RATES OF REACTION

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Rates of reaction Reactions can be very fast, like fireworks or explosives, but they can also be very slow such as an apple turning brown.

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Rates of reaction
Chemical reactions occur when particles of reactant collide with enough energy to react.

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Speeding up reactions

Anything that increases the chance of effective collision increases the rate (speed) of reaction. Factors include:
Increased surface Area Increased concentration Increased temperature Use of a catalyst
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Surface area
The reactions of solids can clearly only take place at the surface of the solid. If we break a solid into smaller pieces we get more area and a faster reaction.

Molecules collide with the surface of the solid

Extra surface for molecules to collide with.

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Surface area
If we grind up a solid to a powder we massively increase the surface area. We therefore massively increase the rate of any reaction

Slow

Very fast

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An indigestion tablet fizzes in water but fizzes much faster if it is crushed. Which glass has the crushed tablet?

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Concentration
Reactions in solution involve dissolved paticles that must collide before reaction is possible. The more crowded (concentrated) the solution, the faster the reaction.

Collisions infrequent

Collisions frequent
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Pressure Reactions involving gases are affected by the pressure of the gases present. If we cover one end of a bicycle pump and push in the plunger we increase the pressure.
Low pressure High pressure

What we are doing is squeezing the gas molecules closer together or making them more concentrated. And so - pressure speeds up gas reactions
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 The Haber Process, in which nitrogen reacts with hydrogen to form ammonia, is carried out at 200 atmospheres pressure. How and why will this affect the rate of reaction?
The particles will be 200 times closer together and so will collide much more often. The reaction will be much faster.
compress

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Temperature
At higher temperatures molecules move faster. As a result there are more collisions per second and so a faster reaction occurs. Slow molecules are also less likely to lead to a reaction than fast ones.

Fewer collisions per second

More collisions per second

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 Food spoils because of chemical reactions that occur. Why does food remain usable for so much longer if it is kept in a freezer?
The reactions that cause the food to go off will be slower because there will be fewer and softer collisions between molecules at a reduced temperature.

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 Before microwave ovens were common many people used pressure cookers. It was a pan that stopped the water boiling until it reached about 115oC. How would this help cooking?
The molecules move faster and collide more often and with more energy. Cooking times were greatly reduced.

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Activation energy Chemical reactions involve the formation of Energy is Activation bonds between atoms often before new given but out as energy bonds can be formed ones have to be newold bonds needed to broken. form break existing This means that there has to be enough energy bonds (activation energy)to start breaking the old bonds before a reaction can occur.

Reactants

Old bonds start to break

New bonds form

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Activation energy
Most reactions are exothermic (give out heat) overall but there is still a need for energy to get the reaction started.

Activation energy

Break old bonds

Energy taken in

Form new bonds

Energy given out

Reaction
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1. Why doesnt petrol catch fire when it is poured through air? 2. Why is just one spark enough to create a major explosion?

1. Energy is needed to break the bonds in petrol before new bonds can be formed by a reaction with oxygen.
2. Once some of the bonds in one petrol molecule have been broken the subsequent reaction with oxygen gives out enough energy to break the bonds in several other petrol molecules - and so on.

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Catalysts
For chemical reactions to occur: Existing bonds have to begin breaking so that new ones can be formed. The molecules have to collide in such a way that the reacting parts of the molecules are brought together.

Catalysts can help with either or both of these processes.

A catalyst is a substance that speeds up a reaction without getting used up in the process.

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Catalysts
In the presence of a nickel catalyst vegetable oil and hydrogen react to form margarine. Nickel adsorbs hydrogen gas onto its surface in such a way that the bond holding the hydrogen molecule together becomes stretched. This partial breaking of the bond lowers the activation energy making hydrogen more reactive.

H H H H H HH H H HH H

Ni Ni Ni Ni Ni Ni
catalyst

The stretching of the H-H bond lowers the activation energy and helps hydrogen react with the oil
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Catalysts
Other catalysts, especially enzymes, absorb molecules in a way that not only stretches bonds but also brings the reacting parts of reactants right next to each other.

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Catalysts
Catalysts are used in the manufacture or application of a huge number of products.
Biological soap powder uses biological catalysts (enzymes) Enzymes in pineapple help cooked ham to be more tender.

