5.

TOPIC: 5.2 INTRODUCTION TO RATE LAW

ENDURING UNDERSTANDING:
TRA-3 Some reactions happen quickly, while others happen more slowly and depend on reactant concentrations and
temperature.
LEARNING OBJECTIVE:
TRA-3.B Represent experimental data with a consistent rate law expression.
ESSENTIAL KNOWLEDGE:
TRA-3.B.1 Experimental methods can be used to monitor the amounts of reactants and/or products of a reaction and to
determine the rate of the reaction.
TRA-3.B.2 The rate law expresses the rate of a reaction as proportional to the concentration of each reactant raised to a
power.
TRA-3.B.3 The power of each reactant in the rate law is the order of the reaction with respect to that reactant. The sum of
the powers of the reactant concentrations in the rate law is the overall order of the reaction.
TRA-3.B.4 The proportionality constant in the rate law is called the rate constant. The value of this constant is
temperature dependent and the units reflect the overall reaction order.
TRA-3.B.5 Comparing initial rates of a reaction is a method to determine the order with respect to each reactant.
EQUATION(S):
N/A

NOTES:
Since a rate of reaction can only be determined experimentally, we can use experimental data to write a Rate Law.
A rate law describes how the rate of reaction is proportional to the concentration of each reactant raised to a
power.
Example:
Reaction : D + 2C → AB
The rate law for this reaction might be found, experimentally, to be: Rate = k[D]0[C]1

This reaction would be described as zeroth order with respect to D and first order with respect to C. This means
that if the concentration of D is changed it will not affect the rate of the reaction. If the concentration of C is
changed, then the rate of reaction will change by the same factor, if C is x2, then the rate is x2, if C is x4, then the
rate is x4 etc.

The sum of the exponents describes the overall rate law; this reaction would be first order.

NOTE: The coefficients have nothing to do with the rate law. The rate law can only be discovered by experiment.

The constant, k, is different for each reaction and set of conditions. The value for k is dependent on temperature. It
is known as the rate constant. You will often be asked to solve for this value and to provide the units. The units
for k describe the overall reaction order.

Reaction order Units for k (time = sec, min, hours, etc.) Example reactions
0 M/time Rate = k[A]0
1 1/time Rate = k[A]
2 1/M time Rate = k[A]2
Rate = k[A][B]
3 1/M2time Rate = k[A]3
Rate = k[A][B]2
Rate = k[A][B][C]
n 1/M(n-1)time Rate = k[A]n

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 5.2
Comparing the initial rates of each individual reactant allows us to determine how each reactant affects the rate of
the reaction. We can then write a rate law for the reaction. This is often known as the Method of Initial Rates.

You should look at the tables of data provided and see where only one variable changes, to see the effect on the
rate.
Change to variable Effect on rate Reaction order
×𝑛 No change(× 𝑛 )0 0
×𝑛 ×𝑛 1
×𝑛 ×𝑛 2 2
×𝑛 ×𝑛 3 3

Example:
A + B → 2C
Experiment Initial [A] Initial [B ] Initial Rate of formation of C
(M) (M) (M/sec)
1 1.0 1.0 0.015
2 1.0 2.0 0.030
3 3.0 1.0 0.135
Look at the data; in the table we can see that there are 2 experiments with the same value for A, and 2 experiments
with the same value for B. (The concentration is held constant.)

If we hold A constant, we can inspect the data. When A is constant and B is doubled, the rate doubled. This means
that the reaction is first order with respect to B. When B is held constant and A is tripled the rate increased by a
factor of 9 (0.135/0.015 = 9), nine is 32. This means that the reaction is second order with respect to A.

The overall rate law would be: Rate = k [A]2[B] The overall reaction order = 2+1 = 3, so third order.

Plugging in the values, we can solve for the value of k.

0.015 M/sec = k [1.0 M]2[1.0 M]

0.015 M/sec = k (1.0 M3)

0.015 𝑀/𝑠𝑒𝑐
=𝑘
(1.0 𝑀3 )

0.015 1/𝑀2 𝑠𝑒𝑐 = 0.015 𝑀−2 𝑠𝑒𝑐 −1 = k

If more than one variable changes then it is a little trickier to determine by inspection. You can compare two
experiments like this:

𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 2 𝑅𝑎𝑡𝑒 𝑘 [𝐴 ] 𝑛 [𝐵 ] 𝑚
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 1
= 𝑅𝑎𝑡𝑒2 = (𝑘2 ) ([𝐴2 ]) ([𝐵2 ])
1 1 1 1
Example:
Experiment Initial [A] Initial [B ] Initial Rate of formation of C
(M) (M) (M/sec)
1 1.0 1.0 0.0016
2 4.0 1.0 0.0064
3 2.0 2.0 0.0064
Look at the data; in the table we can see that there are no experiments with the same value for A, but there are 2
experiments with the same value for B. Start with finding the reaction order with respect to A.

Comparing experiment 1 and 2, when B is held constant, A is multiplied by 4; this caused the rate to be increased
by the same factor (x4) so we can see that the reaction is first order with respect to A.

To figure out the reaction order for B, we can use the equation above.
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 5.2
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 3 0.0064 𝑀/𝑠𝑒𝑐 𝑘 [2.0 𝑀] 1 [2.0 𝑀] 𝑚
= = ( 2) ( ) ( )
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 1 0.0016 𝑀/𝑠𝑒𝑐 𝑘1 [1.0 𝑀] [1.0 𝑀]

Since k is the same for both, we can cancel it out

𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 3 0.0064 𝑀/𝑠𝑒𝑐 [2.0 𝑀] 1 [2.0 𝑀] 𝑚

𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 1
= 0.0016 𝑀/𝑠𝑒𝑐
= ( [1.0 𝑀]
) ([1.0 𝑀])
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 3
= 4 = (2) (2)𝑚
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 1

𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 3
𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 1
= 2= (2)𝑚
m= 1
Thus this reaction is first order with respect to B as well.
The overall rate law would be: Rate = k [A][B] The overall reaction order = 1+1 = 2, so second order.

