Kinetics (2)

Experimental study of the rate of a reaction with variation of reactant concentration. Rates of reaction There is a wide diversity in the rates of chemical reactions. Many take place rapidly e.g. precipitation, explosions, neutralisation, others take place at moderate speeds e.g. zinc + dilute sulphuric acid, and some are very slow e.g. iron rusting. All chemical processes occur at a definite rate under a particular set of conditions. The rates of chemical reactions can be determined by measuring the decrease in concentration of reactants, or the increase in concentration of products, with time. There are a number of methods which can be used to follow the progress of a reaction, all of which depend on the detection of some physical change which takes place as the reaction proceeds. Suitable methods include; 1. Measuring the volume of gas evolved (or consumed) at intervals using a gas syringe e.g. for CaCO3 (s) + HCl(aq) 2. Measuring the electrical resistance of a solution. 3. Measuring the change in colour of a solution with a colourimeter. 1. 4. Removing samples (aliquots) from the reacting mixture and titrating. Measurements of this type do not give the reaction rate directly but only the concentration of reactants or products at a particular time. The rate of reaction for any particular concentration of reactant can be obtained by drawing a tangent at the appropriate point on the curve of a concentration/ time graph and determining the gradient. As the rate of reaction is constantly changing it is usually quoted in terms of the initial reaction rate.

[A]I

Concentration [A]T

T1

T2

Time

Rate of reaction = rate of change of concentration = gradient Gradient = [A]I [A]T T2 T1 Mind Breaker 3.0g of excess marble (CaCO3) are added to 100cm3 of dilute hydrochloric acid. Figure below shows the graph of volume of carbon dioxide produced against time. Calculate (a) the average rate of reaction (b) the concentration of hydrochloric acid in mol dm-3

(1 mol of any gas occupies 24dm3 at room conditions)

Simple rate equation in the form: rate = k[A]x[B]y with indices either zero or integral; the rate constant and order of reaction. (Integrated rate equations are not required). Rate Equations The rate of a reaction is measured as the rate at which reactants disappear or the rate at which products appear i.e. the change in concentration per unit time. The exact relationship between the rate of reaction and the concentrations of reactants and products in any particular reaction can only be determined experimentally. The rate of reaction can be found by measuring the concentration of reactants or products at regular intervals during the course of the reaction. A concentration/ time graph can then be plotted.

[reactant]

[product]

Time

Time

As the reactants are consumed during the reaction, the reaction rate decreases as the reaction proceeds. The rate of reaction is directly proportional to the rate of disappearance of reactants. For a general reaction aA + bB cC the rate of formation of C (or the rate of disappearance of A and B) is proportional to the powers of the concentrations of A and B. i.e.

Rate = k[A]x[B]y

This expression is called the rate equation where k is the rate constant x is the order of reaction with respect to A y is the order of reaction with respect to B x + y is the overall order of reaction. Example 1 H2(g) + I2(g) 2HI(g)

In this reaction we can see that H2 and I2 will disappear at the same rate but HI will be formed at twice this rate. From experiment it can be determined that Rate = k[H2]1[I2]1 The reaction is 1st order with respect to hydrogen and 1st order with respect to iodine and 2nd order overall.

Mind Breaker Write the expression of the rate equation for the following; a) 2H2 + 2O2 b) 2W (g) + Y (s) 2HO2 Z (g).

c) CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l) d) 2NO(g) + H2(g) N2O(g) + H2O(g)

Units of the rate constant These will be determined by the rate equation and will change for different reactions. 1st order rate = k[A] mol dm-3 s-1 = k x mol dm-3 k = mol dm-3 s-1 = s-1 mol dm-3 2nd order rate = k[A] [B] mol dm-3 s-1 = k x mol dm-3 x mol dm-3 k= mol dm-3 s-1 = mol dm-3 s-1 -3 -3 mol dm x mol dm mol2 dm-6

= mol-1 dm3 s-1

Mind Breaker 1. Complete the table below with the correct unit for the rate constant Order No Unit for constant , k rate Zero Order 1st order 2nd order 3rd order

