5 Chemical Kinetics

Chemical kinetics is the study of reaction rates, factors that affect rates of chemical reactions and theory of reaction rate. (I) Rates of chemical reactions (i) The rate of a chemical reaction is the measure of the extent of the reaction as it proceeded with time. The rate of a chemical reaction is measured in terms of change in the amount or the concentration of a reactant or a product within a certain time interval. Change in amount or concentration of a reactant or a product Time

(ii)

Rate =

Unit: mol s-1 or mol dm-3 s-1 (iii) The rate of reaction can be expressed in three different ways: average rate initial rate instantaneous rate 1. Average rate is a measure of the change in the amount or concentration of a reactant or a product in a given period of time. For example, in a chemical reaction, a total of 0.18 g carbon dioxide gas is given out in 1 minute at room temperature. (R.a.m. : C = 12.0; 0 = 16.0) Average rate = = = = = Example 1 In the hydrolysis of an ester at a constant temperature of 398 K, the concentration of the ester decreases from 1 M to 0.75 M in 4 minutes. What is its average reaction rate? Solution: 0.18 / 1 g min-1 0.18 / 60 g s-1 0.003 g s-1 0.003 /44 mol-1 s-1 6.8 10-5 mol s-1

5 Chemical kinetics - 1

2. Initial rate and instantaneous rate Consider the reaction: A B

The concentration changes of A and B are shown in the following figure:

As shown in the above figure, the concentration varies with time. The reaction rate at any given time, the instantaneous rate is equal to the slope of the tangent to the curve at that point. At the beginning of the reaction, the rate is the fastest and is called the initial rate.

5 Chemical kinetics - 2

Example 2

The change in concentration of a reactant X in a chemical reaction is represented by the graph above. Using the graph, find the (a) initial rate; (b) average rate for the time period from 1 to 2 minute; and (c) instantaneous rate at the third minute. Solution:

5 Chemical kinetics - 3

(II) Rate equations A rate equation is a mathematical equation that shows the rate in terms of changes in concentrations of substances. For a chemical reaction, c = change in concentration of a reactant or a product t = time interval for the reaction Average rate = When c t

t0, we obtain the instantaneous rate: lim t 0 c t dc = dt

Instantaneous rate =

If t = t0, the instantaneous rate is known as the initial rate. Consider the following reaction, A + B 2C The rate equation of the reaction is: Rate = d [B] d [A] = t t = 1 2 d[C] dt

where d[A] and d[B] = decrease in concentrations of reactants A and B respectively, d[C] = increase in concentration of product C, dt = represents a very short time interval, A negative sign appears before d[A]/dt and d[B]/dt because the concentration of the reactants decrease during the reaction. In general, for the reaction aA + bB cC + dD where a, b, c and d represent coefficients in a balanced chemical equation. Rate = 1 d[A] = 1 d[B] a dt b dt = 1 d[C] c dt = 1 d[D] d dt

(III) Methods of measuring rate of a chemical reaction The rate of a reaction can be determined experimentally by measuring either the amounts of reactants used up or the amounts of products formed within a certain time interval. Two general methods: Chemical methods By following the amount or concentrations of reactants or products ( c) with time ( t) at a constant temperature environment (because temperature affects reaction rate).
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 Physical methods By following the change in physical properties of reactants and products such as (1) determining the volume of gas liberated and (2) measuring the light intensity (colorimetric measurement) at different times during the chemical reaction. (i) Chemical methods titration General procedures: 1. Reactants are put in separate flasks in a thermostatic bath (so that the temperature can be kept constant). 2. The reactants are mixed and kept in the thermostatic bath and a stop watch is started. 3. A small samples of reaction mixture are extracted for chemical analysis at certain time intervals. The reaction in the sample mixture can be quenched by: (a) rapid cooling in ice, (b) removing one of the reactants by another chemical reaction, (c) diluting with a large volume of cold water (d) removing the catalyst (in reactions under the effect of catalyst). Quenching is necessary because the process of analysis itself takes time and quenching slows down the reaction abruptly and the reaction is assumed to be stopped. 4. Record the time when the reaction mixture is quenched. 5. The concentration of one of the reactants or products present in the reaction mixture can then be determined by an appropriate titration. Example: The reaction rate of alkaline hydrolysis of ester can be determined by titration method. Reaction: CH3COOCH3(l) + NaOH(l) CH3COONa(aq) + CH3OH(aq) Theory: As the reaction proceeds, the concentration of NaOH decreases, and the rate of decrease of NaOH can be taken as the reaction rate.

