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# Chapter 1

:

Rate of Reaction

1. Rate of Reaction Rate of reaction is the speed at which reactants are converted into products in a chemical reaction. Different chemical reactions occur at different rates. Slow reaction The time taken for a slow reaction is long. The rate of reaction for a slow reaction is low. Examples: A piece of newspaper turning yellow The weathering of limestone by acid rain Rusting of a water pipe

Fast reaction The time taken for a fast reaction is short. The reactants are quickly converted to the products. The rate of reaction is said to be high Examples: Fading of dyes on a shirt under hot sun Cooking a chicken using a microwave oven Burning of petrol in a car engine Striking a match Ripening of tomatoes

2. Observable changes for measuring rate of reaction Precipitation formation Volume of a gas liberated Observable changes Colour change Change in mass during the reaction

During the reaction of magnesium ribbon with dilute hydrochloric acid, HCl, two visible changes are

-

Decrease in the mass of marble chips (reactant)

-

Increase in the volume of carbon dioxide gas, CO2 (product) Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g)

Pressure changes Temperature changes

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3. Rate of reaction is measured by:
Rate of reaction

=

change in selested quantity time taken

Example: Magnesium ribbon and dilute hydrochloric acid

Rate of reaction

=

decrease in mass of magnesium ribbon (reactant) time taken

Rate of reaction
4 Average rate of reaction -

=

increase in volume of hydrogen gas (product) time taken

is the average value of the rate of reaction within a specified period of time.

5. Rate of on reaction at a give time is the actual rate of reaction at that instant It is also known as the instantaneous rate of reaction Gradient of the curve at that instant

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Activity Aim: To determine the average rate of reaction and the instantaneous rate of reaction Apparatus: 150 cm3 conical flask, 50 cm3 measuring cylinder, stopper with delivery tube, burrette, retort stand and clamp, stopwatch, basin and electronic balance Materials: 5 g of granulated zinc, 0.1 mol dm–3 hydrochloric acid and water. Procedure: 1. 25 cm3 of 0.1 mol dm–3 hydrochloric acid is measured and pored into a conical flask. 2. About 5 g of granulated zinc is weighed using an electronic balance. 3. A burette is filled full with water. It is then inverted into a basin containing water and clamped vertically using a retort stand. 4. The water level in the burette is adjusted to 50 cm3 mark. 5. The set up of the apparatus is shown in Figure 1.

6. The granulated zinc is added into the conical flask containing hydrochloric acid. 7. The conical flask is closed immediately with a stopper which is joined to delivery tube. At the same time, the stopwatch is started. 8. The conical flask is shaken steadily throughout the whole activity. 9. The volume of gas collected in the burette by downward displacement of water is recorded at 30-second intervals for a period of 5 minutes. 10. The results are recorded in a table. Results:
Time (s) Burette reading (cm3) Volume of gas (cm )
3

0 50.00

30 38.00

60 30.00

90 26.00

120 23.00

150 20.00

180 18.50

210 17.50

240 17.00

270 17.00

300 17.00

0.00

12.00

20.00

24.00

27.00

30.00

31.50

32.50

33.00

33.00

33.00

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1. To calculate the average rate of reaction: a) Average rate of reaction for the overall reaction b) Average rate of reaction in the first minute c) Average rate of reaction in the second minute 2. To calculate the instantaneous rate of reaction: a) Instantaneous rate of reaction at 30 seconds b) Instantaneous rate of reaction at 90 seconds Observation 1. Gas bubbles are produced. 2. Liberation of gas is the fastest at the beginning. Then, liberation of gas slows down and stops at 240 s. 3. From the graph plotted, it can be seen that the gradient of the curve decreases with time. The gradient becomes zero at 240 s. Conclusion: The rate of reaction decreases with time and then becomes zero. Explanation: 1. Reaction between hydrochloric acid and zinc produces hydrogen gas and zinc chloride solution. Inference 1. Hydrogen gas is produced. 2. The reaction is the fastest at the beginning. The reaction slows down and then is complete at 240 s. 3. The rate of reaction decreases with time. The rate of reaction becomes zero at 240s.

