Reaction Rates Practice Questions 1.

Define reaction rate Reaction rate is the change in the amount of reactants or products per unit time. 2. You can follow some reactions by measuring electrical conductivity. What causes this change in conductivity? The change in number of ions in the solution causes a change in conductivity. 3. In a clock reaction, how does time relate to the rate of the reaction? The shorter the time it takes to have a colour change in a reaction the faster the rate of reaction. 4. When plotting a graph to work out reaction rate, what variable is on the x-axis? Time (s).

Exam Questions 1. The reaction between iodine and propanone in acidic conditions was investigated. I2(aq) + CH3COCH3(aq) CH3COCH2I (aq) + H+(aq) +I-(aq) 1. Apart from colorimetry, suggest, with a reason, one method that could be used to follow the reaction rate. (2m) There is an increase in the number of ions so follow the reaction by measuring electrical conductivity. OR there is an increase in H+ ions so follow using a pH meter. Outline how the rate of reaction with respect to propanone, at any particular time, could be determined. (3m) Plot a graph of propanone concentration against time. The gradient of a tangent to the curve is equal to the rate of reaction so draw a tangent at a particular time and calculate the gradient. 2. Benzene diazonium chloride (BDC) decomposes in acidic aqueous solution. C6H5N2Cl(aq) + H2O (l) C6H5OH(aq) + HCl(aq) + N2(aq) The following data was collected at 25C. Time(s) 0 10 20 30 40 Conc of BDC 0.20 0.070 0.025 0.0098 0.0031 (moldm-3) a) Using the data provided, plot a graph and use it to determine the rate reaction after 15 seconds. (6m) On graph paper b) Suggest an alternative method that could have been used to follow this reaction. (2m) The volume of nitrogen, using a gas syringe Or the pH using a pH meter.

Orders of Reaction

 The order of reaction with respect to a particular reactant tells you how the reactants concentration affects the rate. You can only find the orders of reaction from experiment The shape of a rate-concentration graph tells you the order To plot a rate-concentration graph find the gradient of the curve or straight line of the concentration-time graph. Horizontal line (zero order) means changing concentration doesnt change the rate. Straight line (1st order) through origin, the rate is proportional to the concentration. A curve (2nd order). The rate is proportional to [] . Note in theory, a curve could mean a higher order than 2 but you wont be asked about them. Half-life (t) of a reaction is the time it takes for half of the reactant to be used up. You can use half-life to work out orders of reaction besides the shape of a rate-concentration graph. Half-lives can be used to distinguish btw 1st and 2nd orders using the concentration-time graphs. The half-life of 1st order is constant but half-live of 2nd order is not constant. Practice Questions 1. If a reaction is first order with respect to a reagent, what happens to the rate if the concentration of that reagent is doubled? The rate doubles as well. 2. Sketch rate-concentration graphs for zero, first and second order reactions. X-axis is concentration, y-axis is rate. Zero horizontal line, First straight line through the origin, Second curve. 3. How does the half-life change with time in a first order of reaction? Half-life stays constant. 4. Describe 2 ways to determine the order of a reaction using a concentration-time graph. Use half-life to distinguish between the first and second order of reaction of the concentrationtime graph. Use the concentration-time graph to find the rate of reactions and using the answers plot a rate-concentration graph. Rate-concentration graphs: Zero order horizontal line, first order straight line through the origin and second order a curve. Exam Questions 1. The decomposition of Hydrogen Peroxide is a first order reaction. a) Under certain conditions, the decomposition has a half-life of 250s. If the original concentration of hydrogen peroxide was 2.0 mol dm-, complete the table of results for this decomposition. (2m) Time(s) 0 250 500 750 1000 [HO] mol 2.0 1.0 0.5 0.25 0.125 dm- 2. Sketch a rate-concentration graph for this decomposition. (3m) On graph paper.

2. The table shows the results of an experiment on the decomposition of nitrogen (V) oxide at constant temperature. Time(s) 0 50 100 150 200 250 300 [NO] 2.50 1.66 1.14 0.76 0.50 0.32 0.22 (mol dm) a) Plot a graph of these results. (3m) on graph paper. b) From the graph, find the times for the concentration of NO to decrease: (4m) (i) to half its original concentration, 85 seconds (ii) from 2.0 mol dm-, 31 seconds half-life from 2.0 concentration110 seconds 31 seconds = 81 seconds c) Giving a reason, deduce the order of reaction. (2m) The order of reaction is 1 because the half-life of approximately 85 seconds is independent of concentration .

