Reaction Kinetics
Reaction Kinetics
CHEMISTRY NOTES
Reaction Kinetics
Rate of reaction
We can calculate rate of reaction by measuring a decrease/ increase in concentration of a particular
product.
Rate of reaction = change in concentration
Time taken for this change
Units of concentration are usually expressed in moldm‐3 units of time are usually expressed in seconds.
1. Convert the following into the units of mol/dm3s
a. .254 g of I2 consumed in1 hour in a reaction mixture of volume 1 dm3 (Ar [I2]= 127)
b. 0.0440g ethyl ethanoate formed in 1 min from a mixture of volume 400 cm3. Mr
[CH3OOOC2H5] = 88.0
Sampling
Bromo‐ethane reacts with sodium hydroxide solution as follows
CH3CH2Br + OH‐ CH3CH2OH + Br‐
During the course of the reaction, both bromo‐ethane and sodium hydroxide will get used up. However,
it is relatively easy to measure the concentration of the sodium hydroxide at any one time by doing a
titration with some standard acid ‐ for example, with hydrochloric acid of a known concentration.
Continuous
A familiar example of this is the catalytic decomposition of hydrogen peroxide that we have already
looked at above as an example of an initial rate experiment.
MnO2
2H2O2 (aq) 2H2O (l) + O2 (g)
This time, you would measure the oxygen given off using a gas syringe, recording the volume of oxygen
collected at regular intervals. So the practical side of this experiment is straightforward, but the
calculation isn't. You will have to work out the concentration of hydrogen peroxide remaining in the
solution for each volume of oxygen you record.
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Conductivity measurements. The electrical conductivity of a liquid depends on the number of
ions present.
2H2O2 (aq) + 2I‐(aq) + 2H+ (aq)
2H2O (l) + I2 (aq)
During the course of the reaction, as hydrogen ions and iodide ions get used up, the conductivity
of the mixture will fall.
2. a. Suggest a suitable method for following the progress of each of these reactions
i. 2H2O2 (aq) + 2I‐(aq) + 2H+(aq)
2H2O (l) + I2 (aq)
ii. HCOOCH3(aq) + H2O (l) HCOOCH3(aq)+ CH3OH(aq)
MnO2
iii. 2H2O2 (aq) 2H2O (l) + O2 (g)
‐ +
iv. BrO3(aq) + 5Br (aq) + 6H (aq) 3Br2(aq) + 3H2O(l)
b. Why is it essential that the temperature is kept constant when measuring the
progress of a reaction?
CH2CH2CH2(cyclic) CH3CH=CH2(g)
You can follow reaction proceedings by measuring decrease in concentration of cyclo‐propane, or
increase in concentration of propene. You will end up with a set of values for concentration of (in this
example) propene against time. You can plot these values to give a concentration‐time graph which will
look something like this:
1.2
[Propane] / moldm‐3
1
0.8
0.6
0.4
0.2
0 Time
0 5 10 15 20 25 30 35 40
Time 0 0.27 0.5 0.68 0.83 0.95 1.05 1.13 1.17
You can see that in the first 5 minutes the concentration of propene increases from 0 to 0.27 moles , so
we can write rate of reaction is =∆[propene] / ∆time, which is = 0.27/5 = 0.054 mol/dm3. Min
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Now let’s consider decrease in the [] of cyclo propane. The below graph shows how to draw tangent,
[cyclopropane] with Time
[cyclopropane] with Tme
1.5
1.23
1
the slope at 10 min gives the rate of loss of 0.82
cyclopropane 10 min after the start
0.67
0.55
0.45
0.37 0.33
0 5 10 15 20 25 30 35 40
and calculate the rate of reaction at particular point on the graph. The procedure is
Select a point on the graph, corresponding to a particular point (10 min in this example)
Draw a straight line at this point (in this case the red line) this is tangent.
Extend the tangent to meet the 2 axes of the line. In this case it meets the Y axis @ 1.4 moles,
and the X axis @ 35 min.
Calculate the slope of the tangent; this is the measure of the rate of reaction.