Procedures: 1. Methyl ethanoate is added to dilute NaOH and immediately a sample of the reaction mixture is removed by a pipette. 2. The sample is added to a conical flask containing ice water. (The cooling and dilution of the reaction mixture decreases the reaction rate sufficiently / stop the reaction for chemical analysis.) 3. The sample is titrated with standard HCl, using phenolphthalein as indicator. The volume of HCl required to reach end point is noted. 4. The process is repeated several times at regular time intervals. 5. The volume of HCl required to reach end point is plotted against time. Since the volume of HCl used is proportional to the amount / concentration of NaOH present in the reaction mixture, the reaction rate can be found. Although chemical methods can be applied to most reactions which react slowly, however there are disadvantages: 1. A large amount of sample is required. 2. Reaction still proceeds while withdrawing samples. If the reaction is too fast, the time noted will not be accurate.
5 Chemical kinetics - 5

(ii)

Physical methods (a) Physical method - Determining the volume of gas formed This method is for reactions which produce gaseous products, for example, 1. hydrogen gas is given out in the reaction between zinc and dilute hydrochloric acid; Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g) 2. carbon dioxide gas is given out in the reaction between calcium carbonate and dilute hydrochloric acid; CaCO3(s) + 2HCl CaCl2(aq) + H2(g) + H2O(l) 3. oxygen gas is given out in the decomposition of hydrogen peroxide. H2O2(l) H2O(l) + O2(g) Reaction rates of the above reactions can be followed by recording the volume of the gas given out at various times, using a gas syringe as shown in the following diagram.

The following plot is expected to be obtained: Total volume

Time For successful measurements, the gas must not be too soluble in the solution, otherwise, the measured volume of gas will be smaller than expected.
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(b)

Physical method colorimetric measurement For chemical reactions such as those shown below, there is a colored reactant or product. The reacting mixture will have a change in color intensity as the concentrations of the colored reactants or products change. The change in color intensity can be followed by a colorimeter. 1. Oxidation of methanoic acid by bromine Br2(aq) + HCOOH(aq) 2Br-(aq) + 2H+(aq) + CO2(g) orange colorless all products are colorless 2. Oxidation of oxalate ion by manganate(VII) ion 2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq) violet colorless colorless 2Mn2+(aq) + 10CO2(g) + 8H2O(l) very pale pink colorless colorless A colorimeter is an instrument used to measure the color intensity of a solution.

Light source

Absorbance is a numerical value showing the amount of light absorbed by the reaction mixture. It is a direct measure of the color intensity of a solution or the concentration of the colored reactant or product in the reaction mixture. The absorbance of different concentrations of the standard colored solution is recorded. A calibration curve is obtained by plotting the absorbance against the concentration of the standard colored solution. The light intensity detected in experiments can be converted into concentration units, using the calibration curve.

Absorbance

[sample]
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(IV)

Factors influencing reaction rates Rates of reactions are affected by the following factors: concentration of reactants temperature pressure surface area of reactants catalyst light. (i) Effect of concentration of reactants The effect of concentration of reactants on the reaction rate can be studied by reacting identical samples of calcium carbonate powder with different concentration of hydrochloric acid.

volume of CO2

(a) (b)

(c) (a) = 2.0 M HCl (b) = 1.0 M HCl (c) = 0.5 M HCl

t1

t2

t3

time

Figure: Graph showing the relationship between volume of carbon dioxide released and concentration of HCl. Results: 1. The reaction with a higher concentration of hydrochloric acid is completed in a shorter time (t1) than that with the lower concentrations (t2, t3).

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2.

Slopes of curve (a) are higher than that of curve (b) which in turn are higher than that of curve (c) at any given time. The same volume of carbon dioxide is evolved in each case because the same mass (which is limiting) of calcium carbonate is used. The higher the concentration of reactants, the higher is the rate of reaction.

Conclusion:

Explanation: As the concentration of reactant increases, the reactant particles become more crowded and closer. This increases the chance of effective collision (collision which leads to reaction). (ii) Effect of temperature 1. 2. An increase in temperature of reaction will increase the reaction rate. Explanation: As the temperature increases, kinetic energy of reactant particles increases. This in turn increases both the collision frequency and the fraction of reactants possessing sufficient energy (activation energy) for starting the reaction. The reaction between sodium thiosulphate and hydrochloric acid may be used to study the relation of reaction rate and temperature. Sulphur is formed as sodium thiosulphate reacts with hydrochloric acid according to the following equation: Na2S2O3(aq) + 2HCI(aq) 2NaClaq) + SO2(g) + H2O(l) + S(s) The rate of reaction can be determined by measuring the time needed for precipitating sufficient yellow sulphur (one of the products) to hide the cross (written on paper and placed underneath the conical flask) from our vision. Thermostats are used in the experiment to ensure that the temperature is constant throughout the experiment. The shorter the time for the cross to disappear, the faster is the average rate of reaction. 1 i.e. average rate time for cross to disappear

3.

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Look down at the cross from above

mixture of HCl and Na2S2O3 solution white paper

time = t seconds cloudy liquid white paper

cross

Cross becomes invisible

Figure: An experimental set-up to study the change in rate of reaction with temperature.

