Learning Activity Sheet

GENERAL CHEMISTRY 2 Week 7B: Rate Laws

LEARN
Rate Law

Rate laws are mathematical equations that describe relationship of the rate of chemical reaction with its
reactant concentration. The general form of rate laws is:

R = k [A]x[B]y
where: R = reaction rate; [A], [B] = molar concentration of the reactants, k = rate constant at a given
temperature; x, y = reaction orders. The rate constant k and the reaction orders are determined experimentally by
observing how the rate of a reaction changes as the concentrations of the reactants are changed. The rate constant k
is independent of the reactant concentrations, but it does vary with temperature.

The reaction orders in a rate law describe the mathematical dependence of the rate on reactant
concentrations. Referring to the generic rate law
R = k [A]x[B]y
the reaction is x order with respect to A and y order with respect to B. For example, if x = 1 and y = 2, the reaction is
first order in A and second order in B. The rate law in this case is
R = k [A] [B]2
The overall reaction order is simply the sum of orders for each reactant. For the example rate law above, the
reaction is third order overall (1 + 2 = 3).

More examples:

1. Given the rate law: R = k[H2O2]

a. What is the rate order in hydrogen peroxide (H2O2)? First order
b. What is the overall rate order? First order

2. Given the rate law: R = k[C4H6]2

a. What is the rate order in C4H6? Second order
b. What is the overall rate order? Second order

3. Given the rate law: R = k[H+][OH-]

a. What is the rate order of each reactant? [H +]  first-order; [OH-]  first order
b. What is the overall rate order? Second order

4. An experiment shows that the reaction of nitrogen dioxide with carbon monoxide:

NO2(g)+CO(g)→NO(g)+CO2(g)

is second order in NO2 and zero order in CO at 100 °C. What is the rate law for the reaction?

R = k[NO]2[CO]0 = R = k[NO]2

Method of Initial Rites

This method involves measuring reaction rates for multiple experimental trials carried out using different
initial reactant concentrations. Comparing the measured rates for these trials permits determination of the reaction
orders and, subsequently, the rate constant, which together are used to formulate a rate law. We’ll consider the
following experimental data on a study on the reaction of nitrogen oxides in the ozone layer, which results to ozone
hole.
The reaction is as follows:

NO (g) + O3 (g)  NO2 (g) + O2 (g)

The following were determined at 250C:

Trial [NO] (mol/L) [O3] (mol/L) 𝛥[NO2 ]

(M/s)
𝛥𝑡
1 1 x 10-6 3 x 10-6 6.60 × 10−5
2 1 x 10-6 6 x 10-6 1.32 × 10−4
3 1 x 10-6 9 x 10-6 1.98 × 10−4
4 2 x 10-6 9 x 10-6 3.96 × 10−4
5 3 x 10-6 9 x 10-6 5.94 × 10−4

From these data, we can determine the rate law and rate constant for the reaction at 250C.

We begin by writing the general form of the rate law for the reaction:
R = k[NO]x[O3]y
We can determine the value of x or y by taking advantage of the fact that at certain trials, one of the reactants is has
constant concentration while the other changes. Let’s find x first, noting that at trial 4 and 5, its concentration changes
while [O] is constant. We will use the data in trial 4 and 5.

For trial 4:
R4 = k[2 x 10-6]x[9 x 10-6]y
For trial 5:
R5 = k [3 x 10-6][ 9 x 10-6]y

We will take the ratio between the rate laws (R4/R5):

3.96𝑥10−4 𝑘 (2𝑥10−6 )𝑥 (9𝑥10−6 )𝑦

=
5.94𝑥10−4 𝑘 (3𝑥10−6 )𝑥 (9𝑥10−6 )𝑦
We can simply this into:
3.96 (2)𝑥
=
5.94 (3)𝑥

3.96 2
= ( )𝑥
5.94 3

0.667 = 0.667x

We’ll convert this to logarithmic equation. We know that ac = b  loga b =c

log0.667 0.667 = x
3.96 2 2
Also, for loga a= 1 (Technically ≠ 3 since 3 is non-terminating, however, this is a very good estimate):
5.94
x=1
Following the same procedure (using trials 1 and 2 or trials 1 and 3), we will arrive at:
y=1

Therefore, our rate law is:

R = k[NO]1[O3]1 = k[NO][O3]

We can now compute for k using the information in any of the trials, using trial 1
 𝑅1
𝑘=
[NO][O3 ]

6.60𝑥10−5
𝑘=
(1𝑥10−6 )(3𝑥10−6 )

k = 2.20 x 107 L/mol-s

This large value of k means that this reaction is fast. A smaller k value means otherwise.

(Note: the unit of k will depend on the reaction order. It is not always L/mol-s. When you solve k, make sure to
include the units to see how they cancel. I did not do so due to encoding difficulty).

Application
Answer the following practice questions. The answers are provided for you to verify your answer.

1. Acetaldehyde decomposes when heated to yield methane and carbon monoxide according to the equation:
CH3CHO(g)→CH4(g)+CO(g)
Determine the rate law and the rate constant for the reaction from the following experimental data:

𝛥[CH3 𝐶𝐻𝑂]
Trial [CH3CHO] (M) (M/s)
𝛥𝑡

1 1.75 × 10−3 2.06 × 10−11

2 3.50 × 10−3 8.24 × 10−11
3 7.00 × 10−3 3.30 × 10−10

Answer:

rate = k[CH3CHO]2
k = 6.73 × 10-6 L/mol/s

Reading Assignment:

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

2. What is activation energy and how does a catalyst affects reaction rate?