Chemical Kinetics Lab:

The formaldehyde clock

reaction

Summer Math Institute 2012

Amber M. Hupp
Assistant Professor, Chemistry
College of the Holy Cross

Modified from P.W.W. Hunter, Chemistry Laboratory Manual (CHEM 162), Michigan State University
 Thermodynamics or
Kinetics?
Thermodynamics if a reaction occurs
Kinetics how fast the reaction occurs
and route the reaction takes
Examples :
how fast unwanted chemical substances
break down (environmental)
how long before chemicals like drugs
metabolize in the body(biological)
how fast will this fuel ignite to run my car
(energy!)
 Reaction Mechanisms

Tells us how the reaction proceeds

Chemical reactions occur through a
series of steps (intermediate reactions)
Some steps are fast, some slow
Slowest step in mechanism determines
rate
Cant go any faster than slowest step!
 Clock Reactions

A visible change occurs when a certain

point in the reaction is reached
(typically the end point)

Time is inversely proportional to rate

The longer a reaction takes, the slower the
rate must be
Something we can measure in the lab!
 Clock Reaction
Demonstration
This is a complicated clock reaction
called the Briggs-Rauscher Reaction

Goes through 10 to 15 cycles

Chemical oscillator is due to changes in
iodine and iodide ion concentrations in
solution (several chemical equations)

B.Z. Shakhashiri, Chemical Demonstrations: A handbook for Teachers of Chemistry, V2, 1983, p248
 Formaldehyde-Bisulfite
Reaction
A simpler example of a clock reaction

Step 1:
HSO3- + H2O SO32- + H3O+ Fast
Step 2:
H2O + HCHO + SO32- CH2(OH)SO3- + OH- Slow

Produce OH- (basic!) Can use pH indicator

phenolphthalein
Colorless to pink at certain pH
Modified from P.W.W. Hunter, Chemistry Laboratory Manual (CHEM 162), Michigan State University
B.Z. Shakhashiri, Chemical Demonstrations: A handbook for Teachers of Chemistry, V4, 1983, p70
 Rate of F-BS reaction

Rates depend on initial concentrations

of reactants
A change in either one will affect
reaction rate
Rate = k [formaldehyde]a [bisulfate-
sulfite]b

The order of each reactant (a & b) add

to give the overall reaction order
 Orders of Reactions what
do they mean?
For the general reaction X Z
Say a reaction is first order in X
Then as the concentration of X doubles,
the rate also doubles

Say a reaction is second order in X

Then as the concentration of X doubles,
the rate quadruples

Shows concentration dependence on rate

 How to calculate the order
of the reaction?
Rate = k [formaldehyde]a [bisulfate-sulfite]b
Hard to understand what to change and what
to hold constant so lets rearrange by taking
log of both sides
log(rate) = log(k) + a log[formaldehyde] + b log[bisulfate-sulfite]

If the concentration of F is held constant, then

(a log[F] ) is constant and we can plot log(rate)
vs (b log[BS]) to get order with respect to BS
 Experimental Set-up
The concentrations of each reactant will be varied, while holding the other
reactant constant. The time for each reaction to go to completion (in
seconds), via a color change of phenolphthalein, will be recorded in the table.

Reaction
Trial [F] (mL) [BS-S] (mL) Rate (1/s)
Time (s)
1 5 2.5 31.6
2 5 5 31.2
3 5 10 31.7
4 5 15 31.9
5 5 5 15.8
6 10 5 7.9
7 15 5 5.0
8 20 5 3.5
T. Cassen, J. Chem. Ed. 53(3), 1976, pg 197
Experimental Results
Reaction
Trial [BS-S] (mL) log[BS-S] log(rate)
Rate (1/s)
1 2.5 0.399 0.03165 -1.499
2 5 0.698 0.03205 -1.494
3 10 1.0 0.0315 -1.500
4 15 1.17 0.03135 -1.500

Reaction
Trial [F] (mL) log[F] log(rate)
Rate (1/s)
5 5 0.698 0.0632 -1.19
6 10 1.0 0.1265 -0.897
7 15 1.17 0.200 -0.699
8 20 1.30 0.285 -0.544
 Graphs
0

-0.4

Log (rate) -0.8

-1.2

-1.6
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
Log[BS]
 Graphs
0

-0.4

f(x) = 1.07x - 1.95

Log (rate) -0.8

-1.2

-1.6
0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
Log[F]
 Conclusions
Reactant Slope of line Order
F 1 1
BS-S 0 0
Overall
1
reaction order:

Order of overall reaction is one.

Reaction depends directly on

concentration of formaldehyde, but does
not depend on bisulfite
B.Z. Shakhashiri, Chemical Demonstrations: A handbook for Teachers of Chemistry, V4, 1983, p70
 Points of interest

Dependent vs independent variables

Calculation of slope
Using log function to simplify
expression
Significant figures/digits
Fluctuation in measurement/results
Can perform experiment if desired and
use discovery style