35 x 60
The value of ‐6.67 x 10‐4 refers to the rate of change of cyclopropane concentration
The negative value of slope is because the reactant concentration is decreasing.
This is the rate of reaction when the cyclopropane concentration is 1.00 mol/dm3
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Time / min [cyclo propane] / mol/dm3 [Propene] / mol /dm3
0 1.50 0.0
5 1.23 0.27
10 1.00 0.50
15 0.82 0.68
20 0.67 0.83
25 0.55 0.95
30 0.45 1.05
35 0.37 1.13
40 0.33 1.17
3. a.
i. Plot data in the table above for increase in propene concentration with time
ii. Calculate the rate after 10 min, by drawing a tangent
b. Use the same method to calculate the rate of reaction at propene concentration of
0.00 mol/dm3, 0.30 mol/dm3 and 0.90 mol/dm3.
c. Calculate following
i. Calculate the concentration of cyclo‐propane when the concentration of
propene at 0.00, 0.30, 0.50 and 0.90 mol/dm3.
ii. Plot a graph of rate of reaction against [cyclopropane]
Rate equations
The rate constant and rate equations
[cyclopropane] / mol/dm3 Rate / mol/dm3sec Rate/ [cyclopropane] / S‐1
‐3
1.50 1.00 x 10 6.67 x 10‐4
1.00 6.67 x 10‐4 6.67 x 10‐4
‐4
0.50 3.30 x 10 6.67 x 10‐4
The third column in the table shows that the rate of reaction is proportional to the cyclopropane
concentration. We can express this mathematically as
Rate of reaction = k x [cyclopropane]
The proportionality constant k, is called the rate constant, Rate equations can only be found from
experimental data, they cannot be found from stoichiometric relationships. Consider table below
Stoichiometric equation Rate equation
H2(g) + I2(g) 2HI(g) Rate = k[H2][I2]
2NO(g) + CO(g) + O2(g) NO2(g) + CO2(g) Rate = k[NO]2
2H2(g) + 2NO(g) 2H2O(g) + N2(g) Rate = k[H2][NO]2
‐ ‐ +
4BrO3 (aq) + 5Br (aq) + 6H (aq) 3Br2(aq) + 3H2O(l) Rate = k[BrO3‐][Br‐][H+]2
You can see in equation 1 that the rate of reaction is proportional to the [] of both H2 and I2, however in
equation 2 CO and O2 do not appear in the rate equation, even though they are present in
stoichiometric equation. Similarly in equation 3 & 4 there is no stoichiometric relationship.
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4. Write rate equations for each of following reactions
a. Cyclopropane Propane,
Where rate of reaction is proportional to the [Cyclopropane]
b. H2(g) + I2(g) 2HI(g)
Where rate of reaction is proportional to the [HI] 2
Where rate of reaction is proportional to [C12H22O11] and [H+]
d. 2HgCl2(aq) + K2C2O4(aq) Hg2Cl2 + 2KCl(aq) + 2CO2(g)
Where rate is proportional to the [HgCl2] and to the square of the [K2C2O4]
Order of reaction
The order of a reaction shows how the concentration of a reagent affects the rate of reaction. The order
of a reaction with respects to a particular reactant is the power to which the concentration of that
reactant is raised in the rate equation.
2H2(g) + 2NO(g) 2H2O(g) + N2(g) Rate = k[H2][NO]2
In the above rate equation Rate = k [H2][NO] 2 we say
This reaction is first order with respect to H2
Second order with respect to NO2
The reaction is over third order (since the sum of 1+ 2 = 3)
If there is a reactant which is present in the reaction but not in the rate equation , we say 0
order with respect to that reactant.
