Chapter 1.

2 Consolidation

Energetics and enthalpy changes

ANSWERS

Q1. A student writes the following in an examination answer: In an endothermic reaction, the temperature goes up as heat energy is taken in so the molecules in the reaction have more thermal energy. Explain carefully where the student has gone wrong. In an endothermic reaction the temperature goes down, because thermal energy from the surroundings is transferred to chemical energy that becomes locked up in chemical bonds. In an exothermic reaction, chemical energy that was locked up in chemical bonds is transferred to the surroundings, heating them up. Q2. Draw an energy profile for an exothermic reaction where the activation energy is numerically less than the enthalpy change.

Note that the arrows (double headed if you want) must be carefully drawn to indicate exactly the energy change associated with these changes. Q3. Define the following terms: (a) specific heat capacity: This is the amount of energy required raise the temperature of 1 g of a substance by 1 K. (b) standard enthalpy change of reaction: This is the enthalpy change for a reaction under the standard conditions of 298 K, 1 atmosphere pressure, 1 mol dm-3 solution concentration and substances in their normal physical states for these standard conditions. (c) standard enthalpy change of combustion: This is the enthalpy change that occurs when one mole of a substance undergoes complete combustion under the standard conditions of 298 K, 1 atmosphere pressure, 1 mol dm-3 solution concentration and substances in their normal physical states for these standard conditions. (d) standard enthalpy change of formation: This is the enthalpy change when one mole of a compound is formed from its elements under the standard conditions of 298 K, 1 atmosphere pressure, 1 mol dm-3 solution concentration and substances in their normal physical states for these standard conditions. (e) standard enthalpy change of atomisation: This is the enthalpy change when one mole of gaseous atoms of an element is formed from the element under the

standard conditions of 298 K, 1 atmosphere pressure, 1 mol dm-3 solution concentration and substances in their normal physical states for these standard conditions. (f) standard enthalpy change of neutralisation: This is the enthalpy change when one mole of an acid is just neutralised by an alkali under the standard conditions of 298 K, 1 atmosphere pressure, 1 mol dm-3 solution concentration and substances in their normal physical states for these standard conditions.

Q4. In this question, use the following: molar mass of zinc = 65.4 g mol -1. 1.308 g of zinc was

added to an excess of copper (II) sulphate solution. The heat energy produced was measured and found to be 4.40 kJ. (a) In what piece of equipment would you carry out this reaction? Why? A calorimeter to minimise heat losses to the surroundings. (b) How many moles of zinc reacted? Number of moles = mass/molar mass = 1.308 / 65.4 = 0.0200 moles (c) Calculate the standard enthalpy change for this reaction, giving the correct sign and units and an appropriate number of significant figures. Enthalpy change = Heat evolved/moles = 4.40 kJ / 0.0200 = -220 kJ mol-1 Q5. Write balanced equations, including state symbols, for the formation of one mole of each of the following compounds from their elements under standard conditions. (a) calcium oxide Ca(s) + O2(g) CaO(s) (b) potassium bromide K(s) + Br2(l) KBr(s) (c) sodium hydroxide Na(s) + O2(g) + H2(g) NaOH(s) (d) ethanol 2C(s) + 3H2(g) + O2(g) C2H6O(l)

Q6. 100 cm3 of 0.02 M copper (II) sulfate solution was put in a calorimeter and an excess of magnesium powder was added. The temperature of the solution rose by 2.5 oC. (a) Write a balanced equation for the reaction, including state symbols. Mg(s) + CuSO4(aq) MgSO4(aq) + Cu(s) (b) Calculate the number of moles of copper (II) ions used. Moles of copper = cV/1000 = 0.02 x 100/1000 = 0.002 moles (c) Calculate the heat energy evolved per mole of copper ions. Assume that the heat evolved was used only to heat the solution, and that the density and specific heat capacity of the solution are the same as those of water (1.0 g cm -3 and 4.2 J g-1 K-1

respectively). Give the correct sign and unit in your answer, and quote your answer to an appropriate number of significant figures. Heat evolved = cmT = 4.2 x 100 x 2.5 = 1050 J Enthalpy change per mole = -1050/0.002 = -525 000 = -525 kJ mol-1 (d) Rewrite the equation as an ionic equation, omitting spectator ions. Mg(s) + Cu2+(aq) Mg2+(aq) + Cu(s)