2. The instantaneous rate of reaction at 30 seconds is higher than that of 90 seconds. This is because a) the concentration of hydrochloric acid is higher at 30 seconds b) the total surface area of granulated zinc is larger at 30 seconds 3. The rate of reaction decreases with time because the concentration of hydrochloric acid and the total surface area of granulated zinc decreases with time. When all the concentration of hydrochloric acid is completely reacted, the rate of reaction becomes zero.

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Size of Reactants

Concentration of Reactants

Factors Affecting the Rate of Reaction

Temperature and Pressure

Catalysts

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B I 1.

Factors Affecting the Rate of Reaction Effect of surface area on the rate of reaction For a fixed mass of solid reactant, the smaller the size of the reactant, the larger will be the total exposed surface area, thus the higher will be the rate of reaction. Examples: i. ii. iii. CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + CO2 (g) + H2O (l) Mg (s) + 2HCl (aq)  Mg Cl2 (aq) + H2 (g) Zn (s) + H2SO4 (aq)  ZnSO4 (aq) + H2 (g)

Experiment Aim: To investigate the effect of size of a reactant on the rate of reaction Problem statement: Does small size of marble chips increase the rate of reaction? Hypothesis: The smaller the size of marble chips, the higher the rate of reaction. Variables: Manipulated variable: size of marble chips Responding variable: Rate of reaction Controlled variables : Mass of marble chips, volume and concentration of HCl acid, Temperature Apparatus: 50 cm3 measuring cylinder, 150 cm3 conical flask, stopper with delivery tube, basin, burette, electronic balance and stopwatch Materials: 0.1 mol dm–3 hydrochloric acid, 2 g of large marble chips, 2 g of small marble chips and water Procedure: 1. 40 cm3 of 0.1 mol dm–3 hydrochloric acid is measured and pored into a conical flask. 2. About 2 g of large marble chips are weighed using an electronic balance. 3. A burette is filled full with water. It is then inverted into a basin containing water and clamped vertically using a retort stand. 4. The water level in the burette is adjusted to 50 cm3 mark. 5. The set up of the apparatus is shown in Figure 2.

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6. The large marble chips are added into the conical flask containing hydrochloric acid. 7. The conical flask is closed immediately with a stopper which is joined to delivery tube. At the same time, the stopwatch is started. 8. The conical flask is shaken steadily throughout the whole experiment. 9. The volume of gas collected in the burette by downward displacement of water is recorded at 30-second intervals for a period of 5 minutes. 10. The results are recorded in a table. 11. The experiment is repeated using 2 g of small marble chips to replace 2 g of large marble chips. All the conditions remain unchanged. Results: Experiment 1: Large marble chips
Time (s) Burette reading (cm3) Volume of gas (cm3) 0 50.00 30 43.00 60 38.00 90 34.00 120 30.00 150 27.50 180 25.00 210 23.00 240 21.00 270 20.00 300 19.00

0.00

7.00

12.00

16.00

20.00

22.50

25.00

27.00

29.00

30.00

31.00

Experiment 2: small marble chips
Time (s) Burette reading (cm ) Volume of gas (cm )
3 3

0 50.00

30 39.00

60 32.00

90 27.00

120 22.50

150 19.00

180 16.00

210 13.50

240 11.50

270 10.00

300 9.00

0.00

11.00

18.00

23.00

27.50

31.00

34.00

36.50

38.50

40.00

41.00

Calculation: From your graph, 1. To calculate the average rate of reaction at 200 seconds: a) Experiment 1 b) Experiment 2 c) By comparison, the average rate of reaction for experiment 2 is higher than experiment 1 at 300 seconds. 2. To calculate the instantaneous rate of reaction at 120 seconds:

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a) Experiment 1 b) Experiment 2 c) By comparison, the instantaneous rate of reaction for experiment 2 is higher than experiment 1 at 120 seconds. Observation 1. Gas bubbles are produced. 2. Liberation of gas is the fastest at the beginning and it slows down later. Inference 1. Carbon dioxide gas is produced. 2. The reaction is the fastest at the beginning. The reaction slows down and then is complete at 240 s. 3. From the graph plotted, it can be seen that the initial gradient of the curve for the experiment using small marble chips is higher than the initial gradient of the curve for the experiment using large marble chips. Conclusion: 1. small marble chips have a higher rate of reaction. 2. The hypothesis is accepted. Explanation: 1. The reaction between hydrochloric acid and marble chips produces carbon dioxide gas, calcium chloride solution and water. 3. The rate of reaction for the experiment using small marble chips is higher that the rate of reaction for the experiment using large marble chips