5. For each of the reactions in Question 4, from a‐d, state
i. The order of reaction w.r.t. each reactant
ii. The overall order of reaction
Units of K
Consider following rate equation
Rate = k [H2][NO] 2
[H2][NO] 2
(mol/dm3) (mol/dm3)2
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6. State the units of k according to each of the following rate equations
a. Rate = k [NO]2
b. Rate = k [NH3]
c. Rate = k [BrO3‐]Br‐[][H+]
d. Rate = k [cyclopropane]
Plot a graph of reaction rate against the [reactant]
Plot a graph of [reactants] against time
Deduce successive half‐lives from graphs of [] against time
Chart Title
3.5
3 zero order rate of reaction = K
reaction rate / mol /dm3 s
2 1st Order
1.5 Zero Order
first order rate of reaction = [R]]
1 2nd order
0.5
0
0 5 10 15 20 25 30 35 40
concentration of reactant mol/dm3
A graph of reaction rate against [R] tells us whether a reaction is zero, first or 2nd order. It is very rear to
find order w.r.t. an agent higher than 2nd order.
7. Draw sketches of reaction rate against concentration of the reactant in bold for each of the
following reactions.
a. 2NO(g) + CO(g) + O2(g) NO2(g) + CO2(g) Rate = k[NO]2
b. 2HI(g) H2(g) + I2(g) Rate = k
‐ ‐
c. (CH3)CCl + OH (CH3)COH + Cl Rate = [(CH3)CCl]
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Graphs of concentration of reactants against time.
The above graphs show how to distinguish between zero, first and second order reactions by plotting a
graph of concentration against time. For a zero order reaction the graph is a straight line, the rate of
reaction is the slope, the reaction proceeds at same rate regardless the [R].
For 1st and 2nd order the graph is a curve. The curve for second order is much deeper. It also appears to
have a relatively longer tail.
8. For each of the reaction a‐c, in Q 7, draw a sketch graph to show how the concentration of the
bold reactant changes with time.
Half Life
2
t 1/2 = 17 min
1
t 1/2 = 17.3 min
t 1/2 = 16.7 min
0 Half Life
0 5 10 15 20 25 30 35 40 45 50 55 60
Half‐life t ½ is the time taken for the concentration of a reactant to fall to half of its original value. The
above chart shows three successive half‐lives, you can see that they are fairly close.
∆[cyclopropane] / moldm‐3 Half‐life / min
4.00 ‐‐2.00 17.0
2.00 – 1.00 34.3 ‐ 17.0 = 17.3
1.00 – 0.50 51.0 – 34.3 = 16.7
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Now remember
A zero order reaction has successive half‐lives which decrease with time
A 1st order reaction has successive half‐lives which are constant with time
A zero order reaction has successive half‐lives which increase with time
9. Benzenedizonium chloride C6H5N2Cl, decomposes at room temperature.
C6H5N2Cl (aq) + H2O (l) C6H5OH (aq) + N2 (g) + HCl (aq)
a. Describe how this reaction can be monitored
b. Using the data in the table below to plot a graph of [C6H5N2Cl] against time.
Time / s [C6H5N2Cl] / 10 ‐4 moldm‐3
0 5.8
200 4.4
400 3.2
600 2.5
800 1.7
1000 1.2
1200 0.8
1400 0.5
1600 0.3
c. From your graph find the value of two successive half lives
d. Use the value of these half‐lives to deduce the order of the reaction
Progress of the reaction can be followed by measuring the initial rate of formation of iodine. Below table
is obtained
Arrange the equation in terms of k
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K = rate = 3.5 x 10‐6 = 1.75 x 10‐2 dm3mol‐1s‐1
[H2O2][I‐] [0.0200] x [0.0100]
T1/2 = 0.693/ k. where t1/2 is the half‐life measured in s. We can re‐write this in the form. K=0.693/t1/2so
for the first order reaction where cyclopropane converts to propene, half‐life was 17 min.
Convert min to seconds. 17 min x 60 = 420sec
Substitute the value in the formulae
K = 0.693 / 420= 6.79 x 10 ‐4 dm3mol‐1s‐1
10. Use the data from experiment 2 and 3 to calculate the rate constant for the following
reaction.
b. Use the formulae t1/2 =0.693 / k to calculate a value for a reaction which is first order
and has a half‐life of 480sec.
c. A first order reaction has a rate constant of 9.63 x 10‐5 s‐1. Calculate the half –life of
this reaction.
