Chemistry Term 2 STPM Chapter 7 Chemical Energetics

Question 3

Which of the following equations represent the combustion of a compound?

1
A. C(s) + 0 (g) ---> CO(g)
2 2
1
B. H2(g) + 0 (g) —> H2O (g)
2 2
9 5 1
C. CH3NH2(I) + 02(g) ---> CO2(g) + H20(1) + N2(g)
2 2 2

D. C6H12(g) + 9 02(g) ---> 6CO2(g) + 6H20(1)

Answer: C

The standard enthalpy of combustion ∆HC°, of a substance is defined as "the heat

evolved when one mole of the substance is completely burned in excess oxygen
under standard conditions.

In A, the complete combustion of carbon should yield CO2

In B, the physical state of water should be "liquid"

In C, any nitrogen present in the compound will be converted to N 2(g)

In D, the physical state of C61-112 should be "liquid".

' Exam Tips’

Complete combustion of carbon yield's carbon dioxide, whereas complete

combustion of hydrogen yields water and not steam.

Question 4

Which of the following represents the thermochemical equation neutralisation?

A NaOH(s) + HCI(aq)  NaCl(aq) + H20(1)

B Ca(OH)2(aq) + H2S04(1)  CaS04(aq) + 2H20(1)

C NH3(g) + HCI(g) NH4C1(s)

D KOH(aq) + HNO3(aq) KNO3(aq) + H20(1)

Answer: D
The standard enthalpy of neutralisation of an acid by a base is defined as "the
heat evolved when one mole of If+ ions from an acid is neutralised by one mole of
OH- ions from a base to form water:' In A, NaOH should be in the aqueous form.
In B, H2SO4 should be in the aqueous form and CaSO 4, is a solid. In C, both
ammonia and the acid should be in aqueous form. In D, all the physical states are
correct.

Common errors:

Some students fail to note that acids and alkalis used in neutralisation reactions
must be in aqueous form.

Question 5

What is the enthalpy change represented by the equation

ZnSO4.7H20(s) + aq  Zn2+(aq) + S042-(aq)

A The ionisation energy of zinc sulphate.

B The lattice dissociation energy of zinc sulphate.

C The enthalpy of hydration of zinc sulphate.

D The enthalpy of solution of zinc sulphate.

Answer: D

The standard enthalpy of solution is defined as "the enthalpy change when one
mole of solute dissolves in water to form an infinitely dilute solution under
standard conditions".

Question 6

When 28.00 g sodium chloride was dissolved in 600 cm 3 distilled water, the
temperature of the solution decreased by 1.0°C. Calculate the enthalpy of solution
of sodium chloride. [Specific heat capacity of solution = 4.20 J g-1 °C -1

density of solution = 1.0 g cm-3]

A +5.25 kJ mol-1

B +7.00 kJ kJ mol-1
C —5.25 kJ mol-1

D —7.50 kJ mol-1

Answer : A
mass 28.00
Moles of NaC1 = = =0.48
molar mass [23+35.5]

Quantity of heat absorbed, q = mxcx∆ T= 600 x 4.20 x 1.0 = 2520 J.

2.52
Enthalpy of solution per mole of NaCl, = +5.25 kJ mol-1
0.48 mol

Question 12

The standard enthalpy of combustion of butanol is -2 676 kJ mol -'. 3.7 g butanol
was used to heat 500 cm3 water. If the heat transfer is only 80% efficient, what
will be the temperature rise of the water? [Specific heat capacity of solution =
4.20 J g-' °C-1; MR butanol = 74]

A. 48°C B. 51°C C. 60°C D. 65°C

Answer: B
mass 3.7
Mole of butanol = = =0.05 mol
molar mass 74

Quantity of heat evolved, = mol x molar heat of combustion

= 0.05 x 2 676 = 133.8 kJ

Since the heat transfer is only 80% efficient, 133.8 x 0.80 = 107 kJ

Quantity of heat evolved, q = m.c.∆T

107 000 = 500 x 4.2 x ∆T

∆T = 51.0°C

Exam Tips

The heat transfer from the flame to water is less than 100% because heat is lost
to the surroundings.

Common Errors

Some students did not change the unit of heat from "kJ" to Joules when using the
formula, q = m.c. ∆T

Question 13

When an unknown mass of ethanol was burnt, the temperature of 1 dm3 water
contained in a copper beaker increased by 7.2°C. If the enthalpy of combustion

of ethanol is -1 350 kJ mol-', determine the mass of ethanol burnt.

[Specific heat capacity of solution = 4.20 J g-1 °C-1; density of solution = 1.0 g cm -
3
,MR of ethanol = 46].

A 1.03 g B 1.55g C 1.88g D 2.25g

Answer :A

Quantity of heat evolved, q= m x c x ∆T = 1 000 x 4.2 x 7.2 = 30 240 J = 30.24 kJ

heat evolved 30.24 kJ
heat evolved 30.24
Moles of ethanol = = = 0.0224
molar heat 1350

Mass of ethanol = 0.0224 x 46 = 1.03 g

Question 14

A slice of sweet potato weighing 3.20 g was burned in a bomb calorimeter and
produced a temperature rise of 4.6°C. In the same calorimeter, combustion of
0.285 g sample of benzoic acid, C6H5COOH produced a temperature rise of 2.90°C.
The enthalpy of combustion of benzoic acid is -3 227 kJ mol-1. If an average
sweet potato weighs 150 g, how much energy can be obtained from an average
sweet potato? [MR of benzoic acid = 122]

A 502 kJ B 537 kJ C 561 KJ D 585kJ

Answer: C

0.285
Mole of benzoic acid = =¿ 2.34 x 10-3 T
122

The amount of heat released by a burning sample of benzoic acid

= 2.34 x 10-3x 3227 = 7.54 kJ

7.54 kJ
Heat capacity of calorimeter, c = =¿ 2.60 kJ °C-1
2.90
2.64 x 4.6
Hence, ∆H of sweet potato = c. ∅ = =¿3.74 kJ g
3.20

The energy content of 120 g sweet potato = 3.74 x 150 = 561 kJ

Question 15

When 0.01 mol of a carbonate, MCO3 was dissolved in 100 cm3 of 0.20 mol dm -3
sulphuric acid, the temperature of the acid increased by 7.2°C. What is the
reaction enthalpy in kJ mol-1?

[Specific heat capacity of solution = 4.20 J g-1 °C-1; density of solution = 1.0 g cm -
3
].

A -182.0 B -215.2 C -276.6 D -302.4

Answer : D
Question 18

When 0.60 g benzoic acid C7H602 (∆Hc° = - 3230 kJ mol-1) was completely burnt in a
bomb calorimeter, the temperature of the water in the calorimeter rises by i 1.50
K. The complete combustion of 3.60 g of oxalic acid, H2C204 in the same
calorimeter causes a temperature rise of 0.95 K.

[MR benzoic acid = 122, M, oxalic acid = 90].

(a) Calculate the heat capacity of the calorimeter.

(b) Determine the enthalpy of combustion of oxalic acid. :

Answer
mass 0.60
(a) Moles of benzoic acid = = =4.92 x 10-3
molar mass 122

Quantity of heat evolved = 4.92 x 10-3 (3 230) = 15.89 kJ

Quantity of heat absorbed by calorimeter = c. ∆T = 15.89 kJ

15.891
Heat capacity of calorimeter, c = = 10.59 kJ
1.50
mass 3.60
(b) Moles of oxalic acid, H2C204= = = = 0.04
molar mass 90

Quantity of heat evolved from the combustion of 0.04 moles oxalic acid =
c. ∆T = 10.59(0.95) = 10.06 kJ
10.06
Enthalpy of combustion of oxalic acid = = -251.5kJ
0.04

Section C Essay Questions)

Question 19

A 1.50 dm3 sample of ethane gas and oxygen, measured at 25°C and 101 kPa, was
allowed to react at constant pressure in a calorimeter which, together with : its
contents, had a heat capacity of 5.30 kJ K. The complete combustion of the ethane
gas to carbon dioxide and water caused a temperature rise in the • calorimeter of
6.180 K. [Enthalpy of combustion of ethane is -1 560 Id mol -1]
(a) Define the enthalpy of combustion of ethane.

(b) Write an equation for the combustion of ethane.

(c) Calculate the quantity of heat liberated.

(d) (i) Calculate the quantity of ethane in the mixture.

(ii) Determine the mole percent of ethane in the original mixture.

Answer:

(a) The amount of heat released when one mole of ethane is completely burned at
standard conditions.
7
(b) C2H6(g) + 0 (g)  2CO2(g) + 3 H20(1)
2 2

Common Errors

When writing a thermochemical equation for combustion, it must be for one mole
of the substance. Students must not multiply the above equation by 2 to get rid of
the fraction as this would produce an equation with 2 moles ethane.

(c ) Quantity of heat liberated = c. ∆T = 5.30(6.180) = 32.8 kJ

32.8
(d) (i) Moles of ethane = = 0.021
1560
PV 101 x 103 x 1.50 x 10−3
(ii) Total moles of gas, n = = =0.0611
RT 8.31 x 298

Percentage of ethane in mixture - 0. x 100% = 34. 4%

7.2 Hess' Law

Section A

Question 1

In Thermite Reaction, a reactive metal such as aluminium is used to reduce iron(Ill)

oxide to iron. What is the enthalpy change when 2.0 moles iron(III) oxide is
reduced by 3.0 moles aluminium?

