A2 Chapter 6

Kinetics II

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 Experimental methods for measuring
the rate of reaction
• 1) Titration
• 2) Colorimetry
• 3) Change of mass of reaction mixture
• 4)Volume of gas evolved
• 5) Infrared spectroscopy
• 6) Electrical conductivity

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 Example
Titration method

(1) Mix the reactants and start a clock

(2) In every 5 minutes, remove 10 cm3 of the solution which is
quenched by cold sodium hydrogencarbonate solution
(3) Titrate the iodine present with standard sodium thiosulfate solution,
adding starch when the iodine colour has faded to a straw colour
(4) Record the burette reading once the blue-black colour has vanished
(5) Repeat the experiment
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 Example
Titration method

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 Rate equations (P157-158)

k = rate constant

Caution: rate order can never be determined by the chemical

equation. It can only be determined by carrying out the
experiment.
Example:
CH3COCH3 (aq) + I2 (aq) →CH2ICOCH3 (aq) + H+ (aq) + I- (aq)
Rate = k 【CH3COCH3】 【H+】
What does it imply? 5
 Determine the unit of k (P170)
Sometimes, it is necessary to deduce the unit of rate constant k:
For example, if rate = k 【A】
The overall order = 1

How about if rate = k 【A】 × 【B】 × 【C】?

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 Deduction of order of reaction
• Consider a reaction:
• A+ B+ C → product
• The initial rate is measured when all three reactants have
the same concentration
• Change the concentration of A (Others keep constant)
• If the rate does not alter, the reaction is zero order with
respect to A
• If the rate doubles, it is first order with respect to A
• If the rate increases by a factor of 4, it is second order with
respect to A.
• Repeat the experiment by alter the concentration of B and
C respectively.

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 Initial rate
• Measure the time t, for a certain amount of
the mixture to react.
• Then assume that 1/ t is a measure of the
rate.

• This assumption is only valid if the

concentration of the reactant falls by no more
than 10% during the time of the experiment.

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 Initial rate
Carry out the experiment
with different concentration.

At the very beginning, the slope is constant.

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 Initial rate

Plot a graph of 1/t against the concentration

http://www.chemguide.co.uk/physical/basicra
tes/experimental.html 10
Worked example (P169)

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 Half-life 半衰期
Worked example (P163)

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 Half-life 半衰期

• The time taken for half of a reactant to be

used up during a reaction process.

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 Half-life and radioactive decay
• Radioactive decay is a first order reaction
• The half-life is constant.
• Many radioactive elements have very long
half-lives:
• Examples: 14C (5730 years)
239
• Pu (24000 years)
• N =No e-kt

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 Example
• After 500 years, a sample of radium-226 has
decayed to 80.4% of its original mass. Find the
half-life of radium-226.

http://math.usask.ca/emr/examples/expdeceg.html 15
Carbon-14 dating

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Typical curves for different orders of reaction

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Features of different orders of reaction

Concentration VS time Rate VS concentration

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 Clock reaction
Iodine clock reaction (P162)

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 Iodine clock reaction
Determining the rate order

The order with respect to one reactant (e.g. H2O2)

can be determined by using a large excess of the other
reactants (I- and H+) so that their concentrations
remain effectively constant throughout the reaction.

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 Clock reaction
Sulfur clock reaction (P163)

• Measure the time taken for sufficient sulfur to be

produced to hide the X when looking down
through the beaker
• Vary the concentration of S2O32- but keep the total
volume constant

• http://www.youtube.com/watch?v=CH8gH7xKCx
Q

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 Altering the order by the method of
excess reagent (P178)

If 【B】is much higher than 【A】，

the change in 【B】during the reaction will
be negligible.

Determine the rate order with respect to A

by using the initial rate method. 22
 Arrhenius equation
Relationship between
rate constant and activation energy (P179)

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Determine the activation energy
by Arrhenius equation

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Worked example P179

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 Worked example P180
Determine the activation energy

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 Worked example P181
Determine the activation energy

Assume that 1/time is proportional to the rate of reaction 27

The hydrolysis of primary halogenalkanes
The SN2 mechanism

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The hydrolysis of tertiary halogenalkanes
The SN1 mechanism
Step 1 (Rate-determining step)

Step 2

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Worked example P174

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 Example P175
The iodination of propanone in acidic solution

Step 1

Step 2

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 Example P175
The iodination of propanone in acidic solution
Step 3

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 Pseudo-zero-partial-order reactions
Enzyme VS Substrate
• If 【Substrate】 >> 【Enzyme】, the reaction has an
apparent zero partial order

• If 【Enzyme】 >> 【Substrate】, the reaction is the

first order with respect to the substrate.

• https://en.wikipedia.org/wiki/Enzyme_kinetics

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