CHM152LL LAB MANUAL DETERMINATION OF A RATE LAW

Determination of a Rate Law

INTRODUCTION
Reaction rate
The faster a chemical reaction occurs, the greater the measured reaction rate. The greater the
reaction rate, the faster the reactants convert into products. We can express rates as the change
per second in the concentration (or pressure) of any specified reactant or product.
Rate law
A rate law shows how the rate of a chemical reaction depends on the concentrations of reactants.
Rate laws for all reactions have the same general form, but the values of parameters will change
from reaction to reaction. For a general chemical reaction equation:
aA + bB + cC +… → … + xX + yY + zZ (1)
the rate law has the general form:
rate = k [A]p [B]q [C]r … (2)
where k represents the rate constant and p, q, and r represent the reaction rate orders with respect
to reactants A, B, and C. The square brackets denote the units of molar concentration
(moles/liter), as usual. (If reactants exist in the gas phase, we can use partial pressures in place of
concentrations.) In this experiment, you will perform your laboratory work in order to determine
the details of the rate law for a particular chemical reaction:
2 I–(aq) + H2O2 (aq) → I2 (aq) + 2 H2O (l) (in acidic soln) (3)
You must measure the reaction rate, and then calculate the values of the rate constant (k) and
orders (p & q) for the rate law:
rate = k [I–]p [H2O2]q (4)
Preparing for the experiment
Background reading
Read and thoroughly understand this section of the lab manual and the Kinetics chapter in the
lecture textbook.
Preparing the lab notebook
Write a brief outline of the planned lab procedure in your notebook. Include the hazardous
properties of all lab chemicals, both reactants and products. You may use the safety data sheets
(SDSs) in the lab binder, or search for the hazards on a website such as http://www.hazard.com.
Look for flammability, toxicity (including route of exposure, organs affected, LD50,
carcinogenicity, reproductive hazards, etc.), chemical incompatibility, and recommended first aid
and spill responses.
Leave space to record significant experimental details, such as the stock reagent concentrations
(taken from the stock-bottle labels), descriptions of the instruments used (e.g. pipettes,
thermometers, clocks), and the names of your coworkers. Prepare a table that will allow you to
record the required data:

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Table 1: Sample lab notebook data table

Burette Buffer KI Starch Na2S2O3 Water H 2O 2 temp. time
Trial # readings (mL) (mL) (mL) (mL) (mL) (mL) (°C) (sec)

final

1 initial

delivered

etc.

PROCEDURE
1. Hydrogen peroxide readily decomposes in the presence of organic material, so thoroughly clean
all glassware, and do not dry it with a lint-producing cloth or paper towel.
2. Prepare the two solutions for each reaction run as shown in Table 2, below. For each run,
Solution B will contain only hydrogen peroxide (H2O2), and solution A will contain potassium
iodide (KI, as a source of iodide), a buffer (to stabilize [H+]), starch (which acts as an indicator
for I2), and sodium thiosulfate (Na2S2O3, as a source of thiosulfate ion). Solution A will also
contain enough distilled water to bring the total volume of the reaction system up to 16.00 mL.
Measure all volumes with burettes or transfer pipettes, and record the actual volume
measurements in your notebook to a precision of 0.01 mL.
Table 2: Recommended composition of trial solutions
Trial # Solution A Solution B

Buffer 0.1 M KI Starch 0.02 M Na2S2O3 Distilled Water 0.3 M H2O2

1 2.00 mL 0.80 mL 1.00 mL 2.00 mL 7.80 mL 2.40 mL

2 2.00 mL 1.60 mL 1.00 mL 2.00 mL 7.00 mL 2.40 mL

3 2.00 mL 2.40 mL 1.00 mL 2.00 mL 6.20 mL 2.40 mL

4 2.00 mL 2.40 mL 1.00 mL 2.00 mL 4.60 mL 4.00 mL

5 2.00 mL 2.40 mL 1.00 mL 2.00 mL 3.00 mL 5.60 mL

3. For each run, prepare Solution A in a clean 50 mL Erlenmeyer flask. Add the prescribed volume
of each solution to the flask, and swirl the flask to mix thoroughly. Avoid agitating the solution,
as atmospheric O2 interferes with the reaction and confuses the results. Record the solution
temperature to 0.1°C precision. For each run, measure the prescribed volume of Solution B into a
beaker, then record the solution temperature. Use a separate thermometer for each solution. If the
temperatures of Solutions A and B deviate more than 0.5°C, check with your instructor. We
expect both solutions to start at room temperature.
4. One of the lab partners will time the reaction, and another partner will combine the two solutions
and briefly swirl them together, then watch for the appearance of the blue color. Measure the