[∆Hf, (Al203) = -1 676 Id mol-1; AHf (Fe203) = -825 Id mol-1]

A -855.0 kJ

B -1276.5 kJ

C -1 702.2 kJ

D -3 404.8kJ

Answer: B

2A1(s) + Fe203(s) 2Fe(s) + Al203(s)

∆ H =∆ Hf (Al203) = =∆ Hf (Fe203) = -1 676 - (-825) = -851 kJ

Iron(III) oxide is in excess and the limiting reagent is aluminium.

3 moles Al reduces 1.5 mol Fe203

Question 4

The standard heats of combustion per mole of butane, C4H10(g), hydrogen, H2(g),
and 1,3-butadiene, C4H6(g) are -2 878 kJ, -286 kJ and -2 540 kJ respectively.
What is the heat of hydrogenation of 1,3-butadiene?

C4H6(g) + 2H2(g) -> C4H10(g)

A -234 kJ mo1-1 B -325 kJ mo1-1

C -370 kJ mo1-1 1 D -408 kJ mo1-1

Answer: A

13
C4H10(g) + 0 (g) ---> 5H20(1) + 4C02(g) ∆,H = -2 878
2 2

2 H2 (g) + 02 (g) --> 2H2O(1) ∆,H = 2( -286)

11
C4H10(g) + 0 (g) ---> 3H20(1) + 4C02(g) ∆,H = -2540
2 2

C4H10(g) + 2H2(g)  C4H10(g) ∆,H = x

∆,H = -2 878 + 2(-286) +( -2540) = -234 kJ mo1 -1

Question 5

The enthalpy changes for two reactions are given by the equations below.

Pb(s) + 02(g) --> Pb02(s) AH = -277.4 kJ mo1-1

C(s) + O2(g) -> CO(g) ∆,H = -110.5 kJ mo1-1

What is the enthalpy change for the following reaction?

Pb02(s) + 2C(s) Pb(s) + 2C0(g)

A +56.4 kJ

C +249.2 kJ

B +166.9 kJ

D +387.9 kJ

Answer: A

Pb02(s) -> Pb(s) + 02(g) ∆H = +277.4

2 C(s) + 02(g) -> 2 C0(g) ∆H = 2 (-110.5)

Pb02(s) + 2 C(s) -> Pb(s) + 2 C0(g) AH = x

∆H = (+277.4) + 2(-110.5) = +56.4 kJ mo1-1

Common Errors

Students must remember to change the reaction enthalpy from (-) to (÷) when the
thermochemical equation is reversed.
:0Dinitrogen tetraoxide, N204 dissociates to form nitrogen dioxide NO2 N204(g)
---> 2NO2(g) AH = + 58.20 Id mo1-1

....................

If the standard enthalpy of formation for N204 is 9.68 Id mot-1, what is the
standard enthalpy of formation for NO2? • A +24.27 Id mo1-1 • B +33.94 Id ma-1
C +36.15 Id mo1-1 D +38.50 Id mol-1

Answer: B N204(g) 2NO2(g) AH = 2 AHt.°(NO2) - AI-11(N204) +58.20 = 2x - 9.68

x = +33.94 kJ moI-'

Que§titin

When heated strongly, potassium chlorate(V) decomposes to form potassium

chloride and oxygen.

K003(s) --> KCI(s) +102(g) If the heat of formation of KCIO3 and KCI are -391.2
Id mo1-1 and - 436.7 Id mo1-1 respectively, what is the enthalpy change when 20 g
KCIO3 is heated? [Relative atomic mass: 0 = 16; CI = 35.5; K = 39] A 6.88 kJ B
7.42 kJ C 8.15 kJ D 8.801d

Answer: B

Moles of KCIO3 = mass = 20 = 0.163 molar mass 122.5 Enthalpy of reaction = (-

436.7) - (-391.2) = - 45.5 kJ mol-1 Quantity of heat evolved, AH = 45.5 x 0.163 =
7.42 kJ

• italifr"TrfirM7‘.. Eln36, Deterrnine the enthalpy change for the decompositron

of potassium chlorate(V).r.

lie% ,c4r14,, "

'Om
Question 11

Phosphorus trichioride, PC13 and phosphorus pentachioride, PC15 are both used in
the industrial preparation of organic compounds. The enthalpy change for the
preparation of these two chlorides from white phosphorus are given by the
equations:

P4(s) + 6C12(g) --> 4P03(1) ∆H° = -1 280 kJ

P4(s) + 10C12(g) -> 4PCl5(1) ∆H°° = -1 774 kJ

What is the enthalpy for the dissociation of PCl 5 into phosphorus trichioride and
chlorine?

A -30.9kJmo1-1 B -123.5 kJmo1-1 C +30.9 kJmo1-1 D +123.5 kJmo1-1

Answer: D
P4(s) + 6C12(g) --> 4P03(1) ∆H° = -1 280 kJ

P4(s) + 10C12(g) -> 4PCl5(1) ∆H°° = -1 774 kJ

4PCl5(g) 4PC13(l) -+4 C12(g) ∆H° = 4x

4x = (-1 280) + (+1 774) = +494 kJ kJmo1 -1

x = +123.5 kJmo1-1

Question 12

The enthalpies of formation for ethene, C 2H4 and decane, C10H22 are 52.0 kJ
kJmo1-1 and -6 780 kJ kJmo1-1 respectively. When decane was cracked, only
ethene and hydrogen are formed, according to the equation below.

C10H22 (1) 5 C2H4 (g) + H2(g) • How much heat energy is required to crack 1.0 mol
of decane into ethene and hydrogen?

A -4090 kJ B -5 525 kJ C +7 040 kJ D +8825 kJ

Answer: C

10 C(s) + 11 H2 (g) ----------------------------------------------------------------------- C10H22(l)

∆H1
5∆H2 ∆H3
5 C2H4(g) + H2(g)

∆H1 = Enthalpy of formation (of decane)

∆H2 -= Enthalpy of formation (of ethene)

∆H3 = Enthalpy of reaction (cracking of decane)

= [5∆H2- ∆H1 ]

According to Hess's law, ∆H3 = [5∆H2- ∆H1 ] = 5(52.0) - (-6 780) = +7 040 kJmo1-1
Question 13

The energy diagram for the combustion of methanol is shown below.

Energy

C(s) +2H2(g) + 202(g)

+238.7 KJ -394.0 KJ
CH3OH (l) -> 3/2 O2(g)
CO2(g) + 2H2(g) + 02(g)

- 571.4 KJ

C02(g) + 2H20(g)

Which of the following statements is not true?

A. The enthalpy of combustion for methanol is -726.7 kJ mo1-1

B. The enthalpy of formation for methanol is -238.7 kJ mo1 -

C. The enthalpy of formation of water is -285.7 kJ mo1 -1

D. The enthalpy of combustion of hydrogen is -571.4 kJ mo1-1

Answer: D
From the given diagram,
3
CH3OH(1) + 0 (g) -> CO2(g) + 2H20(l)
2 2

Enthalpy of combustion of methanol = +(238.7) + (-394) + (-571.4) = -726.7 mo1 -1

Enthalpy of formation of methanol is -238.7 kJ mo1-1
1
C(s) + 2H2(g) + 02(g )  CH3OH(1) ∆H3 = -238.7 kJ mo1-1
2

Enthalpy of formation of water = (-571.4 + 2) = -285.7 kJ mo1 -1 (or enthalpy of

combustion of hydrogen)

(b) ∆H = [Atomisation enthalpy (S) + (02)] - 2 Bond enthalpy S - 0 -297 =

278.8 + 2(249.2) - 2 (S - 0)

Bond enthalpy (S - 0) = 537.1 kJ mol-1

Question 17

The standard heat of formation of carbon dioxide, water and glucose, C 6H1206(s)
are -394, -286 and -1 274 kJ mol-1 respectively

(a) Calculate the standard enthalpy of combustion of glucose at 298 K.

(b) Sketch an enthalpy diagram for the process.

(c) If 1.0 g of glucose is completely burnt in a bomb calorimeter, how much heat
energy will be released?

Answer:

(a) C6H1206(s) + 602(g) -> 6CO2(g) + 6H20(1)

∆H = 6 ∆Hfo (CO2) + 6∆Hfo (H20) - ∆Hfo C6H1206)

= [6(-394) + 6(-286)] – (-1 274)

= -2 806 kJ mol-1
(b) Energy (kJ)

Energy(kJ)

6C(s) +6H2(g) + 902(g) .

∆Hf( C6H12O6)

CH3OH (l) -> 3/2 O2(g) 6∆Hf( C6H12O6) + 6 ∆H1 H2O

-394.0 KJ
6C02(g) + 6H20(g)

(c) Relative molecular mass of C6H1206 = 6(12) + 12 + 6(16) = 180

Mol of glucose = = 5.56 x 10-3 molar mass = 1/180

Heat energy = 5.56 x 10-3 x 2 806

= 15.6 kJ

Question 18

Potassium hydrogen carbonate, KHCO3 reacts with dilute hydrochloric acid to form
salt, water, and carbon dioxide gas.

(a) When 2.82 g potassium hydrogen carbonate was added to 100.0 cm 3 of 1.0 mol
dm-3 hydrochloric acid, the temperature of the solution decreases by 1.6°C.