Time / s

1 Time / s-1

Temperature / oC

Temperature / oC

From the above graphs, we know: 1. 2. 3. As the temperature increases, reaction rate also increases. The graph is not a straight line. The steep slope indicates that a small increase in temp results in a great increase in reaction rate. For many reactions, a temperature rise of 10oC doubles the reaction rate.

4.

5 Chemical kinetics - 10

(iii) Effect of pressure 1. Affects only the reaction rate of reactions involving gaseous reactants because solids and liquids are incompressible. The pressure of a gas can be increased by decreasing its volume. Therefore, as the pressure increases, the concentration of the gas also increases. As a result, the distance between reacting particles decreases. This leads to more collision / effective collision between reacting particles. Therefore, reaction rate increases.

2.

(iv) Effect of surface area 1. A solid reactant in form of finely divided powder has a much larger surface area than that in the form of lumps or grains, as illustrated by dividing a cube into 64 small cubes sown in the diagram below.

2.

The smaller the size of a solid reactant, the greater is the surface area of contact between the reactants. This will result in more effective collision between the reacting particles and therefore the reaction rate increases. The reaction between calcium carbonate and hydrochloric acid can be used to study the effect of surface area of a solid reactant on the rate of reaction. CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2Ol) + CO2(g) Equal masses of calcium carbonate chips (marble chips) and calcium carbonate powder are allow to react with excess 1.0 M hydrochloric acid solution at constant temperature respectively, using the apparatus set-up shown below.

3.

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gas syringe

plunger

marble chip HCl

Figure. Apparatus set-up to investigate the effect of surface area on reaction rate.

Volume of CO2 / cm3

powdered CaCO3

marble chips

Time / s
end of reaction for powdered CaCO3 end of reaction for marble chips

Figure. A graph of volume of carbon dioxide against time for the reaction between HCl and powdered CaCO3 and marble chips

4.

The rate of reaction is faster in calcium carbonate powder than that of calcium carbonate (marble) chips. This is due to the increase in surface area of calcium carbonate powder. This leads to a much higher chance of contact between calcium carbonate and hydrochloric acid particles.

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(v)

Effect of catalyst 1. A catalyst is a substance that alters the rate of a chemical reaction and remains chemically unchanged at the end of the reaction. Catalysts are commonly used in industries. For example, iron filings are used in the Haber Process; platinum or vanadium(V) oxide are used in the Contact Process. Our body reactions are catalyzed by specific enzymes. The decomposition of hydrogen peroxide to water and oxygen can be used to show the effect of catalyst. At room temperature, the reaction is extremely slow. 2H2O(aq) 2H2O(1) + O2(g) However, if a small amount of manganese(IV) oxide is added, the reaction rate increases significantly. Manganese(IV) oxide acts as a catalyst for the decomposition of hydrogen peroxide. Note: A positive catalyst increases the rate of a chemical reaction, while a negative catalyst decreases the rate of a chemical reaction. gas syringe

2.

3.

plunger

MnO2 H2O2

Figure. Apparatus set-up to investigate the effect of catalyst on reaction rate.

2g of powdered MnO2 Volume of O2 / cm3

1. MnO2 in powdered form is more efficient in increasing the reaction rate. 2. The chemical nature and mass of MnO2 is not changed at the end of the reaction. 3. Only a small amount of MnO2 is required to bring about the catalytic effect. Once a sufficient amount if catalyst is used, any further amount of MnO2 will have no further effect on the reaction rate.

2g of MnO2 in lump form

without MnO2 Time / min

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(vi) Effect of light 1. Light of a particular wavelength can increase the rate of photochemical reactions. 2. For some photochemical reactions, the presence of light is essential for the reactions to take place. Example: Reaction of silver bromide to form silver metal in black-and-white photographic film can only take place in the presence of light. 2AgBr(s) 2Ag(s) + Br2(g) 3. Light (uv light) can increase the rate of substitution of hexane by bromine. CH3CH2CH2CH2CH2CH3 + Br2 CH3CH2CH2CH2CH2CH2Br + HBr Ultraviolet light (uv) provides energy to split up Br2 molecule to Br radical. The free radical is highly reactive as it carries an unpaired electron. uv Br Br 2Br When bromine liquid is added to hexane under diffuse sunlight, the reddish brown color of bromine disappears quickly as a mixture of the colorless substituted compound is formed. However, there are no observable changes if the experiment is performed in darkness.

