Answers to CHEM1101 Quiz 3

1. A process is spontaneous if Go < 0, where Go = Ho - TS o . Hence, the reaction is spontaneous when Ho - TS o < 0 If Ho = +50 kJ mol-1 = +50 103 J mol -1 and S o = +100 J K-1 mol-1, (+50 103 J mol -1) - T (+100 J K-1 mol-1) < 0 (+50 103 J mol -1) T> (+100 J K-1 mol-1) T > 500 K An endothermic reaction becomes more favourable as the temperature is increased (Le Chatelier's principle). The correct answer is C. 2. The First Law of Thermodynamics gives the internal energy change, U, as the sum of the heat change, q and the amount of work done, w: U = q + w The work done when a gas changes volume by an amount V against an opposing pressure p is w = -pV and so U = q - pV As the system receives heat, q is positive. As V = V final - V initial, it is positive for the expansion of a gas and so w is negative: if the gas expands, it has to push against the external pressure and it does work. Hence: U = (+385 J) - (140.0 103 Pa) (+1.60 10-3 m3 ) = +161 J where the SI unit of pressure (Pascal) and volume (m3 ) have been used. Note, however, that as 1 kPa = 103 Pa and 1 m 3 = 10 -3 L, 1 kPa 1 L = 1 J. The correct answer is B. 3. The change in the entropy of the universe, universeS o , is the sum of the change in the entropy of the system, system S o , and the surroundings, surroundingsS o . By definition, the entropy change associated with a heat change q at a temperature T is given by: surroundingsS o = q surroundings T

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Since any heat given to the surroundings is lost from the system (and vice versa), q surroundings = -q system At the constant pressure, q system = system Ho so surroundingsS o = Overall, this gives: universeS o = system S o system Ho T -system Ho T

In this expression everything on the right-hand side refers to changes in the system so the "system" labels are usually removed: universeS o = S o Ho T

As with other thermodynamic quantities Ho and S o are defined as 'final minus initial': Ho = fHo (final) - fHo (initial) S o = S o (final) - S o (initial) The condensation of water refers to the process gas to liquid. Hence, condensationHo = fHo (liquid) - fHo (gas) = (-286 kJ mol-1) - (-242 kJ mol-1) = -44 kJ mol-1 condensationS o = S o (liquid) - S o (gas) = (70 J K-1 mol-1) - (189 J K-1 mol-1) = -119 J K-1 mol-1 Hence, at T = 398 K: universeS o = S o Ho T = (-119 J K -1 mol-1) (-44 103 J mol -1) (398 K) = -8 J K-1 mol-1

As universeS o < 0, the process is non-spontaneous and so water vapour does not condense to form liquid water at 398 K (as expected). The correct answer is A. 4. As with other thermodynamic quantities S o is defined as 'final minus initial': S o = S o (products) - S o (reactants) The main factors influencing the entropy of a system are: Volume - entropy increases with volume. Occupation of a larger volume spreads the energy available out. Temperature - entropy increaes with temperature. The more energy a system has, the more ways there are to distribute the energy out amongst the molecules. Physical state - the entropy of gases >> liquids > solids and solutions > solids. The more freedom the molecules