(i) Write an equation for the reaction.

(ii) Calculate the enthalpy change for the reaction per mole of potassium hydrogen
carbonate. [Specific heat capacity of solution = 4.20 J g-1 °C-1; density of solution
= 1.0 g cm-3]

(b) When 2.35 g of potassium carbonate was added to 40.0 cm3 of 1.0 mol dm -3
hydrochloric acid, the temperature of the solution increases by 3.4°C. Write an
equation for the reaction and calculate the enthalpy change for the reaction per
mole of potassium carbonate.

(c) Potassium hydrogen carbonate decomposes on heating to form potassium •

carbonate, carbon dioxide and water. Using your answers from (a) and (b),
determine the enthalpy change for the thermal decomposition of potassium
hydrogen carbonate.

Answer:

(a) KHCO3(s) + HC1(aq) -> KC1(aq) + CO2(g) + H20(1)

mass 2.82
Moles of KHCO3 = = = 0.0282 mol
molar mass 100

Moles of HCl = MV /100(1.0)= 0.10 (excess)

Heat absorbed =m x c x ∅= 100 x 4.2 x 1.6 = 672 J = 0.672 kJ

= +23.8 kJ mol -1

(b) K2CO3(s) + 2HC1 (aq) -> 2KC1(aq) + CO2(g) + H20(1)

2.35
(c) Moles of K2CO3 = = 0.017 mol
138

MV No. of moles of HCI = 40(1.0) = 0.04 (excess)

Heat liberated = mc∅ = 40 x 4.2 x 3.4 = 571 J = 0.571 kJ-0.571 kJ

0.571
AH = = -33.6 kJ mol-1
0.017

Common Errors

Students must remember to write in "-" sign to show that the reaction is
exothermic.
Answer: B

A Born-Haber cycle is mainly used to calculate lattice energies that cannot be

measured directly. The cycle applies Hess' Law to calculate the lattice enthalpy by
comparing the standard enthalpy change of formation of the ionic compound (from
the elements) to the enthalpy required to make gaseous ions from the elements.

Question 3

Which of the following equations represent the standard enthalpy of atomisation •

for magnesium?

A. Mg(s) Mg(g)

B. Mg(s) --> Mg2+(s) + 2e-

C. Mg(s) —> Mg2+(g) + 2e-

D. Mg(g) Mg 2+(g) + 2e-

Answer: A

The enthalpy of atomisation is the enthalpy change that accompanies the total
separation of all atoms in a chemical substance (either a chemical element or a
chemical compound).

Question 4

Which of the following factors affects the lattice energy of a compound?

A. The charge on the anion and cation.

B. The radii of the metal and non-metal atoms.

C. The electronegativity of the anion and cation.

D. The ionisation energy of the cation and anion.

Answer: A

The lattice energy of a compound depends on the charges and radii of the cation
and anion in the compound.
Which of the following statements is not true about the Born-Haber cycle?

A It is an application of Hess's Law.

B It must include the heat of formation of an ionic crystal.

C It can be used to determine the enthalpy of hydration.

D It can be used to determine the lattice energy of a compound.

Answer: C

A Born-Haber cycle is mainly used to calculate lattice energies that cannot

measured directly. The enthalpy of hydration of a compound can be measure
directly using a calorimeter.

Which of the following compounds is expected to have the highest lattice energy?
A NaCl B MgO C Al203 D PbBr2

Answer: C

Aluminium oxide is expected to have the highest lattice energy as the ionic ra( of
AP+ and 02- ions are very small and the charges of the cation and anion a high.

Exam Tips

The lattice energy of a compound is directly proportional to the charge of its

cation and anion and is inversely proportional to the radii of its cation and anion.
Question 7

The lattice energy of rubidium fluoride, RbF and Caesium Chloride , CsCl are 760
kJ mol-1 and 650 kJ mol-1 respectively. What is the expected lattice energy of
caesium fluoride, CsF?

A 420 kJ mol-1 B 570 kJ mol-1 C 660 kJ mol-1 D 720 kJ mol-1

Answer: D

The charges of the cations and anions are the same in all cases but the caesium ion
is larger than the rubidium ion, whereas the fluoride ion is smaller than the
chloride ion.

Question 11

A, B, X, and Y are elements from the same period. The lattice energies of two
compounds, MX3 and PY are as given.

Compound AX3 BY
∆H (kJ mol-1) -3 008 -1 095

Which of the following statements is correct?

A AX3 is less stable than BY.

B AX3 is less ionic in nature than BY.

C AX3 has a higher melting point than BY.

D 3 008 kJ heat energy is given off when one mole of AX3 is formed from its
elements.

Answer: B

Since the elements are from the same period, A must be a Group 13 element and X
is a Group 17 element. B must be a Group 12 element and Y is a Group 16 element.
Since A3+ has a high charge density, its ionic compound would have covalent
character due to its high polarising power. Since AX3 is less ionic in nature, its
melting point could be lower than that of BY.
Common. Errors

Some students mistakenly relate high lattice energy with high melting point
without considering the polarisation effect of ions with high charge density.

Question 12

Using the following data, determine the lattice formation energy of sodium
chloride. Enthalpy of atomisation of Na(s) = +107 Id mo1-1 Enthalpy of atomisation
of C12(g) = +122 Id mo1-1 First ionisation energy of Na(g) = +496 Id mo1-1 First
electron affinity of Cl(g) = -349 Id mo1-1 Enthalpy of formation of NaCI(s) = -411
Id mo1-1 A -855 Id mo1-1 B -1 276.5 Id mo1-1 C -787 Id mol-1 D -3 404 kJ mo1-1

Answer: C

Na'.(g) 116+496 Na(g) 1[F107 Na(s)

▪ CI (g) > 11-349 CI(g) AM. -411 11+122 ▪ 1/2 Cl2(9)

NaCI(s)

Construct a Born-Haber cycle for the overall process.

-411 = (+107) + (+496) + (+122) + (-349) + 6,1-/ AH = -787 kJ mai'

,Question 13

The radius and charge of six ions are shown in the table below.

Ion

P+

T2+

X-
)72-

{ Radius/pm

150 140

180

150

200

Which of the following shows the correct placement of the lattice energies of the
ionic solids PX, P2Z, TY, and TZ starting with the one with the lowest numerical
value first? A PX, P2Z, TZ, TY C P2Z, PX, TY, TZ B PX, P2Z, TY, TZ D TY, TZ, PX,
P.7

Answer: A The lattice energy of a compound is directly proportional to the charge

of its cation and anion and is inversely proportional to the radius of its cation and
anion.

Lattice energy of PX cc I(+1)(-1)1 x 1 (150 + 180) 330 (+1)(-2) 1 Lattice energy of

P2Z cc (150 + 200) cc 2 350 1(+2)(-2)1 4 (140 + 150) cc 290 I(+2)(-2)I 4 (140 +
200) cx 340

Lattice energy of TY cc

Lattice energy of TZ cc

The lattice formation energies of potassium chloride, KCI and calcium chloride,
CaCl2 that were determined from calculations using the Born-Haber cycle are
compared with the actual lattice energies obtained from experiments.

Lattice formation. energy. , KCI CaC12 Born-Haber (kJ mar) - 711 -2 258
Experiment (kJ mor) - 720 -2 293 Difference in lattice energy (kJ mo1-1) 9 35

Which of the following correctly explains the arge difference between these two
values of the lattice formation energy of CaCl2? A The K+ ion is smaller than Ca2+
ion. B KI exhibits more ionic behaviour than CaCl2. C The Ca2+ ion has a lower
charge density than the K.' ion. D The melting point of CaCl2 is higher than the
melting point of KCI.
Answer: B The theoretical lattice energy values come from calculations using the
Born-Haber cycle, which assumes a 100% ionic character in the ionic compounds.
The closer the experimental value to the calculated value, the more ionic is the
actual lattice of the compound. The charge density of the Ca2+ ion which is higher
than that of the potassium ion can polarise the electron cloud of the chloride ion.

.,',%7'.'t'' '...r.eirkr-r.Wr'',";.9r,,. 4,i,,,; ., :" -sr " **17 clisiatWarif ' Exam Tips , . ,
, , * A t.AT"' .;'' The measured lattice energy of an ionic con-ipOund does not
differ much from its theoretical value.

Section B

Structured Questions

Qt&ii-dii 18

The diagram below shows an energy level diagram of the Born Haber cycle used for
the calculation of the lattice energy of lead(II) bromide, PbBr2 from experimental
data.

Energy

II

III

IV

A Pe(g) Br2(I)

PI32'(g) + 2Br(g)

Pb(s) + Eir2(1)

(a) For each of the four empty lines labelled I, II, III and IV, write in the
formulae for the species present at that stage in the cycle. (b) Calculate the
enthalpy of formation of lead (II) bromide. Enthalpy of atomisation of Pb = +195.0
Id mo1-1 First ionisation energy of Pb = +715.6 Id mor Second ionisation energy of
Pb = +1 450.5 Id mol-1 Bond dissociation enthalpy of Br2 = +192.8 Id mol-1 Electron
affinity of bromine = -324.7 Id mo1-1 Lattice formation energy of PbBr2= -671.0
Id mo1-1

Answer: (a) I: Pb2+(g) + 2Br(g) II: Pb+(g) + Br2(1) III: Pb(g) + Br2 (1) IV: PbBr2(s)
(b) L H = 195.0 + 715.6 + 1 450.5 + (192.8) + 2(-324.7) + (-671.0) = +1 233.5 kJ mol-'
The Solubility of Solids in Liquids

Section A

Question 1

Which of the following ions has the highest hydration enthalpy? A Pb2+ C 01-1- B
C2042- D Al3+

Answer: D Aluminium ion, AP' has the smallest ionic radius and the highest charge.