2. Plot a rate/concentration graph for the following condition

Rate

Rate

Rate

Rate [C]0

[C]

Rate [C]1

[C]

Rate [C]2

[C]

Determining the order of reaction The order of reaction with respect to any reactant can be found by inspection of the experimental data linking concentration of reactants and the rate of reaction. Example 2 For the thermal decomposition of ethanal (CH3CHO) at 800K the following data was determined. [CH3CHO] Rate of decomposition of CH3CHO -3 mol dm mol dm-3 s-1 0.100 9 x 10-7 0.200 3.6 x 10-6 0.400 1.44 x 10-5 (a) Deduce the rate equation for the reaction. When the concentration doubles the rate increases by four times. Rate = k[CH3CHO]2 (b) (b) Calculate the rate constant k for this equation at 800K giving its units. Rate = k[CH3CHO]2 From the table 9 x 10-7 = k[0.100]2 9 x 10-7 = -2 1 x 10 = 9 x 10-5 mol-1 dm3 s-1 mol-1 dm3 s-1

k=

Units k = mol dm-3 s-1 mol2 dm-6

(c) (c) Calculate the rate of decomposition at 800K at the instant when [CH3CHO] = 0.25 mol dm-3. Rate = k[CH3CHO]2 = 9 x 10-5 mol-1 dm3 s-1 x (0.25) mol2 dm-6 = 5.625 x 10-6 mol dm-3 s-1

Example 3 2H2(g) + 2NO(g) Initial [NO] 6 x 10-3 6 x 10-3 6 x 10-3 1 x 10-3 2 x 10-3 3 x 10-3 2H2O(g) + N2(g) Initial [H2] 1 x 10-3 2 x 10-3 3 x 10-3 6 x 10-3 6 x 10-3 6 x 10-3 Initial rate 3.19 x 10-3 6.36 x 10-3 9.56 x 10-3 0.48 x 10-3 1.92 x 10-3 4.3x 10-3

(a) Deduce the rate equation.

(b) What are the value and units for the rate constant?

Mind Breaker 1. The initial rates of the reaction 2A + B 2C + D at various concentrations of A and B are given below: [A] moldm-3 0.01 0.02 0.01 [B] moldm-3 0.20 0.20 0.40 Initial rate /moldm-3s-1 0.10 0.20 0.40

a) What is the order of reaction with respect to A and B? b) What is the overall order of reaction? c) What is the rate constant? d) What will be the rate of the reaction if the concentrations of A and B are both 0.01 moldm-3? 2. For the reaction 2NO(g) + H2(g) N2O(g) + H2O(g), the following rate data were collected: Initial [NO]/M 0.60 1.20 1.20 Initial [H2]/M 0.37 0.37 0.74 Initial rate/Ms-1 3.0 x 10-3 1.2 x 10-2 1.2 x 10-2

What is the rate constant for the reaction? 3. For the reaction PCl3 + Cl2 PCl5, the following data were obtained: Experiment No. 1 2 3 [PCl3]/M 0.36 0.36 0.72 [Cl2]/M 1.26 0.63 0.63 Rate /Ms-1 6.0 x 10-4 1.5 x 10-4 3.0 x 10-4

What is the rate constant?

4. Hydrogen peroxide decomposes in aqueous solution: 2H2O2(aq) 2H2O(l) + O2(g) The following results show how the rate of decomposition varies with initial hydrogen peroxide concentration: [H2O2]/moldm-3 0.05 0.10 0.20 0.30 Deduce the rate constant. Rate/moldm-3s-1 3.64 x 10-5 7.41 x 10-5 1.51 x 10-4 2.21 x 10-4

5. The following data were obtained in a series of experiments on the rate of the reaction between compounds A and B at a constant temperature. Experiment 1 2 3 (i) Initial concentration of A/mol dm3 0.12 0.36 0.72 Initial concentration of B/mol dm3 0.15 0.15 0.30 Initial rate/mol dm3 s1 0.32 103 2.88 103 11.52 103

Deduce the order of reaction with respect to A.