Manufacture of fertiliser via the Haber Process involves use of an iron catalyst. Synthetic materials like polyester are made using a catalyst.

Plastics are made using catalysts.

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Inside car engines some of the nitrogen and oxygen from the air combine to form poisonous nitrogen oxide. Inside the exhaust system a catalyst encourages decomposition back into nitrogen and oxygen. 1. Copy the energy profile for the uncatalysed reaction and draw in new lines showing how the presence of a catalyst will alter the profile.

2NO2

N2 + 2O2

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Measuring reaction rates

Rate implies we are measuring how things change over a period of time. To measure the rate of a reaction we have to track the manner in which the amount of product (or reactant) changes over time.

Rate of gas formation can be measured using a syringe.

For a reaction in which sulfur is precipitated we can time how long the solution takes to go cloudy.

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Slower and slower

Reactions do not proceed at a steady rate.
They start fast and get slower and slower.

This is not surprising because the reactant concentration (and the chance of collision) gets lower and lower as time progresses.
fast slower very slow stopped

25

75

100

Percentage completion of reaction

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Rates and Graphs

These show the increasing amount of product or the decreasing amount of reactant.
Amount of product

Amount of reactant

Shallow gradient Slow reaction

Steep gradient Fast reaction

Steep gradient Fast reaction

Shallow gradient Slow reaction

Time

Time
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Rate graphs and reactant concentrations

All product

Amount of product

Mix of reactant
And product
Reactant Concentration falls

Rate of Reaction falls Gradient of graph decreases All reactant

Time
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Some Reaction Rates Experiments

The following slides describe the four chemical reactions that are commonly used as examples.

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Acid and marble

Marble chips are calcium carbonate. They react with acid to evolve a gas.
calcium carbonate + hydrochloric acid

calcium chloride

+ water

+ carbon dioxide

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

The gas given off can be collected in a syringe and readings taken every 30 seconds or so. Glass tube Gas syringe

Hydrochloric acid Marble chips

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Acid and marble

1. Measure the agreed mass of marble chips 2. Set up the syringe, flask and connector 3. Measure the acid / water. 4. Add the marble chips and quickly insert the bung and start stop clock. 5. Take syringe readings at 30 second intervals.

Time

Reading

0s

0 cm3

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Acid and marble

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Acid and metal Reactive metals (eg. Magnesium) react with acid to evolve hydrogen gas.
magnesium + hydrochloric acid
magnesium

+ hydrogen

chloride

Mg(s)

+ 2HCl(aq)

MgCl2(aq)

+ H2(g)

As the gas given off leaves the flask the total mass of the flask and its contents decreases slightly. Readings of the mass(g) can be taken. Typically at 1 minute intervals.
11.73 11.71 11.80 11.72 11.74 11.77

HCl Mg

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Acid and metal 1. Measure the agreed volume of acid / water into the conical flask. 2. Have a loose plug of cotton wool to prevent spitting of droplets of liquid. 3. Have a piece of magnesium of known mass ready. 4. Add the magnesium, place the cotton wool in the neck and start taking mass readings immediately.
Cotton wool HCl Mg 11.73 11.71 11.80 11.72 11.74 11.77

Time 0s 60

Reading 0 cm3

120

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Acid and metal

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Decomposition of Hydrogen Peroxide

Hydrogen peroxide decomposes into water and oxygen.
Hydrogen peroxide

water

+ oxygen

2H2O2(aq)

2H2O(l)

+ O2(g)

Oxygen gas is given off and can be measured using a gas syringe or a balance. The reaction is catalysed by a wide range of solids.
Remember the catalyst NEVER produces more product - just quicker
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Acid and Sodium Thiosulphate In this reaction sulphur is precipitated which makes the solution turn cloudy.
+ hydrochloric sodium + water + sulphur + sulphur Sodium acid thiosulphate chloride dioxide

Na2S2O3(aq)

+ 2HCl(aq)

2NaCl(aq) + H2O(l) + SO2(g) + S(s)

The effect of changing conditions such as temperature or concentrations can be studied by measuring how long it takes to produce enough sulphur to make the solution opaque (non see-through).

