the rate-determining step represents the rate law for
the overall reaction!
16-69
An example:
NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n
Rate law: rate = k[NO2]2
Step 1: NO2(g) + NO2 (g) NO3(g) + NO(g) Rate1 = k1[NO2]2
Step 2: NO3(g) + CO(g) NO2(g) + CO2(g) Rate2 = k2[NO3][CO]
Step 1 is slow and rate-determining; Step 2 is fast.
NO3 is an intermediate!
Thus, if k1 = k, the rate law for Step 1 (rate-determining) is the

same as the experimental rate law!
16-70
Correlating the Mechanism with the Rate Law
Chemical mechanisms can never be proven

unequivocally! But potential chemical mechanisms
can be eliminated based on experimental data.
Three Key Criteria for Elementary Steps
1. The elementary steps must add up to the overall equation.
2. The elementary steps must be physically reasonable.
3. The mechanism must correlate with the rate law.
16-71
Reaction Energy Diagram for the two-step NO2-F2 reaction
2NO2(g) + F2(g) 2NO2F(g)

rate = k[NO2][F2]
Two transition states and

one intermediate are involved.
The first step is

rate-determining.
The reaction is exothermic

(thermodynamics).
16-72
What happens when a fast reversible step(s) occurs prior to the
rate-determining step?
2NO(g) + O2(g) 2NO2 (g)
Rate law: rate = k[NO]2[O2]
Proposed Mechanism
Step 1: NO(g) + O2(g) NO3(g) fast and reversible
Step 2: NO3(g) + NO(g) 2NO2(g) slow; rate-determining
Rate laws for the two elementary steps:
Step 1: rate1 (fwd) = k1[NO][O2]; rate1 (rev) = k-1[NO3]

Step 2: rate2 = k2[NO3][NO]
Step 2 (rate-determining) contains [NO3] which does

not appear in the experimental rate law!
16-73
If Step 1 is at equilibrium, then....
rate1 (fwd) = rate1 (rev)

or
k1[NO][O2] = k-1[NO3]
Solving for [NO3]:
[NO3] = (k1/k-1)[NO][O2]
Substituting into the rate law for rate-limiting Step 2:
rate2 = k2[NO3][NO] = k2 (k1/k-1)[NO][O2][NO] = [(k1k2)/k-1][NO]2[O2]
Conclusion: The proposed mechanism is consistent

with the kinetic data.
16-74
Catalysis: Enhancing Reaction Rates
Catalyst: increases reaction rate but is not consumed in the reaction
A catalyst increases reaction rate (via increasing k) by lowering the

activation energy (barrier) of the reaction.
Both forward and reverse reactions are catalyzed; reaction

thermodynamics is unaffected!
The catalyzed reaction proceeds via a different mechanism

than the uncatalyzed reaction.
16-75
Energy diagram of an uncatalyzed and catalyzed reaction
Note that both reactions

exhibit the same
thermodynamics!
The catalyzed
and
uncatalyzed
reactions occur
via different
pathways.
16-76
Uncatalyzed reaction:
A + B product
Catalyzed reaction:
A + catalyst C
C + B product + catalyst
Types of Catalysts
 Homogeneous: exists in solution with the reaction mixture

 Heterogeneous: catalyst and reaction mixture are in different phases
16-77
16-78
Homogeneous Catalysis
The Mechanism of Acid-catalyzed

Organic Ester Hydrolysis
R-COOR’ + H2O + H+ R-COOH + R’OH + H+

ester acid alcohol
The reaction rate is slow at neutral pH (pH 7.0), but

increases significantly at acidic pH (pH 2).
H+ ion catalyzes the reaction at low pH; what is the

molecular basis for the catalysis by H+?
16-79
Proposed reaction mechanism for the H+-catalyzed
hydrolysis of an organic ester
resonance forms
H O H O
O fast H O
R C R C
+ R C R C
H + H O
O O
O O R C
R' R'
R' R' O
R'
resonance hybrid
H O H O
R C O H R C O H H+ O
+
O H O H R C O H
slow, rate- all fast
R' determining R' OH
step
R'
Figure 16.23
16-80
Heterogeneous Catalysis: Metal-catalyzed
hydrogenation of ethylene
H2C CH2 (g) + H2 (g) H3C CH3 (g)
Ni, Pd or Pt
16-81 Figure 16.24

