OVERVIEW

Rates of Reaction

Overview
Reaction Rates

Definition of Reaction Rates

Experimental Determination of Rate
Dependence of Rate on Concentration
Change of Concentration with Time
Temperature and Rate; Collision and Transition-State
Theories.
Arrhenius Equation

Reaction Mechanisms
Elementary Reactions
Rate Law and the Mechanism
Catalysis

Reaction Rates
Deal with the speed of a reaction and controlled by:
Proportional to concentrations of reactants
Proportional to catalyst concentration; catalyst = a substance
that increases the rate of reaction without being consumed in
the reaction.
Larger surface area of catalyst means higher reaction rate
(more sites for reaction to take place).
Temperature: Higher temperature of reaction means faster.

Definition of Reaction Rate

Reaction rate = increase in
concentration of product of a
reaction as a function of time or
decrease in concentration of
reaction as a function of time.
Thus the rate of a reaction is:

0.090

Concentration, M

Rate A

Concentration vs Reaction Time

A + 2B --> 3C

conc change A [ A ]

time change
t
[ A ]2 [ A ]1
t 2 t1

Init
Rate
0.045

Inst.
Rate
Ave.
Rate

0.000
0

250
Tim e, s

Rates are expressed as positive numbers. For the reaction in

the graph we have:
RA

[ A ]
t

RB

[B]
t

RC

[C]
t

500

Reaction Rates and Stoichiometry

A + B C; RC = RA = RB.
A + 2B 3C; R 1 R 1 R
A

E.g.Calculate the rate of decomposition of HI in the

reaction: 2HI(g) H2(g) + I2(g). Given: After a
reaction time of 100 secs. the concentration of HI
decreased by 0.500 M.
For the general reaction: aA + bB cC + dD
a
a
a
R A RB R C RD
b
c
d

E.g. For the reaction 2A + 3B 4C + 2D; determine

the rates of B, C and D if the rate of consumption of A
is 0.100 M/s.

Rate Laws and Reaction Order

Rate Law an equation that tells how the reaction rate depends on the
concentration of each reaction.
Reaction order the value of the exponents of concentration terms in
the rate law.
For the reaction: aA + bB cC + dD, the initial rate of reaction is
related to the concentration of reactants.
Varying the initial concentration of one reactant at a time produces
rates, which will lead to the order of each reactant.
The rate law describes this dependence: R = k[A]m[B]n where k = rate
constant and m and n are the orders of A and B respectively.
m = 1 (A varied, B held constant) gives R = k[A]. Rate is directly
proportional to [A]. Doubling A doubles R
m = 2 (A varied, B held constant) gives R = k[A]2. The rate is proportional
to [A]2. Doubling A quadruples R.

E.g. Determine order of each reactant:

HCOOH(aq) + Br2(aq) 2H+(aq) + 2Br(aq) + CO2(g) R = k[Br2]
E.g. The formation of HI gas has the following rate law: R = k[H2][I2].
What is the order of each reactant?

Experimental Determination of a Rate Law: First

Order
Varying initial concentration of reactants
changes the initial rate (usually all but
one held constant) like one with two
unknowns.
Initial rate is the initial slope of the
graph shown.
As the initial concentration of that
compound increases so does the rate.

Concentration vs Reaction Time

A + 2B --> 3C

[A] 0, M

0.100

0.000
0

250

500

Tim e, s

Initial Rate vs. [A]o

Initial rate vs. [A]o plotted.

If straight line then reaction is first order
and slope is rate constant.

0.0005
0.0004

Ro

Second order rate law determined in

like manner.

0.050

0.0003
0.0002
0.0001
0.0000
0.00

0.03

0.05
[A]o

0.08

0.10

Rate Law for All Reactants

Order for all components done same way.
E.g. Determine the reaction order for each reactant from the table.
(aq)+5Br(aq)+6H+(aq)3Br2(aq)+3H2O(l)
BrO
3

[BrO3 ]o
0.10
0.20
0.10
0.20

[Br]o
0.10
0.10
0.30
0.10

[H+]o
0.10
0.10
0.10
0.15

Ro
1.2
2.4
3.5
5.4

Eg. 2: Determine the reaction orders for the reaction indicated from
the data provided.
A + 2B + C Products.
[A]o
2.06
0.87
0.50
1.00

[B]o
3.05
3.05
0.50
0.50

[C]o
4.00
4.00
0.50
1.00

Ro
3.7
0.66
0.013
0.072

Integrated Rate Law: FirstOrder Reaction

For a first order reaction, Rate = [A]/t = k[A] or RA = d[A]/dt = k[A].