Rate Equations The bigger the rate constant (k) the faster the rate of reaction. The rate constant is always the same for a certain reaction at a particular temperature. If the concentration of a reactant increase rate increases but not rate constant. If you are given the rate constant, K, the order of reaction and the reactant concentration you can work out the half-life. Each order has an equation you dont need to remember them, but you might be asked to use them. Half-lives can be used to figure out rate equations from a graph. Practice Questions 1. What are the units for rate in a rate equation? Mol dm-3s1 2. What is the order of a reaction if the half-life is independent of the reactant concentration? 1st order. Exam Question 1. The following reaction is second order with respect to NO and first order with respect to H2. Write a rate equation for the reaction and state the overall order of the reaction. (2 marks) Rate = K [NO (g)] 2[H2 (g)] o Remember to include state symbols 2. In a reaction between A and B, the rate equation has been determined to be Rate = k [A] [B] 2 What happens to the reaction rate, at constant temperature, when: 1. The initial concentrations of both A and B are doubled. If A is doubled the reaction rate doubles. If B doubles the reaction rate quadruples. Therefore, the overall rate increases by the factor 2 * 4 = 8

2. The initial concentration of A is halved and B is doubled. If A is halved the reaction rate halves. If B doubles the reaction rate quadruples. Therefore, the overall rate of reaction increases by factor *4 = 2.

Deducing Orders and Rate Equations Experiment Change compared to Ex 1 1 2 Propanone doubled 3 Propanone trebled 4 Iodine doubled 5 Iodine trebled 6 H+ doubled 7 H+ trebled From the table above, you can say Rate of reaction 0.033 0.062 0.092 0.034 0.032 0.058 0.094 Change Rate doubled Rate trebled No change in rate No change in rate Rate doubled Rate trebled

The rate is proportional to propanone, so the order is 1 with respect to propanone The rate is independent of iodine, so the order is 0 with respect to iodine. The rate is proportional to H+, so the order is 1 with respect to H+. With this you can write the rate equation Rate = K [CH3COCH3]1 [H+] 1 [I2] 0 = K [CH3COCH3] [H+]

Practice questions 1. Why are the samples from the reaction between propanone and iodine added to sodium hydrogencarbonate? To stop the reaction in the sample as sodium hydrogencarbonate neutralizes the acid. 2. What is the indicator used when titrating samples of the reaction mixture with sodium thiosulfate? starch 3. In this investigation, why is the concentration-time graph a straight line? The rate of reaction is independent of iodine so the order is zero hence a straight line. 4. If the graph was a curve, where would you measure the gradient? At t = o. Exam questions 1. The table shows the results of a series of initial rate experiments for the reaction between substances D and E. Experiment D (mol dm-3) E (mol dm-3) Initial rate * 10-3 (mol dm-3 s-1) 1 0.2 0.2 1.30

2 3

0.4 0.2

0.2 0.4

5.19 2.61

a) Find the order of the reaction with respect to reactants D and E. Explain your reasoning. Comparing experiment 1 and 2 when D is doubled and E is kept constant the initial rate quadruples and so the order is 2 with respect to D. Comparing the experiment 1 and 3 when E is doubled and D is kept constant the initial rate doubles and so the order is 1 with respect to E. b) Write the rate equation for the reaction. Rate = k [D] 2 [E] 2. X and Y react together according to the equation X + 3Y XY3 In a series of experiments carried out at 288K, the following results were obtained experiment Initial X (mol dm-3) Initial Y (mol dm-3) Initial rate (mol dm3 -1 s ) 1 0.100 0.100 0.00198 2 0.100 0.300 0.01801 3 0.200 0.100 0.00401 a) What is the order of reaction with respect to X? Comparing experiment 1 and 3 when X doubles and Y is constant the initial rate doubles so the order is 1. b) What is the order of reaction with respect to Y? Comparing experiment 1 and 2 when Y is tripled and X is kept constant the initial rate increases by a factor of 9 (32 = 9), so the order is 2. 3. Write the rate equation for the reaction between X and Y. Rate = k [X] [Y] 2 4. Experiment [A] / moldm-3 [B] / moldm-3 Initial rate/moldm-3 1 0.2 0.2 3.5*10-4 2 0.4 0.4 1.4*10-3 3 0.8 0.4 5.6*10-3 Determine the overall order of reaction between A and B. Explain how you reached your conclusion. Overall order of reaction = 2nd order Explanation= When doubling BOTH concentrations the initial rate of reaction increased by a factor of 4. Determine the order of reaction with respect to compound B. Explain how you reached your conclusion. Order with respect to B = 0 order