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time elapsed between the mixing of the solutions and the appearance of the colored I2-starch
complex and record it to the nearest second.
5. The five trials in Table 2 allow you to measure only three points in the determination of p and
three points in the determination of q. Additional trials will give greater precision to your final
calculations, if time permits. Check with your instructor.
Measurement of reaction rate
You will measure the rate of reaction (3) by measuring the rate of production of I2. You will
accomplish this by making use of two additional side reactions in which molecular iodine will
participate. First, we use the iodine-starch reaction:
I2 + starch → I2·starch (colored complex) (5)
You may have used this reaction in biology lab to test for starch – we will use it to indicate the
presence of iodine. The gradual appearance of the colored complex in a starch solution (initially
colorless) signals the accumulation of iodine. It does not tell you how much iodine the reaction
produced. To determine the amount of iodine produced, you will use another reaction:
I2 + 2 S2O32– → 2 I– + S4O62– (6)
You perform this secondary reaction only to monitor the I2 production. Molecular iodine and
thiosulfate ion react rapidly to regenerate iodide ion and produce tetrathionate ion. You will
prepare the solutions for your test runs with the starch and a measured amount of thiosulfate
already present. Color will suddenly appear when, and only when, the entire measured amount of
thiosulfate has reacted. You will measure the time elapsed between the mixing of reactants and
the observation of the color. The stoichiometry of equation (6) shows that the amount of iodine
produced should equal half the amount of thiosulfate consumed in the same time. The amount of
thiosulfate consumed should equal the measured amount of thiosulfate initially added. Since you
will express the rate in terms of moles of iodine per liter per second (M/s), not in mol/s, the total
solution volume will also enter into your calculation.
DATA ANALYSIS
You will make a good estimate of the rate by using the approximation
d[I 2 ] Δ[I 2 ]
rate = ≈ , (7)
dt Δt
where ∆[I2] represents the calculated change in the amount of iodine divided by the calculated
total solution volume, and ∆t represents the measured elapsed time. You can make a good
estimate of the rate law by using the initial concentration values of iodide ion and hydrogen
peroxide in the mixture.
Graphical Determination of p and q
To determine the order with respect to iodide ion concentration (the constant p), you will vary
the starting concentration of iodide ion in a series of reaction runs, while holding the starting
concentrations of hydrogen peroxide and hydrogen ion fixed. Under these conditions, any
changes in the reaction rate from trial to trial must result from the changes in iodide

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concentration. Because we hold the concentration of H2O2 constant, we can further simplify the
rate law given by equation (4):
rate = k [I–]p [H2O2]q (4)
q q q
but [H2O2] stays constant, so k [H2O2] stays constant, too. Let k´ = k [H2O2] , so
rate = k´ [I–]p (8)
where k´ represents a pseudo-rate constant which includes the effects of the fixed concentrations.
You will use a graphical approach to determine the rate law parameters, which gives a simple
way to average out the experimental uncertainties of each trial measurement. The graphical
approach relies on the mathematical strategy of data linearization. If you can express the
expected relation between experimental variables in the form of the equation of a straight line,
you can plot a graph of the straight line. Data from real experiments rarely follow the ideal
relation, however. Plotting the straight line coming closest to the greatest number of data points
shows both the expected relationship and the deviation of the data from the ideal. In this
particular lab, you can linearize the data by making use of the properties of logarithms. Recall
the following:
If a and b represent any positive numbers, and n represents any number, then
log ab = log a + log b, (9)
n
log a = n log a. (10)
Taking the logarithm of both sides of equation (6) yields:
log rate = log k´ [I–]p. (11)
Applying equation (7) to equation (9) gives:
log rate = log k´ + log [I–]p. (12)
Using equation (8) in equation (10) gives:
log rate = log k´ + p log [I–]. (13)
We can rearrange equation (11) into the form of the equation of a straight line (i.e., the form y =
mx + b):
log rate = p log [I–] + log k´. (14)
So if you plot the logarithm of the rate against the logarithm of the iodide ion concentration, the
resulting graph should follow a straight line, with its slope equal to p and its y-intercept equal to
log k´.
In trials 3-5, you measured the rate as you held the iodide and hydrogen ion concentrations fixed
and varied the concentration of hydrogen peroxide. After linearizing the data in a way like that
shown above, you can plot
log rate = q log [H2O2] + log k´´ (15)
to determine the value of q.
To determine the value of k, substitute your measured or calculated values for the reaction rate,
reactant concentrations, and reaction orders into equation (4), then solve for k. Use the values
obtained for each of the five (or more) reaction runs and average them to get your best estimate