Step1. Plot a graph to show how the concentration of a particular reactant changes with time
Step 2. Take tangents at various points along the curve corresponding to a particular [R]
Step 3. Calculate the slope at each concentration selected. The rate of reaction is calculated from the
slope of the graph.
Step 4. Plot a graph of rate of reaction against concentration.
Worked example
Methanol reacts with HCl acid at 25oC. The products are chloromethane and water
CH3OH (aq) + HCl (aq) CH3Cl (aq) + H2O (l)
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Equimolar amounts of methanol and HCl are mixed at 25oC. the progress of the reaction is followed by
Taking a small sample of the reaction mixture, time to time
Titrating the sample to find the [] of a particular reactant. The data obtained is as follow
tangent to the curve at 600 min gives reaction rate at 600 min
= 1.480 mol dm‐3 = 1.23 x 10‐5 mol dm‐3 S‐1
2000 x 60 s
2
1.5
[HCl] / mol dm‐3
0.5
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time / min
Step 2. Raw tangents to the curve at various points, e.g. as the one drawn at 600 min. corresponding to
[HCl]= 1.04 mol/dm3
Step 3. For each tangent calculate the gradient and then the rate of reaction. The rate corresponding to
[HCl] = 1.04 moldm‐3, as shown in the above example.
Rate of equation = = 1.480 mol dm‐3 = 1.23 x 10‐5 mol dm‐3 S‐1
2000 x 60 s
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The table shows rates corresponding to five different concentrations of HCl
Plot a graph of rate of reaction against [HCl] or [CH3OH]
Rate of reaction/ mol/dm3 s ‐1
0.00004
0.000035
0.00003
0.000025
0.00002
0.000015
0.00001
0.000005
0
[HCl] or/and [CH3OH] /mol/dm3
The graph suggests that this it’s overall a second order reaction, but with respect to what? There are
three possibilities
Rate = k[CH3OH][HCl]
Rate = k[CH3OH]2
Rate = k[HCl]
Further experiments need to be carried out to confirm one of these possibilities.
Worked example
Nitrogen oxide, N2O5 decomposes to nitrogen oxide and oxygen
N2O5 (g) 4NO2 (g) + O2 (g)
The table below shows how the initial rate of reaction varies with the initial [N2O5]
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Initial concentration [N2O5] / moldm‐3 Initial rate / 10‐5 moldm‐3s‐1
3.00 3.15
1.50 1.55
0.75 0.80
Initial rate / 10‐5 moldm‐3s‐1
4
3
2
1 [NO2]
0
0 0.75 1.5 3
0 0.75 1.5 3
[NO2] 0 0.8 1.55 3.15
The above graph shows that the initial rate of reaction is directly proportional to initial [N2O5]
Rate of reaction ἀ [N2O5]
Rate of reaction = k [N2O5]
12. a. State the order of the reaction for the decomposition of nitrogen oxide
b. Use the data for 3 mol/dm3 N2O5 to calculate a value for the rate constant, for this
decomposition.
Worked example
The equation below describes the reaction of propane with iodine. Hydrogen ions catalyze this reaction.
H+
CH3COCH3 + I2 CH3COCH2 + HI
The progress of the reaction can be followed by using a calorimeter. The brown color of I2 fades as the
reaction proceeds. The experimental results are shown below
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Note that
Comparing experiment 1 & 2, propanone and iodine concentration are constant.
Doubling the concentration of H+ form 0.625 ‐ 1.25 moldm‐3 doubles the rate of reaction
The reaction is first order with respect to propanone
Comparing experiment 1 & 4, propanone and HCl concentration are constant
Doubling the concentration of iodine from 0.625 x 10‐3 to 1.25 x 10‐3 moldm‐3 has no effect on
the rate of reaction.
The reaction is zero order with respect to Iodine
Comparing experiment 1 & 3, iodine and HCl concentration are constant
Doubling the [] of propanone from 0.25 x 10‐3 to 0.50 x 10‐3 mol/dm3 doubles the rate of
reaction.