2. Based on the graphs plotted, the curve for experiment 2 is steeper than experiment 1 3. This means the rate of reaction for experiment 2 (using small marble chips) is higher than experiment 1 (using large marble chips). This is because small marble chips have a larger total exposed surface area. 4. The curves becomes less steep with time due to the decrease in concentration of hydrochloric acid and mass of marble chips. 5. If both experiments are continued until the reaction is completed, the following graph will be obtained.

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6. Both experiments produce the same maximum volume of carbon dioxide gas. This is because both experiments use the same a) concentration and volume of hydrochloric acid b) mass of marble chips (calcium carbonate) 7. The maximum volume of carbon dioxide gas collected is less than the theoretical volume because a small volume of carbon dioxide gas has dissolved in the water when it is collected in the burette. 8. To overcome the problem, one should pass the carbon dioxide gas through the water for a few minutes before starting the experiment. This is to saturate the water with carbon dioxide before collecting the gas in the burette. Use of collision theory to explain the effect of the size of reactant / total surface area on the rate of reaction 1. When the size of a fixed mass of solid reactant is smaller, the total surface area exposed to collision with the particles of the other reactants is bigger. Thus, the frequency of collision among the reacting particles at the surface of the solid reactant increases. This leads to an increase in the frequency of effective collision and hence, a higher rate of reaction.

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II 1.

Effect of Concentration on the Rate of Reaction The higher the concentration of liquid reactant, the higher the rate of reaction. Examples: i. ii. iii. Na2S2O3 (aq) + H2SO4 (aq)  Na2SO4 (aq) + S (s) + SO2 (g) + H2O (l) CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + CO2 (g) + H2O (l) CaCO3 (s) + 2HNO3 (aq)  Ca(NO3) (aq) + CO2 (g) + H2O (l)

Experiment Aim: To investigate the effect of concentration on the rate of reaction Problem statement: Does high concentration of sodium thiosulphate solution, the shorter the time taken for the mark ‘X ‘ to disappear from sight? Hypothesis: The higher the concentration of sodium thiosulphate solution, the shorter the time taken for the mark ‘X ‘ to disappear from sight. Variables: Manipulated variable: Concentration of sodium thiosulphate solution Responding variable: Time taken for the mark ‘X ‘ to disappear from sight Controlled variables : Temperature, total volume of the reacting mixture, concentration and volume of sulphuric acid, size of conical flask Apparatus: 10 cm3 measuring cylinder , 50 cm3 measuring cylinder, 150 cm3 conical flask and stopwatch Materials: 1.0 mol dm–3 hydrochloric acid, 0.2 mol dm–3 sodium thiosulphate solution, distilled water and white paper with a mark ‘X ‘ at the centre Procedure: 1. 45 cm3 of 0.2 mol dm–3 sodium thiosulphate solution is measured using a 50 cm3 measuring cylinder and pored into a conical flask.

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2. The conical flask is placed on top of a piece of white paper with a mark ‘X ‘ at the centre. 3. 5 cm3 of 1.0 mol dm–3 sulphuric acid is measured using a 10 cm3 measuring cylinder. 4. The sulphuric acid is poured quickly and carefully into the conical flask. At the same time, stopwatch is started immediately. 5. The mixture in the conical flask is swirled for a few time. It is then placed back on the white paper. 6. The mark ‘X‘ is observed vertically from the top through the solution as shown in Figure 3. 7. The stopwatch is stopped immediately once the mark ‘X‘ disappear from sight. 8. The time t required for the mark ‘X‘ to disappear from sight is recorded. 9. The experiment is repeated four more times using different volumes of 0.2 mol dm–3 sodium thiosulphate solution which is diluted with different volumes of distilled water as shown in table below. All other conditions remain unchanged. 10. The results are recorded. Results: Set Volume of 0.2 mol dm–3 sodium thiosulphate solution, V1 (cm3) Volume of distilled water (cm3) Volume of 1.0 mol dm–3 sulphuric acid (cm3) Total volume of the mixture, V2 (cm3) Concentration of sodium thiosulphate solution that reacts, M2 (mol dm–3)
 MV  M2  1 1   V2   

I 45 0 5

II 40 5 5

III 30 15 5

IV 20 25 5

V 10 35 5

Time taken (s)
1 ( s 1 ) Time

18

20

27

41

82

Observation 1. A yellow precipitate formed 2. A pungent smell is produced 3. When the concentration of sodium thiosulphate decreases, the time taken for the mark ‘X‘ to disappear from sight becomes longer.

