Starters for 10

6. Thermodynamics
Answers

2. 6.1. Definitions

Standard enthalpy change, H⦵

Definition; The heat energy change at constant pressure under standard conditions (pressure 100
kPa ; temperature 298 K ). (one mark for both conditions)
(2 marks)

Standard molar enthalpy change of formation, Hf⦵

Definition; The enthalpy change when one mole of a compound is formed from its constituent
elements under standard conditions, with all reactants and products in their standard states.

e.g. Hf⦵ (NH3); 1/2 N2(g) + 3/2 H2(g) → NH3(g)

(3 marks)

Standard molar enthalpy change of combustion, Hc⦵

Definition; The enthalpy change when one mole of a compound is completely burned in excess
oxygen under standard conditions, all reactants and products in their standard states.

e.g. Hc⦵ (C4H10); C4H10 + 13/2 O2 → 4 CO2 + 5 H2O

(one mark for symbols, one for balancing)

(3 marks)

Mean bond energy

Definition; The enthalpy change when 1 mole of a particular type of bond is broken or made (all
species in the gas phase) averaged over many different molecules
(2 marks)

6.2. Calorimetry
Possible improvements / corrections include (any 10 from);

1. The beaker needs some form of insulation (or a polystyrene beaker should be used)

2. An accurate thermometer is needed (not one that records −10 to 100 C)

3. The thermometer is placed too near the surface of the mixture. It must be in the centre.

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 4. The liquids are not allowed to equilibrate to similar temperatures before use; the H 2SO4 is removed
from the fridge!
5. Only two readings were taken before the addition of the H2SO4. It is therefore impossible to draw a
line to indicate the average temperature of the NaOH before addition.

6. It is more usual to mix the reagents on the 3rd minute say and take no measurement at this point
then measure the temperature again on the 4th, 5th minutes etc.
7. There is no mention of the mixture being stirred.

8. Not all temperatures are recorded to 1 decimal point in the student’s results table
9. A straight line is drawn for the temperature of the solution after addition of the H 2SO4 despite the
fact that the temperature clearly drops more steeply initially – better extrapolation needed.

10. A volume of 100 cm3 is indicated in the student’s calculation for the energy transferred. The volume
is in fact 150 cm3 (100 cm3 of NaOH and 50 cm3 of H2SO4).

11. The calculation requested is per mole of NaOH reacting. This reaction involves two equivalents of
NaOH so the final enthalpy change must be divided by 2.

NOTE The experimental data is made up and in no way represents the real enthalpy of neutralisation of
NaOH.

6.3. Hess’s law

1. (a) 4 C(s) + 5 H2(g) → C4H10(g)
(1 mark equation + balancing; 1 mark state symbols)

(b) C4H10(g) + 6 ½ O2(g) → 4 CO2(g) + 5 H2O(g)

(1 mark equation; 1 mark balancing)
(NOTE Must be combustion of 1 mole of C4H10)

(c) C4H10(g) + 6 ½ O2(g) → 4 CO2(g) + 5 H2O(g)

Hc⦵ = [−(−134.5) + (4 × −394) + (5 × −242)]
4× 5×
−134.5 −394 −242 = −2651.5 kJ mol−1
kJ mol−1 kJ mol−1 kJ mol−1
(1 mark for the cycle or equiv)
4 C(s), 5 H2(g), 6 ½ O2(g) (1 mark answer)

2. (a) 2 C(s) + 3 H2(g) + ½ O2(g) → CH3CH2OH(l)

(1 mark equation + balancing; 1 mark state symbols)
(b) 2 C(s) + 3 H2(g) + ½ O2(g) → CH3CH2OH(l)
2× 3× Hf⦵ = [(2 × −394) + (3 × −242) − (−1367)]
−394 −242 −1367
kJ mol−1 = −147 kJ mol−1
kJ mol−1 kJ mol−1

2 CO2(g), 3 H2(g), ½ O2(g) (1 mark for the cycle or equiv)

(1 mark answer)

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6.4. Using bond enthalpies
1.

Bonds broken / kJ mol−1 Bonds made / kJ mol−1

1 × C―C 1 × 347 4 × C=O 4 × 805
5 × C―H 5 × 413 6 × O―H 6 × 464
1 × C―O 1 × 358
1 × O―H 1 × 464
3 × O=O 3 × 498
Total energy in = 4728 kJ mol−1 Total energy out = 6004 kJ mol−1

(1 mark balanced equation)

(2 marks bonds broken /made)
Hc⦵ (CH3CH2OH) = Total energy in – total energy out

= 4728 kJ mol−1 – 6004 kJ mol−1

= –1276 kJ mol−1 (1 mark correct sum)

2. 39 kJ mol−1 of energy must be put in to the reaction to initially convert the liquid ethanol into gaseous
ethanol. Hence, the total energy in becomes 4728 kJ mol−1 + 39 kJ mol−1 = 4767 kJ mol−1. Therefore the
more correct Hc⦵ [CH3CH2OH(l)] = 4767 kJ mol−1 – 6004 kJ mol−1 = –1237 kJ mol−1

(1 mark)

3. Number of moles in 1 g = 1 g ÷ Mr (CH3CH2OH) = 1 g ÷ 46 g mol−1 = 0.022 moles (1 mark)

−1
Theoretical heat transferred by 1 g = 0.022 moles × 1237 kJ mol = 26.9 kJ (1 mark)

26891 J = mass of water × 4.2 J K−1 mol−1 × 40 K

 mass of water = 26891 J / (4.2 J K−1 g−1 × 40 K)
= 160 g (1 mark)

Density of water = 1 g cm−3, therefore 160 g has a volume of 160 cm3 (1 mark)

4. either Mean bond enthalpies are averages of the bond enthalpies in many different compounds.
Therefore they are not exact for the specific bonds in ethanol
or There is considerably loss of heat to the environment / copper calorimeter that is not
included in the calculations for the experimental enthalpy of combustion of ethanol. This loss
of heat would result in an experimental value that is lower than the actual value.
or The heat capacity of the copper calorimeter has not been taken into account meaning that
the heat transferred into the copper is not included in the calculation.

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BY-NC-SA 4.0. “new name” is licensed under CC-BY-NC-SA 4.0 by “name of user”.