(V) Rate equations and the order of reactions (i) Rate equation or Rate law A rate law is an equation that expresses the rate of reaction in terms of the molar concentrations of the species in the overall reaction. From experimental / empirical observation, the rate of reaction is often shown to be proportional to the molar concentrations of the reactants raised to a simple power. For a reaction of the form aA + bB products Rate = k [A]x [B]y The above expression is known as the rate law or rate equation where k = the rate constant of the reaction x = the order of reaction with respect to reactant A y = the order of reaction with respect to reactant B x + y = the overall order of the reaction x and y are constants for a particular reaction and can only be determined experimentally.
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Rate constant k, Depends on temperature. Value is determined by experiments. Greater values of k means faster reaction rate. Units of k depend on the order of the reaction. Order of the reaction zeroth first second third Units of k mol dm-3 s-1 s-1 mol-1 dm3 s-1 mol-2 dm6 s-1

(ii)

Zeroth order reaction For a zeroth order reaction A product Rate = k [A]0 = k

1. The rate of reaction is independent of the concentration of reactant. 2. By plotting rate against [A], a horizontal straight line is obtained. Rate Slope = 0

[A]

3. Examples of zeroth order reactions: The decomposition of HI(g) on a hot gold surface, at high pressure. gold surface 2HI(g) H2(g) + I2(g) Reason: At high pressure, the gold surface is always saturated with adsorbed HI(g). Hence, any further increase in gas pressure / concentration cannot increase the surface concentration of Hl(g). Therefore, the reaction rate become independent of the concentration of reactant HI(g).

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(iii) First order reaction 1. For a first order reaction Rate = k [A] A product

(The rate is directly proportional to the concentration of the reactant)

2. A graph of rate against [A] will give a straight line of slope k. Rate

Slope = k

[A] 3. Examples of first order reactions: 2H2O2(aq) 2H2O(1) + O2(g) 2N2O5(g) 4NO2(g) + O2(g) All radioactive decay, e.g.
226 88

Rate = k [H2O2] Rate = k [N2O5]

4

Ra

222 86

Rn

He

Rate = k [Ra]

(iii) Second order reaction There are two types of second order reaction 1. Rate depending on one reactant only: The reaction rate is directly proportional to the square of the concentration of the reactant A. By plotting rate against [A]2, a straight line of slope k is produced. A products Rate = - d[A] / dt = k [A]2 Rate Slope = k

[A]2 Example: 2NOCl(g) 2NO(g) + Cl2(g)

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Rate = k [NOCl]2

2.

Rate depending on two reactants: A + B products Rate = - d[A] / dt = - d[B] / dt = k [A] [B] (for constant [B]) (for constant [A])

The reaction is first order with respect to A and B respectively. Rate Rate

Slope = k when [B] = constant [A] 3. Examples: H2(g) + I2(g) 2HI(g) 2NO2(g) 2NO + O2 CH3Br + OH CH3OH + Br

Slope = k when [A] = constant [B]

Rate = k [H2] [I2] Rate = k [NO2]2 Rate = k [CH3Br][OH]

CH3COOC2H5 + OH CH3COO + C2H5OH Rate = k [CH3COOC2H5][OH]

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(iv) Calculations involving rate equations Example 3 For a reaction between A and B, experiments with different initial concentrations of A and B were carried out. The results were as follows: Initial Concentration of A (mol dm3) 0.01 0.02 0.01 Initial Concentration of B (mol dm3') 0.02 0.02 0.04 Initial Rate (mol dm3 s1) 0.0005 0.0010 0.0020

Experiment 1 2 3 (a) (b) (c)

What is the order of reaction with respect to A and with respect to B ? Calculate the rate constant using results of experiment 1. What is the rate equation for the reaction ?

Solution:

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Example 4 Samples of bromomethane were dissolved in dilute aqueous ethanol and reacted with sodium hydroxide solution. Several experiments were carried out, at constant temperature, using different initial concentrations of each bromomethane and hydroxide ions. The initial rate of reaction was determined in each case and the results were shown in the following table. Experiment A B C D E F [CH3Br] / mol dm3 0.010 0.010 0.010 0.020 0.040 0.080 [OH] / mol dm3 0.0050 0.010 0.020 0.020 0.020 0.020 Rate / mol dm3 s1 0.107 0.216 0.425 0.856 1.72 3.42

Used the data to establish a rate equation for the alkaline hydrolysis of bromomethane. Solution:

5 Chemical kinetics - 19

Example 5 (a) (c) Write an equation for the decomposition of hydrogen peroxide. Tabulated below are the initial rate of decomposition of hydrogen peroxide at different concentrations. Plot a graph of initial rate against concentration. [H2O2] / mol dm3 Initial rate / 104 mol dm3 s1) (d) 0.100 0.59 0.175 1.04 0.250 1.50 0.300 1.80

From the graph, find the order of reaction and rate constant.

Solution:

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(VI) Integrated rate equations (i) Zeroth order reaction For a zeroth order reaction Rate = d[A] =k dt A product

Integrating,

A d[A] = A0

t
0

k dt

Gives

[A] = k t + [A]0

where [A]0 is the initial concentration of A. [A] [A]0 slope = - k

A graph of [A] against time t gives a straight line, with slope = - k and y-intercept =[A]0

0 (ii) First order reaction For a first order reaction, Rate = d[A] = k [A] dt ln[A] ln[A]0 A product

d[A] [A] = k t Integrating the above equation

slope = - k

d[A] A0 [A]

t kt
0

Gives

ln A = k t + ln[A]0

0 t

The above integrated rate equation can also be written as ln [A]0 = k t [A]

ln [A]0 [A]

slope = k

0 t
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Half-life The time taken for half of the reactant to be converted to the product is known as the half-life ( t1/2) of the reaction. The half-life is the time required for the concentration of A to decrease from [A]0 to 1/2 [A]0. For a first order reaction, ln [ A]0 = k t [A]0

ln 2 = k t Therefore, t = ln 2 = 0.693 k k

From the above expression, we know that for a first order reaction, the half-life is a constant and independent of the initial concentration of reaction.

