TUTORIAL 11: REACTION KINETICS

TOPIC 11.1 : REACTION RATE 1. (a) (b) Define reaction rate. Write the differential rate equation for the following reactions. i. ii. iii. 2. I(aq) + OCl(aq) Cl(aq) + OI(aq) 3O2(g) 2O3(g) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

Consider the reaction: N2(g) + 3H2(g) 2NH3(g) Suppose that at a particular moment during the reaction, molecule of hydrogen is reacting at the rate of 0.074 M s1 . Calculate the rate of (a) (b) formation of ammonia. depletion of nitrogen. Explain the following terms. i. ii. iii. (b) rate law rate constant half-life A product i. ii. iii. Write the rate law . Determine the unit of rate constant. Sketch the graphs of rate of reaction versus concentration of A for zero, first and second order reactions.

3.

(a)

Consider the reaction:

4.

The conversion of cyclopropane to propene in the gas phase is a first order reaction with a rate constant of 6.7 10-4 s1 at 500 oC.

CH2 H2C CH2

H2C

CH CH3

(a) (b) (c)

If the initial concentration of cyclopropane was 0.25 M, calculate the concentration after 8.8 min. How long will it take for the concentration of cyclopropane to decrease from 0.25 M to 0.15 M? How long will it take to convert 74% of the starting material to propene?

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TUTORIAL 11: REACTION KINETICS The reaction of nitric oxide with hydrogen at 1280C is 2NO(g) + 2H2(g) N2(g) + 2H2O(l) The following data was collected at this temperature : Initial rate /M s1 1.25 105 5.00 105 10.00 105

5.

Experiment 1 2 3

[NO]/M 5.00 103 10.00 103 10.00 103

[H2]/M 2.00 103 2.00 103 4.00 103

Based on the data, determine i. ii 6. the rate law. the rate constant.

The data below were obtained from the following reaction at 27oC . CH3CH(Cl)CH3 + NaOH CH3CH(OH)CH3 + NaCl Reaction rate/M min1 3.0 10-3 6.0 10-3 9.0 10-3

Expt. 1 2 3

[CH3CH(Cl)CH3]/M 0.15 0.15 0.45

[NaOH]/M 0.25 0.50 0.25

(a) (b)

What is the order with respect to each reactant? Write the rate equation.

7.

The decomposition of dinitrogen pentoxide with the rate constant of 5.1 104 s1 at 45oC is given below: 2N2O5(g) (a) (b) 4NO2(g) + O2(g)

Calculate the concentration of N2O5 after 3.2 min if the initial concentration is 0.25 M . If the initial concentration of N2O5 is 0.35 M, calculate the time needed for the concentration to be reduced i. ii. to 0.08 M. by 62%.

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TUTORIAL 11: REACTION KINETICS

8.

Iodine atoms combine to form molecular iodine in the gas phase: I(g) + I(g) I2(g)

The rate constant for the above reaction is 7.0 109 M1 s1 at 23C. (a) (b) If the initial concentration of iodine atoms is 0.086 M, calculate the concentration after 2.0 min. Calculate the half-life of iodine atoms if the initial concentration is i. ii. 9. 0.42 M 0.60 M

The data listed in the table below were obtained from the following decomposition : A products

Time/min 0 5 10 15 25

[A]/M 1.00 0.63 0.46 0.36 0.25

ln [A] 0.00 -0.46 -0.78 -1.02 -1.39

1 [A ]
1.00 1.60 2.20 2.80 4.00

(a) (b) (c)

Establish the order of the reaction by graphical method. Determine the rate constant, k. Determine the half-life, t1/2, if [A]0 = 1.00 M.

TOPIC 11.2: COLLISION THEORY AND TRANSITION STATE THEORY 1. What is meant by activation energy?

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TUTORIAL 11: REACTION KINETICS

TOPIC 11.3 : FACTORS AFFECTING REACTION RATE 1. Explain the effect of temperature on reaction rate based on Maxwell-Boltzmann distribution curve.

2.

The following equation shows the decomposition of HI(g):

Pt
2HI(g) (a) (b) (c) 3. H2(g) + I2(g) What is the function of platinum?