The hydration energy of an ion is directly proportional to its charge and inversely
proportional to its radius.

Question -2,

The enthalpy of solution of sodium chloride is +6 kJ mol-'. If the lattice energy of

sodium chloride is -776 Id mo1-1 and the hydration enthalpy for Na+ ions is -406
Id mol-1, what is the hydration enthalpy of Chons? A -312 Id mot-' C -388 Id mol'
B -364 Id molts' D -406 Id mol-'

Answer: B Enthalpy of solution = Hydration energy (cation + anion) - Lattice

formation energy +6 = [(-406) + Hydration energy (anion) - (-776)] Hydration
energy (C1-) = -364 kJ mol-'

ueston .3

The enthalpy change for the reaction of two different acids and sodium hydroxide
is given below: HCI(aq) + NaOH(aq) NaCI(aq) + H20(1) 6,1-1= -57.3 Id mol-'
Reaction I HF(aq) + NaOH(aq) NaF(aq) + H20(1) AH = -63.5 Id mol-' Reaction II

Why is the neutralisation enthalpy for Reaction II higher? A HF is a weaker acid

than HC1. B Dilute sodium hydroxide was used in Reaction I. C Enthalpy of
hydration was also released in Reaction II. D Reaction I was not carried out under
standard conditions.

Answer: C In reaction II, a considerable amount of heat energy (enthalpy of

hydration of F-) was released due to the small size of the F- ion. 47"13tagliir-

small sized ion has high hydration energy. A large amount of heat energy is
released when the ion is hydrated. fir
Question .4

The enthalpy change for the reaction of dilute hydrochloric different alkalis is
given below: HCI(aq) + KOH(aq) KCI(aq) + H20(1) DH = - 57.3 kJ mol-' HCI(aq) +
NaOH(s) NaCI(aq) + H20(1) AH = - 96.5 Id mol-'

acid and two

Reaction 1 Reaction 11

Why are the enthalpies for the two reactions different? A Dilute potassium
hydroxide was used in Reaction I. B Enthalpy of solution was also involved in
Reaction II. C Enthalpy of sublimation of sodium hydroxide was also involved in
Reaction D Enthalpy of neutralisation in Reaction I was not carried out under
standard conditions.

Answer: B In reaction II, heat energy was released when the solid sodium
hydroxide dissolves in water.

Common Errors

The physical state of all the reactants must be carefully considered. During
neutralisation, H+(aq) + OH-(aq) H20(1)

Question 5.

Which of the following factors affect the solubility of an ionic compound ? I

Hydration enthalpy of the ions II The lattice energy of the compound III The
ionisation energy of the ions IV The melting point of the ionic compound A I and II
only C 1,111 and IV only B II and Ill only D 11,111 and IV only

11 Chemistry Term 2 STPM Chapter 7 Chemical Energetics

Answer: D Generally, a compound is soluble in water if its hydration energy is

larger than its lattice energy. When heated, the oxidation state of copper remains
the same, +2.

21'r
Compare the enthalpies of the given reactants and products. A substance wit.
lower enthalpy is more stable.

Section B

Question 1:0

When one mole of hydrated calcium chloride crystals, CaCl2.6H20 was dissolved in
a sufficiently large amount of water, the heat energy absorbed is +14.7 kJ. The
heat energy released when one mole of anhydrous calcium chloride, CaCl2was
dissolved in a sufficiently large amount of water is 82.7 kJ. (a) Write two
thermochemical equations for the reactions above. (b) Determine the enthalpy for
the reaction below. CaCl2(s) + 61-I20(1) ---> CaC12.6H20(s) (c) Sketch and label an
energy profile diagram for all three reactions.

Answer: (a) CaC12.6H20(s) + aq CaC12(aq) CaCl2(s) + aq CaC1, (aq)

Common Errors

+14.7 kJ mol-' -82.7 kJ mol-'

Students must remember to state the physical state of all reactants and products
in the thermochemical equation.

(b) tH = -(+14.7) + (-82.7) = -97.4 kJ mol-' (c) Energy A CaCl2(S) (aq)

CaCl2(aq)

-82.7 kJ mor'

CaC12.6H20(s) + aq

-97.4 kJ mor'

;Question _

The lattice lattice energies and enthalpy of hydration of several ionic crystals are
given in the table below.

r Ionic crystal Lattice energy (kJ ma') Enthalpy of hydration (kJ mot-') AW -1 145
-1 080 BK -1 022 -1 592 _ CN -884 -620 DP -927 -731
Using the data in the table above, (a) Calculate the enthalpy of solution for each
ionic crystal. (b) Arrange the ionic crystals in order of decreasing solubility.

Answer: (a) Enthalpy of solution = Hydration enthalpy - Lattice formation energy

For AW, enthalpy of solution = (-1 080) - (-1 145 ) = + 65 kJ mol-' For BK, enthalpy
of solution = (-I 592) - (-1 022) = -570 kJ mol-' For CN, enthalpy of solution = (-
620) - (-884) = + 264 kJ mol-' For DP, enthalpy of solution = (-927) - (-731) = -196
kJ mol-' (b) Solids with increasingly positive enthalpies of solution do not dissolve
easily in water. In order of decreasing solubility, BK > DP > AW > CN

Question 14

When 3.15 g anhydrous copper(II) sulphate was added to 100.0 cm3 water and
stirred, the temperature rise recorded was 3.1°C. [Specific heat capacity of
solution = 4.20 J °C-1; density of solution = 1.0 g cm-3]. (a) Calculate the quantity
of heat energy released when anhydrous copper(II) sulphate is added to water. (b)
Calculate the enthalpy of solution of copper(II) sulphate (c) The solubility of
CuSO4 is 21.2 g /100 cm3 of water at 20°C. If a 1.0 mol dm-3 solution of hot
aqueous copper sulphate solution is cooled to 20°C, how many grams of copper
sulphate crystals, CuSO4.5H20 will be formed?

Answer: (a) Quantity of heat released =mxcxe= 100.0 x 4.2 x 3.1 = 1302 J = 1.302
kJ mass = 3.15 (b) Moles of CuSO4 - molar mass 159.5 = 0.0197

OH = 1.302 kJ = - 66.1 kJ mo1-1 0.0197 mol

2. Based on the cycle below, what is the atomisation enthalpy of oxygen?

Enthalpy (kJ)

Ce(g) + 0(g)

H = 141 Ca2*(g) + 0-(g)

Ca2*(g) + 02-(g)

vH = +790

Ce(g) + 1/2 02(g)

1 AEI = + 1 690 AH = - 3 401 Ca(g) + 1/2 02(9)

A1-1 + 177 Ca(s) + 1/2 02(9)

IDH = - 636 CaO(s)

A +108 kJ mo1-' B +249 kJ mot-1 C +390 kJ mo1-1 D +498 kJ mo1-1

Answer: C The equation for the atomisation of oxygen is, 1 T02(g) 0(g) From the
diagram, +636 + 177+ 1 690 + x -141 +790 =3 401 x = +249

"" ' Ekam Tsps

wW

Add all the energies in the same direction and minus the energies in the opposite
direction. Ar.

3, The standard enthalpies of formation of several compounds are given below.

Compound AH°f /kJ- mo1-1 CO2 -394 H2O -286 C3H4 +184

Using Hess's law, the value for the standard enthalpy of combustion of propyne,
C3H4 is A -1 938 kJ mol-' C +864 kJ mol-' B -86 kJ mol-t D +1 938 kJ mot-1

Answer: A

3C(s) + 2H2(g)

AH

C3H4(g) 3CO2(g) + 2H20(1) = Enthalpy of formation (CO2+ H20) = [AHe 3(CO2) +

2AH, (H20)] AH2 = Enthalpy of combustion (of propyne) According to Hess's law,
OH, = + 6H2 [ARC 3(CO3) + ZAH, (H,0)] = AHf° + Alt° (propyne) Lit° = [3(- 394) +
2(-286)] - 184 = -1 938kJ mol-1

Section C

18. Glucose is a simple sugar with molecular formula, C6H1,06. The combustion of
carbon, hydrogen and glucose provide energy. The standard enthalpies of
combustion for carbon, hydrogen and glucose are -394.0 kJ mo1-1, -286.0 kJ mot-1
and -2 813.0 kJ mol-' respectively. (a) Define the standard enthalpy of formation
of glucose. [2 marks] (b) Draw a labelled energy level diagram relating to the
enthalpies given above, and calculate the standard enthalpy of formation of
glucose. [8 marks] (c) The enthalpy of solution of silver chloride and sodium
chloride are +72 kJ mol-1 and +5 kJ mol-' respectively. Explain the difference
between the solubilities of silver chloride and sodium chloride in terms of bonding.
[5 marks]
2. The thermochemical equation for the neutralisation reaction of sulphuric acid by
aqueous solution of potassium hydroxide is given below. 2KOH(aq) + H2SO4(aq) -->
K2SO4(aq) + 2H20(1) AH° = -114 kJ What is the standard enthalpy of
neutralisation, in kJ for the reaction between nitric acid with an aqueous solution
of sodium hydroxide? A -28.5 C -114 B -57 D -228

Answer: B Enthalpy of neutralisation is defined as "the heat energy released when

1 mol H" ions from an acid neutralised 1 mol OH- ions from an alkali to form 1 mol
water." 2 KOH(aq) + H2SO4(aq) --> K2SO4(aq) + 2H,0(1) 6,H = -114 kJ In the
neutralisation of nitric acid and sodium hydroxide, one mole of water molecules is
produced.