6. The initial rate of the reaction between substances A and B was measured in a series of experiments and the
following rate equation was deduced. Rate = k [A][B]2 (i) Complete the table of data below for the reaction between A and B.

Expt

Initial [A] /mol dm3 0.020 0.040

Initial [B] /mol dm3 0.020 0.040 0.040

Initial rate /mol dm3 s1 1.2104

1 2 3 4 5

2.4104

0.060 0.040

0.030 7.2104

(ii)

Using the data, calculate a value for the rate constant, k and state its units.

Relationship between the rate equation and mechanism. (Limited to the alkaline hydrolysis of primary and tertiary alkyl halides). Reaction Mechanisms Chemical equations show the reactants taking part and the products formed but can say nothing about what takes place during this change. Most reactions take place in a series of distinct steps called a reaction mechanism. A reaction mechanism can only be worked out from the rate equation for a reaction, not from the stoichiometric equation. Rate Determining Step Most chemical reactions are more complicated than the equation for the reaction would imply. For example, a reaction with more than three reacting species is unlikely to take place in a single step, as the probability of three particles colliding and reacting instantaneously is extremely small. Only the concentrations of those reactants taking part in the slowest step appear in the rate equation. The rate of the slowest step is the limiting factor for the rate of reaction as a whole and is known as the rate determining step. If the change A + C D Proceeds by the mechanism A B slow, rate determining step B + C D fast The rate at which D is formed will depend on the rate at which A produces B, not on how quickly B reacts with C. The rate equation would be of the form Rate = k[A]x Molecularity The term molecularity is used to indicate the number of reacting species taking part in the rate determining step. If one molecule is involved in bond cleavage during the rate determining step the process is said to be unimolecular. AB A + B If two molecules are involved the process is bimolecular. AB + C A + BC Molecularity must be a whole number.

Hydrolysis of alkyl halides R-X + OHR-OH + X-

Kinetic studies indicate that there are two mechanisms depending on whether the alkyl halide is primary or tertiary. Primary By experiment it is found that Rate = k [R-X] [OH-] The reaction is first order with respect to both the hydroxide and halogenoalkane. This suggests that the slow rate determining step is bimolecular. CH3CH2Br + OHCH3CH2OH + Br-

CH3 HOH C H Br HO H

CH3 C H Br

CH3 HO C + BrH H

Tertiary Rate = k[R-OH] The reaction is first order with respect to the halogenoalkane and zero order with respect to hydroxide This suggests that the slow rate determining step is unimolecular. (CH3)3CBr + OH(CH3)3COH + Br-

The following mechanism has been proposed. Step 1 CH3 SLOW CH3 C Br
rate determining step

CH3 C+ + Br-

CH3

CH3 Step 2 CH3 FAST CH3 C+ CH3 + OHCH3

CH3

CH3 C CH3 OH

Mind Breaker 1. Propose the possible reaction mechanism for hydrolysis of CH3CH2Cl CH3(CH3)2I

Qualitative effect of temperature on rate constants and its relationship to activation energy. Simple graphical interpretation in terms of molecular kinetic energies. Simple collision theory. For any reaction it is found that the rate constant k and the activation energy E a are related by the equation k = A x e-Ea/RT
Some bonds in a molecule must break before it can react and form new bonds. Energy is needed to break these bonds is called the activation energy. Reactant molecules must be given enough energy to pass the activation energy barrier to react. The activation energy and the rate constant are linked by the Arrhenius equation. k=Ae-Eact/RT where k=rate constant, e = the base of natural logarithms, A is a constant for any given reaction, Eact = the activation energy, R = the gas constant, T = the temperature in K. The Arrhenius equation shows that the rate constant (k) decreases if the activation energy (Eact) increases. A reaction will have a small rate constant if it has a large activation energy. The activation energy for a reaction can be calculated as follows. ln k = ln Ae-Eact/RT ln k = ln A + ln e-Eact/RT ln k = ln A - Eact/RT log k=log A - Eact/2.3RT log k=log A - Eact/2.3R * 1/T