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Example 6 The half-life of a radioactive isotope A is 1997 years. How long does it take for a sample of A to decay to 20% of its original radioactivity? Solution:

Example 7 The decomposition of benzenediazonium chloride in aqueous solution is a raection of first order and proceeds according to the following equation: C6H5N2Cl(aq) C6H5Cl(l) + N2(g) A certain solution of benzenediazonium chloride contains initially an amount of this compound which gives 80 cm3 of nitrogen on complete decomposition. It is found that, at 300C, 40 cm3 of nitrogen are evolved in 40 minutes. How long after the start of the decomposition will 70 cm3 of nitrogen have been evolved ? (All volumes of nitrogen are measured at the same temperature and pressure.) Solution:

5 Chemical kinetics - 23

(iii) Second order reaction For a second order reaction, d[A] = k [A]2 dt A product

Rate =

1 [A] slope = k

Integrating

d[A] 2 A0 [A]

t k dt
0

1 [A]0 t 1 [A]0

Gives 1 [A] = kt +

Example 8 In the decomposition of gaseous hydrogen iodide, the following experimental data were obtained. Time (min) [HI] (mol dm )
-3

0 0.500

120 0.250

240 0.167

360 0.125

480 0.100

Determine the order of decomposition of gaseous hydrogen iodide graphically. Solution: (Manhattan 2: 44) [HI] (mol dm-3) H2 0.250 0.167 0.125 0.100 ln [HI] 1/ HI] (mol3 dm-3)

Time (min) 0 120 240 360 480

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Example 9 In the Journal of the Chemical Society for 1950, Hughes, Ingold and Reed report some kinetic studies on aromatic nitration. In one experiment ethanoic acid containing 0.2% water was used as a solvent and pure nitric acid was added to make a 7 M solution. The kinetics of the nitration of ethylbenzene, C6H5C2H5, were studied with the following results at 200 C. Time / min 0 8.0 11.0 13.0 16.0 21.0 25.0 [C6H5C2H5] / mol dm1 0.090 0.063 0.053 0.049 0.037 0.024 0.009

Determine an order of reaction from these results. Solution:

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(iv) Carbon -14 dating The determination of the dates of archaeological and geological events can be based on the half-lives of naturally occurring radioisotopes such as carbon-14. All radioactive isotopes decay at a constant rate that is defined by their half-life. Like all other radioactive decay reactions, the decay of carbon-14 follows a first order reaction. Carbon-14, with its half-life of 5730 years, is suitable for determining the age of objects that are thousand years old. Origin of carbon-14 in the atmosphere Carbon-14 is continuously formed in the upper atmosphere when high energy neutrons produced by cosmic radiation from space collide with nitrogen-14 according to the following nuclear reaction:
14 7 N
14

1 n 0

14 6 C

1p 1

CO2 is, however, decompose continuously through -particle production:

14 C 6

14 7 N

0 1

Over the years, the rates for the above two processes have become equal, and the amount of 14CO2 in the atmosphere remains approximately constant. Origin of carbon-14 in living things Together with ordinary non-radioactive carbon dioxide (12CO2), 14CO2 is incorporated into plants by photosynthesis and into animals through food chains. Principal of carbon-14 dating If an organism is alive, the 14C : 12C ratio remains the same as in the atmosphere. When the organism dies and incorporation of carbon stops, the 14C : 12C ratio decreases as 14C slowly changes to nitrogen by -emission, following a first order reaction.
14 C 6

14 7 N

0 1

Hence, by measuring the ratio of 14C to 12C in the plants or animals after their death, the time since death can be determined. Uses of carbon-14 dating Carbon-14 dating can be used to date plant and animal fossils and ancient carbon-containing relics such as bone, wood, cloth and leather that were derived from once-living matter. Calculation If we know the half life of C-14 decay (= 5730 tears), k can be calculated from the following: t = ln 2 = 0.693 k k

5 Chemical kinetics - 27

If [A]0 and [A]t are known, t can be calculated from the following: ln [A]0 = k t [A]t where [A]0 [A]t k t = number of C-14 atoms in a plant specimen at ancient time = number of C-14 atoms in a plant remains at present = rate constant for radioactive decay of C-14 = age of plant specimen

Example 10 Given that a piece of wood from ancient China has a count rate of 10 per minute, and the count rate from the same mass of a similar piece of modern wood is 15 per minute. If the half-life of carbon-14 is 5570 years, determine the age of the wood from ancient China. Solution:

5 Chemical kinetics - 28

(VII) (i)

The effect of temperature on reaction rate Activation Energy 1. For any reaction to occur, old bonds have to be broken before the formation of new chemical bonds can take place. Hence, energy must be supplied to start a reaction. 2. Reactant particles must collide for a reaction to take place. However, reaction will not always be resulted when particles collide because they may not have sufficient energy for breaking bonds. 3. The minimum amount of energy required to start a chemical reaction is known as the activation energy, Ea.

