Rates of Chemical Reactions II.

The Iodination of Acetone

The rate at which a chemical reaction occurs depends on several factors: the nature of the
reaction, the concentrations of the reactants, the temperature, and the presence of possible
catalysts. All of these factors can markedly influence the observed rate of reaction. Some
reactions at a given temperature are very slow indeed; the oxidation of gaseous hydrogen or wood
at room temperature would not proceed appreciably in a century. Other reactions are essentially
instantaneous; the precipitation of silver chloride when solutions containing silver ions and
chloride ions are mixed and the formation of water when acidic and basic solutions are mixed are
examples of extremely rapid reactions. In this experiment we will study a reaction that, in the
vicinity of room temperature, proceeds at a moderate, relatively easily measured rate. For a given
reaction, the rate typically increases with an increase in the concentration of any reactant. The
relation between rate and concentration is a remarkably simple one in many cases, and for the
reaction
aA + bB  cC
the reate can usually be expressed by the equation
rate = k[A]m[B]n (1)
where m and n are generally, but not always, integers, 0, 1, 2, or possibly 3; [A] and [B] are the
concentrations of A and B (ordinarily in moles per liter); and k is a constant, called the rate
constant of the reaction, which makes the relation (and units) quantitatively correct. The numbers
m and n are called the orders of the reaction with respect to A and B. If n is 1, the reaction is said
to be first order with respect to the reactant A. If n is 2, the reaction is second order with respect
to reactant B. The overall order is the sum of m and n. In this example the reaction would be
third order overall.
The rate of a reaction is also significantly dependent on the temperature at which the
reaction occurs. An increase in temperature increases the rate, an often-cited rule being that a
10°C rise in temperature will double the rate. This rule is only approximately correct;
nevertheless, it is clear that a rise of temperature of say 100°C could change the rate of a reaction
appreciably.
As with the concentration, there is a quantitative relation between reaction rate and
temperature, but here the relation is somewhat more complicated. This relation is based on the
idea that to react, the reactant species must have a certain minimum amount of energy present at
the time the reactants collide in the reaction step; this amount of energy, which is typically
furnished by the kinetic energy of motion of the species present, is called the activation energy for
the reaction. The equation relating the rate constant k to the absolute temperature T and the
activation energy Ea is
 Ea
log10  k    constant (2)
2.30 RT
where R is the gas constant (8.314 J/mole·K for E, in J per mole). By measuring k at different
temperatures we can determine graphically the activation energy for a reaction. In this experiment
we will study the kinetics of the reaction between iodine and acetone:

Chemistry 153 3­1
 O O
H3C CH3 H3C CH2I
(aq) + I2 (aq)  (aq) + H+ (aq) + I- (aq)
The rate of this reaction is found to depend on the concentration of hydrogen ion in the solution
as well as presumably on the concentrations of the two reactants. By Equation 1, the rate law for
this reaction is
rate = k[acetone]m[I2]n[H+]p (3)
where m, n, and p are the orders of the reaction with respect to acetone, iodine, and hydrogen ion,
respectively, and k is the rate constant for the reaction.
The rate of this reaction can be expressed as the (small) change in the concentration of I 2,
[I2], that occurs, divided by the time interval t required for the change:
rate = -[I2]/ t (4)
The minus sign is to make the rate positive [I2] is negative). Ordinarily, since rate varies as the
concentrations of the reactants according to Equation 3, in a rate study it would be necessary to
measure, directly or indirectly, the concentration of each reactant as a function of time; the rate
would typically vary markedly with time, decreasing to very low values as the concentration of at
least one reactant becomes very low. This makes reaction rate studies relatively difficult to carry
out and introduces mathematical complexities that are difficult for beginning students to
understand.
The iodination of acetone is a rather atypical reaction, in that it can be easily investigated
experimentally. First of all, iodine has color, so that one can readily follow changes in iodine
concentration visually. A second and very important characteristic of this reaction is that it turns
out to be zero order in [I2]. This means (see Equation 3) that the rate of the reaction does not
depend on [I2] at all; [I2]0 = 1, no matter what the value of [I 2] is, as long as it is not itself zero.
Because the rate of the reaction does not depend on [I2], we can study the rate by simply
making I2, the limiting reagent present in a large excess of acetone and HI ion. We then measure
the time required for a known initial concentration of I2, to be used up completely. If both
acetone and H+ are present at much higher concentrations than that of I2, their concentrations will
not change appreciably during the course of the reaction, and the rate will remain, by Equation 3,
effectively constant until all the iodine is gone, at which time the reaction will stop. Under such
circumstances, if it takes t seconds for the color of a solution having an initial concentration of I2,
equal to [I2], to disappear, the rate of the reaction, by Equation 4, would be
rate = -[I2]/t = - [I2]0/t (5)
Although the rate of the reaction is constant during its course under the conditions we have set
up, we can vary it by changing the initial concentrations of acetone and H+ ion. If, for example,
we should double the initial concentration of acetone over that in Mixture 1, keeping [H+] and [I2]
at the same values they had previously, then the rate of Mixture 2 would, according to Equation
3, be different from that in Mixture 1:
rate 2 = k(2A)m[I2]n[H+]p (6a)
m n + p
rate 1 = k(A) [I2] [H ] (6a)

Chemistry 153 3­2
Dividing the first equation by the second, we see that the k's cancel, as do the terms in the iodine
and hydrogen ion concentrations, since they have the same values in both reactions, and we obtain
simply
rate 2  2 A
m m
 2A
   2
m
(6)
rate 1  A m
 A 
Having measured both rate 2 and rate 1 by Equation 5, we can find their ratio, which must be
equal to 2m. We can then solve for m either by inspection or using logarithms and so find the
order of the reaction with respect to acetone.
By a similar procedure we can measure the order of the reaction with respect to H + ion
concentration and also confirm the fact that the reaction is zero order with respect to I2, Having
found the order with respect to each reactant, we can then evaluate k, the rate constant for the
reaction.
The determination of the orders m and p, the confirmation of the fact that n, the order
with respect to I2, equals zero, and the evaluation of the rate constant k for the reaction at room
temperature comprise your assignment in this experiment. You will be furnished with standard
solutions of acetone, iodine, and hydrogen ion, and with the composition of one solution that will
give a reasonable rate. The rest of the planning and the execution of the experiment will be your
responsibility.

Experimental Procedure
Select two regular test tubes; when filled with distilled water, they should appear to have
identical color when you view them down the tubes against a white background.
Draw 50 mL of each of the following solutions into clean, dry, 100-mL beakers, one
solution to a beaker: 4 M acetone, 1 M HC1, and 0.005 M I2. Cover each beaker with a watch
glass.
With your graduated cylinder, measure out 10.0 mL of the 4 M acetone solution and pour
it into a clean 125-mL Erlenmeyer flask. Then measure out 10.0 mL 1 M HCl and add that to the
acetone in the flask. Add 20.0 mL distilled H2O to the flask. Drain the graduated cylinder,
shaking out any excess water, and then use the cylinder to measure out 10. 0 mL of the 0.005 M
I2 solution. Be careful not to spill the iodine solution on your hands or clothes.
Noting the time on your wristwatch or the wall clock to 1 second, pour the iodine solution
into the Erlenmeyer flask and quickly swirl the flask to mix the reagents thoroughly. The reaction
mixture will appear yellow because of the presence of the iodine, and the color will fade slowly as
the iodine reacts with the acetone. Fill one of the test tubes 3/4 full with the reaction mixture, and
fill the other test tube to the same depth with distilled water. Look down the test tubes toward a
well-lit piece of white paper, and note the time the color of the iodine just disappears. Measure
the temperature of the mixture in the test tube.
Repeat the experiment, using as a reference the reacted solution instead of distilled water.
The amount of time required in the two runs should agree within about 20 seconds.
The rate of the reaction equals the initial concentration of 1, in the reaction mixture
divided by the elapsed time. Since the reaction is zero order in I, and since both acetone and H +