Inference 1. A yellow precipitate formed is sulphur 2. Sulphur dioxide gas is produced 3. When the concentration of sodium thiosulphate decreases, the production of the yellow precipitate of sulphur becomes slower. Thus, the rate of reaction decreases

Conclusion: 1. An increase in concentration of sodium thiosulphate increases the rate of reaction 2. The hypothesis is accepted.

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Explanation: 1. The reaction between sulphuric acid and sodium thiosulphate solution produces sodium sulphate solution, sulphur, sulphur dioxide gas and water. Chemical equation: Ionic equation: 2. Based on the graph I, the curve implies that as the concentration of sodium thiosulphate solution becomes lower, the time taken for the mark ‘X‘ to disappear from sight becomes longer. 3. Based on graph II, the straight line implies that the concentration of sodium thiosulphate solution is directly proportional to
1 . Time

4. In other words, the concentration of sodium thiosulphate solutions is direct proportional to the rate of reaction. 5. Conical flask of the same size and shape are used in this experiment. If a bigger conical flask is used, the time taken for the mark ‘X‘ to disappear from sight becomes longer. 6. This is because bigger conical flask has a larger base area. The mixture of 50 cm3 solution becomes shallower. A bigger amount of yellow precipitate is needed to turn the mark ‘X‘ invisible from sight. 7. If the experiments is repeated using 1.0 mol dm–3 ydrochloric acid to replace 1.0 mol dm–3 sulphuric acid, the rate of reaction will decreases. 8. This because hydrochloric acid is a strong monoprotic acid whereas sulphuric acid is a strong diprotic acid. Although the concentration of acids is the same, the concentration of hydrogen ions in sulphuric acid is twice the concentration of hydrogen ions in hydrochloric acid. Use of collision theory to explain the effect of concentration on the rate of reaction 1. When the concentration of the solution of a reactant increase, the number of particles per unit volume of the solution of this reactant also increase. 2. with more particles per unit volume of the solution, the number of collisions per unit time between the reacting particles increases. 3. Thus, the frequency of effective collision increases and hence, the rate of reaction increases

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III 1. 2.

Effect of temperature on the rate of reaction As the temperature of the reactant increases, the rate of reaction increases. At higher temperature, the reactant particles have greater kinetic energy resulting in a higher speed of movement and thus more frequent effective collisions.

3. 4

Cooling a mixture will slow down the particles and fewer collisions take place. Temperature is directly proportional to the rate of reaction. That is, the higher the temperature, the higher the rate of reaction. Experiment Aim: To investigate the effect of temperature on the rate of reaction Problem statement: Does high temperature of sodium thiosulphate solution decrease the time taken for the mark ‘X ‘ to disappear from sight? Hypothesis: The higher the temperature of sodium thiosulphate solution, the shorter the time taken for the mark ‘X ‘ to disappear from sight. Variables: Manipulated variable: Temperature of sodium thiosulphate solution Responding variable: Time taken for the mark ‘X ‘ to disappear from sight Controlled variables : Concentration and volume of sodium thiosulphate solution, concentration and volume of sulphuric acid, size of conical flask Apparatus: 10 cm3 measuring cylinder , 50 cm3 measuring cylinder, 150 cm3 conical flask, stopwatch, thermometer, Bunsen burner and wire gauze. Materials: 1.0 mol dm–3 hydrochloric acid, 0.2 mol dm–3 sodium thiosulphate solution, distilled water and white paper with a mark ‘X ‘ at the centre Procedure: 1. 50 cm3 of 0.2 mol dm–3 sodium thiosulphate solution is measured using a 50 cm3 measuring cylinder and pored into a conical flask. 2. The temperature of the solution is measured using a thermometer. 3. The conical flask is placed on top of a piece of white paper with a mark ‘X ‘ at the centre. 4. 5 cm3 of 1.0 mol dm–3 sulphuric acid is measured using a 10 cm3 measuring cylinder. 5. The sulphuric acid is poured quickly and carefully into the conical flask. At the same time, stopwatch is started immediately. 6. The mixture in the conical flask is swirled for a few time. It is then placed back on the white paper.

