Tutorial Chemical Energetics Part I Solutions | Hydrogen | Sodium Chloride

Dunman High School

2010 Year 5 H2 CHEMISTRY
Tutorial: Chemical Energetics (Part I )

A Calorimetric Calculations

















1 A flame calorimeter was used to find the standard enthalpy change of combustion of
propan–1–ol. The following information was obtained during the experiment:

Heat capacity of apparatus = 3.01 kJ K
–1

Mass of propan–1–ol burned = 2.40 g
Initial temperature = 27.3°C
Maximum temperature = 52.3°C

(a) Explain, with the aid of a chemical equation with state symbols, what is meant by the
standard enthalpy change of combustion of propan–1–ol.

The standard enthalpy change of combustion of CH
3
CH
2
CH
2
OH is
the energy change when one mole of CH
3
CH
2
CH
2
OH is
completely burnt in oxygen under standard conditions.

CH
3
CH
2
CH
2
OH(l) +
2
9
O
2
(g) → 3CO
2
(g) + 4H
2
O(l)


Steps to calculate ∆H

Step 1: Write the balanced equation (where possible)

Step 2: Calculate apparent amount of heat absorbed/ released by
reaction, Q’ using Q’ = mcAT

Step 3: Calculate actual amount of heat absorbed/ released by reaction,
Q, using Q’ (no heat loss to surrounding)
or Q’ =
100
x
Q (x% efficiency)

Step 4: Calculate n where n = no. of moles of water (neutralisation)
n = no. of moles of substance (combustion)
Step 5: Calculate enthalpy change using AH
rxn
= +
n
Q

where (–) for exothermic reaction and (+) for endothermic reaction
‘C’
(not ‘c’)
Temp   ∆H < 0
2008 Year 5 H2 CHEMISTRY
2

(b) Calculate the amount of heat evolved during the combustion. [75250 J]
Amount of heat evolved,
Q’ = C∆T = Q (assume 100% efficiency)
= 3.01×10
3
× (52.3 – 27.3)
= 75250 J



(c) Calculate the standard enthalpy change of combustion of propan–1–ol.
[Specific heat capacity of water is 4.18 J g
–1
K

] [–1881250 J mol
–1
]
No. of mol. of CH
3
CH
2
CH
2
OH burnt, n =
M
m
=
0 . 60
40 . 2
= 0.04000
∆H
c
ө
(CH
3
CH
2
CH
2
OH) = –
OH CH CH CH
n
Q
2 2 3
= –
0400 . 0
75250

= – 1881250 J mol
–1

(d) Why would inadequate supply of air lead to error in the above results?

Inadequate supply of air leads to incomplete combustion of
propan–1–ol. This leads to a decrease in the amount of heat
evolved and hence inaccuracy in the ∆H
c
ө
(CH
3
CH
2
CH
2
OH).



Since specific heat
capacity, ‘c’ not
mentioned, use heat
capacity, ‘C’
Refers to actual amount of heat ‘Q’
∆H
c
ө
(CH
3
CH
2
CH
2
OH)
2008 Year 5 H2 CHEMISTRY
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2 The standard enthalpy change of combustion of propane is –2200 kJ
mol
–1
. A 2.40 dm
3
sample of propane was burned under a container of
water originally under r.t.p. conditions.
Given that the process was 75% efficient, calculate the mass of water in
the container that could be heated to 80°C. [718 g]

No. of mol. of CH
3
CH
2
CH
3
burnt, n =
m
V
V
=
0 . 24
40 . 2
= 0.100

Actual amount of heat evolved, Q = –∆H
c
ө
(CH
3
CH
2
CH
3
) × n
= –(–2200×10
3
) × 0.100
= 220000 J

Since process is 75 % efficient,
Apparent amount of heat absorbed by water, Q’
=
100
75
Q (Actual amount of heat evolved by burning propane)

Apparent amount of heat absorbed by the water, Q’
=
100
75
× Q =
100
75
× 220000 = 165000 J


Since Q’ = mc∆T
¬ 165000 = m × 4.18 × (80.0 – 25.0)


Mass of water heated, m =
0 . 55 18 . 4
165000
×
= 718 g




∆H
θ
c
(C
3
H
8
) = – Q / no of moles C
3
H
8

Obtain from Data Booklet
2008 Year 5 H2 CHEMISTRY
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3 The chemical reaction between 30 cm
3
of 1.0 mol dm
–3
sodium hydroxide
solution and 20 cm
3
of 1.0 mol dm
–3
sulphuric acid solution in a plastic
cup gave rise to a temperature rise of 7.3°C due to neutralisation. The
process efficiency was expected to be 90%.

