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Page 1 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
2 Which one of the following equations shows the enthalpy change of formation of carbon
monoxide? [J88/III/13]
A
C (s) + ½ O2 (g)→ CO (g)
B
C (s) + O (g) → CO (g)
C
C (s) + CO (g) → 2CO (g)
2
D
C (g) + ½ O (g) → CO (g)
2
3 The enthalpy changes of formation of gaseous ethene and gaseous ethane are +52 kJ mol−1
and −85 kJ mol−1 respectively at 298K.
What is the enthalpy change of reaction at 298K for the following process? [N90/I/6]
C2H4 (g) + H2 (g) → C2H6 (g)
4 Which equation represents the change corresponding to the enthalpy change of atomisation
of iodine? [J97/III/7]
A
½ I2 (s)→ I (g)
B
I (s) → 2I (g)
2
C
½ I (g) → I (g)
2
D
I (g) → 2I (g)
2
Hydrazine was used as a fuel for the Messerschmidt 163 rocket fighter in World War II and
for the American Gemini and Apollo spacecraft. It has the following structure.
Page 2 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
6 Which equation defines the lattice energy of the ionic compound XY? [J96/III/6]
7 For which of the following is the lattice energy likely to have the greatest magnitude? [J91/I/9]
A Lithium fluoride
B Lithium iodide
C Sodium iodide
D Sodium fluoride
8 For which of the following ions is the enthalpy change of hydration likely to be the most
exothermic? [J94/IV/6]
ionic radius / nm charge on ion
A 0.065 +2
B 0.095 +1
C 0.135 +2
D 0.169 +1
Reaction Coordinate
Which of the following statements about the reaction are true?
Page 3 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
12 The equation for the complete combustion of octane, C8H18, is given below.
C8H18 (l) + 12 ½ O2 (g) → 8CO2 (g) + 9H2O (l)
Using the following enthalpy changes of formation, draw an energy cycle to calculate the
enthalpy change of combustion of octane. [J98/I/3a] [Ans: −5476 kJ mol−1]
∆Hf (C8H18) = − 250 kJ mol−1
∆Hf (H2O) = − 286 kJ mol−1
∆Hf (CO2) = − 394 kJ mol−1
∆Hc(C8H18)
C8H18 (l) + 12 ½ O2 (g) 8CO2 (g) + 9H2O (l)
+8O2 (g) 8∆Hf(CO2) 9∆H (H O) =
f 2
∆Hf(C8H18) = 8(-394)
= –250 kJ mol–1 –1 9(-286) kJ mol–1
kJ mol
+ 9/2 O2 (g)
8C (s) + 9H2 (g)
13 The enthalpy changes for 2 reactions are given by the equations below:
2Fe (s) + 3/2O2 (g) → Fe2O3 (g) ∆H = −822 kJ mol−1
C (s) + ½ O2 (g) → CO (g) ∆H = −110 kJ mol−1
What is the enthalpy change for the reaction 3C (s) + Fe2O3 (s) → 2Fe + 3CO (g)?
[Ans: +492 kJ mol−1]
Must identify that the 2 ∆H provided are ∆Hf of Fe2O3 and CO respectively.
∆Hrxn = ∑∆Hf (products) − ∑∆Hf (reactants)
= 3(−110) – (−822)
= +492 kJ mol−1
b By using appropriate bond energy data from the Data Booklet, calculate a value for the
standard enthalpy change of the following reaction. [Ans: −278 kJ mol−1]
≡
H–C C–H + 2H2 → CH3CH3
∆Hrxn = ∑ energies of bonds broken – ∑ energies of bonds formed
≡
= 2(C−H) + (C C) + 2(H−H) – 6(C−H) – (C−C)
= 2(+410) + (840) + 2(+436) – 6(+410) – (+350)
= −278 kJ mol−1
Page 4 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
c The actual ∆Hrxn of the reaction in (b) is −304 kJ mol−1. Suggest a discrepancy between this
actual value and that calculated in (b).
Bond energies quoted in the Data Booklet are average values from many different
molecules. They are not the actual bond energies given in the molecules represented in the
equation.
15 Construct a Born−Haber cycle for formation of Al2O3 from its elements and calculate the
lattice energy of Al2O3 from the following data :
[Ans: −15300 kJ mol−1]
3((–141) + (+790))
kJ mol–1
2Al3+ (g) + 6e + 3O (g)
2(+578 + 1817
+2745) kJ mol–1
2Al (g) + 3O (g)
L.E.
