Exp.

17 – video (time: 36:06 minutes)

Exp. 17: Kinetics: Determination of the

order of a reaction

Chemical Kinetics – is the study of rates of

chemical reactions. The rate of a chemical
reaction describes how fast a reaction proceeds.

(basically: how quickly are reactants consumed

and products produced)
Exp 17 experiment:

I-
2 H2O2 (aq)  2H2O (l) + O2 (g)

Decomposition of hydrogen peroxide catalyzed by

iodide ion

General expression for this reaction (rate law):

Rate = k [H2O2]x [I-]y

Rate = k [H2O2]x [I-]y

Note: brackets typically refers to concentration in M.

k is the specific rate constant and is related to a particular

rxn and temperature

x and y are referred to as the order of the reactant; it

describes how the reactant concentration affects the rate of
the reaction. Values are typically a positive integer but not
always.

orders determined experimentally not by stoichiometry of

balanced equation
1) A + A  A2 elementary (slow)
2) A2 + B  C elementary (fast)
2A + B  C molecular
Order of a reactant is determined by the effect changing the
reactant conc has on rate

Change conc of reactant = 0 order (must be present)

and rate remains same
20 x rate = rate
30 x rate = rate

Change conc of reactant = 1st order (linear)

and rate changes same 21 x rate = 2rate
31 x rate = 3rate

Change conc of reactant = 2nd order (square)

and rate changes to the sq
of change 22 x rate = 4rate
32 x rate = 9rate
3rd order? 23 x rate = 8 rate

Overall order of reaction equals the sum of all the

orders.
x + y + … = overall order

How do we determine the order? Collect data

carefully with a well designed experiment
Ex. A + B  P rate = k [A]x [B]y

[A] [B] rate

Exp 1 1M 1M 1M/s Two ways:
1.) inspection
Exp 2 1M 2M 2M/s

Exp 3 2M 1M 8M/s

Compare exp1/exp2, [B] doubles and rate doubles, linear effect

y= 1: 1st order

Compare exp1/exp3, [A] doubles and rate is eight-fold; cube effect

x= 3: 3rd order

Rate = k [A]3 [B]

Ex. A + B  P rate = k [A]x [B]y

[A] [B] rate

Exp 1 1M 1M 1M/s
Exp 2 1M 2M 2M/s 2.) initial rate method
Exp 3 2M 1M 8M/s

Find x:
exp3 rate3 = k[A3] x [B3] y
exp1 rate1 = k[A1] x [B1] y

8M/s = k[2M] x [1M] y

1M/s = k[1M] x [1M] y

8 = 2x
log 8 = log 2x = x log 2

x = log 8 = 3
log 2
Solving for k; we will use exp 3 data, but you can use any set

rate3 = k[A3] x [B3] y

8M/s = k[2M] 3 [1M]

8 M/s =k
(2M)3(1M)

8 M/s =k
(8M3)(1M) M: 1 – 3 – 1 = – 3
M0.25 = M-1.10
M 0.50 M 0.85
1 /s =k
M3 M: 0.25 – 0.50 – 0.85 = – 1.10

k = 1 M-3 s-1

rate = 1 M-3 s-1 [A]3 [B] overall order = 3 + 1 = 4th

In experiment 17, rate of H2O2 decomposed will be
determined by plotting volume of O2 gas generated vs. time.
Y axis X axis
We will do 3 different experiments but only once each

KI, mL H2O, mL H2O2, mL rate, mL/min

Exp 1 10.00 15.00 5.00 slope1

Exp 2 20.00 5.00 5.00 slope2

Exp 3 10.00 10.00 10.00 slope3

Note: each group only needs 50 mL of KI and H2O2 will be

given out by the TA as needed.
Pg 117 describes how the experiment will be conducted

Important points:
- levels of buret and drying tube must be equal for readings
- you can dump excess water out
- make sure all air bubbles are out
- check for leaks
- Add H2O2 just before you are ready for exp to begin
-wait 1 – 2 mL before call time “0 min”
note: we are following the change in volume over a
particular change in time; therefore, it doesn’t matter when
call time zero.
 Plot cumulative volume, mL vs time, min

time, vol reading Cumulative vol.,

min mL mL
0.00 2.00 0.00
1.00 4.10 2.10
2.00 6.15 4.15
3.00 8.30 6.30
4.00 10.45 8.45
5.00 12.30 10.30
Graphing:
-Must have a descriptive title
-Label both axis with units
-Large graph over majority of page, select axis increments
which allows for this
Graph 30 blocks available on x axis and 5 minutes of data:

5 min = 0.16 min  0.20 min

30 blocks block block

-Legend explaining data

-Best line, not connecting the dots, and do not force
through zero
Slope of each line gives the rate for that experiment.

Slope= rise = y = mL = y2-y1 = rate mL

run x time x2 – x1 min

Note: pick points on best line, not data points

In this experiment, we are using volume instead of

concentration in our rate unit. Notice in the experiment that
the total volume is held constant to 30 mL in every
experiment (volume of water changes to assure this).

This means that because the way the experiment is

designed that the original conc. of KI / H2O2 and total
volume cancel out leaving the volume of solution the only
variable.
Conc of KI in experiment 1

(0.100 M KI) (10.00 mL) = conc KI1

30.00 mL

Conc of KI in experiment 2

(0.100 M KI) (20.00 mL) = conc KI2

30.00 mL

When compare exp 1 what happens? KI2 = 2 x KI1

because of vol
exp 2

Therefore, in this experiment mL α conc and the slope

of the line equals the rate
Overall goal of experiment is to report the rate law
expression for the decomposition of H2O2 :

Rate = k (H2O2, mL)x (I-, mL)y

Must give k with units, x, y, and overall order