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have to move around, the more the energy will be spread out. Number of particles - other things being equal entropy increases with the number of particles. The more molecules there are, the more ways of spreading out the energy there are. If gaseous particles are lost to produce extra particles which are trapped in solids, however, this effect can be less important than point (3). If the pressure is increased, the volume occupied by the gas will decrease. Occupation of a smaller volume decreases the spread of the energy available out and so the entropy decreases in process B. All the other processes increase the entropy (see above). The correct answer is B. 5. The equilibrium constant, K p , is a reflection on the balance between reactants and products at equilibrium: a very large value of K p is consistent with the equilibrium mixture containing predominately products a very small value of K p is consistent with the equilibrium mixture containing predominately reactants From Le Chtelier's principle, an exothermic reaction becomes less favourable and an endothermic reaction becomes more favourable if the temperature is increased. If the equilibrium constant decreases when the temperature is increased, the reaction must be exothermic: rHo < 0 If the equilibrium constant increases when the temperature is increased, the reaction must be endothermic: rHo > 0 K p is smaller at the higher temperature: the reaction is exothermic and so rHo < 0. For an exothermic reaction, the yield of products is increased by lowering the temperature. K p is larger at the lower temperature indicating that more product is formed when the temperature is lowered. The correct answer is D. 6. In general, when manipulating equilibrium constants: If the direction of an equation is reversed, the new equilibrium constant is the reciprocal of the original If the cofficients in an equation are multiplied by a factor, the equilibrium constant is raised to a power equal to that factor The reaction is reversed and multiplied by a factor of 1/2. Hence, the new equilibrium constant, K p (new) is given as: 1 K p (new) = (K p (original))1/2 = 1 (60.6)1/2 = 0.128

The correct answer is C. 7. For any reaction, Ho = fHo (products) - fHo (reactants)

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where fHo is the enthalpy change for the formation of a species from its elements in their standard states at 298 K and 100 KPa. For elements in standard states, fHo = 0. C(s) and H2 (g) are elements in their standard states so have fHo = 0. The enthalpy change for the second reaction is just: Ho = so fHo (products) - fHo (reactants) = fHo (C 2 H6 (g)) = -85 kJ mol-1 fHo (C 2 H6 (g)) = -85 kJ mol-1

For the first reaction, Ho = so fHo (products) - fHo (reactants) = fHo (C 2 H6 (g)) - fHo (C 2 H4 (g)) = -137 kJ mol -1 fHo (C 2 H4 (g)) = (fHo (C 2 H6 (g) - (-137)) kJ mol-1 = ((-85) - (-137)) kJ mol-1 = +52 kJ mol-1

The correct answer is E. 8. In general, explosives generate considerable heat when they react and produce a large amount of gas. Explosive reactions are almost always extremely exothermic. Statement B is false. The correct answer is B. 9. The initial concentrations of A and B are: number of moles [A] = volume number of moles [B] = volume = (10.0 L) = (10.0 L) (5.00 mol) = 0.500 M (4.00 mol) = 0.400 M

As [A] equilibrium is 0.35 M, the change in [A] is (0.400 - 0.35) M = 0.05 M. From the chemical equation, Two B are lost for every A that reacts: [B] is decreased by 0.10 M One C is made for every A that reacts: [C] is increased by 0.05 M. Hence [A]equilibrium = 0.35 M [B]equilibrium = (0.500 - 0.10) M = 0.40 M [C]equilibrium = (0.00 + 0.05) = 0.05 M The equilibrium constant is therefore [C(g)] Kc = [A(g)][B(g)]2 = (0.05 M) (0.35 M)(0.40 M)2 = 0.89

The correct answer is E.

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10. Le Chtelier's principle can be used to predict how a reaction which is at equilibrium will respond to a change. It can be expressed in the form: If a chemical system at equilibrium experiences a change in concentration, temperature, volume, or partial pressure, then the equilibrium shifts to counteract the imposed change and to restore the equilibrium. If the volume of the container is changed, the concentrations change. Concentration is equal to the number of moles / volume. If the volume of the container is increased, the concentrations decrease. If the volume of the container is decreased decreased, the concentrations increase. If the volume of the container is increased, the concentrations decrease. If the volume is decreased, the pressure inside the container increases. The reaction will shift to try to reduce the pressure: it will shift to the side with the fewest moles of gas. If the volume is increased, the pressure inside the container decreases. The reaction will shift to try to increase the pressure: it will shift to the side with the mosr moles of gas. For this reaction, 3 mol of gaseous reactant (i.e. 1 mol of A(g) and 2 mol of B(g)) goes to 1 mol of gaseous product (i.e. 1 mol of C(g)). If the volume of the container is decreased, the pressure inside the container will increase. The reaction will shift towards products as this will decrease the number of moles of gas present, and will decrease the pressure. The correct answer is D.

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