Plugging in the values from any of the trials, we can solve for the value of k.
0.0064 M/sec = k [4.0 M][1.0 M]

0.0064 M/sec = k (4.0 M2)

0.0064 𝑀/𝑠𝑒𝑐
=𝑘
(4.0 𝑀2 )

0.0016 1/𝑀𝑠𝑒𝑐 = 0.0016 𝑀−1 𝑠𝑒𝑐 −1 = k

I DO:
Consider the reaction: CO(g)+NO3(g)→NO2(g)+CO2(g)
Several experiments were conducted and the data is shown below:
Experiment Initial [CO] Initial [NO3] Initial Rate of formation of NO2
(M) (M) (M/sec)
1 0.120 0.720 1.68 x 10 -2
2 0.120 0.360 8.40 x 10 -3
3 0.0300 0.360 2.10 x 10 -3

A) What is the reaction order with respect to CO?

First order
B) What is the reaction order with respect to NO3?
First order
C) What is the overall reaction order?
Second order
D) What is the rate law for this reaction?
Rate = k[CO][NO3]
E) What is the value of k with units?
1.68 x10-2 M/sec= k(0.120 M CO)(0.720 M NO3)
1.68 x10-2 M/sec= k 0.0864 M2
0.194 M/secM2 = k
0.194 sec-1M-1 = k

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 5.2
WE DO:
Consider the reaction: 2NOCl(g)→2NO(g)+Cl2(g)
The rate law shows that it is a bimolecular reaction: Rate = k[NOCl]2
When the initial concentration of NOCl is 0.391M, the rate is 9.32 x 10-3M/sec.
a) Find the value for k with units.

b) What will the rate of reaction be when the concentration of NOCl is 0.634M, if the
reaction takes place at the same temperature?

YOU DO:
1) Given the reaction 2A + B → C, with the rate law: Rate = k[A]0[B]2
A) What is the overall reaction order?
2
B) When the concentration of A and B were 0.023 M and 0.054 M, the reaction rate was 8.31x10-2 M/sec,
calculate the value for k (with units).
8.31 x 10^-2 = k(0.023)^0 x (0.054)^2
k = 8.31 x 10^-2 / 1 x 0.054^2 k = 28.50 M/sec
C) Given the same amount of the reactants shown in part B, calculate the concentration of A when the
concentration of B is 0.050 M.
(8.31 x 10^-2) / (28.5 x 0.050^2) = ln(1.16) = 0.15 M

2) Given the following data:

Experiment Initial [X] Initial [Y] Initial Rate of formation of Z (M/sec)
(M) (M)
1 0.50 0.35 3.0 x 10 -4
2 1.0 0.70 1.2 x 10 -3
3 1.0 0.35 3.0 x 10 -4
The data in the table is for the reaction: X + 2Y → Z
a) What is the order of reaction with respect to X?
0
b) What is the order of reaction with respect to Y?
2

c) What is the overall rate law?

Rate = k[Y]^2

d) Using the experiment 1 data, calculate the value for k, with units.
3.0 x 10^-4 / (0.35)^2 = 2.45 x 10^-3 L/mol

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 5.2
3) Given the reaction: 2NO2(g) + 7H2(g) → 2NH3(g) + 4H2O(l)

With the rate law: Rate = k [NO2][H2]2

If the reaction is first studied with 2.0 M for each of the reactants, by what factor will the rate change if
the concentrations are changed to 4.0 M for both of the reactants?
By a factor of 8.

4) Given the reaction: O2(g) + 2 NO(g) → 2 NO2(g)

With the rate law: Rate = k [O2]2 [NO]

What happens to the rate if the concentration of O2 is doubled? And why?

It will quadruple because the order for O2 is 2 so and 2^2 is 4.

5) Given the reaction:

Cr2O72−(aq) + 3HNO2(aq) + 5H+(aq) →2Cr3+(aq) + 3NO3−(aq) + 4H2O(l)

A student studies the kinetics of the reaction and their data is shown below:
Initial [Cr2O72−] Initial [HNO2] Initial [H+] Initial Rate of
Experiment
(M) (M) (M) reaction (M/s)
1 0.25 0.48 0.10 2.1 x 10-3

2 0.25 0.24 0.30 6.3 x 10-3

3 0.50 0.24 0.10 8.4 x 10-3

4 0.25 0.24 0.10 2.1 x 10-3

a) What is the order of reaction with respect to Cr2O72−?
2
b) What is the order of reaction with respect to HNO2?
0
c) What is the order of reaction with respect to H+?

d) What is the overall rate law?

Rate = k[Cr2O7)^2 [H+]
e) Using the experiment 1 data, calculate the value for k, with units.
(2.1 x 10^-3) / (0.25^2 x 0.10) = 0.336 L^2/mol^2 s

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 5.2
6) Given the reaction and data below, answer the following questions
A + B → 2C
Experiment Initial [A] Initial [B ] Initial Rate of formation of C
(M) (M) (M/sec)
1 0.015 0.24 3.1 x 10 -3
2 0.030 0.48 6.2 x 10 -3
3 0.045 0.24 3.1 x 10 -3
a) What is the reaction order for A? Explain
0 because as A increases, there is no effect on the rate.
b) What is the reaction order for B? Explain
1 because as B doubles, the rate doubles, and 2 = 2^1.
c) What is the value for k including units?
3.1 x 10^-3 / 0.24 = 0.013 1/s

d) Write the overall rate law for this reaction.

Rate = k[B]