The widely
separatedam
ino acid
groups that
form the
active site of
an enzyme
The enzyme, chymotrypsin

Figure B16.4
A protease (hydrolyzes proteins)
16-82
Two Models of Enzyme Action
lock and key
induced fit
Figure B16.5 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
16-83
Tools of the Laboratory
Spectrophotometric monitoring of a reaction
Figure B16.1
16-84
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Tools of the Laboratory
Figure B16.2
Conductometric monitoring
of a reaction
Figure B16.3
Manometric monitoring
of a reaction
16-85

Chapt16 Lecture

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapt16 Lecture

Uploaded by

Copyright:

Available Formats

Chapter 16

Kinetics: Rates and Mechanisms of Chemical

16.1 Factors that influence reaction rates

16.2 Expressing the reaction rate

16.3 The rate law and its components

16.4 Integrated rate laws: Concentration changes over time

16.5 Reaction mechanisms: Steps in the overall reaction

16.6 Catalysis: Speeding up a chemical reaction

The study of reaction rates, the changes in concentrations of

Quantitative relationships through the derivation of a rate law

Kinetics can reveal much about the mechanism of a reaction.

Reactant Concentration: molecular collisions are required for

reaction rate a collision frequency a concentration

Physical State: molecules must mix to collide

When reactants are in different phases, the more finely divided

Temperature: molecules must collide with sufficient energy to react

Higher T translates into more collisions per unit time and

reaction rate a collision energy a temperature

Figure 16.3 steel nail in O2 steel wool in O2

Other factor: reaction

reaction rate = the changes in [reactants] or [products] per unit time;

Average rate of reaction = - ([A2] - [A1]) / (t2 - t1)

rate is always = - D[A] / Dt

Also, reaction rate = + D[B] / Dt

C2H4(g) + O3(g) C2H4 O(g) + O2(g)

time (s) concentration of O3 (mol/L)

0.0 3.20 x 10-5

Reaction rate varies with time as the reaction proceeds!

C2H4(g) + O3(g) C2H4O(g) + O2(g)

Data show that the average rate decreases as the

Curved line indicates change

reaction rate = (instantaneous)

initial rates: measured to avoid

C2H4(g) + O3(g) C2H4O(g) + O2(g)

Plots of [C2H4] and [O2]

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

rate = - D[H2]/Dt = - D[I2]/Dt = 1/2 D[HI]/Dt

rate = D[HI]/Dt = -2 D[H2]/Dt = -2 D[I2]/Dt

For the general reaction: aA + bB cC + dD

PROBLEM: Because it generates a nonpolluting product (water vapor),

The rate law expresses the reaction rate as a function of reactant

The derived rate law for a reaction must be consistent

For a general reaction: aA + bB + ..... cC + dD

(for a unidirectional (one-way) reaction)!

1. Measure initial rates (from concentration measurements)

3. Calculate the rate constant

rate = k[A] first order overall (rate a [A])

NO(g) + O3(g) NO2(g) + O2(g)

rate = k[NO][O3] second order overall

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

rate = k[NO]2[H2]1 third order overall

Reaction orders cannot be deduced from the

Reaction orders are usually positive integers or zero.

Reaction orders can be fractional or negative.

(b) The reaction is 3/2-order in CH3CHO and 3/2-order overall.

O2(g) + 2NO(g) 2NO2

To find m and n: A series of experiments is

1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3

2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3

3 1.10 x 10-2 2.60 x 10-2 12.8 x 10-3

4 3.30 x 10-2 1.30 x 10-2 9.60 x 10-3

5 1.10 x 10-2 3.90 x 10-2 28.8 x 10-3

6.40 x 10-3 mol/L/s

Thus, the reaction is first order with respect to O2.