Department of Chemistry

Name:____________________
University of Texas at Austin

Kinetics Practice – Supplemental Worksheet KEY

Determining reaction mechanism based on initial rate data

1. A reaction has the experimental rate law, rate = k[A]2.

a. How will the rate change if the concentration of a is tripled?

If rate1=k[A]2, then rate2=k[3A]2=32* k[A]2=9* k[A]2=9* rate1.

So the rate would be 9 times faster.

b. How will the rate change if the concentration of A is halved?

1 1 1 1
If rate1=k[A]2, then rate2=k[ A]2= ( )2* k[A]2= * k[A]2= * rate1.
2 2 4 4
So the rate would decrease. It would be a fourth of the original rate.

2. A reaction has the experimental rate law, rate = k[A].

a. How will the rate change if the concentration of a is tripled?

If rate1=k[A], then rate2=k[3A]=3* k[A]=3* rate1.

So the rate would be 3 times faster.

b. How will the rate change if the concentration of A is halved?

1 1 1
If rate1=k[A], then rate2=k[2A]= (2)* k[A]= 2 * rate1.
So the rate would decrease. It would be one half of the original rate.

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014

 Department of Chemistry
Name:____________________
University of Texas at Austin

3. Three mechanisms for the reaction NO2(g) + CO(g)  CO2(g) + NO(g) have been
proposed:

a. Mechanism A
Step 1: NO2(g) + CO(g)  CO2(g) + NO(g)
b. Mechanism B
Step 1: NO2(g) + NO2(g)  NO(g) + NO3(g) (slow)
Step 2: NO3(g) + CO(g)  CO2(g) + NO2(g) (fast)
c. Mechanism C
Step 1: NO2(g) + NO2(g)  NO(g) + NO3(g) (fast, equilibrium)
Step 2: NO3(g) + CO(g)  CO2(g) + NO2(g) (slow)

Which mechanism agrees with the following initial rate data:

Experiment Initial [NO2] Initial [CO] Initial Rate

number (mol/L) (mol/L) (M/s)
1 0.133 0.074 0.144
2 0.399 0.074 1.296
3 0.133 0.370 0.144

These types of problems can be tackled in a three steps

 Step 1: What is the rate law that matches up with the initial rate data given?

We see that when we triple the NO2 concentration, the rate is 9 times greater.
This means the reaction is second order with respect to NO2.
We see that when we increase the concentration of CO by 5 times, the rate
does not change. This means the reaction is zero order with respect to CO.
Thus, the experimental rate law is rate=k[NO2]2

 Step 2: What are the rate laws of the proposed mechanisms?

Mechanism A: rate=ka[NO2][CO]
Mechanism B: rate = kb[NO2]2
Mechanism C: rate=kc[NO3][CO] (We do not need to solve this further to
eliminate the intermediates because we know that [CO] is not in the
experimental rate law. Thus, this mechanism does not agree with the
experimental data.)

 Step 3: Which mechanism matches up with the experimental rate law?

The rate law for mechanism B and the experimental rate law match up. So,
mechanism B agrees with the initial rate data.

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014

 Department of Chemistry
Name:____________________
University of Texas at Austin

4. Three mechanisms for the reaction O2(g) + 2 NO(g)  2 NO2(g) have been
proposed:

a. Mechanism A
Step 1: O2(g) + NO(g)  NO3(g) (fast, equilibrium)
Step 2: NO3(g) + NO(g)  NO2(g) + NO2(g) (slow)
b. Mechanism B
Step 1: NO(g) + NO(g)  N2O2(g) (slow)
Step 2: O2(g) + N2O2(g)  N2O4(g) (fast)
Step 3: N2O4(g)  NO2(g) + NO2(g) (fast)

Which mechanism agrees with the following initial rate data:

Experiment Initial [O2] Initial [NO] Initial Rate

number (mol/L) (mol/L) (M/s)
1 0.210 0.122 0.136
2 0.420 0.122 0.272
3 0.210 0.244 0.544

 Step 1: What is the rate law that matches up with the initial rate data given?

rate=k[O2][NO]2

 Step 2: What are the rate laws of the proposed mechanisms?

Mechanism A: ratea=ka[O2][NO2]2 because

[NO3 ]
rateslow=kslow[NO][NO3] and Kstep1=[O
2 ]∗[NO]
so [NO3] = Kstep1[O2][NO]
so ratea= ka[O2][NO]2 where ka= kslow* Kstep1)

Mechanism B: rateb = kb[NO]2

 Step 3: Which mechanism matches up with the experimental rate law?