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1.

2. 3.

4.

5.

Measure the agreed volume of thiosulphate / water into the conical flask. Prepare a piece of paper with a cross drawn on it. Measure the required volume of acid in a measuring cylinder. Add the acid to the flask, start the clock, swirl the flask. Look down through the flask until the cross disappears. Note the time.

Look down here

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1. 2.

Imran studied the effect of temperature upon the time it took for the flask to go cloudy. Sketch a graph of the results. Using the reactions at 25oC and 40oC, explain how the time taken lets you work out the relative rate of reaction.

120 100 80 60 40 20 0 20

Time(s) vs Temp(oC) Temp (oC)

Time

Time taken (s)

25 30 35 40 45 50 30
Temp

100 60 40 25 15 10 50
60

40

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Some Rates Questions

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A pupil performed an investigation into the rate of reaction between a metal and an acid. The results below where obtained.
Time /seconds Volume of gas (cm3) 0 0 10 25 20 80 30 40 50 273 60 282 70 282 80 282

179 245

i) Plot a graph of gas volume (y-axis) against time (x-axis) ii) When was the rate of reaction fastest? iii) Use the graph to find the volume of gas produced after 35 seconds. iv) Use the graph to tell after how long the reaction stopped. v) On the graph sketch a line showing the experiment repeated at a higher temperature.

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Answer

Experimental Results
300 250
200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 Time / seconds

ii) The reaction was fastest at about 25 seconds as the gradient of the line is highest at this point. iii) About 175 cm3 iv) About 55 seconds. v) Higher temperature reaction is in red.

Volume / cm3

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A flask was connected to a gas syringe by a glass delivery tube. 30cm3 of water and 0.5g of manganese dioxide were added to the flask. Then 5cm3 of hydrogen peroxide was added and the stopper quickly fitted. Readings of the volume of gas produced were taken every 10 seconds.
Time /seconds Volume /cm3

0 0

10 18

20 30 40 50 60 70 80 30 40 48 53 57 58 58

i) Plot a graph of volume of gas (y-axis) against time (x-axis). Label this curve A. ii) Without emptying the flask another 10cm3 of water and a further 5cm3 of hydrogen peroxide were added. Sketch the shape of the second experiment and label it B.
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Answer
70 60 50 40 30 20 10 0
0

Volume of gas / cm3

A B

Time (s)
10 20 30 40 50 60 70 80 90 100 110 120

Notes: Curve B is an experiment with half the concentration of hydrogen peroxide. This should produce about half the rate as shown by a line with half the gradient of A. However, the same amount was added so 58cm3 of gas will still be produced.
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Time /seconds Mass loss /g Mass loss /g

0 15

30

45

60

75

90

120

0 0.21 0.45 0.67 0.85 1.01 1.13 1.31 1.41 1.48 1.51 1.54 1.56 1.58 1.59

Time /seconds 150 180 210 240 300 360 420

i) The results above were obtained from an experiment where the loss in mass was recorded as lumps of zinc reacted with hydrochloric acid. Plot a graph of mass loss (y-axis) against time (x-axis). ii) On the graph sketch the lines you would expect if a) the concentration of acid was reduced, b) the temperature was increased.
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Answer

(b) (a)

loss in mass /g

1.5 1 0.5 0 0 200 400

600

Time / seconds

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Which of these would speed up the rate at which magnesium dissolves in acid? A. B. C. D. Cool the acid. Cut up the magnesium. Add water. Coat the magnesium in oil.

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Why does breaking up solids increase the rate of reaction? A. B. C. D. Makes more solid. Creates more energy. Increases surface area. Increases the concentration.

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Why does temperature increase the rate of reaction? A. B. C. D. Acts as a catalyst. Increases the concentration. Increases number of molecules. Makes collisions more frequent and harder.

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Why does a catalyst increase the rate of reaction? A. Provides a route with a lower activation energy. B. Helps provide energy for the reaction. C.Increases the speed of reactant molecules. D. Reduces the number of molecular collisions.

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Why do most reactions start fast and get slower and slower? A. They run out of energy. B. They run out of catalyst. C. The concentration of reactant molecules gets less and less. D. The surface area increases.

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