2(+325) +
3(+249) kJ mol–1
2Al (s) + 3/2 O2 (g)
0
∆Hf (Al2O3)
= –1676 kJ mol–1 Al2O3 (s)
By Hess Law,
LE = −15300 kJ mol-1
Page 5 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
Section B: Discussion Questions
MCQ
1. The standard enthalpy changes of formation of carbon dioxide and water are –394 kJ mol−1
and –286 kJ mol−1 respectively. If the standard enthalpy change of combustion of propyne,
C3H4, is –1938 kJ mol−1, what is its standard enthalpy change of formation? [N88/III/13]
2. The enthalpy change for the neutralisation given below is – 114 kJ mol−1.
2NaOH (aq) + H2SO4 (aq) → Na2SO4 (aq) + 2H2O (l)
Predict the value for the enthalpy change for the following neutralisation.
Ba(OH)2 (aq) + 2HCl (aq) → BaCl2 (aq) + 2H2O (l)
What is the enthalpy change in the decomposition of PCl5 to PCl3 and Cl2? [J03/I/7]
4. From which of the following reactions can the bond energy of the C−F bond be determined
by using only the standard enthalpy change of the reaction? [N99/III/9]
5. The value of the enthalpy change for the process represented by the equation below
Na (s) → Na+ (g) + e−
is equal to [N96/IV/8]
Page 6 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
6. 50 cm3 of 2.0 mol dm3 hydrochloric acid, HCl, were placed in a plastic cup. To this, 50 cm3 of
2.0 mol dm3 sodium hydroxide, NaOH, were added. The temperature rose from 31.0 to
42.0 oC. Assuming the density of the resulting solution is 1.01 g cm3 and its specific heat
capacity is 3.91 J g1 K1, calculate the enthalpy for the reaction
7. 0.0600 mol of Al powder was added to 100.0 cm3 of 0.250 mol dm−3 silver nitrate solution in a
polystyrene cup. The temperature rose from 20.5 ○C to 30.2 ○C.
Calculate the enthalpy change of reaction for Al (s) + 3Ag+ (aq) → Al3+ (aq) + 3Ag (s),
assuming the density of the solution is 1.00 g cm−3 and its specific heat capacity is 4.18 J g−1
○ −1
C [Ans: −487 kJ mol−1]
n = 0.0600mol
Al
100.0
n = 0.250 × = 0.02500mol
Ag+ 1000
Energy required to boil the water = 500 x 4.18 x 75.= 156 750 J
= 209 kJ
Page 7 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
9. Hydrazine is used as rocket fuel and to prepare gas precursors used in air bags.
Approximately 260 thousand tonnes of hydrazine are manufactured annually. Liquid hydrazine
undergoes combustion according to the following equation:
N2H4(l) + O2(g) → N2(g) + 2H2O(l)
A chemist conducted an experiment to determine the standard enthalpy change of combustion
of hydrazine. In the experiment, 0.210g of hydrazine was burnt as fuel to heat up a beaker
containing 200 cm3 of water. The temperature of water rose by 4 oC. You may assume the
process has 80 % efficiency.
(i) Explain what is meant by standard enthalpy change of combustion of hydrazine. [1]
Standard enthalpy change of combustion (∆Hcθ) of hydrazine is the energy released when one
mole of the hydrazine is completely burnt in oxygen at 298K and 1 atm.
∆Hf(N2H4 (l)
N2 (g) + 2H2 (g) (g)) N2H4 (l)
By Hess’ law,
Page 8 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
(iv) The standard enthalpy change of formation of hydrazine gas is +235 kJ mol1.
Using appropriate data from the Data Booklet, draw an energy level diagram to calculate the
average bond energy of N−H bond in hydrazine.
energy [3]
2N (g) + 4H (g)
B.E.(N−N) +
4xB.E.(N−H)
B.E.(N≡N) +
N2H4 (g)
2xB.E.(H−H)
∆Hf(N2H4)
= +235 kJ mol1
N2 (g) + 2H2 (g)
0
By Hess Law,
+ 235 + (+160) + 4 x B.E(N−H) = +994 + 2(+436)
B.E (N−H) = 368 kJ mol−1
(v) Suggest a reason for the difference in the N−H bond energy value obtained from (iv) with the
value given in the Data Booklet. [1]
The bond energy values obtained from the Data Booklet are average values and would differ
from the experimental values.
10. Draw an energy cycle to calculate the enthalpy change for the reaction
PbO2 (s) + 2CO (g) Pb (s) + 2CO2 (g)
given the following enthalpy changes.