Explanation = When [B] is constant and [A] doubles the rate of reaction increase by a factor of 4 as well. Since the order of reaction with respect to [A] is 2nd order and overall reaction is 2nd order hence the order with respect to [B] is 0 order. 5. Iodine and propanone react in acid solution according to the equation. I2 + CH3COCH3 CH3COCH2I + HI The rate equation for the reaction is found to be Rate = k[CH3COCH3] [H+] How can you tell that H+ acts as a catalyst in this reaction? H+ is present in the rate equation but not present in the stoichiometry equation which tells us that H+ is not chemically involved in the reaction but changes the rate of reaction. Rates and Reaction Mechanisms Rate determining step is the slowest step in a Multi-step reaction. Overall rate is determined by the step with the slowest rate, i.e the rate-determining step. If a reactant appears in the rate equation it must be affecting the rate so this reactant must be in the rate-determining step. Rate-determining step doesnt have to be the first step in a mechanism. The reaction mechanism cant usually be predicted from just the chemical equation. The order of a reaction shows the number of molecules of that reactant which are involved in the rate-determining step. Practice questions 1. In a multi-step reaction, whats the name given to the step with the slowest rate? Rate-determining step. 2. Knowing the order of reaction is important for suggesting a rate-determining step. Why? To know how many molecules of that reactant is involved in the rate-determining step. 3. In the reaction of iodine with propanone, why doesnt iodine appear in the rate equation? Rate is independent ofconcentration iodine and so is not involved in the rate determining step. Exam Questions 1. The following reaction is first order with respect to H2 and the first order with respect to ICl. H2(g) + 2ICl(g) I2(g) + 2HClg) a) Write the rate equation for this reaction. Rate = k [H2(g)] [ICl] b) The mechanism for this reaction consists of two steps. i. Identify the molecules that are in the rate-determining step. Justify your answer.

1 molecule of hydrogen gas and I molecule of iodine chloride. These molecules are in the rate equation. The orders of the reaction tell you how many molecules of each reactant are in the rate-determining step. ii. A chemist suggested the following mechanism for the reaction. 2ICl(g) I2(g) + Cl2(g) slow H2(g) + Cl2 2HCl(g) fast Suggest, with reasons, whether this mechanism is likely to be correct. This mechanism is incorrect because hydrogen is not in the slow step equation which is one of the molecules involved in the slow step OR the order of reaction with respect to ICl is 1 so there must only be only one molecule of ICl in the rate-determining step. 2. The reaction between HBr and O2 was studied at 400 C. 4HBr(g) + O2 2H2O(g) + 2Br2(g) rate = k[HBr][O2] a) What is the order of reaction with respect to each reactant? The order of reaction with respect to HBr is 1 and the order of reaction with respect to O2 is 1. b) What species must be involved in the rate-determining step, and in what molar ratio? HBr and O2 in the molar ratio of 1:1. c) The following steps have been suggested for the mechanism. Re-write them in the correct order and label the rate-determining step. 2HBrO + 2HBr 2H2O + 2Br2 HBr + O2 HBrO2 HBrO2 + HBr 2HBrO In correct order: HBr + O2 HBrO2 HBrO2 + HBr 2HBrO 2HBrO + 2HBr 2H2O + 2Br2 Halogenoalkanes and Reaction Mechanisms 2 different types of mechanisms for nucleophilic substitution SN1 and SN2 SN1 reactions only involve 1 molecule or ion in the rate-determining step SN2 reactions involve 2 molecules, 1 molecule and 1 ion, or 2 ions in the rate determining step. Primary halogenoalkanes only react by the SN2 mechanism Secondary halogenoalkane react by SN1 and SN2 mechanism Tertiary halogenoalkane react by SN1 mechanism. Rate-determining step