1 NaOH(aq) + HNO3(aq) NaNO3(aq) + H20(1) API = 124 - 57 kJ

3. Which compound has the lowest lattice energy? A CaC12 C K20 B CsCl D MgC12

Answer: B

IQ". Qn-I Lattice energy a (r+

charge Or size

CsCI has the lowest product charge and the largest ionic radii. Cation radius: Cs+ >
K+ > ca2+ Mg2 Anion radius: Cl- > 02-

l't21 Chemistry Term 2 STPM Chapter 7 Chemical Energetics

MCO3 + H2SO4 MSO4 + H2O + CO2 Mole of H2SO4 = MV 0.20(100)= 0.02 1 000 1
000

H2SO4 is in excess Quantity of heat released = mc8 = 100 x 4.2 x 7.2 = 3 024 J
3.024 kJ = 0.01 mol Reaction enthalpy = - -302.4 kJ mol''

16

The following table shows the change in the enthalpy of combustion of a few
hydrocarbons.

Alkane C2H6 C4H10 C7H16 Akic° (kJ mar) -1 560 -2 880 -4 848

The complete combustion of 0.05 mol of a hydrocarbon W releases 176.5 kJ. What
could be the molecular formula of W if W is also an alkane? A C3H8 C C61-114 B
C81-112 D C8H18

Answer : B

From C,H6to C7H16, there is an increase of 5 -CH, units Average enthalpy of

combustion of one -CH, unit =[-4 848 - (-1 560)] 5 = -657.5 kJ mo1-'

Enthalpy of combustion of W = 176.5: 0.05 = -3 530 kJ mol-' 0.05 The difference

in the enthalpy of combustion of W and C41-110 = [-3 530 - (-2 880)] = -650 kJ
Hence, W has one - CH2 unit more than C4H10 W is C31112

rwA4,-.fro, The larger the nurnber of carbon and hydrogen atoms in the
comPO7nci,7the7mOre 1-.--i,:pk,„trTrvist„..r, ' — xam Tips --- ---.r., ..,,r3 ','.0.1.*
'-...,i"-;'' ''" '''-,"''"' ;;''',,r. '''t;'=174." exothermic is the enthalpy of combustion.
Determine the number of - CH, units from the difference in the enthalpies of
combustion.

Question 8

100 cm3 potassium hydroxide solution of concentration 0.80 rnol dm-3 and : 120
cm' of 1.00 mol dm-3 nitric acid were mixed in a calorimeter. The final
temperature is 4.8°C higher than the original temperature of the two solutions.
[Specific heat capacity of solution = 4.20 J g-' °C-1; density of solution = 1.0 g cm-
9 (a) Calculate the number of moles of each reactant. (b) Calculate the quantity of
heat energy released. (c) Determine the enthalpy of neutralisation. (d) Write a
thermochemical equation for the reaction. (e) Sketch and label an energy profile
diagram for the reaction.

Answer:

(a) Moles of KOH = MV 100(0.80)= 0.08 1 000 1 000 No. of moles of HNO3 = MV 1
000 = 1 000 120(1.00) = 0.12 (excess) (b) Total volume of solution = 100 + 120 =
220 cm3 Quantity of heat evolved, AH = m x c x 8 = 220 x 4.20 x 4.8 = 4 435J =
4.44 kJ

(c) Since HNO3 used is in excess,

44 kJ Enthalpy of reaction per mole of KOH = 4. = -55.5 kJ mol-1 0.08 mol

ExamTips• Determlne whether any of reactants given in the question is in excess:

leactants that are in excess are disregarded in calculations.

(d) KOH(aq) + HNO3(aq) KNO3(aq) + H20(1)

Common Errors

r Ali = -55.5 kJ tnol-'

When writing a thermochemical equation, students must state the correct physical
state of the reactants and products.

(e) Energy A

KOH(aq) + HNO3(aq

ON —55.5 kJ mom'

KNO3(aq) + H20(I)

9
The standard enthalpies of combustion of graphite and hydrogen are -394 kJ mol-'
and -286 Id mol-' respectively. If the standard enthalpy of formation of ethane is
-20.0 Id mol-', what is the standard enthalpy of combustion of ethane in kJ mol-'?
A -1220 C -1537 B -1305 D -1626

Answer: D Write a balanced equation for the combustion and formation of each
compound. C(s) + 02(g) ---> CO2(g) AH = -394 Equation 1 H2(g) + ÷02(g) --> H20(1)
AH = -286 Equation 2 2C(s) + 3H2(g) ---> C2H6(g) DH = -20 Equation 3 Write a
balanced equation for the combustion of ethane. C2H6(g) + 7T02(8) --> 3H20(1) +
2CO2(g) Equation 4 To obtain equation 4, multiply equation 1 by (2) to get 2 moles
of carbon dioxide. Multiply equation 2 by (3) to get 3 moles water. Reverse
equation 3 so that ethane is on the right-hand side of the equation. Hence, 2C(s) +
202(g) —' 2CO2(g) AH = -394 (x 2) 3H2(g) +1-02(8) ---> 3H20(1) AH = -286 (x 3)
C2H6(g) ---> 2C(s) + 3H,(g) AH = +20 By adding all the above three equations, we
obtain 7 C2H6(g) + --y- 02(g) --> 3H20(1) + 2CO2(g) Hence, AHD = [2(- 394) + 3(-
286) + (+ 20)] = - 1 626 kJ mol-' Another method of determining the enthalpy
change is by constructing an enthalpy diagram.

2C(s) + 3H2(g)

6.H,

C2H8(g)

2CO2(9) 3H20(1)

AH, = Enthalpy of combustion (of carbon and hydrogen) = [2A.E1c(C) + 3AH(H2)

AH2 = Enthalpy of combustion (of ethane) According to Hess's law, AH, = AH7 +
AH2 [2AH, (C) + 3Afic (H2)] = AHf° + AH`' (ethane) AHZ = [2(- 394) + 3(- 286) -
(-20)] = -1 626 kJ mol-'

The standard enthalpy of formation of carbon dioxide, water and nitromethane,

CH3NO are -394 Id mol-', -286 Id mol-' and -113 Id mol-' respectively. What is

the standard enthalpy of combustion of nitromethane in kJ mol-1?

A -520 B -710 C -1537 D -1626

Answer: 13 C(s) + 02(g) --> CO2(g) AH = - 394 3 —H (g) + -0 (g) -> 0(1) AH = 2 2 4 1
2 -- 2 2 2 CH3NO(1) --> C(s) + -}-H2(g) + N2(g) + +02(g) AH = +113.0

5 3 1 CH3NO(1) + — 4 --02(8) T H20(1) + CO2(g) + N2(g)

x = (-394) + +(-286) + 113.0 = - 710 kJ mol-'

xam Ips

AH = x

_.:;44:4.4_-;,1-7. 10.-, Write balanced equations for the formation of carbon droxi
e, wafer -and nitromethane. Use Hess's Law and rearrange the written equations
to obtain the enthalpy of combustion of nitromethane. R

L1IG.LJULL.111 7 .L aii IAA Le J 1 r 1111 ur ICy....G1 f IGIUGE...

Ofiwttio-ui 2;

The standard enthalpies of combustion of graphite and hydrogen are -394 kJ mol-
land -286 kJ mol-1 respectively. If the standard enthalpy of formation of ethane
is -20.0 Id mol-', what is the standard enthalpy of combustion of ethane in kJ
mol-'? A -1220 C -1537 B -1305 D -1626

Answer: D Write a balanced equation for the combustion and formation of each
compound. C(s) + 02(g) --> CO2(g) AH = -394 Equation 1 H2(g) + 4 02(g) --> H20(1)
AH= -286 Equation 2

2C(s) + 3H2(g) -> C2H6(g)

AH = -20 ...Equation 3

Write a balanced equation for the combustion of ethane. 7 C2H6(g) + —2 O2(g) ->
3H20(1) + 2CO3(g) AlIc° ..Equation 4 To obtain equation 4, multiply equation 1 by
(2) to get 2 moles of carbon dioxide. Multiply equation 2 by (3) to get 3 moles
water. Reverse equation 3 so that ethane is on the right-hand side of the equation.
Hence, 2C(s) + 202(g) --> 2CO2(g) AH= -394 (x 2) 3H,(g) + 2 02(g) 3H20(1) AH =
-286 (x 3) C2H6(g) -> 2C(s) + 3H,(g) AH= +20 By adding all the above three
equations, we obtain C2H6(g) + —7 O2(g) -> 3H20(1) + 2CO2(g) Hence, Alt° = [2(-
394) + 3(- 286) + (+ 20)] = - 1 626 kJ mol-' Another method of determining the
enthalpy change is by constructing an enthalpy diagram.