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7. The mark ‘X‘ is observed vertically from the top through the solution as shown in Figure 4. 8. The stopwatch is stopped immediately once the mark ‘X‘ disappear from sight. 9. The time t required for the mark ‘X‘ to disappear from sight is recorded. 10. The experiment is repeated using 50 cm3 0.2 mol dm–3 sodium thiosulphate solution at 350C, 400C, 450C and 500C respectively. All other conditions remain unchanged. 11. The results are recorded. Results: Set I II III IV V Observation 1. A yellow precipitate formed 2. A pungent smell is produced 3. When the temperature of sodium thiosulphate decreases, the time taken for the mark ‘X‘ to disappear from sight becomes shorter. Temperature (0C) 30.0 35.0 40.0 45.0 50.0 Time, t (s) 50 28 20 15 12 Inference 1. A yellow precipitate formed is sulphur 2. Sulphur dioxide gas is produced 3. When the temperature of sodium thiosulphate decreases, the production of the yellow precipitate of sulphur becomes faster. Thus, the rate of reaction increases
1 (s–1) Time

Conclusion: 1. An increase in temperature of sodium thiosulphate increases the rate of reaction 2. The hypothesis is accepted. Explanation: 1. The reaction between sulphuric acid and sodium thiosulphate solution produces sodium sulphate solution, sulphur, sulphur dioxide gas and water. Chemical equation:

Ionic equation:

2. Based on the graph I, the curve implies that as the temperature of sodium thiosulphate solution becomes higher, the time taken for the mark ‘X‘ to disappear from sight becomes

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shorter. 3. Based on graph II, the straight line implies that the temperature of sodium thiosulphate 1 solution is directly proportional to . Time 4. In other words, the temperature of sodium thiosulphate solutions is directly proportional to the rate of reaction. Use of collision theory to explain the effect of Temperature on the rate of reaction 1. When the temperature increase, the average kinetic energy of the reacting particles increases. 2. The particles move faster and collide more often with one another. The frequency of collision among the reacting particles increases. 3. Particles also have more energy to overcome the activation energy. 4. These changes increase the frequency of effective collision. 5. Hence, the rate of reaction increase. Use of collision theory to explain the effect of Temperature on the rate of reaction 1. when the pressure of gaseous reactant increases, the particles are compressed to occupy a smaller volume. The number of gas particles per unit volume increases. 2. The frequency of collision among the reacting particles increases. 3. This increases the frequency of effective collision. 4. Hence, the rate of reaction increases.

Lower pressure results in less collision among Higher pressure results in more collision particles as the particles are far from one among particles as the particles are pushed another. near to one another.

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IV Effect of catalyst on the rate of reaction 1. A catalyst is a substance which alters the rate of a chemical reaction while it remains chemically unchanged at the end of the reaction. 2. A positive catalyst increases the rate of reaction whereas a negative catalyst (inhibitors) decreases the rate of reaction. 3. Most catalysts are transition elements or compounds of transition elements such as iron, nickel and copper (II) sulphate, CuSO4.

Only a small amount of catalyst is needed to increases the rate of reaction. An increase in the quantity of catalyst will increase the rate of reaction but only a very slight increase

Alters the rate of reaction

Catalyst

It is specific in its action. It can only catalyse a particular reaction

During a reaction, catalyst remains chemically unchanged but may undergo physical changes. For example, catalyst may turn into powder during the reaction
Experiment Aim:

Does not change the quantity of products formed

To investigate the effect of catalyst on the rate of reaction Problem statement: Does the presence of a catalyst increase the rate of reaction? Hypothesis: The presence of a catalyst increase the rate of reaction. Variables: Manipulated variable: the presence of the catalyst Responding variable: Rate of reaction Controlled variables : Mass of zinc granules, volume and concentration of HCl acid, Temperature