Practice Questions 1. Which sort of bromoalkane is 2-bromobutane primary, secondary or tertiary? Secondary

2. What is the role of the hydroxide ion in the hydrolysis of a halogenoalkane? Nucleophile 3. What do the terms SN1 and SN2 mean? Nucleophilic substitution mechanism 1 and Nucleophilic substitution mechanism 2. 4. What is the order of reaction with respect to hydroxide ions in the hydrolysis of a tertiary halogenoalkane? Order of reaction with respect to hydroxide ions is 1. Exam Questions 1. For the reaction between NaOH and 1-chloropropane CH3CH2CH2Cl + NaOH CH 3CH2CH2OH +NaCl Which one of the following is the correct rate equation? D Rate = k [CH3CH2CH2Cl] [NaOH] 2. The hydrolysis of 2-bromo-2-methylpropane by hydroxide ions follows an SN1 mechanism. Which one of the following is the rate-determining step? Answer is A 3. The following equation shows the hydrolysis of 1-iodobutane by hydroxide ions: CH3CH2CH2CH2I + OH- CH3CH2CH2CH2OH + Ia) Is 1-iodobutane a primary, secondary or tertiary iodoalkane? Primary. b) Write the rate equation for this reaction. Rate = k [CH3CH2CH2CH2I] [OH-] c) What type of mechanism is involved in this reaction? SN2 d) Write equation(s) to show the detailed mechanism of this reaction.

Always remember for the 1 step mechanism it should be carbon atom in the centre, the halogen on the right and the nucleophile on the left, the rest of the alkyl groups on the top and the hydrogen groups on the bottom. The activated complex must have brackets and a negative sign and it forms a Y shape with 2 straight lines sticking out at the sides.

Arrhenius equation links rate constant with activation energy and temperature K = Ae-Ea / RT K= rate constant, A = another constant, Ea = activation energy, T = temperature, R = gas constant (8.31 J k-1 mol-1), e = the ex button on the calculator and shows an exponential relationship. As activation energy gets larger, K gets smaller so a slower rate. As T increases, k increases. Arrhenius equation in logarithmic form In K =In A Ea/RT = a constant Ea / RT Note: In is a button on your calculator. The equation above can be used to create an Arrhenius plot. An Arrhenius plot is always a straight line graph

 Plot an Arrhenius plot by plotting In K against 1/T (x-axis) With Arrhenius plot you can find the gradient that is -Ea /R and hence the activation energy. Another way to calculate Ea is using the iodine-clock method. In this method the rate is inversely proportional to time hence 1/t. This means that 1/t can be used instead of K (rate constant) in the Arrhenius equation Examples of heterogeneous catalyst: Nickel in the hydrogenation of vegetable oil, Platinum and rhodium in catalytic converters in cars and vanadium (v) oxide in contact process. Heterogeneous catalyst can be poisoned. A poison is a substance that clings on to the surface of the catalyst more strongly than the reactant preventing the catalyst from getting involved in the reaction its meant to be speeding up. Practice Questions 1. The Arrhenius equation can be written as In k = a constant Ea / RT. What do the terms k, T and R represent. K = rate constant, T = temperature and R = Gas constant 2. The Arrhenius equation is k = Ae-Ea / RT. Which one of the following answers is true as Ea increases? D = K decreases and rate of reaction decreases. 3. Give three examples of heterogeneous catalysts. Rhodium and platinum catalysts, vanadium pentoxide, nickel. 4. Explain how a catalyst works. A catalyst provides an alternative pathway with lower activation energy. The catalyst is chemically unchanged at the end of the reaction. Exam Questions 1. Finely divided iron catalyses the reaction of nitrogen and hydrogen in the Haber process. Which of the following statements is incorrect? C The iron provides an alternative route of higher activation energy. 2a) Explain what is meant by the term activation energy. Activation energy is the minimum amount of energy particles need to react. b) With the help of energy profiles, explain how catalyst works. (in book) Explanation: Catalysts provide an alternative pathway with lower activation energy for a reaction. At lower activation energy there are more molecules with the required kinetic energy to react. Thus, more successful collision take place which increase the average rate of reaction. c) The table gives values for the rate constant of the reaction between hydroxide ions and bromoethane at different temperatures. i. Complete the table and then plot a graph of In K (y-axis) against 1/T (xaxis). T k 1/T In k

305 313 323 333 344 353 ii. iii.

