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.