Collision theory Collision theory is based on the idea that reactions occur when particles collide. However not every collision results in reaction. Reaction will only occur if the collision has a certain minimum value of energy called the activation energy, Ea, which is characteristic for each reaction. Some reactions require that the particles collide with the correct orientation to one another so that particles possess the correct collision geometry. Such collisions are said to be activated. Reaction rate = collision frequency x fraction of activated particles

Ea Energy reactants products

Reaction co-ordinate

The observed increase in reaction rate is due to the number of particles which possess sufficient energy to overcome the activation energy barrier Ea. If collision energy < Ea no reaction collision energy Ea - reaction occurs Mind Breaker 1. What is activation energy ?

2. What happen to the value of rate constant , k if a) Ea increase ? b) Temperature increase ? c) Catalyst are added ? d) Pressure increase ?

Qualitative explanation of the effects of concentration, temperature and catalysis on rate of reaction in terms of the distribution of molecular kinetic energies and activation energy, where appropriate

Energy
reactants

Ea

intermediate

products

Reaction co-ordinate STEP 1 reactants intermediate (SLOW)

This step proceeds slowly as reactant bonds are broken and the activation energy barrier Ea is overcome. This is the rate determining step which governs the overall rate of reaction. STEP 2 intermediate products (FAST)

This step proceeds rapidly as there is only a small activation energy barrier to overcome.

Concentration Temperature The rates of most chemical reactions increase dramatically for only small increases in temperature. For many gaseous reactions the reaction rate is approximately doubled by a rise in temperature of about 10 oC. The observed increase in reaction rate with temperature rise is not simply due to an increase in the average velocity of the particles resulting in a greater number of collisions per second. (A 10 oC rise results in an increase in collision frequency of only about 1-2%). The increase in reaction rate is due to the increased number of particles which possess the activation energy. This is because the proportion of activated molecules increases rapidly

T2>T1 T1 Number of molecules T2

K.E. (kJ mol ) or velocity As shown by the graph as the temperature increases, the number of particles with energy Ea (shown by the shaded areas) increases rapidly. The lower the activation energy barrier the faster a reaction takes place. Reactions with Ea ~80 kJmol-1 take place fairly rapidly at room temperature. In general reactions between covalent molecules tend to have high activation energies and are slow. Reactions between ions tend to have low activation energies and are rapid. Mind Breaker
1. (a)

-1

Ea

State what is meant by the term activation energy of a reaction. (b) State in general terms how a catalyst increases the rate of a chemical reaction. (c) The curve below shows the MaxwellBoltzmann distribution of molecular energies, at a constant temperature, in a gas at the start of a reaction. On this diagram the most probable molecular energy at this temperature is indicated by the symbol Emp and the activation energy by the symbol Ea.

Number of molecules

E mp

Ea

Energy

Consider the following changes. (i) (ii) The number of molecules is increased at constant temperature. The temperature is decreased without changing the number of molecules.

2. (a) Catalysts are needed in some chemical reactions. Explain what is meant by the term catalyst.

(b)

The graph below shows the distribution of molecular energies for an uncatalysed mixture of reactants. The energy corresponding to the activation energy for this reaction (EA) is also shown.

EA

(i)

Label the axes and draw a line on the graph to indicate a possible activation energy for the catalysed reaction. Label this line EA (catalysed). What does the shaded area on the graph represent?

(ii)

(iii) Describe the function of a catalyst in a chemical reaction.