∆Hf [PbO2(s)] = −486 kJ mol1, ∆Hf [CO(g)] = –110 kJ mol1 and ∆Hf [CO2(g)] = –394 kJ mol1
[Ans: −82 kJ mol1]
Page 9 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
11. Methanol can be produced from methane by a two−step process.
Step 1 CH4 (g) + H2O (g) CO (g) + 3H2 (g) ∆H = x kJ mol−1
Step 2 CO (g) + 2H2 (g) CH3OH (g) ∆H = –102 kJ mol−1
(i) Use the following enthalpy changes of formation to calculate the value of x in Step 1.
(ii) Using the enthalpy change of reaction you have calculated in Step 1 in (a), and any relevant
bond energy terms in the Data Booklet, deduce a value for the bond dissociation energy of the
carbon−oxygen bond in carbon monoxide. [Ans: +1045 kJ mol−1]
∆Hrxn = ∑ energies of bonds broken – ∑ energies of bonds formed
12. By using the following data, draw an appropriate energy cycle and calculate the enthalpy
change of hydration of the
(i) Chloride ion [Ans: − 378 kJ mol1]
(ii) Iodide ion [Ans: − 317 kJ mol1]
and comment on the difference in their values.
Energy
NaI (s)
Page 10 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
∆Hsol = −LE(NaX) + ∆Hhyd(Na+) + ∆Hhyd(X−)
Draw a suitable Bond−Haber cycle to enable one to determine the enthalpy change for the
reaction 2K (s) + H2 (g) → 2KH (s) [Ans: −124 kJ mol−1]
2 x 1st EA of H
2 x 1st IE of K
2K (g) + 2H (g) 2K+ (g) + 2H (g)
BDE(H–H)
2K (g) + H2 (g) [or 2x∆Hatm (H)]
2 x LE (KH)
2x∆Hatm (K)
0 2K (s) + H2 (g)
By Hess Law,
+ 2(+90) + (+436) + 2(+418) + 2(−78) −2(−710) = ∆Hrxn
∆Hrxn = −124 kJ mol1 (note that ∆Hrxn = 2∆Hf(KH))
Page 11 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
14. Calcium reacts with water to form aqueous calcium hydroxide.
Ca (s) + 2H2O(l) Ca2+ (aq) + 2OH− (aq) + H2 (g) ∆Hrxn
Some enthalpy changes are listed below.
By using data in this question and relevant data in the Data Booklet, draw an energy level
diagram to determine ∆Hrxn for the above reaction.
+590 + 1150
= +1740 kJ mol1 Ca2+(aq) + 2H+(aq) + 2OH–(aq) + 2e
Ca(g) + 2H2O(l)
+178 kJ mol1
Ca(s) + 2H2O(l) –796 kJ mol1
∆Hrxn
Ca2+(aq) + 2OH–(aq) + H2(g)
Energy change when one mole of CaSO4 is completely dissolved in a solvent to form an
infinitely dilute solution under standard conditions.
Page 12 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
−1
(ii) Given: ∆Holattice (CaSO4) = −2704 kJmol
−1
∆Hohydration 2+
(Ca ) = −1562 kJmol
− −1
∆Hohydration (SO42 ) = −1160 kJmol
Using Hess’ Law, calculate the enthalpy change of solution of calcium sulfate. Based on the
value that you have calculated, comment on the solubility of calcium sulfate.
(iii) Using relevant data from the Data Booklet, predict the relative solubility of calcium sulfate,
barium sulfate and lead(II) sulfate.
Ionic radius: Ca2+ (0.099 nm) < Pb2+ (0.120 nm) < Ba2+ (0.135 nm)
q q qq
∆H sol = ∆Hhyd – LE = + + − − + −
r+ r− r+ + r−
Since q+, q− and r− is the same for all 3 sulfates,
as cationic radius increases from Ca2+ to Pb2+ to Ba2+,
q+ q+q−
• the magnitude of for ∆Hhyd of cations decreases to a greater extent than that of
r+ r+ + r−
in LE
[because the sum of ionic radii, (r+ + r−), in LE increases by a smaller extent due to the
large anionic radius of SO42−.]
q+
• becomes less exothermic faster than the reverse lattice energy, –L.E., becoming less
r+
endothermic.