Explain, with the aid of a chemical equation with state symbols, what is
meant by the standard enthalpy change of neutralisation.

H
+
(aq) + OH

(aq) → H
2
O(l)
The standard enthalpy change of neutralisation is the energy
evolved when one mole of water is formed from the neutralisation
between acid and alkali under standard conditions.

Calculate the standard enthalpy change of the neutralisation reaction.
[Assume specific heat capacity of the solution to be 4.18 J g
–1
K
–1
and its
density to be 1 g cm
–3
] [–56507 J mol
–1
]

½H
2
SO
4
(aq) + NaOH(aq)  ½Na
2
SO
4
(aq) + H
2
O(l)

Apparent amount of heat evolved, Q’
= mc∆T = (30 + 20) × 4.18 × 7.3 = 1525.7 J
Q’ =
100
90
× Q (given 90% efficiency)
Actual amount of heat evolved, Q =
90
100
× 1525.7 = 1695.2 J
No. of mole of H
2
SO
4
=
mol 0200 . 0 1
1000
20
= ×

No. of mole of NaOH =
mol 0300 . 0 1
1000
30
= ×

NaOH is the limiting reagent.
Hence no. of mole of H
2
O formed, n = 0.0300
∆H
n
ө
= –
O H
n
Q
2
= –
0300 . 0
2 . 1695
= – 56507 J mol
–1





2008 Year 5 H2 CHEMISTRY
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B Calculations Using Bond Energy














4 Suppose that ethene and steam react to give carbon monoxide and hydrogen with an
enthalpy change of 254 kJ mol
–1
as given.
C
2
H
4
(g) + 2H
2
O(g) ÷ 2CO(g) + 4H
2
(g)

(a) Explain, with the aid of a chemical equation with state symbols, what is meant by the
bond energy of C÷O.

C÷O(g) ÷ C(g) + O(g)
The bond energy of C÷O is the average energy absorbed when one
mole of C÷O bonds is broken in the gaseous state to form C and
O atoms.

(b) With the aid of appropriate bond energy data from the Data Booklet, calculate the
bond energy of C÷O bond in carbon monoxide. [+1046 kJ mol
–1
]
reactants products

C
2
H
4
(g) + 2H
2
O(g) ÷ 2CO(g) + 4H
2
(g)

2 2 4

4 (C–H) 2(2)(O–H)

∆H
rxn
= [BE(C=C)+4BE(C–H)+4BE(O–H)] – [2BE(C÷O)+4BE(H–H)]
BE(C÷O) =
2
1
{[610+4(410)+4(460)]–254–4(436)} = + 1046 kJ mol
–1

Definition: Bond energy of X–Y bond is the average energy absorbed
when one mole of X–Y bonds is broken in the gaseous state to
form X and Y atoms. i.e XY (g)  X (g) + Y (g)

Application: – A measure of bond strength
– Used to calculate enthalpies of reactions
Formula
AH
rxn
= E BE of bonds broken in rxts
– E BE of bonds formed in pdts

- Energy is absorbed in bond breaking in reactants: endothermic (+)
- Energy is released in bond formation in products: exothermic (–)
C C
H
H H
H
C O
H
O
H
H H
2008 Year 5 H2 CHEMISTRY
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5 Under mild conditions, the catalytic hydrogenation of ethyne, H–C≡C–H
yields ethane. Under extreme conditions, the catalytic hydrogenation of
nitrogen N≡N, yields ammonia.

