A2 CHEMISTRY: UNIT 4.

3 KINETICS RATES OF REACTION EXAM QUESTIONS

1. For the reaction: 2NO(g) + O2(g) the rate equation for the forward reaction is: Rate = k [ NO] 2 [ O 2 ] (a) (i) Deduce the units for the rate constant k.
(1)

2NO2(g)

(ii)

State and explain how the rate of reaction would change if the concentration of O2 was doubled, all other factors remaining constant.
(2)

(iii)

State and explain how the rate of reaction would change if the concentration of NO was halved, all other factors remaining constant.
(2)

(b)

(i)

What is the overall order of the reaction?

(1)

(ii)

Explain on the basis of collision theory why this reaction is unlikely to occur in a single step.
(2)

(c)

The first step in a possible mechanism for the reaction above is: 2NO (i) N2O2

Draw dot and cross diagrams to show the electronic structures of the two molecules NO and N2O2. What feature of the electronic structure of NO would suggest that this is a likely first step in the reaction?

(4)

(ii)

Explain why the enthalpy change for this step is 163 kJ mol1, given that the average bond energy for the NN bond in compounds of nitrogen is +163 kJ mol1.

(2)

(iii)

Explain why this step does not control the rate of the reaction. Assuming there is one further step in the reaction write an equation for this.

(2)

(d)

(i)

Deduce the effect of increasing the temperature on the position of equilibrium in the first step of the mechanism in (c).

(2)

(ii)

Discuss the economic implications of increasing the temperature on the overall process, if NO2 was made industrially by this process.

(3)

2.

(a)

Benzene diazonium chloride, C6H5N2Cl, in acidic solution is stable below 5 C but decomposes rapidly in a first order reaction when heated to 50 C. C6H5N2Cl(aq) + H2O(1) C6H5OH(aq) + HCl(aq) + N2(g) Describe an experiment that could be used to follow this reaction. Your answer should include a diagram of the apparatus that you would use and a statement of the measurements that you would make.

.. .. ..
(5)

(b)

The decomposition of hydrogen peroxide is also a first order reaction 2H2O2(aq) 2H2O(1) + O2(g) At 50 C it is very much slower than the decomposition of benzene diazonium chloride of the same concentration. (i) Write the rate equation for the decomposition of hydrogen peroxide. ....
(1)

(ii)

Comment on the relative values of the activation energies and the rate constants for the decomposition reactions above. Activation energies ............................................... ... Rate constants ................................................... ...
(2)

(iii)

Explain, in terms of collision theory, the effect on reaction rates of increasing the temperature to 60 C. .... .... .... .... ....
(3)

(iv)

The decomposition of hydrogen peroxide is catalysed by iodide ions. Explain why reactions are speeded up by a catalyst. .... .... ....
(2)

(c)

The lodination of propanone CH3COCH3 + I2

a c id c a ta ly s t

CH2ICOCH3 + HI

was studied with an excess of propanone and an acid catalyst. The variation of concentration of iodine as a function of time is shown below.

[ I2]

tim e What is the order of this reaction with respect to iodine? Give your reasoning. .. .. ..
(3) (Total 16 marks)

ANSWERS
1. (a) (i) (ii) mol2dm6s1 doubles (1) because it is first order or rate and concentration of oxygen directly proportional (1) ( 1 2 )2 = 1 4 (1) rate 4 (1) or rate 4 (1) because 2nd order (1)
1 4

2 2 1 2

(iii) (b) (i) (ii) (c) (i)

3 (1) very unlikely for 2 molecules of NO and 1 molecule of O2 to collide simultaneously (1) in correct orientation (1)
+ + + + +

N + + O + (1) O N-N bond (1) no error (1) no shape required must show electron pairs , if not then penalise (-1) unpaired electron / only 7 electrons / odd electron (1) but not just electron deficient
+ +

+ +

+ +

(ii)

bond energy refers to breaking of N-N bond (1) in this reaction this bond is formed or it is the reverse process sign of H changes (1) because rate depends on O2 as well or this step is not the rds or the rate is controlled by the other reaction (1) N2O2 + O2 2NO2 (1) accept multiples equilibrium moves in endothermic direction or reaction is exothermic in forward direction (1) so moves to the left (1)

(iii)

(d)

(i)

(ii)* increase in T would increase the rate of reaction and hence the rate of production of NO2 (1) costs too high if temperature too high (1) quality of language (1) 2. (a) Diagram Reasonable apparatus for the reaction vessel(1) Gas syringe or upturned gas burette to collect gas (1) Water bath at 50C (1) Measurements volume of gas(1) at intervals of time (1) OR Diagram with flask in water bath etc. (1) Remove samples (1) at timed intervals (1) Quench by cooling / diluting (1) Titrate vs alkali (1) OR if done via pH change measurements max 3 If done by mass change method max 3 i.e. diagram with water bath-measure-time intervals (i) (ii) Rate = k [H2O2] (1) Ea of H2O2 reaction > Ea of benzene diazonium chloride reaction (1)

5 1

(b)

k of peroxide reaction < k of benzene diazonium chloride reaction(1) (iii) speed / energy of molecules increases (1) more molecules have E Ea(1) (rate faster) as greater proportion of collisions results in reaction(1) Note These points could be made on a Maxwell-Boltzmann diagram

(iv)

provides (alternative) route (1) with lower Ea (1) Note The second mark is consequential on the first it is not stand alone. 2

(c)

order wrt I2 : zero(1) slope / gradient constant (1) therefore rate constant (1) Note There are several ways the last two points could be expressed. e.g. a plot of gradient vs conc of iodine is horizontal or the line is straight therefore the rate is constant. But if first order would be curve does not answer the question fully (Max 2) 3
[16]