H = -ve

Draw and label the potential energy profile for the reaction with and without platinum. Give another two factors that can influence the reaction rate and explain your answer.

The rate constant of a reaction is 3.46 10-2 s1 at 298 K. Calculate the rate constant at 350 K if the activation energy for the reaction is 50.2 kJ mol1. The rate constant of a reaction at 463 K is 2.52 105 s1 and at 503 K is 6.30 104 s1. Determine the activation energy for the reaction.

4.

5.

Rate constants, k for decomposition of hydrogen iodide at different temperatures are given in the table below : Rate constant, k ( mol1 dm3 s1) 3.75 10-9 6.65 10-6 1.15 10-3 7.75 10-2

Temperature (K) 500 600 700 800

(a) (b)

Write the Arrhenius equation. Determine the activation energy for the decomposition of hydrogen iodide graphically from the above data. [The gas constant, R = 8.314 J K1 mol1]

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TUTORIAL 11: REACTION KINETICS

OBJECTIVE QUESTIONS 1. The rate of formation of water from the reaction: 2MnO4(aq) + 6H+(aq) + 5H2O2(aq) 2Mn2+(aq) + 8H2O(l) + 5O2(g) is 0.035 M s-1. What is the rate of H2O2 being reacted? A. B. C. D. 8.75 x 10-4 M s1 2.19 x 10-3 M s1 8.75 x 10-3 M s1 2.19 x 10-2 M s1

2.

For the reaction: A + 2B C + 2D, the initial rate, What is the value of A. B. C. D.

d[ A] is 2.6 x 10-2 M s1. dt

d[ B] ? dt

6.5 x 103 M s1 1.3 x 102 M s1 2.6 x 102 M s1 5.2 x 102 M s1

3.

If a reaction is described as zero order with respect to reactant A, this means that A. B. C. D. A is a catalyst in the reaction. A is not involved in the rate determining step. the value of the rate constant is independent of A. the rate of reaction is inversely proportional to the concentration of A.

4.

The following data were measured for the reaction: 2NO(g) + Cl2(g) 2NOCl(g) Reaction rate (mol dm3 hr 1) 1.19 4.79 9.59 Concentration (mol dm3) NO 0.50 1.00 1.00 Cl2 0.50 0.50 1.00

Choose the rate equation for the reaction. A. B. C. D. rate = k[NOCl]2 rate = k[NO][Cl2 ] rate = k[NO]2[Cl2] rate = k[NO][Cl2]0.5

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TUTORIAL 11: REACTION KINETICS

5.

The initial concentration of an active substance in an aqueous solution of medicine is 5.0 x 103 mol dm3. After 20 months, an analysis shows that its concentration becomes 4.2 x 103 mol dm3. Determine the decay duration of this medicine by assuming the decomposition of the active substance is a first order reaction. [Decay duration of the medicine is the time required as it decomposes 10% of the initial concentration]. A. B. C. D. 9 months 12 months 18 months 23 months

6.

The reaction A + 2B products was found to have the rate law, rate = k[A] [B]2. Predict by what factor the rate of reaction will increase when the concentration of B is doubled and the concentration of A remained unchanged. A. B. C. D. 2 4 6 8

7.

Half-life of a reaction increases with initial concentration if the reaction is A. B. C. D. zero order first order second order none of the above

8.

The half-life of a radioactive element is 50 minutes. How long will it take for the element to decay by 87.5%? A. B. C. D. 1.67 hours 2.00 hours 2.25 hours 2.50 hours

9.

If activation energy, Ea for a certain biological reaction is 50 kJ mol1, how many times will the rate of the reaction increase when body temperature increases from 37C to 40C? A. B. C. D. 1.00 1.15 1.20 2.00

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TUTORIAL 11: REACTION KINETICS The rate of a reaction increases by a factor of 45 as the temperature rises from 25C to 55C. Calculate the activation energy of the reaction. A. B. C. D. 66 kJ mol1 103 kJ mol1 166 kJ mol1 203 kJ mol1

10.

SUMMARY OF OPTIONS A I only B I and II only C II and III only D I, II and III

11.

The reaction : Q products is believed to be of first order. Which of the following graph(s) is/are correct? I. ln[Q]

t II [Q] t

III

Rate [Q]

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