2C(s) + 3H2(g)

C21-18(g)

1A

2CO2(g) + 3H20(1)

AH, = Enthalpy of combustion (of carbon and hydrogen) = [2AH(C) + 3.AHc(H2)

AH2 = Enthalpy of combustion (of ethane) According to Hess's law, AH-1 = AH; +
AH2 [2AH (C) + 3AH (H2)] = AI-1; + AH: (ethane) Alt° = [2(- 394) + 3(- 286) - (-
20)] = -1 626 kJ mol-'

Ofietliiija

/6.H2

The standard enthalpy of formation of carbon dioxide, water and nitromethane,

CH3NO are -394 kJ mol-', -286 kJ mol-' and -113 kJ mol-' respectively. What is
the standard enthalpy of combustion of nitromethane in kJ mol-'?

A -520 B -710 C -1537 D -1626

Answer: B C(s) + 02(g) -> CO2(g) AH = - 394 H2 4 (g) + 02 2 (g) -> —3H2 2 0(1) ± =
--(-286) 2 —3 CH3NO(1) -> C(s) + i-H2(g) + -12-N2(g) + ÷02(g) AH = +113.0

CH3N0(1) + 4 —5 02 2 (g) -> .,0(1) + CO,(g) + 2 —1 N2 (g) ± 1-1 X = (-394) + .22-(-

286) + 113.0 = - 710 kJ mol-'

mittuji

47-71ww • exam Tips

AR = x

fir' 4

Write balanced equations for the formation of carbon dioxide, water and
nitromethane. Use Hess's Law and rearrange the written equations to obtain the
enthalpy of combustion of nitromethane.
itt.,= Chemistry Term 2 STPM Chapter 7 Chemical Energetics

Qtieiticiii

Several reaction enthalpies are given as below. C(s) + 02(g) -> CO2(g) AH = -394 kJ
mol" 2C(s) + H2(g) --> C2H2(g LH = +227 kJ mol" H2(g) + 2-02(g) --> H200) AH =
-286 kJ mol" Use the above reactions and their respective enthalpy changes to
calculate the enthalpy change for the combustion of ethyne, C2H2. C2H2(g) +
5202(g) --> 2CO2(g) + H20(l)

A -907 kJ mol" B -1 101 kJ mol" C -1 282 Id mol" D -1 301 Id mol"

Answer: D C2H2(g) -> 2C(s) + H2(g) 2C(s) + 202(g) --> 2CO3(g) H2(g) +-j2-• O2(g)
--> H20(1)

AH = -227 kJ AH = 2(-394) kJ AH = -286 kJ

C2H2(g) + 5 -> 2CO3(g) + H20(1) Hence, OH = [-227 + 2(-394) + (-286)] = -1 301 kJ

mo1-1

EXam-Tips •

Rearrange the given equations to obtain the thermochemical equation for the
combustion of ethyne. Multiply the individual reaction enthalpies with the
appropriate stoichiometric coefficients before adding up the reaction enthalpies".

Question 9

When 28.0 g of nitrogen reacts with oxygen to form nitric oxide, NO, and nitrogen
dioxide, NO2, 103.0 kJ of heat was required. If no nitrogen remained, calculate
the mass of nitric oxide, NO formed. [LHf (NO) = 90.3 Id mol-', AH, (NO) = 33.2
Id mol-']

A 4.8 g B 9.6 g C 19.2 g D 24.3 g

Answer: C

mass 28.0 Moles of N2 = molar mass8 = = 1.0 2 If moles of nitrogen that reacts
to form NO is y, then moles of nitrogen that reacts to form NO2 is (1 - y) 1 1 T --2
—N2(g) + O2(g) NO(g) y mole 2y mole -2 1 --N2(g) + O2(g) --> NO2(g) (1 - y)mole
2(1 - y)mole QH = 90.3(2y) + [(33.2) x 2(1 - y)] = 103.0 Solving, y = 0.32 Mass of
NO = 2 x 0.32 x (14 + 16) = 19.2 g

6,H = 90.3 kJ
vH = 33.2 kJ

Exam Tips . . Write separate balanced equations for the reaction of nitrogen with
oxygen to form nitric oxide, NO and nitrogen dioxide.

Questions tti

Hydrazine, N2H4 disproportionates to form ammonia and nitrogen gases. 3N2H4

(I) -> 4NH3(g) + N2(g) Calculate the standard enthalpy change (in Id) for the
above reaction if the standard heat of formation of NH3(g) and N2H4(I) are
-46.0 Id mol-' and 50.6 kJ mot" respectively. A -32.2 C - 218.5 B -64.4 D - 335.8

Answer: D 2 N,(g) 6H2(g) --> 4NH3(g) 3N21-14(g) 3N2(g) + 6H2(g)

AH = 4(-46.0) AH = 3(-50.6)

3N2H4(1) -> 4NH3(g) + N2(g) A.H" = x According to Hess's law, AH = 4(-46.0) +

3(-50.6) = -335.8 kJ

Some students divide the enthalpy obtained by 3 (from the stoichiometric

equation)

unemastry term ;‘,a i enri unapter L..nemical =t;ergeuu.i

Nr." •ter- Compare-the size of the cations—and anions to determine the relative.
lattice energy of the-compounds.

Which of the following best explains why the lattice energy of potassium fluoride,
KF, potassium chloride, KCI, potassium bromide, KBr, and potassium iodide, KI
gradually decreases? A The size of the anion increases. B The compound shows
increasing covalent character. C The electron affinity of the halogen decreases
down the group. D The electronegativity of the halogen decreases down the group.

Answer: A When going down Group 17, the atom and its ion become increasingly
larger. Hence, the lattice energy decreases.

Common Errors
Some students chose correct statements without realising that the magnitude of
lattice energy does not depend on electron affinity or electronegativity.

Why is the lattice energy of MgO higher than the lattice energy of BaO? A The
ionic radius of magnesium is smaller. B Barium has more electrons than magnesium.
C Magnesium has a higher charge density. D The melting point of magnesium oxide
is higher.

Answer: A Since the ionic radius of magnesium is smaller than barium, the lattice
energy of MgO is higher.

Question 10

The diagram below illustrates an energy cycle for the formation of magnesium
oxide.

Mg(s) 1/2 02(g) 11A1-14 Mg(g) 0(g) jjA1-1, Mg*(g) 0-(g) mg2.(g) 02-(g) Which of
the following sets of enthalpies are all endothermic?

AH,

Mg0(s) A

A AH,, AH4, AH5, AH8 B AH,, AH3, AH5, AH, C AH2, AH3, AH4, AH6 D A1-13,
Al-16, AH7, AH8

Answer : C AHD = Enthalpy of atomisation of magnesium (endothermic) AH, = First

ionisation energy of magnesium (endothermic) AH3 = Second ionisation energy of
magnesium (endothermic) • = Enthalpy of atomisation of oxygen (endothermic) • =
First electron affinity of oxygen (exothermic) A115 = Second electron affinity of
oxygen (endothermic) 61-17 = Lattice formation energy (exothermic) • = Enthalpy
of formation (exothermic)

Changes that involves loss of electrons or breaking of bonds have endothermic

enthalpies as these changes require energy for the reaction to occur.

Qiueston 14
The diagram below illustrates a Born-Haber cycle for sodium chloride.

725 Na.(g) + e- + CI(g) Energy A 600 Na'(g) + e + 1/2C12(g) 376 Na'(g) + CI-(g)
108 Na(g) + 1/2C12(g) 0 Na(s) + 1/2C12(g) NaCI(s)

—411

Which of the following can be deduced from the above Born-Haber cycle? A The
electron affinity of chlorine is 2(-349) kJ mol-' B The bond enthalpy of chlorine is
+242 kJ mol-1 C The first ionisation enthalpy of sodium is +600 kJ mol-' D The
lattice formation energy of sodium chloride is -787 Id mol-1

Answer: D From the diagram, The electron affinity of chlorine = (376 - 725) =
-349 kJ mol-' The bond enthalpy of chlorine = (725 - 600) = +125 kJ mol-' Then
first ionisation enthalpy of sodium is (600 - 108) = +492 kJ mot' The lattice
formation energy of sodium chloride = (-376) + (-411) = -787 kJ mot'

*din Tips

The enthalpy change for a reaction can be determined by comparing the

appropriate energy levels in the given diagram.

auemion 45

The change in lattice energy for three halides, X, Y, and Z is as shown in the graph
below.

Lattice A energy

X Which of the following halides could be X, Y, and Z respectively? A KI, SrBr2,

CaF2 B MgF2, CaF2, BaCl2 C NaI, LiCI, CaF2 D BF3, BeCl2, MgI2

Answer: B MgF, is expected to have the highest lattice energy as the ionic radii of
Mg" and F- ions are very small. BaC1, is expected to have the lowest lattice energy
as the ionic radii of Ba2+ and Cl- ions are larger.

tQuestion 1,6

The diagram below illustrates an energy cycle for the formation of potassium
iodide. Which of the following represents the lattice formation energy of
potassium iodide?

K(s) + /2 I2(s)
K(g) + 1(g)

KI(s)

K.(aq) + 1-(aq)

K'(g) + 1-(g)

Answer: B The lattice formation energy is defined as the heat energy released.
when one mole of the ionic compound is formed from its gaseous ions.

