Rate of Reaction and Ionic Equations The rate of a reaction can be measured by the rate at which a reactant is used

up, or the rate at which a product is formed. The temperature, concentration, pressure of reacting gases, surface area of reacting solids, and the use of catalysts, are all factors which affect the rate of a reaction. Chemical reactions can only happen if reactant particles collide with enough energy. The more frequently particles collide, and the greater the proportion of collisions with enough energy, the greater the rate of reaction. Measuring rates Different reactions can happen at different rates. Reactions that happen slowly have a low rate of reaction. Reactions that happen quickly have a high rate of reaction. For example, the chemical weathering of rocks is a very slow reaction: it has a low rate of reaction. Explosions are very fast reactions: they have a high rate of reaction. Reactants and products There are two ways to measure the rate of a reaction: 1. Measure the rate at which a reactant is used up 2. Measure the rate at which a product is formed The method chosen depends on the reaction being studied. Sometimes it is easier to measure the change in the amount of a reactant that has been used up; sometimes it is easier to measure the change in the amount of product that has been produced. Things to measure The measurement itself depends on the nature of the reactant or product: The mass of a substance - solid, liquid or gas - is measured with a balance The volume of a gas is usually measured with a gas syringe, or sometimes an upside down measuring cylinder or burette It is usual to record the mass or total volume at regular intervals and plot a graph. The readings go on the vertical axis, and the time goes on the horizontal axis.

For example, if 24 cm3 of hydrogen gas is produced in two minutes, the mean rate of reaction = 24 2 = 12 cm3 hydrogen / min.

Factors affecting the rate You will be expected to remember the factors that affect the rate of reactions, and to plot or interpret graphs from rate experiments. How to increase the rate of a reaction The rate of a reaction increases if: 1. 2. 3. 4. 5. The temperature is increased The concentration of a dissolved reactant is increased The pressure of a reacting gas is increased Solid reactants are broken into smaller pieces A catalyst is used

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Rate of reaction and changing conditions The graph above summarises the differences in the rate of reaction at different temperatures, concentrations and size of pieces. The steeper the line, the greater the rate of reaction. Reactions are usually fastest at the beginning, when the concentration of reactants is greatest. When the line becomes horizontal, the reaction has stopped. Collisions and reactions You will be expected to explain, in terms of particles and their collisions, why changing the conditions of a reaction changes its rate. Collisions For a chemical reaction to occur, the reactant particles must collide. Collisions with too little energy do not produce a reaction. Changing concentration or pressure If the concentration of a dissolved reactant is increased, or the pressure of a reacting gas is increased: 1. There are more reactant particles in the same volume 2. There is a greater chance of the particles colliding 3. The rate of reaction increases Changing particle size If a solid reactant is broken into small pieces or ground into a powder: Its surface area is increased More particles are exposed to the other reactant There is a greater chance of the particles colliding The rate of reaction increases Changing the temperature If the temperature is increased: The reactant particles move more quickly More particles have the activation energy or greater The particles collide more often, and more of the collisions result in a reaction The rate of reaction increases Using a catalyst Catalysts increase the rate of reaction without being used up. They do this by lowering the activation energy needed. With a catalyst, more collisions result in a reaction, so the rate of reaction increases. Different reactions need different catalysts. Catalysts are important in industry because they reduce costs.

Rate of Reaction and Ionic Equations Electron-half-equations What is an electron-half-equation? When magnesium reduces hot copper(II) oxide to copper, the ionic equation for the reaction is:

You can split the ionic equation into two parts, and look at it from the point of view of the magnesium and of the copper(II) ions separately. This shows clearly that the magnesium has lost two electrons, and the copper(II) ions have gained them.

These two equations are described as "electron-half-equations" or "half-equations" or "ionichalf-equations" or "half-reactions" - lots of variations all meaning exactly the same thing! Any redox reaction is made up of two half-reactions: in one of them electrons are being lost (an oxidation process) and in the other one those electrons are being gained (a reduction process). Working out electron-half-equations and using them to build ionic equations In the example above, we've got at the electron-half-equations by starting from the ionic equation and extracting the individual half-reactions from it. That's doing everything entirely the wrong way round! In reality, you almost always start from the electron-half-equations and use them to build the ionic equation. Example: The reaction between chlorine and iron(II) ions Chlorine gas oxidises iron(II) ions to iron(III) ions. In the process, the chlorine is reduced to chloride ions. You would have to know this, or be told it by an examiner. In building equations, there is quite a lot that you can work out as you go along, but you have to have somewhere to start from! You start by writing down what you know for each of the half-reactions. In the chlorine case, you know that chlorine (as molecules) turns into chloride ions:

The first thing to do is to balance the atoms that you have got as far as you possibly can:

ALWAYS check that you have the existing atoms balanced before you do anything else. If you forget to do this, everything else that you do afterwards is a complete waste of time! Now you have to add things to the half-equation in order to make it balance completely. All you are allowed to add are: 3. electrons

Rate of Reaction and Ionic Equations 4. water 5. hydrogen ions (unless the reaction is being done under alkaline conditions - in which case, you can add hydroxide ions instead) In the chlorine case, all that is wrong with the existing equation that we've produced so far is that the charges don't balance. The left-hand side of the equation has no charge, but the righthand side carries 2 negative charges. That's easily put right by adding two electrons to the left-hand side. The final version of the half-reaction is:

Now you repeat this for the iron(II) ions. You know (or are told) that they are oxidised to iron(III) ions. Write this down:

The atoms balance, but the charges don't. There are 3 positive charges on the right-hand side, but only 2 on the left. You need to reduce the number of positive charges on the right-hand side. That's easily done by adding an electron to that side:

Combining the half-reactions to make the ionic equation for the reaction What we've got at the moment is this:

It is obvious that the iron reaction will have to happen twice for every chlorine molecule that reacts. Allow for that, and then add the two half-equations together.

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But don't stop there!! Check that everything balances - atoms and charges. It is very easy to make small mistakes, especially if you are trying to multiply and add up more complicated equations. You will notice that I haven't bothered to include the electrons in the added-up version. If you think about it, there are bound to be the same number on each side of the final equation, and so they will cancel out. If you aren't happy with this, write them down and then cross them out afterwards!

Multiple Choice 1. Why does increasing the temperature of the reactants increase the rate of a chemical reaction? A Heat energy causes the particles of the reactants to move faster, and therefore react with each other more frequently B Heat energy helps to lower the amount of overall energy that is required for the reaction to occur Heat energy causes some of the reactants to evaporate, increasing the concentration of the reactants Heat energy increases the size of the molecules of reactants, and therefore the molecules react more frequently

2. Which of the following would decrease the amount of time a glow stick would stay bright? A Decrease the concentration of one of the reactants B C D Increase the size of the glowstick Increase the temperature of the reactants Decrease the temperature of the reactants

3. Why are many types of food stored in refrigerators? A Bacteria do not grow well in dark places B The volume inside the refrigerator decreases the concentration of the food particles, allowing them to decompose more slowly The lower temperatures cause the chemical reactions that spoil food to occur more slowly than usual Refrigerators often contain enzymes that slow the rate of food spoiling reactions

Rate of Reaction and Ionic Equations 4. Which of the following would cause the rate of a chemical reaction to slow? A Increase the temperature of the reactants B C D Increase the concentration of the reactants Increase the surface area of the reactants Increase the volume that the reactants take up

5. The burning splint test is a procedure in a chemistry lab to test for the presence of oxygen. Here, steel wool is used instead of burning splint: What concept does the burning splint test illustrate? A Increasing volume increases reaction rate B Increasing concentration increases reaction rate Increasing surface area increases reaction rate Increasing temperature increases reaction rate

6. Which of the following methods for increasing the rate of chemical reaction increases the effectiveness of the interactions between reactants, instead of just causing the reactant molecules to bump into each other more frequently? A Adding a catalyst to the reactants B C D Increasing the concentration of the reactants Increasing the surface area of the reactants Increasing the temperature of the reactants

7. A chemical reaction between two substances is occurring in an aqueous solution. What can be done to increase the rate of reaction? A Increase the concentration of the reactants by adding more to the solution B C D Add a catalytic converter Rapidly cool the container that the reactants are in Pour the reactants into a large, flat container to increase the surface area

Rate of Reaction and Ionic Equations 8. The process of rusting is actually the oxidation of iron, producing iron oxides. Why does a coating of oil slow the oxidation of iron? A The oil cools the chain so that the rusting reaction occurs much slower B The oil is an anti-catalyst, which actually causes the opposite reaction to occur (anti-rusting) The oil stops oxygen from reaching the iron, and therefore decreases the concentration of oxygen in the rusting reaction The oils surface decreases the surface area of the chain, slowing the rusting reaction