Q7. This question is about a combustion Hess cycle. (a) Write an equation for the complete combustion of one mole of cyclohexane (C6H12) to carbon dioxide and water. Include state symbols. C6H12(l) + 9O2(g) 6CO2(g) + 6H2O(l) (b) Draw up a Hess cycle for the combustion of cyclohexane, using the following as a guide: COMPOUND + OXYGEN Enthalpy of formation of compound ELEMENTS C6H12(l) + 9O2(g) -3919.5 CARBON DIOXIDE + WATER Enthalpies of formation of carbon dioxide and water

6CO2(g) + 6H2O(l) 6(-393.5) + 6(-285.8) = -4075.8

6C(s) + 6H2(g) + 9O2(g)

(c) The standard enthalpy change of combustion of cyclohexane is -3919.5 kJ mol-1, and the enthalpy changes of formation of CO2 and H2O are -393.5 kJ mol-1 and -285.8 kJ mol-1 respectively. Use these values in the cycle you have constructed to determine the enthalpy of formation of cyclohexane, giving the correct sign, units and significant figures in the answer. Enthalpy of formation of cyclohexane = -4075.8 + -(-3919.5) = -4075.8 + 3919.5 = -156.3 kJ mol-1

Q8. This question is about an atomisation Hess cycle. The atomisation energy of methoxymethane, whose displayed formula is shown below, can be found from a Hess cycle

involving its enthalpy of formation, and the enthalpies of atomisation of graphite, hydrogen and oxygen. The Hess cycle has the form: COMPOUND Enthalpy of formation of compound ELEMENTS (a) Use the Hess cycle and the following data to determine the enthalpy of atomisation of methoxymethane: enthalpy of formation of methoxymethane = -184.0 kJ mol-1; enthalpies of atomisation of carbon, hydrogen and oxygen: +714.8, +218.0, +249.2 kJ mol-1 respectively. Remember that enthalpies of atomisation for elements are defined for the formation of one mole of gaseous atoms. Hat CH3OCH3 (g) 2C(g) + 6H(g) + O(g) -184.0 2(+714.8) +6(+218.0) + +249.2 = +2986.8 C(s) + 3H2(g) + O2(g) Hat = -(-184) + +2986.8 = +3170.8 kJ mol-1 SEPARATED ATOMS Enthalpies of atomisation of the elements

(b) If the average bond energy of the C-H bond is +413 kJ mol-1, use your answer to (a) to calculate the bond energy of the C-O bond. 6 x (+413) + 2 x (EC-O) = +3170.8 EC-O = +346.4 kJ mol-1 Extension Q9. The first part of this question is about an experiment to determine the enthalpy change of combustion of propanone, CH3COCH3. The following results were obtained: Heat capacity of apparatus = 3.34 kJ oC-1 Loss of mass of burner = 2.90 g Temperature rise = 25.3 oC (a) (b) Calculate the amount of heat energy (kJ) produced in the experiment.

Heat evolved = (cm)T = 3.34 x 25.3 = 84.5 kJ

Calculate the enthalpy of combustion of propanone, given that its molar mass is 58.0 g mol-1. Mole of propanone = mass / molar mass = 2.90/58.3 = 0.05 moles

Enthalpy of combustion = 84.5 / 0.05 = -1690 kJ mol-1 (c) Construct a Hess cycle and use it to determine the enthalpy of atomisation of propanone, given the following data: -248 kJ mol-1 +715 kJ mol-1 +218 kJ mol-1 +249 kJ mol-1 3C(g) + 6H(g) + O(g) 3(+715) + 6(+218) + + 249

Enthalpy of formation of propanone = Enthalpy of atomisation of carbon = Enthalpy of atomisation of hydrogen= Enthalpy of atomisation of oxygen = CH3COCH3(l) Hat

-248
= +3702 3C(s) + 3H2(g) + O2(g) Hat = -(-248) + +3702 = +3950 kJ mol-1 (d) Use the average bond energies below to calculate another value for the enthalpy of atomisation of propanone: C-H +413 kJ mol-1 C=O +749 kJ mol-1

C-C +346 kJ mol-1

Hat = 2(C-C) + 1(C=O) +6(C-H) = (2x346) + (749) + (6x413) = +3919 kJ mol-1 (e) Comment on the difference between the values calculated in (c) and (d). Bond energies used in (d) are average values determined from a range of compounds.