• ∆Hsol becomes increasingly endothermic (i.e. sulfates becomes less soluble)
⇒ Solubility: CaSO4 > PbSO4 > BaSO4
Page 13 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
16. At a certain temperature, the decomposition of NO2Cl follows a two−step mechanism as
shown:
Step 1 : NO2Cl → NO2 + Cl
The enthalpy change for the overall process is −15 kJ mol−1. For the first step, the activation
energy for the forward reaction is 35 kJ mol1 and that of a reverse reaction is 25 kJ mol1. The
activation energy for the reverse reaction of the second step is 35 kJ mol1. Draw a labelled
energy profile diagram based on the above given data. [2]
= +25 kJ mol
Ea1 (1st step)
-1
= +35 kJ mol
’
Ea2’ (reverse) (2nd step)
-1
= +35 kJ mol
Ea2 (2nd step)
NO2Cl = +10 kJ mol
-1
-1
∆Hrxn = −15 kJmol
NO2 + Cl2
Reaction pathway
Page 14 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
Section C: Assignment [20 marks]
1. By drawing an energy cycle, determine the enthalpy change of formation of methanoic acid,
HCOOH, from the following enthalpies of combustion:
∆Hc(carbon) = −394 kJ mol−1, ∆Hc(H2) = −286 kJ mol−1, ∆Hc(HCOOH) = −263 kJ mol−1, [3]
∆Hf
C (s) + O2 (g) + H2 (g) HCOOH (l)
+ ½ O2 + ½ O2 ∆H (HCOOH) [½ m for each arrow]
∆Hc(carbon) c
+ ∆Hc(H2) (g) (g)
CO2 (g) + H2O (l)
By Hess Law,
∆Hf(HCOOH) + (−263) = −394 + (−286) [½ m]
∆Hf(HCOOH) = −417 kJ mol1 [½ m]
2. Carbon reacts with oxygen to form 2 oxides: carbon monoxide and carbon dioxide.
The standard enthalpy changes of formation for carbon monoxide and carbon dioxide are
−111 kJ mol−1 and −394 kJ mol−1 respectively. The standard enthalpy changes of atomisation of
graphite and oxygen are +715 kJ mol−1 and +248 kJ mol−1 respectively.
a) Define the terms standard enthalpy change of formation and standard enthalpy change of
atomisation. [2]
∆Hf : Energy change when one mole of compound is formed from its constituent elements
in their standard states under standard conditions [1]
∆Hatm: Energy required to form 1 mol of gaseous atoms from its element under standard
conditions [1]
b) Using the information given above, and by drawing a suitable energy level diagram,
calculate the carbon−oxygen bond enthalpy in carbon dioxide. [3]
Energy
C (g) + 2O (g)
∆Hatom(C) +
C (s) + O2 (g) 2∆Hatom(O)
0
∆Hf(CO2) 2xBE(C=O)
CO2 (g)
Page 15 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
c) The carbon−oxygen bond enthalpy of carbon monoxide is +1074 kJ mol−1. Why is the
carbon−oxygen bond enthalpy in carbon monoxide different from that in carbon dioxide? [1]
The carbon−oxygen bond in CO is a triple bond but the carbon−oxygen bond in CO2 is a
double bond. A triple bond (1 sigma, 2 pi) is stronger than a double bond (1 sigma, 1 pi) and
will require more energy to break.
d) Carbon monoxide may be used as a fuel. Using the information given above, calculate the
amount of carbon monoxide required to raise the temperature of 100 g of water by 50 ○C if
the process is only 35% efficient. (Specific heat capacity of water is 4.18 J g−1 K−1) [3]
e) Suggest a possible reason why the process is only 35% efficient. [1]
3. The formation of magnesium oxide from its elements may be represented by a Born−haber
cycle as described below.
∆H3 ∆H6
MgÄ (g) O (g)
∆H1 ∆H4
Mg (s) ½ O2 (g)
∆Hf
MgO (s)
Page 16 of 17
NYJC H2 Chemistry 9647 Tutorial: Enthalpy JC1 2014
a) Name the enthalpy changes represented as ∆H1, ∆H3 and ∆H5. [3]
b) Use IE values from the Data Booklet together with the values:
∆H1 = +150 kJ mol−1, ∆H7 = −3889 kJ mol−1, ∆H4 + ∆H5 + ∆H6 = +950 kJ mol−1
to calculate the enthalpy change of formation of magnesium oxide. [2]
By Hess Law,
∆Hf = ∆H1 + ∆H2 + ∆H3 + ∆H4 + ∆H5 + ∆H6 + ∆H7
= +150 + 736 (1st IE Mg) + 1450 (2nd IE Mg) + 950 – 3889 [1]
= −603 kJ mol−1 [1]
c) The value of ∆H7 for barium oxide is −3152 kJ mol−1. Account for the difference in values of
∆H7 for magnesium oxide and barium oxide. [2]
q +q −
LE ∝ + − , Charges are equal [1]
r +r
Since rMg 2+ < rBa 2+ due to fewer filled electron shells, [1]
LE of BaO is less exothermic than LE of MgO.
Page 17 of 17