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Apparatus: 50 cm3 measuring cylinder, 150 cm3 conical flask, stopper with delivery tube, basin, burette, electronic balance and stopwatch Materials: 0.1 mol dm–3 hydrochloric acid, 5 g of zinc granules, 0.5 mol dm–3 copper (II) sulphate solution and water Procedure: 1. 50 cm3 of 0.1 mol dm–3 hydrochloric acid is measured and pored into a conical flask. 2. About 5 g of granulated zinc is weighed using an electronic balance. 3. A burette is filled full with water. It is then inverted into a basin containing water and clamped vertically using a retort stand. 4. The water level in the burette is adjusted to 50 cm3 mark. 5. The set up of the apparatus is shown in Figure below.

6. The granulated zinc is added into the conical flask containing hydrochloric acid. 7. 5 cm3 of 0.5 mol dm–3 copper (II) culphate solutions is added to the conical flask. 8. The conical flask is closed immediately with a stopper which is joined to delivery tube. At the same time, the stopwatch is started. 9. The conical flask is shaken steadily throughout the whole experiment. 10. The volume of gas collected in the burette by downward displacement of water is recorded at 30-second intervals for a period of 5 minutes. 11. The experiment is repeated without adding 5 cm3 of 0.5 mol dm–3 copper (II) culphate solutions to the conical flask. 12. The results are recorded in a table. Results: Experiment 1: With 5 cm3 of 0.5 mol dm–3 copper (II) culphate solutions (with catalyst)
Time (s) Burette reading (cm3) Volume of gas (cm )
3

0 50.00

30 37.00

60 29.00

90 23.00

120 19.00

150 16.00

180 14.00

210 12.00

240 10.50

270 9.50

300 9.00

0.00

13.00

21.00

27.00

31.00

34.00

36.00

38.00

39.50

40.60

41.00

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Experiment 2: Without 5 cm3 of 0.5 mol dm–3 copper (II) culphate solutions (without catalyst)
Time (s) Burette reading (cm3) Volume of gas (cm )
3

0 50.00

30 43.00

60 38.00

90 34.00

120 30.00

150 27.00

180 25.00

210 22.00

240 21.00

270 19.00

300 18.00

0.00

7.00

12.00

16.00

20.00

23.00

25.00

28.00

29.00

31.00

32.00

Calculation: From your graph, 1. To calculate the average rate of reaction at 200 seconds: a) Experiment 1 b) Experiment 2 c) By comparison, the average rate of reaction for experiment 2 is higher than experiment 1 at 300 seconds. 2. To calculate the instantaneous rate of reaction at 120 seconds: a) Experiment 1 b) Experiment 2 c) By comparison, the instantaneous rate of reaction for experiment 2 is higher than experiment 1 at 120 seconds. Observation 1. Gas bubbles are produced. 2. Liberation of gas is the fastest at the beginning and it slows down later. 3. From the graph plotted, it can be seen that the gradient of the curve for the experiment with a catalyst (copper (II) sulphate solution) is higher than the gradient of the curve for the experiment without a catalyst. Conclusion: 1. The presence of catalyst increase the rate of reaction. 2. The hypothesis is accepted. Explanation: 1. The reaction between hydrochloric acid and zinc produces hydrogen gas and zinc chloride solution. Inference 1. Hydrogen gas is produced. 2. The reaction is the fastest at the beginning and then it slows down. 3. The rate of reaction for the experiment using a catalyst is higher that the rate of reaction for the experiment without a catalyst.

2. Based on the graphs plotted, the curve for experiment 1 is steeper than experiment 2. 3. This means the rate of reaction for experiment 1 (using catalyst) is higher than experiment

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2 (without catalyst). 4. The curves becomes less steep with time due to the decrease in concentration of hydrochloric acid and mass of zinc granules. 5. If both experiments are continued until the reaction is completed, the following graph will be obtained.

6. Both experiments produce the same maximum volume of hydrogen gas. This is because both experiments use the same a) concentration and volume of hydrochloric acid b) mass of zinc granules

Use of collision theory to explain the effect of catalyst on the rate of reaction 1. When a positive catalyst is used in a chemical reaction, it provides as alternative path with a lower activation energy. 2. More colliding particles are able to overcome the lower activation energy. 3. The increases the frequency of effective collision. 4. Hence the rate of reaction increases.