Use of calculus leads to: ln

Allows one to calculate the [A] at any time after the start of the reaction.
E.g. Calculate the concentration of N2O remaining after its decomposition
according to 2N2O(g) 2N2(g) + O2(g) if its rate is first order and [N2O]o = 0.20M,
k = 3.4 s1 and T = 780C. Find its concentration after 100 ms.

Linearized forms: ln[ A ] kt ln[ A ]o or log[ A ]

t log[ A ]o
2.303
Plot ln[A] vs t.
Slope of straight line leads to rate constant, k.
E.g. When cyclohexane(let's call it C) is heated to 500 oC, it changes into
propene. Using the following data from one experiment, determine the first order
rate constant.:
t,min
0.00 5.00 10.00 15.00
[C],mM 1.50 1.24 1.00
0.83

[A]
k
[A]
or
log

t
kt
[ A ]o
2.303
[ A ]o

Half-Life: First Order Reaction

Half-life of First order reaction,
t1/2 = 0.693/k. the time required for
the concentration of the reactant to
change to of its initial value.
i.e. at t1/2 , [A] = [A]o
E.g. For the decomposition of N2O5
at 65 C, the half-life was found to
be 130 s. Determine the rate
constant for this reaction.
For n half-lives t = n*t1/2 [A] =

2n

[A]o

1 / 2[ A]o
ln
k t1/ 2
[ A]o
1
ln k t1/ 2
2
t1/ 2 0.693 / k

1
n ln k n t1 / 2
2
1
ln k tn
2n
1 [ A ]t
n [A]
2
o

SecondOrder Reactions: Integrated Rate

Law
Rate law: R = k[A]2 and the integrated rate equation is:
1
1
kt
[ A ]t
[ A ]o

1
Plot of [ A ] vs. t gives a straight line with a slope of k.
t

1
Half-life is: t1/ 2 k [ A ]
o

E.g. At 330C, the rate constant for the decomposition of

NO2 is 0.775 L/(mol*s). If the reaction is second-order,
what is the concentration of NO2 after 2.5x102 s if the
starting of concentration was 0.050 M?

Reaction Mechanisms

Give insight into sequence of reaction events leading to product

(reaction mechanism).
Each of the steps leading to product is called an elementary
reaction or elementary step.
Consider the reaction of nitrogen dioxide with carbon dioxide which
is second order on NO2:
NO2(g) + CO(g) NO(g) + CO2(g) Rate = k[NO2]2.
Rate law suggests at least two steps.
A proposed mechanism for this reaction involves two steps.
Step 1
Step 2
Overall

2NO2(g) NO3(g) + NO(g)

NO3(g) +CO(g) NO2(g) + CO2(g)
NO2 + CO NO + CO2

NO3 is a reaction intermediate = a substance that is produced and

consumed in the reaction so that none is detected when the reaction is
finished.

The elementary reactions are often described in terms of their

molecularity.
Unimolecular One particle in elementary.
Bimolecular = 2 particles and
Termolecular = 3 particles

Rate Laws and Reaction Mechanisms

Overall reaction order is often determined by the rate determining step.

Use rate law of limiting step; No intermediates!
2NO2(g) NO3(g) + NO(g),
NO3(g) +CO(g) NO2(g) + CO2(g)
NO2 + CO NO + CO2

R1 = k1[NO2]2

Slow

R2 = k2[NO3][CO]

Fast

Robs = k[NO2]2

E.g. Determine the rate law for the following mechanism:

2*[N2O5(g) NO2 (g) NO3 (g) ]

Fast

k2
NO3(g) +NO2(g)
NO2 (g) NO(g) O 2 (g)

Slow

k1

k 1

Fast

k3
NO3 + NO
2NO2 (g)
k obs
2N2O5(g)

4NO2 (g) O 2 (g)

Use steady state approximation. at equilibrium rates of forward and

reverse reactions are same. Use to eliminate intermediates from rate law
equations.
R1 R1
k 1 [N2O5 ] k 1[NO2 ][NO3 ]

or

[NO3 ]

k 1 [N2O5 ]
k 1 [NO2 ]