THE DETERMINATION OF THE RATE EQUATION FOR A REACTION

The purpose of this exercise is to illustrate the calculations you will be doing when you
study the reaction of Hydrogen Peroxide and Iodide ion in the lab. In this exercise, the reaction
under consideration is between ammonium cation and nitrite anion as indicated in the following
equation reaction equation:
1+

1-

NH4 (aq) + NO2 (aq) N2(g) + 2 H2O(l)

Eqn. 1.

For purposes of this exercise, it is assumed that the rate law for the reaction above has the
form:
1+ a
1- b
Rate = k [NH4 ] [NO2 ]

A set of eight experiments was undertaken to determine:

a.
b.

the numerical value of the exponents a. and b. in the reaction equation (in other
words the order of the rate law, and
the numerical value of the rate constant, k.

In these experiments, the initial concentrations of ammonium cation and nitrite anion were
varied in a systematic fashion and the initial rate of the reaction was determined. The data
obtained from those experiments, taken from Chemistry: The Central Science by Brown,
LeMay and Bursten, Eighth Edition, is displayed in the follow table.
Rate for Date the Reaction of Ammonium cation and Nitrite anion in water at 25C
Experiment Number
1
2
3
4
5
6
7
8

1+

Initial NH4
Concentration (M)
0.0100
0.0200
0.0400
0.0600
0.200
0.200
0.200
0.200

1-

Initial NO2
Concentration (M)
0.200
0.200
0.200
0.200
0.0202
0.0404
0.0606
0.0808

Observed Initial Rate

(M/sec)
5.4 x 10-7
10.8 x 10-7
21.5 x 10-7
32.3 x 10-7
-7
10.8 x 10
21.6 x 10-7
32.4 x 10-7
43.3 x 10-7

The important thing to note about the data in the table is that it can be divided into two
subsets of data. In reactions 1 4, the concentration of nitrite anion is being held constant and
only the concentration of ammonium cation is being changed. That means that the dependence
of the rate of reaction on ammonium cation can be determined by analyzing the data for
reactions 1 - 4. Similarly, in reactions 5 8, the concentration of ammonium cation is being held
constant and only the concentration of nitrite anion is being changed. That means that the
dependence of the rate of reaction on nitrite anion can be determined by analyzing the data for
reactions 5 - 8.

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Principles of Chemistry II

Kinetics Pre-Laboratory Exercise

CALCULATIONS
Note1: Use Excel to complete all the calculations. All plots should be printed and submitted as
part of the pre-lab exercise. The template containing the calculations should be saved
under the name PRE_PEROX. Excel functions should be used to determine the slope and
the intercept of all linear plots.
Note2: The calculations can also be completed using a TI-graphing calculator. You should also
do the calculations using your calculator for two reasons. First, it is good practice for
using the calculator. Second, it is a good way to check the Excel calculations.
1.
2.

Construct a table of your results with the following headings:

1+
1Reaction Number
Initial [NH4 ]
Initial [NO2 ]

Construct another table of results by taking the log of the above quantities:
Reaction Number

3.

Rate of Reaction

1+

Log Initial [NH4 ]

1-

Log Initial [NO2 ]

Log Rate of Reaction

1+

Using Excel to plot Log Rate along the y-axis against Log [NH4 ] along the x-axis*. Use
Excel functions to calculate the slope and the intercept of this line. The slope of this line is
equal to the value of exponent "a" in the rate equation. Round the slope to the nearest
integer. The intercept is equal to Log Kapp. Using the relationships derived on the next
page, calculate a value for the rate constant k from Log Kapp. Use the data from reactions
1, 2, 3 and 4 for this plot.
Starting from a general statement of the rate law for this reaction:
Rate = k [NH41+]a[NO21-]b
For solutions 1, 2, 3 and 4, [NO21-] is constant
1-

b
Therefore: Let Kapp = k [NO2 ]

After substituting:

1+

Rate = Kapp [NH4 ]a

a

Take the logarithm of the equation: log Rate = log Kapp [NH41+]

1+ a
Separate the terms being multiplied: log Rate = log Kapp + log [NH4 ]

Remove the exponentiation: log Rate = a log [NH41+] + log Kapp

The general equation for a straight line is: y = mx + B

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Principles of Chemistry II

Defining:

Kinetics Pre-Laboratory Exercise

y = log Rate
m = a (slope)
x = log [NH41+]
B = log Kapp (intercept)

1+
Thus "a" and B can be determined by plotting log [NH4 ] on the x-axis vs. log Rate on the
y-axis for solutions 1, 2, 3, and 4. and drawing the best possible straight line through the
data. The exponent "a" is equal to the slope of the line, and log Kapp is the intercept. The
rate constant k can be calculated from Kapp by recalling the definition of that variable.