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for k. If the five values do not lie close to each other, consult your instructor. Report the values of
k, p, and q with their appropriate units and an estimate of the range of experimental uncertainty.
Curve fitting
The data points from real experiments only rarely will fall exactly on the line or curve that maps
the expected relationship. With real data, the experimenter needs to compromise and find the
simple curve that comes closest to passing through the actual data points. We call the process of
finding that curve (or line) curve fitting. A method of fitting data to a straight line called linear
least-squares fitting has the widest acceptance. Given the experimental data values, the linear
least-squares method begins with a set of estimates for the slope and intercept of the straight line,
then finds the difference between the estimated line and the actual experimental data, then
adjusts the estimated slope and intercept repeatedly until the sum of the squares of the
differences between the estimated line and the experimental data reaches a minimum.
Many computers and some calculators perform the curve fitting quickly. The final output of a
good linear least-squares program will give a set of three parameters: the slope of the line, the y-
intercept of the line, and the correlation coefficient. If the data points all fall exactly on the
calculated line, the correlation coefficient equals 1 exactly. If the points all fall very close to the
line, the correlation coefficient will come out slightly less than 1, such as 0.9999. For this rate
law experiment, we consider values less than 0.999 (called “3 nines”) to show not very good fit
between the calculated line and the experimental data.
Graphing software
This Department has graphing software available for student use; ask at the stockroom. Use the
”Graphical Analysis” program or any high-level spreadsheet (such as Microsoft Excel® or Apple
Numbers®) for plotting and fitting your experimental data. If you aren’t familiar with the
personal computer or one of these particular programs, your instructor or the stockroom staff
may help you get started. After you have entered your rate and concentration data, the program
can compute the logarithms, then plot the data and calculate a simple curve-fit line. The equation
of the calculated line will also appear, showing a slope, intercept and correlation coefficient. The
correlation coefficient, sometimes called R2, shows up on the computer screen as R^2 (read R to
the second power). You can print the plot, and include it in your report.
UNCERTAINTY ANALYSIS
Goodness of fit
The correlation coefficient serves as a “goodness of fit” parameter. If the value of R2 falls under
0.9, we consider the fit as not good. If you find R2 ≤ 0.9, try to imagine what might have caused
the deviation from the expected linear behavior.
Temperature fluctuations
Changes in the temperature of the reaction system will change the value of k. The Arrhenius
equation describes this dependence:
⎛ −E ⎞
k = Aexp⎜ a ⎟ (16)
⎝ RT ⎠

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Do the temperatures fluctuate enough from one trial run to the next to account for the variation in
your calculated values of the rate constant k?
Effect of changing reactant concentrations
Because the I2 + S2O32– reaction regenerates iodide, we hold the value of [I–] essentially fixed
during the entire course of the timed reaction. The buffer acts to hold the [H3O+] fixed. Thus
only [H2O2] can change during the timed reaction. We chose the compositions of the five
solutions for you so that [H2O2] changes very little over the course of each run. Calculate the
change in H2O2 concentration, and make a judgment as to its probable significance.
Uncertainty in stock concentrations
All reagent bottles will be labeled with concentrations given to three significant figures. This will
place a limit on the number of significant figures you can carry in your calculations. Take this
limit into account when you write the uncertainty analysis section of your report.

Be sure to check with your instructor and the lab schedule for the formal report due date.

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