(i) Write equations for the two hydrogenation processes described above.
C
2
H
2
(g) + 2H
2
(g)  C
2
H
6
(g)

N
2
(g) + 3H
2
(g)  2NH
3
(g)

(ii) Explain, with the aid of appropriate bond energy values from the Data
Booklet, the difference in the behaviour of ethyne and nitrogen.
[AH
rxn
(H–C≡C–H): –278 kJ mol
–1
; AH
rxn
(N≡N): –38 kJ mol
–1
]


H–C≡C–H + 2H–H 


AH
rxn
=[BE(C≡C)+ 2BE(C–H) +2BE(H–H)] – [BE(C–C) + 6BE(C–H)]
= – 278 kJ mol
–1


N≡N + 3H–H  2

AH
rxn
= [BE(N≡N) + 3BE(H–H)] – 2[3BE(N–H)] = – 38 kJ mol
–1


Hydrogenation of ethyne is more exothermic than that of nitrogen

Hydrogenation of ethyne require mild conditions while that for
nitrogen require extreme conditions

Alternative: (kinetics stability of the reactants)
Quote N≡N bond energy value and C≡C bond energy value

The N≡N bond energy value is much higher than that of C≡C
bond energy. Hence the N≡N bond is extremely strong hence
large amount of energy required to break the bond in the
reactants hence high activation energy required

C
H
H C H
H
H H
N
H
H
H
2008 Year 5 H2 CHEMISTRY
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6 Some bond energy values are given in the table below:

Bond Bond energy / kJ
mol
–1

Bond Bond energy / kJ
mol
–1

H–H 436 H–H 436
P–P 208 Cl–Cl 244
P–H 322 H–Cl 431
The P–H bond energy is the average of the H–H and P–P values. Explain
why the H–Cl bond energy is not the mean of H–H and Cl–Cl values.

Electronegativity of P≈ H

 H–H, P–P and P–H bonds are non–polar
 BE (P–H) is the average of BE (H–H) and BE (P–P)

Electronegativity of Cl > H
 H–H, Cl–Cl are non–polar while H–Cl bond is polar due to
difference in electronegativity
 BE (H–Cl) is not the average of BE (H–H) and BE (Cl–Cl)

2008 Year 5 H2 CHEMISTRY
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C Other Calculations Methods of AH
θ
rxn




























7 The standard enthalpy change of the following reaction is –156.1 kJ mol
–1
.
MoO
2
(s) + ½O
2
(g) ÷ MoO
3
(s)

(a) The standard enthalpy change of formation of MoO
3
is –745.1 kJ mol
–1
.
Explain, with the aid of a chemical equation with state symbols, what is
meant by this statement.
Mo(s) + 3/2 O
2
(g) ÷ MoO
3
(s)
The standard enthalpy change of formation of MoO
3
is the energy
change when one mole of MoO
3
is formed from its elements i.e.
Mo and O
2
under standard conditions.
2 Methods

(1) Using enthalpy change of formation, AH
f
, method
Formula: AH
rxn
u
= EAH
f
u
(pdts) – EAH
f
u
(rxts)

 Note that AH
f
of element (e.g H
2
) is always zero
 Use only if AH
f
(pdts) and AH
f
(rxts) are provided

(2) Using Hess Law Energy Cycle method
Definition
Hess’ Law: The enthalpy change accompanying a chemical reaction
is the same regardless of the route by which the chemical change
occurs, provided the initial and final conditions are the same.









By Hess Law, AH
1 =
AH
2
+ AH
3
+ AH
4


Note:
 All AH

must have the correct signs
 Multiply a reaction by a factor ¬ multiply AH

by the same factor
 Reverse a reaction ¬ Reverse the sign of AH
AH
1

AH
3

AH
2

AH
4

A
C D
B
2008 Year 5 H2 CHEMISTRY
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(b) Calculate the standard enthalpy change of formation of MoO
2
.
[–589 kJ mol
–1
]
(Use AH
f
Method to solve)

MoO
2
(s) + ½O
2
(g) ÷ MoO
3
(s) ∆H
rxn
ө
= –156.1 kJ mol
–1

∆H
rxn
ө
= ¿∆H
f
ө
(pdts
)
– ¿∆H
f
ө
(rxts)

∆H
rxn
ө
= ∆H
f
ө
(MoO
3
) – [∆H
f
ө
(MoO
2
) +
2
1
∆H
f
ө
(O
2
)]
∆H
f
ө
(MoO
2
)

= –745.1 –
2
1
(0) – (–156.1) = – 589 kJ mol
–1


8 The standard enthalpy change of combustion of cyclohexane is
–3924 kJ mol
–1
. Given that the standard enthalpy changes of
formation of water and carbon dioxide are –286 kJ mol
–1
and
–394 kJ mol
–1
respectively, calculate the standard enthalpy
change of formation of cyclohexane. [–156 kJ mol
–1
]
(Can use AH
f
Method to solve Q8)