4.

Generate the same graph and complete the same linear regression calculations as in
questions 3 above using your graphing calculator.
a.
Enter the data from experiments 1 -4 for the initial concentration of ammonium cation
([NH41+]) into L1 and the data for the initial rate into L2.
b.
Take the log of contents of the L1 data vector and store it L3, and take the log of the
contents of the L2 data vector and store it in L4.
c.
Generate a graph of the data with L3 on the x-axis and L4 on the y-axis. Make sure
that a graph of the data vectors is turned on (STAT PLOT). Use STAT EDIT to view
the minimum and maximum values in the two data vectors. Use WINDOW to set the
minimum values to be graphed. Remember this graph is in the third quadrant, so it
might look a little strange!
d.
Use STAT CALC lin reg to calculate the slope and intercept of the best fit line
through this data.

5.

Using Excel plot Log Rate along the y-axis vs Log [NO21-] along the x-axis*. Use Excel
functions to calculate the slope and the intercept of this line. The slope of this line is equal
to the value of "b" in the rate equation. Round the slope to the nearest integer. The
intercept is equal to Log Kapp. Using relationships for Log Kapp similar to those derived
above for Log Kapp, calculate a value for the rate constant k from Log Kapp. Use the data
from reactions 5, 6, 7, and 8 for this plot.
A derivation similar to that done above may be performed for the determination of the
exponent "b". You should derive the relationships between k, Kapp and "b" for yourself.

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Principles of Chemistry II

Kinetics Pre-Laboratory Exercise

6.

Generate the same graph and complete the same linear regression calculations as in
questions 3 above using your graphing calculator.
a.
Enter the data from experiments 5 -8 for the initial concentration of nitrite anion
([NO21-]) into L1 and the data for the initial rate into L2.
b.
Take the log of contents of the L1 data vector and store it L3, and take the log of the
contents of the L2 data vector and store it in L4.
c.
Generate a graph of the data with L3 on the x-axis and L4 on the y-axis. Make sure
that a graph of the data vectors is turned on (STAT PLOT). Use STAT EDIT to view
the minimum and maximum values in the two data vectors. Use WINDOW to set the
minimum values to be graphed. Remember this graph is in the third quadrant, so it
might look a little strange!
d.
Use STAT CALC lin reg to calculate the slope and intercept of the best fit line
through this data.

7.

Using the values of "a" and "b" obtained above, the rate expression on the first page of the
experiment and your data from the table in step 1 above, calculate a value for the rate
constant k for each solution.

8.

Using the results of step 7, above calculate an average value for the rate constant k and
compare this value of k to the value of k obtained from the plots in steps 9 and 10 above.

9.

Write a completed expression for the rate of reaction for this reaction. For a value for k use
the average of the three determinations.

In these two graphs, the x-axis must start at zero; the y-axis does not need to start at zero.

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Principles of Chemistry II

Kinetics Pre-Laboratory Exercise

REPORT FORM
Rate of Reaction
1.

Table I:
Reaction Number
1
2
3
4
5
6
7
8

2.

Initial [NH41+]

Initial [NO21-]

Rate of Reaction

Log Initial [NH41+]

Log Initial [NO21-]

Log Rate of Reaction

Table II:
Reaction Number
1
2
3
4
5
6
7
8

3.

What is the slope of the line plotted in calculation steps 3 and 4. Round off to the nearest
integer. This is the value of exponent "a" in the rate equation.

4.

What is the slope of the line plotted in calculation steps 5 and 6. Round off to the nearest
integer. This is the value of exponent "b" in the rate equation,

5.

Calculate the value of the specific rate constant k from the y-intercept of the line plotted in
calculation steps 3 and 4. The value of the y-intercept equals Log Kapp. The relationship
between Kapp and k was derived earlier.

6.

Calculate the value of the specific rate constant k from the y-intercept of the line plotted in
calculation steps 5 and 6. The value of the y-intercept equals Log Kapp. The relationship
between Kapp and k was derived earlier.

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Principles of Chemistry II

Kinetics Pre-Laboratory Exercise

7.

Calculate an average value for the specific rate constant k from the 8 different values
calculated in calculation step 12.

8.

Calculate an average value of the specific rate constant k using the values calculated in
steps 5, 6, and 7 of this report.

9.

Write the complete rate of reaction expression for this reaction.

Page 6