0.181 0.468 1.34 3.29 10.1 22.7

0.00328 0.00319 0.00310 0.00300 0.00291 0.00283

-1.709 -0.759 0.293 1.191 2.313 3.127

Measure the gradient of the straight line produced. -10750 Using the Arrhenius equation, In K = a constant Ea /RT, calculate the activation energy of the reaction. (R = 8.31 J K-1 mol-1) 89333 J mol-1 or 89.3 kJ mol-1

Section 2 - Entropy Practice Questions 1. How does the energy of a substance affect entropy? The more energy quanta a substance has the more ways they can be arranged and so the greater the entropy. 2. Why does entropy increase with increasing temperature? The particles have greater energy and so there is a greater number of ways in which the energy can be distributed. 3. Is the change in entropy greater at the melting point of a substance, or at its boiling point? Why? The change in entropy is greater at its boiling point. The substance changes from liquid to gas at boiling point and changes from solid to liquid at melting point. Gas particles have higher entropy than liquid particles so a greater entropy is found at the boiling point of a substance. 4. In each of the following pairs choose the one with the greater entropy value: a) 1 mole of NaCl(aq) and 1 mole of NaCl(aq) b) 1 mole of Br2(l) and 1 mole of Br2(g) B has a greater entropy. Exam Questions 1a) Define the term entropy. Entropy is a measure of the number of ways that particles in a substance can be arranged and the number of ways that energy can be shared out between particles. b) Explain whether each of the following reactions is likely to result in an increase or a decrease in entropy. Give a reason for your answer. i. 2NaNo3(S) 2NaNO2(s) + O2(g)

Increase because the 2 moles of solid are converted into 2 moles of solid and 1 mole of gas. Therefore, there are more particles, and gas particles have more entropy than those in solids. ii. CO2(g) + C(s) 2CO(g) Increase because 1 mole of gas and 1 mole of solid are converted into 2 moles of gas particles and gas particles have more entropy than those in solids. iii. N2(g) + 3H2(g) 2NH3(g) Decrease because 4 moles of gas particles are converted into 2 moles of gas particles and there is less entropy when there are fewer particles. iv. H2(g) + 1/2O2(g) H2O(l) Decrease because 1 moles of gas particles are converted into 1 mole of liquid particle and gas particles have a higher entropy than those in liquids. Also, there is less entropy when there are fewer particles 2. Based on just the equation, predict whether the reaction below is likely to be spontaneous. Give a reason for your answer. Mg(s) + O2(g) MgO(s) It is likely to be non-spontaneous because there is a decrease in entropy. Entropy Change Practice Question What is formula for calculating the total entropy change of a system? Total entropy Stotal = Ssystem + Ssurroundings For a particular reaction, H = -420 kJ mol-1. What is the Ssurroundings at 298 K? Ssurroundings = -H / T = -(-420000)/298 = + 1409.4 J K-1 mol-1 If a chemical reaction is exothermic, what must Ssurroundings be? The change of the surroundings must be positive The decomposition of X has a positive Stotol, but the rate of reaction is measured in thousands of years. What term is used to describe X? X is kinetically inert. Exam Questions 1. When a small amount of ammonium carbonate solid is added to 10cm3 of 1.0 mol dm-3 ethanoic acid, carbon dioxide gas is evolved. This is an endothermic reaction, so the temperature of the reaction mixture drops. (NH4)2 CO3(s) + 2CH3CO2H(aq) 2CH3CO2NH4(aq) + H2O(l) + CO2(g) H > 0 a) Looking at this equation, what would you expect to happen to the entropy of the system during this reaction? Explain your answer. The entropy of the system will increase because 1 mole of solid is combining with 2 moles of substance in solution to produce another solution, a liquid and

1. 2. 3. 4.