3. Fill in the blank with the appropriate answer Change Increase in concentration Decrease in concentration Increase in pressure Decrease in pressure Effect of the rate of reaction Effect on the rate constant

Increase in temperature

Decrease in temperature

Addition of catalyst

QUESTION For the reaction A + B C + D the initial rates for different initial concentrations of reactants were found to be as follows. Initial concentrations mol dm-3 Initial rate mol dm-3 s-1 [A] [B] 1.0 1.0 2.0 x 10-3 2.0 1.0 4.0 x 10-3 4.0 2.0 8.0 x 10-3 (a) Deduce the rate equation and calculate the rate constant in appropriate units. [5]

(b) A reaction profile is a diagram which expresses the relationship between energy and the course of a chemical reaction (reaction co-ordinate). Consider the following sequence A X fast X + B C + D slow Draw a reaction profile for the above reaction in which the activation energy is 250 kJ mol-1 and the enthalpy of reaction is 50 kJ mol-1. [5]

(a) (c) The reaction S + R P

is acid catalysed. The following reaction sequence is proposed: S + H+ SH+ + R SH+ P + H+ (Fast: equilibrium constant = K) (Slow: Rate constant = k)

Write down; (i) an expression for [SH+] in terms of K, [S] and [H+]

[2]

(ii) an expression for the rate of the slow step; and hence

[3]

(iii) an expression for the rate in terms of k, K, [S], [R] and [H+]

[3]

CCEA 1977

Quiz 2 (Kinetics) Tick ( ) for the true statement and ( X ) for the false statement. 1. Unit for rate reaction is mol dm-3 s-1 2. When the order of the reaction is 0 , the unit of the k (rate constant) is s-1 3. A large rate constant mean the reaction is fast reaction 4. When an activation energy is high, the k value also large 5. Unit for the rate of reaction is dm6 mol-2 s-1 when the reaction is third order 6. Half life , is the duration time for the concentration for the reactant reduce by half 7. Hydrolysis of the primary halogenoalkanes is a first step order reaction. 8. The slowest step in the reaction is the rate determination step.

( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )

9. An increase in temperature speeds up the rate of reaction by increasing the rate constant ( ) 10. For many reaction, the rate doubles for each increase of 100C in temperature 11. The rate of a reaction is determined from the chemical equation 12. [B] means the concentration of the reactant B in mol dm-3 s-1 13. Zero order species can be omitted from the rate equation 14. The gradient of the concentration/time graph is measure of the rate constant 15. Hydrolysis of the tertiary halogenoalkanes is a first step order reaction. 16. When the order of the reaction is 1 , the unit of the k (rate constant) is s-1 17. Reaction with order 2 is faster than the order 1 18. Rate constant value greatly depend on temperature only 19. Ferum is an example of homogeneous catalyst in Ostwald process 20. In every increase of 10 0C the rate of reaction increase by log 10 1 ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )

Half Life Half-life is the period of time it takes for a substance undergoing decay to decrease by half. Example 1. The half-life of a radioisotope is four hours. If the initial mass of the isotope was 200 g, the mass remaining after 24 hours undecayed is

Example 2

Use of reaction profiles to illustrate the role of catalysts in providing an alternative reaction pathway with a lower activation energy and to explain the difference between thermodynamic stability and kinetic stability. Examples of homogeneous catalysis involving the formation of an intermediate and heterogeneous catalysis involving chemisorption. Catalysis A catalyst is a substance which alters the rate of a chemical reaction without being used up. There are two main theories of catalysis. Intermediate Compound Theory This theory explains most examples of homogeneous catalsis. The catalyst reacts with one of the reactants to produce an intermediate compound. This produces the required product and regenerates the catalyst. The formation of the intermediate compound requires less energetic collisions between the particles than direct combination. This lowers the activation energy barrier so more particles can react per unit time. (AB) Ea(AB)
(AC + B)

A+B

Ea(AC)

AB

A + B A + C
(catalyst)

AB AC

High energy required for direct combination.

intermediate compound (unstable)

low energy required

AC + B Chemical stability

AB + C
catalyst regenerated

As a chemical reaction proceeds, the change in energy of the system can be described by an enthalpy profile. For an exothermic reaction it would have the form shown below.