Chemistry 153 3­3
ion are present in great excess, the rate is constant throughout the reaction and the concentrations
of both acetone and H+ remain essentially at their initial values in the reaction mixture.
Having found the reaction rate for one composition of the system, it might be well to think
for a moment about what changes in composition you might make to decrease the time and hence
increase the rate of reaction. In particular, how could you change the composition in such a way
as to allow you to determine how the rate depends upon acetone concentration? If it is not clear
how to proceed, reread the discussion preceding Equation 6. In your new mixture you should
keep the total volume at 50 mL, and be sure that the concentrations of H+ and I2, are the same as
in the first experiment. Carry out the reaction twice with your new mixture; the times should not
differ by more than about 15 seconds. The temperature should be kept within about a degree of
that in the initial run. Calculate the rate of the reaction. Compare it with that for the first
mixture, and then calculate the order of the reaction with respect to acetone, using a relation
similar to Equation 6. First, write an equation like 6a for the second reaction mixture, substituting
in the values for the rate as obtained by Equation 5 and the initial concentration of acetone, I, and
HI in the reaction mixture. Then write an equation like 6b for the first reaction mixture, using the
observed rate and the initial concentrations in that mixture. Obtain an equation like 6 by dividing
Equation 6a by Equation 6b. Solve Equation 6 for the order m of the reaction with respect to
acetone.
Again change the composition of the reaction mixture so that this time a measurement of
the reaction will give you information about the order of the reaction with respect to H+. Repeat
the experiment with this mixture to establish the time of reaction to within 15 seconds, again
making sure that the temperature is within about a degree of that observed previously. From the
rate you determine for this mixture find p, the order of the reaction with respect to H+.
Finally, change the reaction mixture composition in such a way as to allow you to show
that the order of the reaction with respect to I2, is zero. Measure the rate of the reaction twice,
and calculate n, the order with respect to I2.
Having found the order of the reaction for each species on which the rate depends,
evaluate k, the rate constant for the reaction, from the rate and concentration data in each of the
mixtures you studied. If the temperatures at which the reactions were run are all equal to within a
degree or two, k should be about the same for each mixture.

Computer Option
If a solution is yellow, it is absorbing some of the blue light that is passing through it. You
could configure the colorimeter on the Vernier system to measure this absorbance vs. time. This
technique may assist you in your next experiment (Kinetics III). Decide on an absorbance value
for the time when the reaction is essentially complete – use this time point for Reaction Time.

Disposal of Reaction Products.

The reagents used in this experiment are nonpolluting and may be discarded down the sink drain.

Data and Calculations

A. REACTION RATE DATA

Chemistry 153 3­4
 Volume (mL) Reaction Time (sec)
Mixture Temp. (°C)
4.0 M Acetone 1.0 M 0.0050 M I2 H2O st
1 Run 2nd Run
HCl
I. 10 10 10 20
II.
III.
IV.

B. DETERMINATION OF REACTION ORDERS WITH

RESPECT TO ACETONE, H+ ION, AND I2 I2

rate = k[acetone]m[I2]n[H+]p (3)

Calculate the initial concentrations of acetone, H' ion, and I2 in each of the mixtures you studied.
Use Equation 5 to find the rate of each reaction.

Mixture [Acetone] [H+] [I2]0 Rate = [I2]0/avg. time

(M) (M) (M) (M/s)
I. 0.80 0.20 0.0010
II.
III.
IV.