a gas. This leads to an increase in disorder. There is also an increase in the number of molecules which will lead to an increase in disorder. b) Explain how this reaction can be both endothermic and spontaneous. The reaction is endothermic so the entropy change of the surrounding will be negative. This means the entropy change of the system must be sufficiently positive to counteract this change. The total entropy change will be positive and the reaction will be spontaneous. 2. Thin ribbons of magnesium burn brightly in oxygen to leave a solid, white residue of magnesium oxide. The equation for this reaction is: 2Mg(s) + O2(g) 2MgO(s) H = -1204kJ mol-1 (at 298 K) S[Mg(s)] = +32.7 J K-1 mol-1, S[O2(g)] = +205 J K-1mol-1, S[MgO(s)] = +26.9 J K-1 mol-1 a) From the equation, predict whether Ssystem for the reaction will be positive or negative at 298 K. Give a reason for your answer. The entropy change of the system will decrease because a solid is combining with a gas to produce only a solid which is a decrease in disorder. b) Using the data given, calculate Ssystem at 298 K. Ssystem = Sproducts - Sreactants = (2*26.9) - (2 *32.7 + 205) = -216.6 J K-1mol-1 c) Calculate Stotal for the reaction. Stotal = -216.6 + -(-1204000/298) = +3823.7 J K-1 mol-1

Dissolving Definition of enthalpy change of solution, enthalpy change of hydration and standard lattice enthalpy. Enthalpy change of solution is the enthalpy change when 1 mole of solute is dissolved in excess solvent that no further enthalpy change occurs on further dilution. Enthalpy change of hydration is the enthalpy change when 1 mole of aqueous ions is formed from gaseous ions. Standard lattice enthalpy is the enthalpy change when 1 mole of solid ionic compound is formed from gaseous ions under standard conditions. Use Hess Law principle to find the enthalpy change of solution. An ionic compound will dissolve in water if Stotal is positive. Smaller ionic size / radii and larger charge increases the amount of energy released and so value of lattice enthalpies and hydration enthalpies is more negative (more exothermic). The enthalpy change of solution tells us the value of the Ssurrounding. So if enthalpy change of solution is endothermic (positive) the Ssystem must be positive and larger value than Ssurrounding so that a positive entropy is produced and the ionic compound can dissolve in water. Stotal = Ssystem + Ssurrounding (-H in joules / T in K), Stotal > 0. Practice Questions 1. Define the term enthalpy change of hydration.

Enthalpy change of hydration is the enthalpy change when 1 mole of aqueous ions is formed from gaseous ions. 2. What other enthalpy changes do you need to know to work out the enthalpy change of solution? Enthalpy change of hydration and standard lattice enthalpy. 3. Why do the hydration enthalpies become more negative along the series: Na+, Mg2+, Al3+? The charge increases along the series. The higher the charge of an ion the more energy is released when an ionic lattice is formed. More energy released means that the lattice enthalpy will be more negative. The factors that affect lattice enthalpy also affects hydration enthalpies. 4. Why does the lattice enthalpy become more negative when the ions involved are smaller in size? The ions are more strongly attracted to one another and they have higher charge density. Hence more energy is released and so lattice enthalpy is more negative. Exam Questions 1. The dissolution of silver iodide is represented as follows: AgI(s) Ag+(aq) + I-(aq) At 298 K: Ssystem = +69.1 JK-1 mol-1, H = +112.3 kJ mol-1 a) Define the term enthalpy change of solution. Enthalpy change of solution is the enthalpy change when 1 mole of solute is dissolved in excess / sufficient solvent that no further enthalpy change occurs on further dilution. b) Write the equation that represents the lattice enthalpy of silver iodide. Ag+(g) + I-(g) AgI(s) c) Calculate Stotal for the dissolution of silver iodide and deduce its solubility in water at 298 K. Stotal = 69.1 + -(112300 /298) = -307.7 J K-1 mol-1. Stotal is negative so silver iodide is insoluble in water at 298K.

2. a) Draw an enthalpy cycle for the enthalpy change of solution of SrF2(s). Label each enthalpy change. In book. First draw the enthalpy change of solution at the top. b) Calculate the enthalpy change of solution for SrF2, from the following data: Hlatt [SrF2(s)] = -2492 kJ mol-1, Hhyd [Sr2+(g)] = -1480 kJ mol-1, Hhyd [F-(g)] = -506kJ mol-1

Enthalpy change of solution = -(-2492) 1480 (2*506) = 0 kJ mol-1 Dynamic Equilibrium