(a) Reaction rates (i) Following the course of a reaction Reactions can be followed by measuring changes in concentration, mass and volume of

Transcription

1 (a) Reaction rates (i) Following the course of a reaction Reactions can be followed by measuring changes in concentration, mass and volume of reactants or products. g Measuring a change in mass Measuring a change in volume

2 Mass of beaker and contents Volume of gas produced Time Time The rate is highest at the start of the reaction because the concentration of reactants is highest at this point. The steepness (gradient) of the plotted line indicates the rate of the reaction.

3 Concentration We can also measure changes in concentration using a ph meter for reactions involving acids or alkalis, or by taking small samples and analysing them by titration or spectrophotometry. product reactant Time

4 Calculating the average rate The average rate of a reaction, or stage in a reaction, can be calculated from initial and final quantities and the time interval. Average rate = change in measured factor change in time Units of rate The unit of rate is simply the unit in which the quantity of substance is measured divided by the unit of time used. Using the accepted notation, divided by is represented by unit -1. For example, a change in volume measured in cm 3 over a time measured in minutes would give a rate with the units cm 3 min -1.

5 Rate = Concentration moll = 50 = 0.001moll -1 s -1 Rate = = = moll -1 s -1

6 The rate of a reaction, or stage in a reaction, is proportional to the reciprocal of the time taken. Rate 1 time Rate is inversely proportional to time. i.e. Rate = 1 time and Time = 1 rate Units: s -1, min -1 etc. Units: s, min etc. See Unit 1 PPA 1 and Unit 1 PPA 2 for examples of clock reactions that use the relationship described above.

7 (ii) Factors affecting rate The rates of reactions are affected by changes in concentration, particle size and temperature. The rate of reaction can be increased by - decreasing the particle size of a solid reactant - increasing the concentration of a reactant in solution - increasing the temperature at which the reaction occurs. The factors which affect reaction rate can be understood more fully by examining the conditions needed for a reaction to take place. For a chemical reaction to occur, reactant particles must collide this is the basis for the Collision theory. The collision theory can be used to explain the effects of concentration and surface area on reaction rates.

8 Collision Theory For a chemical reaction to occur reactants must come into contact (collide). Not all collisions are successful. There are two conditions that are required for a successful collision; (i) The correct collision geometry i.e. reactants must collide with a particular orientation. (ii) Enough energy to break existing bonds within the reactant molecules. The first condition above can be used to help explain the affect of changing the concentration or the particle size. Any factor which increases the number of collisions per second between particles of reactants is likely to increase the rate of reaction.

9 For many reactions a graph of rate against concentration is a straight line showing that the rate is directly proportional to concentration. Rate Concentration

10 The Effect of Temperature on the Rate of Reaction We discovered that the rate of reaction is not directly proportional to the temperature, instead a 10 C rise in temperature roughly doubles the rate. Rate The increase in the number of collisions at a higher temperature is not enough on its own to account for this increase in the rate. Temperature

11 Unsuccessful collision: Activation Energy and Energy Distribution The activation energy is the minimum kinetic energy required by colliding particles before reaction will occur. Successful collision: reactants collide not enough energy to break bonds reactants move apart reactants collide enough energy to break bonds Activation energy products move apart

12 Temperature is a measure of the average kinetic energy of the particles of a substance. Energy distribution diagrams can be used to explain the effect of changing temperature on the kinetic energy of particles. T 1 T 2 The shaded areas represent the total number of molecules which have sufficient energy to react.

13 The effect of temperature on reaction rate can be explained in terms of an increase in the number of particles with energy greater than the activation energy. T 1 T 2 T 2 >T 1 A small rise in temperature causes a significant increase in the number of molecules which have energy greater than the activation energy.

14 Enthalpy Potential energy diagrams Exothermic changes cause heat to be released to the surroundings. During an exothermic reaction potential energy possessed by the reactants is released to the surroundings. The products have less potential energy than the reactants.

15 Endothermic changes cause absorption of heat from the surroundings. In an endothermic reaction the reactants absorb energy from the surroundings so that the products possess more energy than the reactants.

16 The enthalpy change is the energy difference between the reactants and the products. The enthalpy change can be calculated from a potential energy diagram (if drawn to scale). The enthalpy change has a negative value for exothermic reactions.

17 The enthalpy change has a positive value for endothermic reactions. Enthalpy changes are usually quoted in kjmol -1.

18 A potential energy diagram can be used to show the energy pathway for a reaction. products

19 The activated complex is an unstable arrangement of atoms formed at the maximum of the potential energy barrier, during a reaction.

20 If the total energy change for the bond breaking step is less than for the bond making step, the overall reaction will be exothermic.

21 If the reverse is true then the reaction will be endothermic.

22 The activation energy is the energy required by colliding molecules to form an activated complex. In potential energy diagrams the activation energy appears as an energy barrier. The rate of a reaction will depend on the height of this barrier. The higher the barrier the slower the reaction. Note: the rate of reaction does not depend on the enthalpy change. The activation energy can be calculated from potential energy diagrams (if drawn to scale).

23 (iv) Catalysts A catalyst is a substance which alters the rate of a reaction without being used up in the reaction. Catalysts can be classified as either heterogeneous or homogeneous. Heterogeneous catalyst is in a different physical state from the reactants. Homogeneous catalyst is in the same physical state as the reactants. Catalysts are used in many industrial processes. Catalyst Process Reaction Manufacture Revisited in Vanadium(V) oxide Contact 2SO 2 + O 2 2SO 3 sulphuric acid Iron Haber N 2 + 3H 2 2NH 3 ammonia Unit 3 Platinum Ostwald 4NH 3 + 5O 2 4NO + 6H 2 O nitric acid Nickel Hydrogenation Unsaturated oils + H 2 saturated fats Aluminium silicate Catalytic cracking Breaking down long-chain hydrocarbon molecules margarine Unit 2 fuels and monomers for plastics industry Unit 2

24 Heterogeneous catalysts work by the adsorption of reactant molecules. The surface activity of a catalyst can be reduced by poisoning if certain substances are preferentially adsorbed or even permanently attached to the surface of the catalyst. Impurities in the reactants result in the industrial catalysts having to be regenerated or renewed.

25 Catalytic convertors are fitted to cars to catalyse the conversion of poisonous carbon monoxide and oxides of nitrogen to carbon dioxide and nitrogen. The convertors contain honeycomb ceramic material covered with a metal catalyst such as platinum or rhodium. The honeycomb structure is used to increase the surface area of the catalytic convertor. Cars with catalytic converters only use lead-free petrol to prevent poisoning of the catalyst.

26 Enzymes Enzymes catalyse the chemical reactions which take place in the living cells of plants and animals. For example, amylase catalyses the hydrolysis of starch and catalase catalyses the decomposition of hydrogen peroxide in the blood. Enzymes are usually highly specific. The molecular shape of an enzyme usually plays a vital role in its function. substrate Products enzyme

27 Enzymes operate most effectively at a certain optimum temperature and within a narrow ph range. Above this temperature or outwith this ph range the enzyme changes shape (the lock and key no longer fit together) and the enzyme is denatured. Enzymes are used in many industrial processes.