0.1 Chemistry Term 2 STPM Chapter 7 Chemical Energetics

Qiueston 14

The diagram below illustrates a Born-Haber cycle for sodium chloride.

725 Na.(g) + e- + CI(g) Energy A 600 Na'(g) + e + 1/2C12(g) 376 Na'(g) + CI-(g)
108 Na(g) + 1/2C12(g) 0 Na(s) + 1/2C12(g) NaCI(s)

—411

Which of the following can be deduced from the above Born-Haber cycle? A The
electron affinity of chlorine is 2(-349) kJ mol-' B The bond enthalpy of chlorine is
+242 kJ mol-1 C The first ionisation enthalpy of sodium is +600 kJ mol-' D The
lattice formation energy of sodium chloride is -787 Id mol-1

Answer: D From the diagram, The electron affinity of chlorine = (376 - 725) =
-349 kJ mol-' The bond enthalpy of chlorine = (725 - 600) = +125 kJ mol-' Then
first ionisation enthalpy of sodium is (600 - 108) = +492 kJ mot' The lattice
formation energy of sodium chloride = (-376) + (-411) = -787 kJ mot'

*din Tips

The enthalpy change for a reaction can be determined by comparing the

appropriate energy levels in the given diagram.

auemion 45

The change in lattice energy for three halides, X, Y, and Z is as shown in the graph
below.

Lattice A energy

X Which of the following halides could be X, Y, and Z respectively? A KI, SrBr2,

CaF2 B MgF2, CaF2, BaCl2 C NaI, LiCI, CaF2 D BF3, BeCl2, MgI2
Answer: B MgF, is expected to have the highest lattice energy as the ionic radii of
Mg" and F- ions are very small. BaC1, is expected to have the lowest lattice energy
as the ionic radii of Ba2+ and Cl- ions are larger.

tQuestion 1,6

The diagram below illustrates an energy cycle for the formation of potassium
iodide. Which of the following represents the lattice formation energy of
potassium iodide?

K(s) + /2 I2(s)

K(g) + 1(g)

KI(s)

K.(aq) + 1-(aq)

K'(g) + 1-(g)

Answer: B The lattice formation energy is defined as the heat energy released.
when one mole of the ionic compound is formed from its gaseous ions.

Lmerrustry term z I rag unaprer unernicat L.-nergerics

Answer: A The solubility of an ionic compound in water depends on the hydration

enthalpy of the anion and cation and the lattice energy of the compound. Generally,
a compound is soluble in water if its hydration energy is larger than its lattice
energy.

;Question 6::

Which of the following statements regarding the solubility of a compound is

correct? A A compound with low melting point can easily dissolve in water. B A
compound's solubility in water decreases when the temperature of water
increases. C A compound can easily dissolve in water if its hydration enthalpy is
larger than its lattice energy. D A compound will dissolve in water if its lattice
formation energy is larger than the total hydration energies of its individual anions
and cations.
Answer: C It is easier for a compound to dissolve in water if the total hydration
enthalpy of the anions and cations is larger than the lattice energy of the
compound.

,fiiii00(in '7'

Why does the solubility of the Group 2 sulphates decrease from beryllium
sulphate, BeSO4to barium sulphate Ba504? A The charge density of the cation
gradually decreases. B The lattice energy becomes increasingly more exothermic. C
The hydration enthalpy becomes increasingly more exothermic. D From Be to Ba,
the cation radius hardly increase compared to the anion radius.

Answer: D Both the lattice crystal energy and the enthalpy of hydration are
proportional to (charge /size) of ion. Hence, when going down the group, both of
these energies will decrease as the size of the metal cations increases. However
the rate of decrease in lattice crystal energy is slower than the rate of decrease
in lattice crystal energy. This is because the size of the sulphate ion, SO42- is
much larger than the size of the metal cations. So, even though the size of the
cation increases, the increase in (r' + r) is very small.

Question The following graph illustrates the solubility of three ionic compounds, X,
Y, and Z at the same temperature and pressure. Solubility (g/100 cm3 water)

••

XYZ

Which of the following compounds could be X, Y and Z respectively? A LiCI, NaCI,

KCI C MgSO4, CaSO4, BaSO, B KNO3, NaNO3, LiNO3 D Mg(OH)2, Ca(OH)2,
Ba(OH)2

Answer: D The graph shows that the solubility of the compounds increases from X
to Y. When going down Group 2, the solubility of the hydroxides increases, but the
solubility of the sulphates decreases.

"Exam Tins

All Group 1 salts and nitrate salts are soluble in water.

question .9.

The enthalpy of solution of copper(II) sulphate compounds are as follows: • Cu504.

5H20(s) --. CuSO4. 5H20(aq) .6,i-I, = +12 kJ mol-1 • CuSO4(s) ---> CuSO4.
5H20(aq) AH2 = — 67 kJ mo1-1 . Which of the following statements is not
correct? • A Hydrated copper(Il) sulphate crystals are the most energetically
stable. .: B Anhydrous CuSO4 will readily absorb water to form the more stable : .
CuSO4.5H20(aq). ° . C 79 kJ of heat energy must be supplied to convert one mole
of CuSO4.5H20(s) crystals to its anhydrous form. • D The change in colour when
copper(11) sulphate crystals are heated is due to the change in the oxidation state
of copper. • .•

Essay Questions)

Chemistry Terra 2 STPM Chapter 7 Chemical Energetics

(c) 1 000 cm3 of CuSO, (aq) contains 1.0 mol or (249.5 g) CuSO4.5H20 At 20°C,
212 g of CuSO4.5H20 will dissolve in 1 000 cm3 of water Mass of CuSO4.5H20
crystals formed = 249.5 - 212.0 = 37.5 g

Section C

#(16400#1,5.

Some information on enthalpy changes when dissolving calcium chloride, CaCl2 in

water are given below: Lattice energy of calcium chloride = -2 258 Id mol-'
Enthalpy of hydration of calcium ion, Ca2+ = -1 650 k) mol-' Enthalpy of hydration
of chloride ion, Cl- = -364 Id mo1-1 (a) Explain why the enthalpy of hydration has a
negative value. (b) Calculate the enthalpy of solution of calcium chloride, CaC12. (c)
What will be the change in the temperature of 100 cm3 water when 0.05 mol
calcium chloride is dissolved in it? [Specific heat capacity of solution = 4.20 1 g-1
°C-1; density of solution = 1.0 g cm-3] (d) The enthalpy of solution of calcium
bromide ion, CaBr2 is -178 ld mol-'. Determine the enthalpy of hydration of
bromide ion and explain which halide ion is more strongly attracted to water.
[Lattice energy of calcium bromide = -2 132 Id moll

Answer: (a) Heat energy is released when bonds are formed between the ions and
water molecules. (b) Enthalpy of solution = Hydration energy (cation + anion) -
Lattice formation energy = (-1650) + 2(-364) - (-2 258) = -120 kJ mol-' (c) Heat
energy released = 120 kJ x 0.05 = 6 kJ = 6 000 J q=mxcx9 6000=100x4.20x9 0 =
14.3°C

,...xicillisLxy 1G1 LLI. I r IVA ICIIJI.Gl r yr rt.,), —1,c,

(d) The enthalpy of hydration of calcium chloride is more exothermic than that of
calcium bromide. Enthalpy of solution = Hydration energy (cation + anion) - Lattice
formation energy -178 = (-1 650) + 2(x) - (-2 132) x = -330 kJ mol-' Enthalpy of
hydration of bromide ion, Br- = -330 kJ mo1-1 Since the enthalpy of hydration of
chloride ion is more exothermic than that of bromide ion, the chloride ion is more
strongly attracted to water. This could be because of the higher charge density on
the chloride ion which makes the bonds formed with water molecules to be
stronger.

txam Tips -

The enthalpy of hydration of ions is inversely proportional to its ionic radius.

Actua :kSTP,M 2013 !P_aper langan3

1. The equation and value for the enthalpy change when sodium fluoride is added to
water is shown below. H,0 NaF(s) > Na+(aq) + F-(aq) AR° = +0.9 kJ molt Which
statement is true of the above process? A Sodium fluoride does not dissolve in
water. B AH° is the enthalpy of hydration for sodium fluoride. C The solubility of
sodium fluoride increases with temperature. D AH° cannot be determined directly
through an experiment.

Answer: C The positive value for AH° shows that heat energy is absorbed when
sodium fluoride is dissolved in water. When the temperature is increased, the
forward reaction is favoured. Hence, the solubility of sodium fluoride increases
when temperature increases.