Ea reactants H products

enthalpy

Reaction co-ordinate

Compared to the products the reactants are energetically unstable and reactants form products with a release of energy.( H negative). However the reaction will not occur unless the activation energy is supplied. The reactants will be kinetically stable therefore if the activation energy is very high. The reaction

2NH3 (g)

N2 (g) + 3H2 (g)

Ea = +355 kJ mol-1

does not occur at room temperature, but reactions with a low activation energy will be kinetically unstable H2 (g) + Cl2 (g) and occur readily. 2HCl (g) Ea = +25 kJ mol-1

Kinetics
1. Ingold was awarded a Nobel Prize for his investigations into the kinetics of the hydrolysis of bromoalkanes in alkaline aqueous ethanol. RBr + OHROH + Br-

(a) (a) The hydrolysis of bromoalkanes is an example of nucleophilic substitution. Explain this term using the equation shown.

[2] (b) (b) Outline how you could determine the rate of hydrolysis of a bromoalkane. Practical details are not required.

[3] (c) (c) Ingold obtained the following rate constants for the hydrolysis of bromoalkanes. CH3Br C2H5Br CH3CHBrCH3 (CH3)3CBr First order 2.4 x 104 1.0 x 102 Second order 2.1 x 102 7.1 x 103 4.7 x 105 (i) (i) Deduce the units for a first order rate constant.

[2] (ii) (ii) Write a rate equation for the hydrolysis of bromoethane.

[2] (iii) (iii) Deduce the initial rate of hydrolysis of bromoethane, if 50 cm3 of a 0.1 mol dm-3 ethanolic solution of bromoethane is completely mixed with 50 cm3 of alkaline aqueous ethanol which has a concentration of 0.05 mol dm-3 with respect to hydroxide ions.

[3]

(iv) (iv) How would the rate , calculated in part (iii), be affected if the concentration of hydroxide ions was doubled? [1] (v) (v) Suggest why CH3CHBrCH3 should have both a first and second order rate constant. [2] Draw a flow scheme to illustrate the mechanism of the hydrolysis of (CH3)3Br. [3]

(vi)

(vi)

KINETICS OF THE REACTION BETWEEN SODIUM THIOSULPHATE AND HYDROCHLORIC ACID. Aim The purpose of this experiment is to determine the rate equation for the reaction between sodium thiosulphate and hydrochloric acid by determining the order of reaction with respect to sodium thiosulphate and hydrochloric acid. Introduction Sodium thiosulphate and hydrochloric acid react according to the stoichiometric equation Na2S2O3 (aq) + 2HCl (aq) 2NaCl (aq) + H2O (l) + SO2 (aq) + S (s) The rate equation for the reaction is in the form Rate = k [Na2S2O3]s [HCl]t Where k is the rate constant s is the order of reaction with respect to sodium thiosulphate and t is the order of reaction with respect to hydrochloric acid. You will be determining the order of reaction for each reactant by varying the concentration of each species in turn, keeping the others constant. The reaction can be followed using the precipitated sulphur which causes the solution to become opaque. The rate can be determined by measuring the time taken for a line drawn on a piece of paper and placed under the reaction vessel to become obscured. Apparatus 3 x 50 ml burettes 2 x 100ml beakers 0-100 oC thermometer stop clock glass stirring rod Chemicals 0.2M sodium thiosulphate solution 1M hydrochloric acid distilled water

Procedure A Varying the concentration of Na2S2O3 1 1 Set up three burettes in stands for hydrochloric acid, sodium thiosulphate and distilled water. 2 Add 10 cm3 of the hydrochloric acid solution to a 100 cm3 beaker labelled X.

2 3

3 In a separate beaker (Y) place 30 cm3 of the sodium thiosulphate solution and 10 cm3 of water.

4 5 6

4 5 6 Y. 7 8 9

Draw a line on a piece of paper and place beaker Y over it At a convenient time pour the acid from beaker X into beaker Y and start a stop clock. Stir the solution well with a glass rod and watch the line through the solution in beaker

7 8 9

Stop the clock when the line on the paper just disappears. Record the time and the temperature of the mixture in the results table. Repeat the procedure for the rest of the mixtures in the table below.