The reaction is first order with respect propanone.
13. a. Write the rate equation for acid‐catalyzed reaction of iodine with propanone
b. Use your rate equation and the information in above table to calculate a value for the
rate constant for this reaction.
14. An acidified solution of hydrogen peroxide reacts with iodide ions
H2O2 (aq) + H+(aq) + 2I‐(aq) 2H2O(l) + I2(aq)
The rate equation for this reaction is rate = [H2O2 (aq)][I‐(aq], below mechanism has been proposed
for this reaction
H2O2 + I‐ Slow H2O + IO‐
H+ + IO‐ Fast HIO
HIO + I‐ + H+ Slow H2O + IO‐
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Explain why this mechanism is consistent with the rate equation.
Catalysis
Catalysts increase the rate of chemical reaction by providing an alternative pathway of lower activation
energy. There are 2 types of catalysts.
Homogenous Catalysis
This type of catalysis occurs when the catalysts is in the same phase as the reaction mixture.
Homogenous catalysis often involves changes in oxidation number of the involved in catalysis.
Peroxodisulfate ions S2O82‐(aq) oxidize iodide ions to iodine. The reaction is very slow
S2O8 (aq) + 2I‐(aq) 2SO42‐(aq) + I2 (aq)
The Peroxodisulfate and iodide ions both have –ve charge, in order to collide and react they need to
overcome the repulsive forces. Fe3+ ions catalyse the reaction. The catalysis involves two redox
reactions.
Reaction 1. Reduction of Fe3+ and Fe2+ ions by the I‐ ions.
2Fe3+ (aq) + 2I‐ (aq) 2Fe2+ (aq) + I2 (aq)
Reaction 2. Oxidation of Fe2+ ions back to Fe3+ ions by S2O82‐
2Fe2+ (aq) + S2O82‐ (aq) 2Fe3+ (aq) + 2SO42‐ (aq)
in both reaction note that the positively charged ions react with negatively charged. Look at the energy
profile diagram of the reaction. Note that the catalyzed reaction has two energy humps. Because it’s a
two stage reaction.
In order for the reaction to occur the standard
electrode potential of the two reactants should be considered, and the electrode potential of the
catalyst must lie between them. For the above reaction its
Fe3+ (aq) + e‐ Fe2+
EO= + 0.77 V
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15. Which of the pair of the substances below can catalyze the reaction
S2O8 (aq) + 2I‐(aq) 2SO42‐(aq) + I2 (aq)
Explain your answer
i. Ni(s) / Ni2+(aq) Eo = ‐ 0.25 V
ii. Mn3+(aq) / Mn2+(aq) Eo = + 1.49 V
iii. Ce4+(aq) / Ce3+(aq) Eo = + 1.70 V
iv. Cu2+(aq) / Cu+(aq) Eo = + 0.15 V
Heterogeneous Catalysis
Heterogeneous catalysis often involves gaseous molecules reacting at the surface of a solid catalyst. The
mechanism of this catalysis can be explained using the theory of adsorption. Chemical adsorption is
occurs when the molecules become bonded to atoms on the surface of the solid. Transition elements
are good at this.
Diffusion. Nitrogen gas and hydrogen gas diffuse to the surface of the iron.
Adsorption. The reactants molecules are chemically adsorbed onto the surface of the iron.
Reaction. The adsorbed nitrogen and hydrogen atoms react together to form ammonia.
Desorption. The bonds between the ammonia and the surface of iron weaken and are
eventually broken.
Diffusion. Ammonia diffuses away from the surface of the iron.
16. Describe in general terms what is meant by desorption
b. Nickel acts as a catalyst for the hydrogenation of alkenes.
Suggest how nickel catalysis this reaction. By referring to the process of adsorption,
reaction on the metal surface. And desorption.
c. In catalytic converters rhodium catalysis the reduction of nitrogen oxide to nitrogen.
Draw diagrams to suggest
i. How NO is adsorbed onto the surface of the rhodium metal
ii. How nitrogen is formed.
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