9. The rate of a reaction depends upon: the concentration of the reactants. A the temperature of the reaction. B whether or not a catalyst is used. C the nature of the reactants. D All of the above are correct. 11. Which of the following statment(s) about a reaction mechanism is/are true? I. The mechanism is the series of steps needed to complete a reaction. II. The rate of a reaction is only as fast as the slowest step in the mechanism. III. You can usually deduce the reaction mechanism from its reactants and products. A I only B II only C III only D I and II only E I, II, and III

Use your knowledge of collision theory and the energy distribution shown at right to answer questions 11 - 13. Assume that the graph shows the range of energies of collsion of a collection of reactants at two temperatures. 10. Which is the highest temperature? A T1 = T2 B T1 < T2 C T1 > T2 D It is impossible to tell. 11. Which of the curves has the greatest number of collisions possessing the activation energy? A T1 has the greatest number of collisions possessing the activation energy B T2 has the greatest number of collisions possessing the activation energy C Both have an equal number of collisions possessing the activation energy. D It is impossible to tell. 12. If a catalyst were used, how would the distributions change? A Both curves would shift to the right. B Both curves would shift to the left. C The activation energy would shift to the right. D The activation energy would shift to the left.

Rate of Reaction and Ionic Equations E Nothing about the distributions would change.

Use your knowledge of collision theory and the potenial energy digram shown at right to answer questions 14 - 16. Assume the energy values are in Kilojoules.

13. What is the H of the reaction? A + 35 KJ B - 35 KJ C + 25 KJ D - 10 KJ E None of these are correct. 14. Which letter shows the activation energy? A B C D E

15. How would the graph change if the temperature were raised? A A and D would have higher energies. B C would be greater. C The activation energy would decrease. D More than one of the above are correct. E No change in the graph would occur.

Rate of Reaction and Ionic Equations 16.

Rate of Reaction and Ionic Equations 17.

Rate of Reaction and Ionic Equations 18. Three samples of calcium carbonate are placed in flasks for an investigation. In flask E is 5 g of large lumps of calcium carbonate. In flask F is 5 g of medium-sized lumps of calcium carbonate. In flask G is 5 g of small lumps of calcium carbonate. An excess of dilute hydrochloric acid of the same volume is added to each flask. The flasks are placed on three electronic balances. The figure below shows the change in mass of the flasks plotted against time.

(a) (i) Why do the three flasks and contents lose their mass?

(ii) How do the rates of reaction change with time?

(b) (i) Sketch on the same axes the curve you would expect if 10 g of powdered calcium carbonate is used instead of 5 g of large lumps of calcium carbonate. Label this curve H.

(ii) Use collision theory to explain why the size of the lumps affects the rate of reaction.

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19.

(b) In terms of the particle collision theory, explain how a catalyst increases the speed of reaction.

Rate of Reaction and Ionic Equations

20.

Rate of Reaction and Ionic Equations

21.

Sodium thiosulfate solution, Na2S2O3, reacts slowly with dilute hydrochloric acid to form a precipitate. The rate of this reaction can be studied by measuring the time that it takes for a small fixed amount of precipitate needed to obscure a cross on paper. The equation for this reaction is shown below. Na2S2O3 + 2HCl 2NaCl + S + SO2 + H2O (a) Identify the insoluble product of this reaction.

(b) In terms of particles, explain why, at a fixed temperature, you might expect the rate of this reaction to double when the concentration of sodium thiosulfate is doubled and the concentration of hydrochloric acid remains the same.

Rate of Reaction and Ionic Equations

22.

Rate of Reaction and Ionic Equations

23. Methanol, CH3OH, is manufactured industrially by the reaction. CO (g) + 2H2 (g) CH3OH (g) H = - 91 kJ

In the reaction, a mixture of carbon monoxide and hydrogen is passed over a catalyst. a) Name the substances present at equilibrium. [1]

__________________________________________________________________ b) In this reaction, 1.00 mol of carbon monoxide is reacted with excess hydrogen. If the reaction is 75.0% complete, sketch the graph of volume of carbon monoxide against time when a mixture of carbon monoxide and hydrogen are allowed to reach equilibrium over a catalyst. Label relevant values on the graph. [2]

volume of carbon monoxide / dm3 (measured at r.t.p.)

time
c) Suggest why excess hydrogen is used in this reaction. [1] __________________________________________________________________ __________________________________________________________________ __________________________________________________________________ d) The reaction is carried out at a moderate temperature of 300C. After the initial heating to start the reaction, no further heating is required. Explain why. [2] __________________________________________________________________ __________________________________________________________________ __________________________________________________________________

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