Substituting the initial concentrations and the rate from the table above, write Equation 3 as it
would apply to Reaction Mixture II:

Rate II =

Now write Equation 3 for Reaction Mixture I, substituting concentrations and the calculated rate
from the table:

Rate I =

Divide the equation for Mixture II by the equation for Mixture I; the resulting equation should
have the ratio of Rate II to Rate I on the left side, and a ratio of acetone concentrations raised to
the power m on the right, It should be similar in appearance to Equation 6. Put the resulting
equation below:

Chemistry 153 3­5
 (Rate II) / (Rate I) =

The only unknown in the equation is m. Solve for m. m = __________

Now write Equation 3 as it would apply to Reaction Mixture III and as it would apply to
Reaction Mixture IV:

Rate III =
Rate IV =

Using the ratios of the rates of Mixtures III and IV to those of Mixtures 11 or 1, find the orders of
the reaction with respect to HI ion and I2:

(Rate III)/(Rate ___) = p = __________

(Rate IV) /(Rate ___) = n = __________

C. DETERMINATION OF THE RATE CONSTANT K

Given the values of m, p, and n as determined in Part B, calculate the rate constant k for each
mixture by simply substituting those orders, the initial concentrations, and the observed rate from
the table into Equation 3.

Mixture I II III IV Average

k

Chemistry 153 3­6
Prelab Assignment: The lodination of Acetone

1. In a reaction involving the iodination of acetone, the following volumes were used to make up
the reaction mixture:

10 mL 4.0 M acetone + 10 mL 1.0 M HCl + 10 mL 0.0050 M I 2, + 20 mL H20

a. How many moles of acetone were in the reaction mixture? Recall that, for a component A,
no. moles A = MA  V, where M, is the molarity of A and V is the volume in liters of the solution
of A that was used.

__________ moles acetone

b. What was the molarity of acetone in the reaction mixture? The volume of the mixture was 50
mL, 0.050 L, and the number of moles of acetone was found in Part a. Again,

MA = (no. moles A) / (V of soln. in liters)

__________ M acetone

c. How could you double the molarity of the acetone in the reaction mixture, keeping the total
volume at 50 mL and keeping the same concentrations of H+ ion and I2 as in the original mixture?

(continued on next page)

Chemistry 153 3­7
2. Using the reaction mixture in Problem 1, a student found that it took 250 seconds for the color
of the I2, to disappear.

a. What was the rate of the reaction? Hint: First find the initial concentration of I 2 in the reaction
mixture, [I2]. Then use Equation 5.

rate = __________

b. Given the rate from Part a, and the initial concentrations of acetone, H+ ion, and I2, in the re-
action mixture, write Equation 3 as it would apply to the mixture.

rate =

c. What are the unknowns that remain in the equation in Part b?

__________ __________ __________ __________

3. A second reaction mixture was made up in the following way:

20 mL 4.0 M acetone + 10 mL 1.0 M HCl + 10 mL 0.0050 M I 2 + 10 mL H,O

a. What were the initial concentrations of acetone, H+ ion, and I2, in the reaction mixture?

[acetone] __________ M; [H+] __________; [I2] __________ M

(continued on next page)

b. It took 120 seconds for the I2 color to disappear from the reaction mixture when it occurred at
the same temperature as the reaction in Problem 2. What was the rate of the reaction?

Chemistry 153 3­8
 rate __________ units __________

Write Equation 3 as it would apply to the second reaction mixture:

rate =

c. Divide the equation in Part b by the equation in Problem 2b. The resulting equation should
have the ratio of the two rates on the left side and a ratio of acetone concentrations raised to the
m power on the right. Write the resulting equation and solve for the value of m, the order of the
reaction with respect to acetone. (Round off the value of m to the nearest integer.)

m = __________

4. A third reaction mixture was made up in the following way:

20 mL 4.0 M acetone + 10 mL 1.0 M HCl + 20 mL 0.0050 M I 2,

If the reaction is zero order in I2, how long would it take for the I2, color to disappear at the tem-
perature of the reaction mixture in Problem 3?

__________ seconds

Chemistry 153 3­9