EXPERIMENT 3

Chemical km'etics
Chemical kin'etics is' the study of reaction rates and reaction mecham'sms. The reaction rate is defm'ed
as the change in the concentration of the reactants or products as a function of time. The reaction mechanis'm is' a sequence of steps by which the overall change is' accomplished. For a hypothetical reaction

aA+bBch+dD

(1)

the reaction rate, r, can be m'dependently expressed 111' terms of the rate of disappearance of the reactants
or the rate of appearance of the products
1A[A]

1A[B] _ 1A[C]
r-_________
a At
b At
6 At

_ _1A[D]
d

At

(2)

The rate law expresses the reaction rate as a function of concentration at a particular temperature. The
rate law has the form:

r = kIAllBl"

(3)

where k 15' the rate constant charactens'tic of the reaction at a given temperature. The rate constant does
not change as the reaction proceeds, so long as the temperature is' held constant. The exponents x and y
are the reaction orders, also characteristic of the reaction, regardless of temperature. The overall reaction
order is the sum of the reaction orders found 1n' the rate law. All of "156 rate law parameters are experimentally determined.
The kin'etics of the reaction between persulfate, 31032 and iodide, 1 ions Will be studied
expenm'entally.
520.1 (aq) + 21' (aq) ~> 2503 (aq) + 12(aq)

(4)

The proposed rate law for tlus' reaction 15:

r = kl5202a llllv

(5)

In this' experiment, the method of initial rates is' used to determine the reaction orders a: and y. This'
method relies on deterrrumn"g how the rru'hal rate of reaction varies with a particular uutial reactant concentration, provided that all other reactant concentration's are held constant. Consider the kin'etic data in' Table
1.
E___________Table
3: Samle kin'etic data for method of uu"tial rates
[r]. .. [M
________mmal__mmL_Run
Initial rate, M/s [520821. .. [M
1

r;

0.04

0.02

2
3

r;
r3

0.04
008

0.01
0.02

Consider runs 1 and 2. Both runs wrll' have the same form of rate law, only different in the reaction rates
and reactant concentrations. Hence, takm'g the ratio of the rates:
r1 _ k(0.04)(0.02)

r2 ' k(_0.04)=(0.01)v

(6)

Note how the [$2032_]uu-~al, and the In terms will cancel out. Therefore.-

= log
y

104%)

(7)

Applym'g the method to runs 1 and 3 can be used to obtam' :.

Temperature, T also affects the rate of reaction, through the rate constant. Its effect is' explained' by the
collision theory. The collision theory postulates that the rate of reaction is proportional to the number ofe'ecfive collisro'ns between reactant species. Every reaction has an energy threshold that the collidmg molecules
must exceed in order to react. This mm1m"um collision energy is called the activation energy, Ea. The
Arrhenius equation describes the dependence of k on T:
E
1
lnk=-R
(T)+lnA

(8)

where R 15' the gas constant, 8.314 I K1 11101, and A is the Arrhenius constant. Note that Ed and A
are parameters characteristic of the reaction and its mechanism, independent of temperature and concentration. To obtam these parameters, rate constants are obtained at different temperatures. Then, In k is'
plotted as a lmear function of 1 /T. The resultm'g slope and intercept will give the desired parameters.
In this experiment, the rate of 1; formation will be measured to describe the rate of the reaction. The I;
formed from the origm'al reaction is reduced back to I by 82032 ions. When all the $203 ' is used up,
free 1; starts to form m solution. By measurm'g the tim'e taken for the known amount of 1; during that
time can be calculated.

CHEMICALS
Amount

Risk phrases

Ian35
Immmm:m

U1

l328

Chemical

APPARATUS

Alcohol thermometer

Hotplate

Safety phrases

PROCEDURE
Solution Preparatwn'

QWPPN?

Prepare the followm'g solutions by class:

5WD mL 0.2 M KI
5WD mL 0.2 M KC1
500.0 mL 0.1 M K2520;
5WD mL 0.1 M K2504
500.0 mL 4.0 mM N32 82 03 (from N82 5203 - 51120)
100.0 mL of 1% (w/v) fresh starch solution
Morsten 0.20 g of soluble starch with a small amount of H20 until" a smooth paste is' obtam'ed. Pour
slowly mm 20.0 mL of boiling water. The starch solution must be freshly prepared.
NOTE: Keep the solution at 90C100C to avoid starch solution from drymg up.
7. 50.0 mL 0.01 M 01504
Eect of Persulfatc and Iodide Concentrations on the Reaction Rate
NOTE: Runs 1-5 SHOULD be done one at a tlm'e. For each run, label two 50-mL beakers as "A" and "B."
1. Prepare the contents of beakers A and B accordin'g to the volumes presented m' the followrn'g table:

Table 3.1.