Formula Method
C
6
H
12
(l) + 9O
2
(g) ÷ 6CO
2
(g) + 6H
2
O(l) ∆ H
c
θ
(C
6
H
12
)=–3924 kJ mol
–1

∆H
c
θ
(C
6
H
12
)= [6∆H
f
θ
(CO
2
)+6∆H
f
θ
(H
2
O)] – [∆H
f
θ
(C
6
H
12
)+9∆H
f
θ
(O
2
)]

¬∆H
f
θ
(C
6
H
12
)

= [6(–394) + 6(–286)] –9(0)–(–3924) = – 156 kJ mol
–1


9 The standard enthalpy change of dimerisation of ethene to form but–1–
ene, as follows, is –10 kJ mol
–1
:
2CH
2
=CH
2
(g) ÷ CH
2
=CHCH
2
CH
3
(g)
Calculate the standard enthalpy change of combustion of ethene, given that
the standard enthalpy change of combustion of gaseous but–1–ene is –20 kJ
mol
–1
. [–15 kJ mol
–1
]
(Can use Hess’ Law Energy Cycle Method to solve)

Given:
 2C
2
H
4
(g) ÷ C
4
H
8
(g) ∆H
rxn
u

 C
4
H
8
(g) + 6O
2
(g) → 4CO
2
(g) + 4H
2
O(l) ∆H
c
u
(C
4
H
8
)

2008 Year 5 H2 CHEMISTRY
10

Hess’ Law Energy Cycle

∆H
c
u
(C
2
H
4
) = ?
Aim: C
2
H
4
(g) + 3O
2
(g) 2CO
2
(g) + 2H
2
O(l)


½ ∆H
rxn
u
½ ∆H
c
u
(C
4
H
8
)


2
1
C
4
H
8
(g) + 3O
2
(g)

By Hess’ law:
∆H
c
u
(C
2
H
4
) =
2
1
∆H
rxn
u
+
2
1
∆H
c
u
(C
4
H
8
) =
2
1
[–10 + (–20)]= – 15 kJ mol
–1


10 The standard enthalpy changes of combustion of hydrogen, cyclohexane
and benzene are –286 kJ mol
–1
, –3920 kJ mol
–1
and –3268 kJ mol
–1

respectively.

(i) Write a chemical equation to represent the hydrogenation of benzene to
form cyclohexane;

C
6
H
6
(l) + 3H
2
(g) ÷ C
6
H
12
(l)

(ii) Calculate the standard enthalpy change for this reaction using Hess’ law.
[–206 kJ mol
–1
]
(Must use Hess’ Law Energy Cycle Method!)

Given:
 H
2
(g) +
2
1
O
2
(g) ÷ H
2
O(l) ∆H
c
u
(H
2
)
 C
6
H
12
(l) + 9O
2
(g)→ 6CO
2
(g) + 6H
2
O(l) ∆H
c
u
(C
6
H
12
)
 C
6
H
6
(l) +
2
15
O
2
(g)→ 6CO
2
(g) + 3H
2
O(l) ∆H
c
u
(C
6
H
6
)

2008 Year 5 H2 CHEMISTRY
11

∆H
rxn
u
= ?
Aim: C
6
H
6
(l) + 3H
2
(g) C
6
H
12
(l)


∆H
c
u
(C
6
H
6
) 3∆H
c
u
(H
2
) ∆H
c
u
(C
6
H
12
)
+
2
15
O
2
(g) +
2
3
O
2
(g) + 9O
2
(g)
6CO
2
(g) + 6H
2
O(l)


By Hess’ law:
∆H
rxn
u
= ∆H
c
u
(C
6
H
6
)

+ 3∆H
c
u
(H
2
) – ∆H
c
u
(C
6
H
12
)
= –3268 + 3(–286) – (–3920) = – 206 kJ mol
–1


11 The standard enthalpy change of atomisation of carbon and hydrogen
are +715 kJ mol
–1
and +218 kJ mol
–1
respectively. Given that the
standard enthalpy change of formation of methane is –75 kJ mol
–1
,
calculate:

(a) the standard enthalpy of atomisation of methane;
[+1662 kJ mol
–1
]
(Can use Hess’ Law Energy Cycle or Algebraic Method)