Energy

Ea
reactant

Energy

Ea
product

H<0
product reactant

H>0

Reaction coordinate Figure. Ea for an exothermic and endothermic reaction. (ii) Arrhenius equation

Reaction coordinate

If the temperature range is not too great, the dependence of rate constant on temperature can be represented by an empirical equation proposed by Arrhenius in 1889.

k = A e Ea / RT
where

(Arrhenius equation)

k = the rate constant of the reaction, A = a constant (pre-exponential factor) which is independent of temperature, Ea = activation energy of the reaction in J mol1, R = ideal gas constant (8.314 J K1 mol1) T = temperature in Kelvin.

From the Arrhenius equation, it can be seen that an increase in temperature will increase the value of k. Also, the reaction rate increases in an exponential manner.

5 Chemical kinetics - 29

(i)

Determination of activation energy using Arrhenius equation (1) Graphically k = A e Ea / RT Taking natural logarithm on both side of the Arrhenius equation, ln k = ln A Ea RT

or, in terms of base-10 logarithms, log k = logA Ea 2.303RT

A graph of ln k against 1/T (called the Arrhenius plot) yields a straight line with: slope = Ea/R, and y-intercept = ln A. ln k ln A slope = Ea R If the slope of the Arrhenius plot is step: High Ea Reaction rate very sensitive to temp

1 T (2) If rate constants at two different temperature are known ln k1 = ln A Ea / RT1 ln k2 = ln A Ea / RT2 (1) (2): ln k1 = Ea k2 R 1 T1 1 T2 . (1) . (2)

From the above equation, Ea can be calculated.

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Example 11 For the following hydrolysis reaction C6N5N2+Cl(aq) + H2O(1) C6N5OH(aq) + N2(g) + H+(aq) + Cl(aq) the rate constants of the reaction at different temperatures were measured and recorded in the following table. Temperature (K) Rate Constant k (105 s1) 278.0 0.15 298.1 4.10 308.2 20.00 323.0 140.00

Determine the activation energy graphically. (Given: R = 8.314 J K1 mol1) Solution: ln k 1/T (K1)

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Example 12 The rate constant for a reaction at 110oC is found to be twice the value of that at 100oC. Calculate the activation energy of the reaction. Given: R = 8.314 J K1 mol1. Solution:

(VIII) The interpretation of rates of gaseous reactions at molecular level (i) Distribution of molecular speeds in a gas Gas molecules move randomly in different directions at different speeds. Due to collisions with other molecules or walls of containers, the speed of any one gas molecule is changing continually. Thus, it is not possible to talk about the speed of an individual molecule. It is more meaningful to consider their distribution of speeds. Because of the large number of molecules involved, the distribution of molecular speeds is always constant under the same conditions. The distribution of molecular speeds can be described by the MaxwellBoltzmann distribution. The distribution of molecular energies also follows the MaxwellBoltzmann distribution.
No. or fraction of molecules with a given speed

Area under curve: no. or fraction of molecules with speed > v

Speed = v

Speed or energy

5 Chemical kinetics - 32

 At any moment some of molecules have either high or low energies, but most molecules have energies close to the average energy of the system. The area under the graph is proportional to the number of molecules. (ii) Effect of temperature on the distribution of molecular speeds or kinetic energies As the temperature increases, the distribution curve broadens and shift towards higher speed, leading to a wider distribution of speeds (also energies)
No. of molecules 1000 K

1. Increase in the mean / average speed The mean speed increases as the temperature increases (c2 > c1).

1500 K

c1 2. Increase in number (or fraction) of fast moving molecules

c2

Speed

The number of molecules having higher speeds (also higher energies) increases.
No. of molecules 1000 K No. of molecules with speed > C3 at 1000K No. of molecules with speed > C3 at 1000K 1500 K

c3 (iii) Simple collision theory

Speed

1. Collision theory is an attempt to explain reaction rate in terms of the frequency of collisions. For a reaction to occur, the reactant molecules (particles) must collide with each other. Therefore, it is reasonable to relate rate of reaction with the number of collisions occur per unit time (frequency of collisions). However, the reaction rate does not equal to collision frequency of reacting molecules. This is because not all collisions results in chemical reaction. 2. Activation energy Only those collisions of molecules involving sufficient energies will result in reaction. This is because, in general, a reaction will start with an initial breaking of bonds which requires energy. Thus, only those collisions of molecules involving sufficient energies for initial bond breaking will result in reaction.
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Only those collisions involving kinetic energy more than or equal to the activation energy can give rise to reaction. This explains why exothermic processes like combustion of gasoline or coal gas would not occur without the initial input of energy. 3. Collisions with kinetic energy more than or equal to the activation energy will lead to chemical reaction only if the colliding particles are in correct (proper) orientation. Such a collision is known as effective collision. 4. Reaction rate No. of effective collision No. of effective collision = Total no. of collisions Fraction of collisions with proper orientation Fraction of particles with K.E. > Ea