The diffe'rent runs for the effect of persulfate and iodide

concentrations on reaction rate.

Run,
1
2
3
4
5

Beaker A
0.2 M Kl
0.2 M KCl, ml.
10.0
0.0
5.0
5.0
2.5
7.5
5.0
5.0
5.0
5.0

Beaker B (+ 3 drops of fresh starch)

0.1 M K2520;
0.1 M K2504
4.0 mM Na25203
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
75
2.5
5.0
10.0
0.0
5.0

" Condition: room temperature

5 will be referred to as set 1 of run 2 (two more sets will be prepared tn' Part C)
2. Pour the contents of beaker A m'to beaker 8. Immediately start hmm"g the reaction. Stop the timer once the mrxture
turns blue. Measure the temperature of the reaction mixture.

Eject ofTemperature on the Reaction Rate

1. Prepare two more sets of "run 2" (referred to as sets 2 and 3).
2. In a water bath, heat beakers A and B of run 2 (set 2) at around 50C (40C-60C). Mix the contents of
beaker A and beaker B. Immedra'tely start timing the reaction unbl the mix'ture turns blue.

3. Cool beakers A and B of run 2 (set 3) m' an ice bath. Once the temperature has already reached aroun
5C (0C-10C), pour the contents of beaker A mto beaker B and start timing the reaction. Stop the
Ma after a blue solution is observed.

Eect ofCatalyst on the Reaction Rate

1. Prepare a fourth set of run 2.
2. Add 4 drops of 0.01 M CuSO4 1mm'ediately after the contents of beaker A as added to the contents of
beaker 8. Time the reaction until the reaction nuxture turns blue. Compare the reaction time with
set 1.
WASTE DISPOSAL

1. Dts'pose Cu(ll) solutions in inorganic waste jars.

2. All other solutions can be discarded in the sm'k along with copious runnm'g water.

10

DATA TREATMENT
Prepare the followm'g graphs:
1. 1n rate versus 1n[3308"] for runs 2,4, and 5 (constant [11) with the slope of the he equal to the rate
order of 8203
2. ln rate versus ln[l] for runs 1, 2, and 3 (constant [520821) with the slope of the lin'e equal to the rate

order of I
3. In R versns l/T for sets 1, 2, and 3 of mn 2 with the slope multiplied with R equal to the activation
energy
CALCULATIONS
Deterrrun'e the:
1. rate for each setup (M/s) by usmg the concentration of $2032 smce it acts as the lxm'itm'g reactant

2. rate law for reaction between I and 520:

3. activation energy and Arrhenius constant for the reaction

GUIDES FOR DISCUSSION

1. How did the followm'g affect the reaction rate? Explain'.
- Concentration of $2082"
0 Concentration of l
0 Temperature
0 Addition of CuSO4

2.
3.
4.
5.

What is the use of addm'g $2032 in" beaker B?

What caused the change in color of the reaction mixture from colorless to blue?
What is the signicance of the calculated activation energy and Arrhenius constant?
Which mechanism 15' consistent with your rate law? Defend your answer.
0 Proposed mechamsm 1-.
..
_ _mg-l .
2
I014) +I(aq) it 'noun

[1. . . I13) + 3203", ' 2014) + 250420..

0 Proposed mechanism 2:

1(n-q)+5,02

1H"

80) equilibrium

[1...520313(0")

_
_
_ _mgl I
2M, + 2303)
[1. . 3,0313, + 1) '

- Proposed mechanis'm 3:
_
2__n_w,al .
1(aq) + 32030) ~93]?

[I. . . Szoa](3.q_) + [ozq)

3
. 92081010

"" 1m, + 2.903;

0 Proposed mechanism 4:
2_
1 I,(M, + 250W,
2101"" ) + 320;) '

6. How do your results compare to previously done studies? If your results are signicantly different,
explam how the differences could have occurred.
11

Equation of Arrhonlul phi (m 1')

Activation snowy. E. (Id/moi)

L:jom"vulom2