Given:
 C(s) ÷ C(g) ∆H
at
u
(C)

2
1
H
2
(g) ÷ H(g) ∆H
at
u
(H
2
)
 C(s) + 2H
2
(g) → CH
4
(g) ∆H
f
u
(CH
4
)


∆H
at
u
(CH
4
) = ?
Aim: CH
4
(g) C(g) + 4H(g)


∆H
f
u
(CH
4
) ∆H
at
u
(C) 4∆H
at
u
(H
2
)

C(s) + 2H
2
(g)

By Hess’ law:
∆H
at
u
(CH
4
) = –∆H
f
u
(CH
4
)

+ ∆H
at
u
(C) + 4∆H
at
u
(H
2
)
= –(–75) + 715 + 4(218)
= 1662 = +1660 kJ mol
–1
(3 s.f)
2008 Year 5 H2 CHEMISTRY
12




(b) the C–H bond energy. [+415.5 kJ mol
–1
]

Note:
∆H
at
u
(CH
4
) involves breaking 4 mole of C–H bond in 1 mol. of CH
4

to form C and H atoms in the gaseous phase.

∆H
at
u
(CH
4
) = 4BE(C–H)
¬ BE(C–H) =
4
1
(1662) = + 415.5 = + 416 kJ mol
–1


2008 Year 5 H2 CHEMISTRY
13

E Born–Haber Cycle

Important points to remember when drawing Born Haber Cycle:

 Use “” for endo rxn and “” for exo rxn
 Follow the sequence: (label the arrows)

I.E

E.A
(can be exo rxn or endo rxn)



∆H
at

∆H
latt


∆H
f




 If AH
at
(X
2
) value is not given, refer to Data Booklet to obtain
value of BE(X–X)
) A ( H 2 ) A ( BE
2 at 2
u
A =



12 The lattice energy of lithium chloride can be calculated from a Born–
Haber cycle using the following standard enthalpy data:

Enthalpy change of formation of lithium chloride –409 kJ mol
–1
Enthalpy change of atomisation of lithium 159 kJ mol
–1

Enthalpy change of atomisation of chlorine 121 kJ mol
–1

Electron affinity of chlorine –364 kJ mol
–1


(a) Construct a Born–Haber cycle for lithium chloride and use the cycle, with
the aid of appropriate ionisation data from the Data Booklet, to determine
the lattice energy of lithium chloride. [–844 kJ mol
–1
]
Start:
Elements in
standard state
2008 Year 5 H2 CHEMISTRY
14

Given:
∆H
f
ө
(LiCl)
Li(s) +
2
1
Cl
2
(g) → LiCl(s)
–409 kJ mol
–1

∆H
at
ө
(Li) Li(s) → Li(g) 159 kJ mol
–1

∆H
at
ө
(Cl
2
)
2
1
Cl
2
(g) → Cl(g)
121 kJ mol
–1

1
st
IE(Li)


Li(g) → Li
+
(g) + e 519 kJ mol
–1

EA(Cl) Cl(g) + e → Cl

(g) –364 kJ mol
–1

∆H
latt
ө
(LiCl) Li
+
(g) + Cl

(g) → LiCl(s) ?

Born–Haber cycle to determine ∆H
latt
ө
(LiCl):

Li
+
(g) + Cl(g) + e
1
st
IE
(Li)


Li(g) + Cl(g)
EA
(Cl)

Li
+
(g) + Cl

(g)
∆H
at
ө
(Cl2 )


Li(g) +
2
1
Cl
2
(g)

∆H
at
ө
(Li)


Li(s) +
2
1
Cl
2
(g)
∆H
latt
ө
(LiCl)

∆H
f
ө
(LiCl)


LiCl(s)

By Hess’ law:
∆H
f
ө
(LiCl) = ∆H
at
ө
(Li) + ∆H
at
ө
(Cl
2
) + 1
st
IE(Li) + EA(Cl) + ∆H
latt
ө
(LiCl)
¬ ∆H
latt
ө
(LiCl)

= –409 – [159 + 121 + 519 + (–364)
= – 844 kJ mol
–1

From Data
Booklet
2008 Year 5 H2 CHEMISTRY
15

(b) Explain how you would expect the numerical magnitude of the lattice
energy of sodium chloride to compare with that of lithium chloride.
AH
latt
·
÷ +
÷ +
+ r r
q q

- Ionic radius, r
+
: Na
+
> Li
+

- Magnitude of ∆H
latt
ө
:

NaCl < LiCl










13 Suppose calcium can form two ionic compounds with chlorine: calcium(I)
chloride (CaCl) and calcium(II) chloride (CaCl
2
).