(iv) Effect of temperature on reaction rate As the temperature is increased, kinetic energy of molecules increases collision frequency increases the Maxwell-Boltzmann distribution curve shifts to higher speeds fraction of molecules with K.E. > Ea increases no. of effective collision increases therefore, reaction rate increases

(IX) Energy profile The energy profile is a graph showing the changes in potential energy during a reaction. The reactive and unstable species which possesses the maximum potential energy formed during the course of reaction is called the transition state or activated complex. Ef and Eb = the activation energies of the forward and backward reactions respectively
Transition state / Activated complex

Potential energy

Ef
reactant

Eb
H product

Reaction coordinate

H , the enthalpy of reaction

= Eproduct Ereactant = Ef Eb

It is found experimentally that chemical reactions seldom occur in one single step. The series of steps for the conversion of reactants to products is called a reaction mechanism, which can only be determined experimentally. Each step in a reaction mechanism is called an elementary reaction or elementary step. The number of reactant particles that take place in an elementary reaction is called the molecularity.
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(i)

Single-stage reaction Some chemical reactions take place in a single step. A B + C [A---B---C] A + transition state BC

The energy profile for the above reaction is shown below:

[A---B---C] Transition state / Activated complex

Potential energy

Ef
AB

Eb
H A+BC

Reaction coordinate Figure. Energy profile of a single-stage reaction.

Example: Substitution reaction of 1-bromobutane and water. H H H O: H C Br CH2CH2CH3 1-bromobutane H HO C CH2CH2CH3 H 1-butanol The attack of a water molecule on the carbon atom and the escape of the bromine atom to form of a bromide ion take place almost at the same time and is a single-stage reaction. It is a bimolecular reaction. + Br H HO H H C Br CH2CH2CH3

transition state

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(ii)

Multi-stage reaction Stage 1: Stage 2: DE intermediate + + F D F + DF + E E

slow

Intermediate DE

Overall reaction

The slowest stage in a reaction mechanism is the rate determining step. It involves the greatest activation energy Ea, in the reaction. The overall reaction rate depends on the rate of the rate determining step.

Transition state 1

Potential energy

Transition state 2

E1

E2 Intermediate + F

1. E1 and E2 are the activation energies of stage 1 and 2 respectively. 2. E1 > E2 3. Stage 1 is the rate determining step.

DE+F DF+E

Reaction coordinate Example: Hydrolysis of 2-bromo-2-methylpropane Stage 1: CH3 C CH3 Br CH3 Slow
rate determining step

CH3 C CH3 CH3 + Br

2-bromo-2-methylpropane, Stage 2: CH3 C CH3 CH3 Fast + H2O

Intermediate a carbonium ion

CH3 C CH3 OH CH3 + H+

2-methylpropanol

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(iii) Rate laws and reaction mechanism 1. The rate law of an elementary reaction (but NOT of an overall reaction in general) can be written down from its equation. Therefore, the rate law of a unimolecular elementary reaction is first-order in the reactant: A products Rate = k [A]

The rate law of a bimolecular elementary reaction is second-order: A + B products Rate = k [A][B]

2. For a reaction mechanism involving a rate determining step, order of reaction = no. of particles involved in the rate-determining step = molecularity of the rate-determining step 3. A rate law for an overall chemical reaction must be determined by experiment. Once the rate law is determined, a reaction mechanism that is consistent with it can be proposed.

(X) Catalysts A catalyst is a substance that can change (alter) the rate of a reaction but remains chemically unchanged at the end of the reaction. A positive catalyst is one that speeds up a reaction while a negative catalyst decreases the rate of a reaction. Catalysis is the action of the catalyst on the reaction. A catalyst works by providing an alternative pathway for the reaction. Homogeneous catalyst: the catalyst is in the same phase as the reactants. Heterogeneous catalyst: the catalyst is in a different phase from the reactants. Autocatalysis the product of a reaction catalyses the reaction. (i) Characteristics of catalysts 1. 2. 3. 4. 5. The action is specific. The amount of catalyst does not change after the reaction. Only a small amount of catalyst is sufficient. Some catalysts can be poisoned by impurities. For a reversible reaction, a catalyst speeds up both the forward and backward reaction to the same extent. 6. No effect on the enthalpy change of reaction.