The rate law for mechanism A and the experimental rate law match up. So,
mechanism A agrees with the initial rate data.

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014

 Department of Chemistry
Name:____________________
University of Texas at Austin

Going from rate laws to the integrated rate equations

5. The rate law for the reaction C4H9Cl + H2O  C4H9OH + HCl is rate = k[C4H9Cl].
a. What would the integrated rate equation look like for this reaction?

[C4H9Cl](t) = [C4H9Cl]0*e-kt

b. How would a plot of this equation look?

It would be an exponential decay graph similar to

c. How could you find k from the plot?

To find k, you would need to plot ln([C4H9Cl](t)) vs. t (time).

This will a straight line with the equation, ln([C4H9Cl](t)) = ln[C4H9Cl]0 – kt.
Thus, the slope = -k, so k = -slope.

6. The rate law for the reaction 2 NO2  2 NO + O2 is rate = k[NO2]2.

a. What would the integrated rate equation look like for this reaction?

1 1
= + kt
[NO2 ](t) [NO2 ]o

b. How would a plot of this equation look?

1 1
A plot of vs. t (time), would be a straight line with the equation, [NO =
[NO2 ](t) 2 ](t)
1
+ kt
[NO2 ]o

c. How could you find k from the plot?

With the above plot, slope = k, so k = slope.

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014

 Department of Chemistry
Name:____________________
University of Texas at Austin

Activation Energy

7. Given the data below for the reaction of the decomposition of iodoethane into
ethane and hydrogen iodide,

T (K) k (s-1)
660 7.2 * 10-4
680 2.2 * 10-3
720 1.7 * 10-2
760 0.11

a. Calculate the activation energy for the reaction.

These types of problems can be tackled in a two steps

 Step 1: Make an Arrhenius plot, lnk vs. 1/T

To make an Arrhenius plot, you need to enter this data into an excel
spreadsheet, have excel calculate lnk and 1/T, make a scatterplot of lnk vs.
1/T and finally have excel display the trendline and its equation.

Question 7: lnk vs. 1/T

0
0.0013 0.00135 0.0014 0.00145 0.0015 0.00155
-2
y = -25207x + 30.95
lnk

-4
R² = 1
-6
-8
1/T (1/K)

 Step 2: Calculate Ea using the slope of the line

You need the Arrhenius plot because it gives you the line which has the
𝐸 1
generic equation lnk=lnA−( 𝑅𝑎 ) (𝑇).
𝐸
So, the slope of the line in your plot is equal to − 𝑅𝑎. So, Ea = slope*(-R).
Thus, Ea = slope*(-R) = (-25207 K)(-8.314 J K-1 mol-1) = 2.1*105 J/mol =
2.1*102 kJ/mol.

b. What is the value of the rate constant at 400 °C?

400 °C = 673 K
𝐸 1 1
So, lnk=lnA−( 𝑅𝑎 ) (𝑇)= 30.95 -25207(673) = -6.5047
So, k = e-6.5047= 0.0015 = 1.5 *10-3 s-1

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014

 Department of Chemistry
Name:____________________
University of Texas at Austin

8. Given the data below for the reaction of the conversion of cyclopropane into
propene,

T (K) k (s-1)
750 1.8 * 10-4
800 2.7 * 10-3
850 3.0 * 10-2
900 0.26

a. Calculate the activation energy for the reaction.

 Step 1: Make an Arrhenius plot, lnk vs. 1/T

Question 8: lnk vs. 1/T

0
0.0011 0.00115 0.0012 0.00125 0.0013 0.00135
-2
y = -32734x + 35.013
-4
R² = 1
lnk

-6

-8

-10
1/T (1/K)

 Step 2: Calculate Ea using the slope of the line

Ea = slope*(-R) = (-32734 K)(-8.314 J K-1 mol-1) = 2.7*105 J/mol = 2.7*102

kJ/mol.

b. What is the value of the rate constant at 600 °C?

600 °C = 873 K
𝐸 1 1
So, lnk=lnA−( 𝑅𝑎 ) (𝑇)= 35.01 - 32734(873) = -2.4860
So, k = e-2.4860= 0.083 = 8.3 *10-2 s-1

Revised CR 1/16/14 © LaBrake & Vanden Bout 2014