The following information about some standard enthalpy changes is provided:

Lattice energy of calcium(I) chloride –700 kJ mol
–1

Lattice energy of calcium(II) chloride –2197 kJ mol
–1

Enthalpy change of atomisation of calcium 178 kJ mol
–1

Electron affinity of chlorine –362 kJ mol
–1


(a) Draw a Born–Haber cycle in each case to determine the standard
enthalpy change of formation of (i) calcium(I) chloride; (ii) calcium(II)
chloride. [–759 kJ mol
–1
]

Given:
(i) For CaCl;

∆H
f
ө
(CaCl) Ca(s) + ½ Cl
2
(g) → CaCl(s) ?
∆H
at
ө
(Ca) Ca(s) → Ca(g) 178 kJ mol
–1

∆H
at
ө
(Cl
2
) 1/2Cl
2
(g) → Cl(g) ∆H
at
ө
(Cl) = ½BE(Cl–Cl)
= ½ (244)
1
st
IE(Ca) Ca(g) → Ca
+
(g) + e 590 kJ mol
–1

EA(Cl) Cl(g) + e → Cl

(g) –362 kJ mol
–1

∆H
latt
ө
(CaCl) Ca
+
(g) + Cl

(g) → CaCl(s) –700 kJ mol
–1

Note:
Smaller ionic radius
¬ Oppositely charged ions are closer
¬ Electrostatic force of attraction becomes stronger
Hence the larger the magnitude of lattice energy
(Stability of ionic compound is greater)
2008 Year 5 H2 CHEMISTRY
16

Born–Haber cycles to determine (i) ∆H
f
ө
(CaCl)

Ca
+
(g) + Cl(g) + e
1
st
IE(Ca)

Ca(g) + Cl(g)
EA(Cl)

Ca
+
(g) + Cl

(g)
∆H
at
ө
(Cl
2
)

Ca(g) +
2
1
Cl
2
(g)
∆H
latt
ө
(CaCl)

∆H
at
ө
(Ca)

Ca(s) +
2
1
Cl
2
(g)


∆H
f
ө
(CaCl)

CaCl(s)




By Hess’ law:
∆H
f
ө
(CaCl)=∆H
at
ө
(Ca)+∆H
at
ө
(Cl
2
)+1
st
IE(Ca) + EA(Cl) + ∆H
latt
ө
(CaCl)
= 178 +
2
1
(244) + 590 + (–362) + (–700)
= – 172 kJ mol
–1

(ii) ∆H
f
ө
(CaCl
2
)

∆H
f
ө
(CaCl) Ca(s) + Cl
2
(g) → CaCl
2
(s) ?
∆H
at
ө
(Ca) Ca(s) → Ca(g) 178 kJ mol
–1

∆H
at
ө
(Cl
2
) 1/2Cl
2
(g) → Cl(g) ∆H
at
ө
(Cl) = ½BE(Cl–Cl)
= ½ 244
1
st
IE(Ca) Ca(g) → Ca
+
(g) + e 590 kJ mol
–1

2
nd
IE(Ca) Ca
+
(g) → Ca
2+
(g) + e 1150 kJ mol
–1
EA(Cl) Cl(g) + e → Cl

(g) –362 kJ mol
–1

∆H
latt
ө
(CaCl
2
) Ca
2+
(g) + 2Cl

(g) → CaCl
2
(s) –2197 kJ mol
–1


2008 Year 5 H2 CHEMISTRY
17

Born–Haber cycles to determine (ii) ∆H
f
ө
(CaCl
2
)

Ca
2+
(g) + 2Cl(g) + 2e
2
nd
IE(Ca)

Ca
+
(g) + 2Cl(g) + e
2EA(Cl)

Ca
2+
(g)+2Cl

(g)
1
st
IE(Ca)

Ca(g) + 2Cl(g)
∆H
latt
ө
(CaCl
2
)

