DETERMINATION OF A RATE LAW

Objectives:
 To determine the rate law for a chemical reaction.
 To use a graphical analysis of the experimental data.

Introduction:
The rates of chemical reactions are affected by a number of factors. This particular experiment looks at the relationship between the
concentration of reactants and the rate. Consider the reaction A2 + 2B2 → 2AB2. The rate of this reaction is related to the
concentration of each reactant raised to some exponential power. The rate law for this reaction will be:

rate = k[A2]p[B2]q

The exponents p and q designate the order of the reaction with respect to each reactant and are always determined experimentally.
The rate constant, k, varies with temperature but is independent of the reactant concentrations.

In this experiment the rate law for the reaction of hydrogen peroxide, H2O2, with potassium iodide, KI, is determined. When these
reactants are mixed, H2O2 slowly oxidizes I− to elemental I2.

2I−(aq) + H2O2(aq) + 2H+(aq) → I2(aq) + 2H2O

The rate of the reaction can be expressed as: rate = k[I−]p[H2O2]q[H+]r.

When the [H+] is greater than 0.001 M, the reaction occurs too quickly to be measured in the general chemistry lab. However, if [H+]
is less than 0.001 M, the reaction goes proceeds at a measurable rate. In this experiment, we will use a buffer solution (a solution that
resists changes in acidity or basicity in the presence of added H+ or OH−) of sodium acetate, NaC2H3O3, and acetic acid, HC2H3O2, to
maintain a nearly constant [H+] of 1 x 10−5 M. Therefore, since the [H+] stays constant and has no bearing on the rate, the rate law
becomes:

rate = k[I−]p[H2O2]q

In doing the experiment, the first three trials vary the concentration of I− with H2O2 being constant. Thus, the first three trials will
determine the order for I−. The last three trials vary the concentration of H2O2 with I− being constant. Therefore, the order for H2O2
will be determined by the last three trials.

The Reaction Mechanism:

To follow the rate of the reaction, two solutions are prepared:

 Solution A: a solution of I−, starch, thiosulfate ion (S2O32−), and the acetic acid-sodium acetate buffer
 Solution B: H2O2

When solution A and B are mixed, the H2O2 reacts with I−:

equation 1: 2I−(aq) + H2O2(aq) + 2H+(aq) → I2(aq) + 2H2O

To prevent an equilibrium from being established in equation 1, the S2O32− is present to react with the I2 as it is being formed.

equation 2: 2S2O32−(aq) + I2(aq) → 2I−(aq) + S4O62−(aq)

As a result, I− is regenerated and maintains a constant concentration during the course of the reaction until all of the S2O32− is
consumed. When the S2O32− has completely reacted in the solution, the I2 then reacts with the starch to form a deep-blue I2•starch
complex.

equation 3: I2(aq) + starch → I2•starch

The time required for a quantitatively measured amount of S 2O32− to react is the time lapse for the appearance of the deep-blue
solution. This, in turn, measures the rate of I2 production (mol I2/time), which is affected only by the initial concentrations of H2O2 and
I−.
Determining the Order of Reactions:

For I−:

Since H2O2 is constant in the first three trials, any change in the rate of the reaction is due to the changes in [I−]. Therefore the rate
for these trials can be written as:

rate = k’[I−]p • c

c is a constant equal to [H2O2]q and k’ is another rate constant unique to this situation.

In logarithmic form, this rate law can be written as:

log(rate) = log k’ + p log[I−] + log c

Combining constants we get:

log(rate) = p log[I−] + log C

y = mx + b

Therefore a plot of log(rate) vs. log[I−] produces a straight line with the slope equal to p.

For H2O2:

Since I− is constant in the last three trials, any change in the rate of the reaction is due to the changes in [H2O2]. Thus, following the
same sort of logic as for I−, the logarithmic form of the rate law using H2O2 is:

log(rate) = q log[H2O2] + log C

y = mx + b

Thus a plot of the log(rate) vs. log[H2O2] also produces a straight line with a slope that is equal to q.
AP CHEMISTRY LAB REPORT NAME: _____________________________________
DETERMINATION OF A RATE LAW PER: ____

COMPOSITION OF TEST SOLUTIONS

SOLUTION A SOLUTION B
TRIALS
Distilled H2O Buffer 0.3 M KI Starch 0.02 M Na2S2O3 0.1 M H2O2
1 123 mL 25 mL 10 mL 2 mL 10 mL 30 mL
2 113 mL 25 mL 20 mL 2 mL 10 mL 30 mL
3 103 mL 25 mL 30 mL 2 mL 10 mL 30 mL
4 83 mL 25 mL 30 mL 2 mL 10 mL 50 mL
5 63 mL 25 mL 30 mL 2 mL 10 mL 70 mL

DATA TABLE
TRIALS 1 2 3 4 5
Solution Temp
(C)

Time for color

change, Δt (sec)

Mol S2O32ˉ
reacted

Mol I2 produced

Δ(mol I2) / Δt

log (Δ(mol I2) / Δt)

[I]i (mol/L)

log [I]i

[H2O2]i (mol/L)

log [H2O2]i

DETERMINATION OF THE REACTION ORDER, p AND q FOR EACH REACTANT

Using graphing calculators, determine the slope of the following lines. Then write the rate law for the reaction.

log (Δ(mol I2) / Δt) vs log [I]i = p = ___________________

log (Δ(mol I2) / Δt) vs log [H2O2]i = q = ___________________

RATE = ______________________________
 -2-

DETERMINATION OF k’, THE SPECIFIC RATE CONSTANT FOR THE REACTION

Determine the value of k’ for each of the trials. Show your work for trial 1 in the space below the table.

TRIAL 1 2 3 4 5

Value of k

Average value of k

Standard Deviation of k

POST LAB QUESTIONS:

1. State the effect that each of the following changes has on the reaction rate in this experiment. Assume no volume
change in any of the changes in concentrations.

a) an increase in the H2O2 concentration. Explain.

b) an increase in the KI concentration. Explain.

c) an increase in the Na2S2O3 concentration. Explain.

d) the substitution of 0.5% starch solution for one at 0.2%. Explain.

2. Two test reactions are the minimum required to obtain values of p and q in this experiment. How many data points
were used for each determination in the experiment? Explain the advantage that additional test reactions, as
performed in this experiment, have on determining p and q.

3. What would be the appearance of the solution if the Na 2S2O3 solution were omitted?

4. What would be the appearance of the solution if the starch were omitted in the experiment?