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(ii)

Action of catalyst In general, a catalyst is actually chemically involved in the reaction it catalyses. It is consumed in one reaction stage (acts as a reactant) and regenerated in a subsequent stage (acts as a product). For example, Stage 1: Stage 2: A + catalyst A catalyst A catalyst + B A B + catalyst A + B A B

Overall reaction:

The involvement of a positive catalyst causes the reaction to take place via an alternative pathway (the catalytic pathway) involving a lower activation energy.

potential energy

Ea

Ea Ea
Reactants Products

Ea

Reaction pathway without catalyst Reaction pathway with a positive catalyst Activation energy for uncatalysed reaction Activation energy for catalysed reaction

Draw a reaction path for a reaction catalysed with a negative catalyst.

reaction coordinate Figure. Energy profiles of catalysed and uncatalysed reaction pathways.

Kinetic energy Figure. Effect of catalyst on the number of particles possessing kinetic energy greater than activation energy.

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No. of particles

Ea with a positive catalyst

Ea without a catalyst

Ea with a negative catalyst

(iii) Homogeneous catalysis In homogeneous catalysis, all the reactants, products and catalyst exist in a single phase. Homogeneous catalysts are usually involved in the formation of a reactive intermediate compound. Example: Esterification Without catalyst:

methanoic acid

ethanol

ethyl methanoate

With H+ as catalyst: Stage 1 is the rate determining step of the reaction, it can be catalysed by H+ ion which acts as a homogeneous catalyst. A reactive intermediate compound - protonated carboxylic acid is formed. It carries a positive charge and thus is more easily attacked by O on the alcohol. The homogeneous catalyst H+ ion is regenerated at the end of reaction.

Figure. The energy profile of the acid catalysed esterification.

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(iv) Heterogeneous catalysis - Adsorption In heterogeneous catalysis, the catalyst is in a phase different from both the reactants and products. Example: Manganese(IV) oxide is a solid catalyst that can speed up the decomposition of hydrogen peroxide solution into water and oxygen.
MnO2 as catalyst

2H2O2(aq)

2H2O(1) + O2(g)

The solid phase of the catalyst provides an active surface for the reactants to adsorb on. This has the effect of increasing the concentration of the reactants on the surface of the catalyst and weakening the bonds within the reactant molecules. Hence, the catalysed pathway has a lower activation energy.

Uncatalysed pathway

Potential energy

Catalysed pathway

Ea Ea1 Ea2 H2O2 H2O + O2 Reaction coordinate Figure. Energy profile of decomposition of hydrogen peroxide Ea3

(v)

Autocatalysis Autocatalysis is a type of catalysis in which the product of a reaction catalyses the reaction. This causes the reaction rate to increase as the reaction proceeds. Example: Reaction between MnO4 and C2O42 in acid medium In acidic solution, the oxalate ion is converted to the undissociated acid, H2C2O4. 2MnO4 + 5H2C2O4 + 6H+ 2Mn2+ + 10CO2 + 8H2O The reaction between MnO4 and H2C2O4 proceeds slow even at evaluated temperature unless Mn2+ is present as a catalyst. When the first few cm3 of MnO4 are added to a hot solution of H2C2O4, several seconds are required before the purple color of MnO4 disappears. As the concentration of Mn2+ builds up, the reaction proceeds more and more rapidly as a result of autocatalysis.

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(XI) Applications of catalysts Catalysts are widely used in industries, mainly for increasing the rate of reaction for faster production. Appropriate negative catalysts may also be used to hinder the possible side reactions. Moreover, with the use of catalysts, the energy consumption required in production can be reduced. With appropriate catalysts, the reaction can be carried out: at a lower temperature - less energy consumption at a lower pressure reduce the cost of building pressure-resistant reactors Catalysts are widely used in industries. Some of the well-known examples are: 1. Iron is used to produce ammonia in the Haber process N2(g) + 3H2(g)
Fe

2NH3(g)

2. Platinum or vanadium(V) oxide is used in the Contact process for production of sulphuric acid. 2SO2(g) + O2(g)
Pt

2SO3(g)

3. Nickel, platinum or palladium is used in the hydrogenation of unsaturated oils to make margarine. 4. Catalytic converters in car exhaust systems Part of the pollutants in the car exhaust are converted into relatively harmless substances by the action of metal catalysts such as platinum (or palladium) and rhodium in the catalytic converter. These catalysts are coated onto a honeycomb support to increase the surface area for better action. Pt 2CO(g) + 2NO(g) 2CO2(g) + N2(g) harmful gases harmless gases 5. Enzymes as Biological Catalysts Enzymes are proteins that catalyse specific biological reactions. For example, enzymes obtained from yeast have been used in bread making and production of alcohol. During fermentation, glucose is converted to ethanol and carbon dioxide. enzyme C6H12O6(aq) 2CH3CH2OH(aq) + CO2(g) Household products such as washing powders and detergents contain enzymes (proteases, lipase and cellulase) which can break down stains or grease caused by blood, egg, etc.

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