Kinetics: Expression and Rate Law

Dr. Prayoga Suryadarma, STP, MT

Department of Agroindustrial Technology

Unit Process, February 2021

Expressing the Reaction Rate

Reaction rate is measured in terms of the changes in

concentrations of reactants or products per unit time.

For the general reaction A → B, we measure the

concentration of A at t1 and at t2:
change in concentration of A conc A2 - conc A1 D[A]
Rate = =- =-
change in time t2 - t1 Dt

Square brackets indicate a concentration in moles per liter.

The negative sign is used because the concentration of A

is decreasing. This gives the rate a positive value.

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Table 16.1 Concentration of O3 at Various Times in its
Reaction with C2H4 at 303 K

Concentration of O3
Time (s) (mol/L)

0.0 3.20x10-5 D [C2H4]

10.0 rate = -
2.42x10-5 Dt
20.0 1.95x10-5 D [O3]
=-
30.0 1.63x10-5 Dt
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5

Figure 16.5 Three types of reaction rates for the reaction of O3

and C2H4.

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Figure 16.6A Plots of [reactant] and [product] vs. time.

C2H4 + O3 → C2H4O + O2

[O2] increases just as fast as

[C2H4] decreases.

D[C2H4] D[O3]
Rate = - =-
Dt Dt

D[C2H4O] D[O2]
= =
Dt Dt

Figure 16.6B Plots of [reactant] and [product] vs. time.

H2 + I2 → 2HI
[HI] increases twice as
fast as [H2] decreases.

D[H2] D[I2] D[HI]

Rate = - =- = 1
Dt Dt 2 Dt

D[IH] D[H2] D[I2]

Rate = = -2 = -2
Dt Dt Dt

The expression for the rate of a reaction

and its numerical value depend on which
substance serves as the reference.

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In general, for the reaction

aA + bB → cC + dD

where a, b, c, and d are the coefficients for the balanced

equation, the rate is expressed as:

1 D[A] 1 D[B] = 1 D[C] = 1 D[D]

rate = - =-
a Dt b Dt c Dt d Dt

Sample Problem 16.1 Expressing Rate in Terms of Changes in

Concentration with Time
PROBLEM: Hydrogen gas has a nonpolluting combustion product
(water vapor). It is used as a fuel abord the space shuttle
and in earthbound cars with prototype engines:
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?

PLAN: We choose O2 as the reference because its coefficient is 1. For

every molecule of O2 that disappears, two molecules of H2
disappear, so the rate of [O2] decrease is ½ the rate of [H2]
decrease. Similarly, the rate at which [O2] decreases is ½ the rate
at which [H2O] increases.

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Sample Problem 16.1

SOLUTION:
D[O2] 1 D[H2] 1 D[H2O]
(a) Rate = - =- =
Dt 2 Dt 2 Dt

(b) Calculating the rate of change of [H2O]:

1 D[H2O] D[O2]
=- = -(-0.23 mol/L·s)
2 Dt Dt

D[H2O]
= 2(0.23 mol/L·s) = 0.46 mol/L·s
Dt

The Rate Law

For any general reaction occurring at a fixed temperature

aA + bB → cC + dD

Rate = k[A]m[B]n

The term k is the rate constant, which is specific for a

given reaction at a given temperature.

The exponents m and n are reaction orders and are

determined by experiment.
The values of m and n are not necessarily related in any way to
the coefficients a and b.

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 Reaction Orders
A reaction has an individual order “with respect to” or “in”
each reactant.
For the simple reaction A → products:

If the rate doubles when [A] doubles, the rate depends on

[A]1 and the reaction is first order with respect to A.

If the rate quadruples when [A] doubles, the rate depends

on [A]2 and the reaction is second order with respect to [A].

If the rate does not change when [A] doubles, the rate does
not depend on [A], and the reaction is zero order with
respect to A.

Figure 16.7 Plots of reactant concentration, [A], vs. time for

first-, second-, and zero-order reactions.

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Figure 16.8 Plots of rate vs. reactant concentration, [A], for
first-, second-, and zero-order reactions.

Individual and Overall Reaction Orders

For the reaction 2NO(g) + 2H2(g) → N2(g) + 2H2O(g):
The rate law is rate = k[NO]2[H2]
The reaction is second order with respect to NO, first
order with respect to H2 and third order overall.

Note that the reaction is first order with respect to H2

even though the coefficient for H2 in the balanced
equation is 2.
Reaction orders must be determined from experimental
data and cannot be deduced from the balanced
equation.

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Sample Problem 16.2 Determining Reaction Orders from Rate
Laws
PROBLEM: For each of the following reactions, use the give rate law
to determine the reaction order with respect to each
reactant and the overall order.
(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: We inspect the exponents in the rate law, not the coefficients
of the balanced equation, to find the individual orders. We add
the individual orders to get the overall reaction order.

SOLUTION:
(a) The exponent of [NO] is 2 and the exponent of [O2] is 1, so the
reaction is second order with respect to NO, first order
with respect to O2 and third order overall.

Sample Problem 16.2

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

2 2

(c) The reaction is first order in H2O2, first order in I-, and
second order overall. The reactant H+ does not appear in
the rate law, so the reaction is zero order with respect to H+.

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 Determining Reaction Orders

For the general reaction A + 2B → C + D,

the rate law will have the form
Rate = k[A]m[B]n

To determine the values of m and n, we run a series of

experiments in which one reactant concentration
changes while the other is kept constant, and we
measure the effect on the initial rate in each case.

Table 16.2 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.