Beaker X Volume of HCl /cm3 10 10 10 10 10 10

Beaker Y Volume of Na2S2O3 /cm3 30 25 20 15 10 5

Volume of water /cm3 10 15 20 25 30 35

10 Complete the results table. KINETICS OF THE REACTION BETWEEN SODIUM THIOSULPHATE AND HYDROCHLORIC ACID. Aim The purpose of this experiment is to determine the rate equation for the reaction between sodium thiosulphate and hydrochloric acid by determining the order of reaction with respect to sodium thiosulphate and hydrochloric acid. Introduction Sodium thiosulphate and hydrochloric acid react according to the stoichiometric equation Na2S2O3 (aq) + 2HCl (aq) 2NaCl (aq) + H2O (l) + SO2 (aq) + S (s) The rate equation for the reaction is in the form Rate = k [Na2S2O3]s [HCl]t Where k is the rate constant s is the order of reaction with respect to sodium thiosulphate and t is the order of reaction with respect to hydrochloric acid. You will be determining the order of reaction for each reactant by varying the concentration of each species in turn, keeping the others constant. The reaction can be followed using the precipitated sulphur which causes the solution to become opaque. The rate can be determined by measuring the time taken for a line drawn on a piece of paper and placed under the reaction vessel to become obscured. Apparatus 3 x 50 ml burettes 2 x 100ml beakers 0-100 oC thermometer stop clock glass stirring rod Chemicals 0.2M sodium thiosulphate solution 1M hydrochloric acid distilled water

Procedure A Varying the concentration of Na2S2O3 10 1 Set up three burettes in stands for hydrochloric acid, sodium thiosulphate and distilled water. 2 Add 10 cm3 of the hydrochloric acid solution to a 100 cm3 beaker labelled X.

11 12

3 In a separate beaker (Y) place 30 cm3 of the sodium thiosulphate solution and 10 cm3 of water. 4 5 6 Y. 7 8 9 Draw a line on a piece of paper and place beaker Y over it At a convenient time pour the acid from beaker X into beaker Y and start a stop clock. Stir the solution well with a glass rod and watch the line through the solution in beaker

13 14 15

16 17 18

Stop the clock when the line on the paper just disappears. Record the time and the temperature of the mixture in the results table. Repeat the procedure for the rest of the mixtures in the table below.

Beaker X Volume of HCl /cm3 10 10 10 10 10 10 19 10

Beaker Y Volume of Na2S2O3 /cm3 30 25 20 15 10 5

Volume of water /cm3 10 15 20 25 30 35

Complete the results table. 20 15 10 5

Volume of Na2S2O3 30 25 3 /cm Time /s 1/Time s-1 Temperature /oC Average temperature of solutions =

B 1

Varying the concentration of HCl 1 Follow a similar procedure to that for part A, but keep the volume of thiosulphate solution constant at 10.0 cm3 and vary the volume of hydrochloric acid as shown in the table below. Beaker X Volume of HCl /cm3 Beaker Y Volume of Na2S2O3 /cm3 Volume of water /cm3

30 25 20 15 10 5

10 10 10 10 10 10

10 15 20 25 30 35

Complete the results table below. 20 15 10 5

Volume of HCl /cm3 30 25 Time /s 1/Time s-1 Temperature /oC Average temperature of solutions =

Treatment of Results For parts A and B, plot separate graphs of 1/Time against volume of reactant under consideration. 1/Time is proportional to the rate of reaction and the volume of reactant is proportional to the concentration, since the total volume is constant. Deduce from each graph whether the reaction is first order with respect to the reactant under consideration.

If you think the reaction is not first order, plot another graph, as explained below. Suppose that for reactant A Rate = k1[A]n Under the conditions of the experiment, it follows that 1/Time = k2 Vn (where V is the initial volume of reactant) log (1/Time) = nlog V + log k2 This is the equation for a straight line of the form y = mx + c Plotting a graph of log (1/Time) against log V should give a straight line of slope n.

Questions 1. 1. 2. 3. 2.

Write the rate equation for the reaction. What is the overall order of reaction?

3. Compare the rate equation with the stoichiometric equation for the reaction. What is the main difference between the two? How do you explain this difference? 4. 5. How would you calculate the rate constant for this reaction? What are the main sources of error in this experiment?

4. 5.