Essay Questions)

Chemistry Terra 2 STPM Chapter 7 Chemical Energetics

(c) 1 000 cm3 of CuSO, (aq) contains 1.0 mol or (249.5 g) CuSO4.5H20 At 20°C,
212 g of CuSO4.5H20 will dissolve in 1 000 cm3 of water Mass of CuSO4.5H20
crystals formed = 249.5 - 212.0 = 37.5 g

Section C

#(16400#1,5.
Some information on enthalpy changes when dissolving calcium chloride, CaCl2 in
water are given below: Lattice energy of calcium chloride = -2 258 Id mol-'
Enthalpy of hydration of calcium ion, Ca2+ = -1 650 k) mol-' Enthalpy of hydration
of chloride ion, Cl- = -364 Id mo1-1 (a) Explain why the enthalpy of hydration has a
negative value. (b) Calculate the enthalpy of solution of calcium chloride, CaC12. (c)
What will be the change in the temperature of 100 cm3 water when 0.05 mol
calcium chloride is dissolved in it? [Specific heat capacity of solution = 4.20 1 g-1
°C-1; density of solution = 1.0 g cm-3] (d) The enthalpy of solution of calcium
bromide ion, CaBr2 is -178 ld mol-'. Determine the enthalpy of hydration of
bromide ion and explain which halide ion is more strongly attracted to water.
[Lattice energy of calcium bromide = -2 132 Id moll

Answer: (a) Heat energy is released when bonds are formed between the ions and
water molecules. (b) Enthalpy of solution = Hydration energy (cation + anion) -
Lattice formation energy = (-1650) + 2(-364) - (-2 258) = -120 kJ mol-' (c) Heat
energy released = 120 kJ x 0.05 = 6 kJ = 6 000 J q=mxcx9 6000=100x4.20x9 0 =
14.3°C

,...xicillisLxy 1G1 LLI. I r IVA ICIIJI.Gl r yr rt.,), —1,c,

(d) The enthalpy of hydration of calcium chloride is more exothermic than that of
calcium bromide. Enthalpy of solution = Hydration energy (cation + anion) - Lattice
formation energy -178 = (-1 650) + 2(x) - (-2 132) x = -330 kJ mol-' Enthalpy of
hydration of bromide ion, Br- = -330 kJ mo1-1 Since the enthalpy of hydration of
chloride ion is more exothermic than that of bromide ion, the chloride ion is more
strongly attracted to water. This could be because of the higher charge density on
the chloride ion which makes the bonds formed with water molecules to be
stronger.

txam Tips -

The enthalpy of hydration of ions is inversely proportional to its ionic radius.

Actual question STPM 2014 paper 2

Section A

1. The equation and value for the enthalpy change when sodium fluoride is added to
water is shown below. H,0 NaF(s) > Na+(aq) + F-(aq) AR° = +0.9 kJ molt Which
statement is true of the above process? A Sodium fluoride does not dissolve in
water. B AH° is the enthalpy of hydration for sodium fluoride. C The solubility of
sodium fluoride increases with temperature. D AH° cannot be determined directly
through an experiment.

Answer: C The positive value for AH° shows that heat energy is absorbed when
sodium fluoride is dissolved in water. When the temperature is increased, the
forward reaction is favoured. Hence, the solubility of sodium fluoride increases
when temperature increases.

Chemistry Term 2 STPM Chapter 8 Electrochemistry

Question 3

Which of the following equations correctly represents the reaction in the following
half-cell?

H+(aq), Mn04(aq), Mn2+(aq)IPt(s)

A Mn2+ + 2e- ---> Mn B Mn2+ + 4H20 Mn04 + 8H++ 5e-C Mn04 + 4H++ 3e- Mn02 +
2H20 D MnO; + 8H++ 5e- Mn2+ + 4H20

Answer: D A reduction reaction occurs. At the cathode half-cell, the

manganese(VII) ion is reduced to manganese(II) ion by receiving 5 electrons.

:ExarruTips

.nr.'FfKW;;777

Determine the oxidation number of manganese in Mn04 ion.

Question 4

The cell diagram for the Daniell cell is as shown. Zn(s) / Zn2+(aq) II Cu2+(aq) I
Cu(s) • Which of the following equations correctly represents the overall reaction
in the cell? • A Zn2+ + Cu Zn + Cu2+ C Zn2+ + Cu2+ Zn + Cu • B Zn + Cu2+ Zn2+ + Cu
D Zn + Cu Zn2+ + Cu2+

Answer: 13 In the zinc half-cell, zinc atoms are oxidised to zinc ions, whereas in
the copper half-cell, copper(II) ions are reduced to copper atoms.

The cell diagram for an electrochemical cell is as shown. Mg(s) / Mg2+(aq) II

Zn2÷(acl) I Zn(s) Which of the following information is not correct? A Each
magnesium atom loses two electrons in the reaction. B Each zinc ion accepts two
electrons in the reaction. C Electrons flow from the zinc to the magnesium
electrode. D Only the concentration of zinc ions decrease after the reaction.

Chemistry Term 2 STPM Chapter 8 Electrochemistryi

Answer: C In the magnesium half-cell, magnesium atoms are oxidised to magnesium

ions, whereas in the zinc half-cell, zinc ions are reduced to zinc atoms. The
concentration of magnesium ions increases while the concentration of zinc ions
decreases. Magnesium functions as the negative terminal whereas zinc functions as
the positive terminal. Hence, electrons flow from magnesium to zinc through the
wires.

Ouestiori 6

The diagram for the Daniell cell is as shown.

Zinc metal ZnSO4(aq)

Copper metal

CuSO4(aq)

Which of the following statements regarding the cell is not correct? A K+ ions are
discharged at the zinc electrode which is the negative terminal. B The amount of
5042- ions in both beakers remain the same. C Each copper ion accepts two
electrons in the reaction. D Each zinc atom loses two electrons in the reaction.

Answer: A The K+ and Cl ions in the salt bridge enter both solutions to maintain
electrical neutrality in both beakers. K4 ions are attracted to the copper
electrode where electrons enter the electrolyte. The amount of SO42- ions in
both beakers remains the same as sulphate ions are spectator ions. In the copper
half-cell, each copper ion accepts two electrons and is reduced to a copper atom.
In the zinc half-cell, zinc atoms are oxidised to zinc ions by losing two electrons.

Common Errors

Some students wrongly assume that the positively charged ions are discharged at
the zinc electrode which is the negative terminal.

Calculate the temperature rise when 50 cm3 of 1.00 mol dm-3 potassium hydroxide
solution is added to 50 cm3 of 1.00 mol dm-3 nitric acid. [Enthalpy of
neutralisation = - 57.3 kJ mo1-11 A 6.8°C B 7.3°C C 7.7°C D 8.2°C

Answer:: A KOH(aq) + HNO3(aq) —' KNO3(aq) + H20(1) MV50(1.00) = Number of

moles of KOH = HNO3 - 0.050 1 000 = 1 000 Quantity of heat released =
0.050(57 300) = 2 865 J 100 x 4.2 x 0 = 2 865 0 = 6.8°C

QtilettiOliA3

Hydrogen gas burns in air to form water. • 2H2 (g) + 02 (g) 2H20(1) AH = - 572 Id
• How much heat energy (in kJ) is given off if a rocket carrying 200.0 kg of :
hydrogen gas is burnt in excess oxygen? • : A 1.43 x 106 B 1.43 x 107 C 2.86 x 10'
D 4.92 x 10'

Answer: C

Number of moles of H, = mass = 200 000 = 100 000 molar mass 2 Quantity of
heat liberated = 100 000 x (286) = 2.86 x 107 kJ

Common Errors

Some students fail to note that the given value of -572 kJ is for the formation of
2 moles of water.

(titiatiotif9;
The enthalpy of formation of carbon monoxide is - 110 kJ 1 C(s) + I 02(g) CO(g)
However, a mixture of carbon and oxygen gas at 25°C and 1.0 atm does not yield
any carbon monoxide. This is because A the reaction is too exothermic. B the
activation energy is too high. C carbon monoxide is not stable. D carbon is not a
reactive substance.

Answer: B Although the reaction is exothermic, the reaction does not readily
happen at standard conditions due to the high activation energy. Carbon must be
heated for the reaction to occur.

Question 10.: The gaseous oxides of nitrogen such as NO, N20, NO2 and N204
have positive enthalpies of formation because A oxygen has high electron affinity.
B the atomisation enthalpy of nitrogen is very high. C the nitrogen atom has a high
electronegativity. D nitrogen has an extra stability due to its half-filled p orbitals.
............

Answer: B Nitrogen, N2 is rather stable due to the high bond enthalpy of N=N i.e.
994 kJ mol-'

Common Errors

Some students chose statements that are factually correct but are not related to
I the question.

;Question 11

The standard enthalpy of combustion of 2-methylbut-1-ene, C5Fli0 is : -3 114 Id

mot-'. Which of the following compounds is expected to have the

same enthalpy of combustion? A Cyclopentane, C51-110 B Cyclopentene, C51-18 C

Pent-2-ene, C5H,0 D Methylcyclobutane, C51-1,0

. .00••••

Answer: C The enthalpy of combustion of 2-methylbut-1-ene, C51-1i0 and pent-2-

ene, C5Fl10 is the same because both hydrocarbons have the same type and
number of bonds.

..L....t4rA.K.„ rR ,'''''''-'AITZ-ZW Exam Tips - :,7-;..x104.!..fe..,,w-.4 ,,,x,,,,.% '.;:,!

ii. ':',.=';:':::-.;t F::'.' ' • • •.-.•.-:,' :.',.:: ', -;:;:i,,,,L ,::•.,,::,7 '..-, •:.$:,--,'7..:,:;''--c?-
EP'.'e ."; .., . .":7' • - CbmpoundS with .the same number and 'type: of
cci.alerit,bOhds:,:tiSually: have...the same enthalpy of combustion because the
same amount of heat energy is required to break bonds and the same amount of
heat energy is liberated when.the same amount of products are formed.