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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

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Table 16.3 Initial Rates for the Reaction between O2 and NO

O2(g) + 2NO(g) → 2NO2(g) Rate = k[O2]m[NO]n

Initial Reactant
Concentrations (mol/L)
Initial Rate
Experiment (mol/L·s) [O2] [NO]
1 3.21x10-3 1.10x10-2 1.30x10-2
2 6.40x10-3 2.20x10-2 1.30x10-2
3 12.48x10-3 1.10x10-2 2.60x10-2
4 9.60x10-3 3.30x10-2 1.30x10-2
5 28.8x10-3 1.10x10-2 3.90x10-2

Finding m, the order with respect to O2:

We compare experiments 1 and 2, where [NO] is kept
constant but [O2] doubles:
Rate 2 k[O2] m n
2 [NO] 2 [O2] m [O2]2 m
= 2=
m n = m
Rate 1 k[O2] 1 [NO] 1 [O2] 1 [O2]1
m
6.40x10-3 mol/L·s 2.20x10-2 mol/L
=
3.21x10-3mol/L·s 1.10x10-2 mol/L

Dividing, we get 1.99 = (2.00)m or 2 = 2m, so m = 1

The reaction is first order with respect to O2.

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Sometimes the exponent is not easy to find by inspection.
In those cases, we solve for m with an equation of the form
a = bm:
log a log 1.99
m= = = 0.993
log b log 2.00

This confirms that the reaction is first order with respect to O2.

Reaction orders may be positive integers, zero, negative integers, or

fractions.

Finding n, the order with respect to NO:

We compare experiments 1 and 3, where [O2] is kept
constant but [NO] doubles:
n
Rate 3 [NO]3 n 12.8x10-3 mol/L·s 2.60x10-2 mol/L
= =
Rate 1 [NO]1 3.21x10-3mol/L·s 1.30x10-2 mol/L

Dividing, we get 3.99 = (2.00)n or 4 = 2n, so n = 2.

log a log 3.99
Alternatively: n= = = 2.00
log b log 2.00

The reaction is second order with respect to NO.

The rate law is given by: rate = k[O2][NO]2

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Sample Problem 16.3 Determining Reaction Orders from Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust

system. One of these is
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:

Initial Rate Initial [NO2] Initial [CO]

Experiment (mol/L·s) (mol/L) (mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20

Sample Problem 16.3

PLAN: We need to solve the general rate law for m and for n and
then add those orders to get the overall order. We proceed by
taking the ratio of the rate laws for two experiments in which
only the reactant in question changes concentration.
SOLUTION:
To calculate m, the order with respect to NO2, we compare
experiments 1 and 2:
m
rate 2 k [NO2]m2[CO]n2 [NO2] 2 0.080 0.40 m
= = =
rate 1 k [NO2]m1 [CO]n1 [NO2] 1 0.0050 0.10
16 = (4.0)m so m = 2

The reaction is second order in NO2.

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 Sample Problem 16.3

To calculate n, the order with respect to CO, we compare experiments

1 and 3:

0.20 n
n
rate 3 k [NO2]m3[CO]n3 [CO] 3 0.0050
= = =
rate 1 k [NO2]m1 [CO]n1 [CO] 1 0.0050 0.10

1.0 = (2.0)n so n = 0

The reaction is zero order in CO.

rate = k[NO2]2[CO]0 or rate = k[NO2]2

Sample Problem 16.4 Determining Reaction Orders from Molecular

Scenes
PROBLEM: At a particular temperature and volume, two gases, A (red)
and B (blue), react. The following molecular scenes
represent starting mixtures for four experiments:

Expt no: 1 2 3 4
Initial rate (mol/L·s) 0.50x10-4 1.0x10-4 2.0x10-4 ?
(a) What is the reaction order with respect to A? With respect to B?
The overall order?
(b) Write the rate law for the reaction.
(c) Predict the initial rate of experiment 4.
PLAN: We find the individual reaction orders by seeing how a change
in each reactant changes the rate. Instead of using
concentrations we count the number of particles.

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Sample Problem 16.4

SOLUTION:
(a) For reactant A (red):
Experiments 1 and 2 have the same number of particles of B, but
the number of particles of A doubles. The rate doubles. Thus the
order with respect to A is 1.
For reactant B (blue):
Experiments 1 and 3 show that when the number of particles of B
doubles (while A remains constant), the rate quadruples. The
order with respect to B is 2.
The overall order is 1 + 2 = 3.

(b) Rate = k[A][B]2

(c) Between experiments 3 and 4, the number of particles of A

doubles while the number of particles of B does not change. The
rate should double, so rate = 2 x 2.0x10-4 = 4.0x10-4mol/L·s

Table 16.4 Units of the Rate Constant k for Several Overall

Reaction Orders

Overall
Reaction Units of k General formula:
Order (t in seconds)
L order-1
0 mol/L·s
(or mol L-1s-1) mol
Units of k =
1 1/s (or s-1) unit of t

2 L/mol·s
(or L mol-1s-1)
3 L2/mol2·s
(or L2 mol-2s-1)

The value of k is easily determined from experimental rate

data. The units of k depend on the overall reaction order.

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Figure 16.9 Information sequence to determine the kinetic
parameters of a reaction.

Series of plots of
concentration vs.
time

Determine slope of tangent at t0 for

each plot.
Initial rates
Compare initial rates when [A] changes and
[B] is held constant (and vice versa).
Reaction
orders Substitute initial rates, orders, and
concentrations into rate = k[A]m[B]n, and
solve for k.
Rate constant (k)
and actual rate law

Thank you

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