2∆H
at
ө
(Cl
2
)

Ca(g) + Cl
2
(g)


∆H
at
ө
(Ca)

Ca(s) + Cl
2
(g)


∆H
f
ө
(CaCl
2
)

CaCl
2
(s)



By Hess’ law:
∆H
f
ө
(CaCl
2
)

= ∆H
at
ө
(Ca)+ 2∆H
at
ө
(Cl
2
)+ 1
st
IE(Ca)+2
nd
IE(Ca)+
2EA(Cl)+∆H
latt
ө
(CaCl)

= 178 + 244 + 590 + 1150 + 2(–362) + (–2197)
= –759 kJ mol
–1

(b) Comment on the relative numerical magnitudes of the standard enthalpy
change of formation of calcium(I) chloride and calcium(II) chloride.

Formation of CaCl is less exothermic than that of CaCl
2
.
Since magnitude of ∆H
f
ө
(CaCl) is less than that of ∆H
f
ө
(CaCl
2
),
Hence CaCl is energetically less stable than CaCl
2
.


2008 Year 5 H2 CHEMISTRY
18

E Energetics of Aqueous Solution

Definitions:
 AH
θ
sol
= the energy change when one mole of the substance is
completely dissolved in a solvent to form an infinitely dilute
solution under standard conditions.

 AH
θ
hyd
= the energy evolved when one mole of the gaseous ion
is hydrated under standard conditions.

 AH
θ
latt
= the energy evolved when one mole of the solid ionic
compound is formed from its constituent gaseous ions under
standard conditions.

 Memorise how to draw the energy cycle for calculation of
AH
θ
sol
of an ionic compound




AH
θ
sol
= AH
θ
hyd
– AH
θ
latt


Memorise how to draw the energy level diagram for calculation
of AH
θ
sol
of an ionic compound

Exothermic dissolution Endothermic dissolution











From lecture notes
From lecture notes
2008 Year 5 H2 CHEMISTRY
19

14 The lattice energy of lithium chloride is –848 kJ mol
–1
and that of
sodium chloride is –776 kJ mol
–1
. Some enthalpy changes of hydration
are listed below:
Ions AH
θ
hyd
/kJ mol
–1

Li
+
–499
Na
+
–390
Cl

–381
(a) Draw two energy cycles using data in this question to determine the
enthalpy change of solution for these two salts. [–36 kJ mol
–1
]

Energy cycle to determine ∆H
soln
ө
(LiCl):

LiCl(s) Li
+
(aq) + Cl

(aq)


– ∆H
latt
ө
(LiCl)

∆H
hyd
ө
(Li
+
) ∆H
hyd
ө
(Cl

)

Li
+
(g) + Cl

(g)

By Hess’ law:
∆H
soln
ө
(LiCl) = –∆H
latt
ө
(LiCl)

+ ∆H
hyd
ө
(Li
+
) + ∆H
hyd
ө
(Cl

)
= –(–845) + (–499) + (–381)
= – 32 kJ mol
–1

Energy cycle to determine ∆H
soln
ө
(NaCl)
:

NaCl(s) Na
+
(aq) + Cl

(aq)


–∆H
latt
ө
(NaCl)

∆H
hyd
ө
(Na
+
) ∆H
hyd
ө
(Cl

)

Na
+
(g) + Cl

(g)

By Hess’ Law:
∆H
soln
ө
(NaCl) = –∆H
latt
ө
(NaCl)

+ ∆H
hyd
ө
(Na
+
) + ∆H
hyd
ө
(Cl

)
=

+ 5 kJ mol
–1



2008 Year 5 H2 CHEMISTRY
20

(b) Comment on the relative solubilities of sodium chloride and lithium
chloride.

The dissolution process for LiCl is exothermic compared to the
dissolution process for NaCl which is endothermic.
Hence, LiCl is more soluble in water than NaCl

(c) State the significance of the relative numerical magnitude of the lattice
energy of sodium chloride compared to lithium chloride

AH
latt
·
÷ +
÷ +
+ r r
q q

- Ionic radius, r
+
: Na
+
> Li
+

- Magnitude of ∆H
latt
ө
:

NaCl < LiCl
- LiCl is more stable than NaCl since ∆H
latt
ө
LiCl is more
exothermic.

(d) Explain how you would expect the numerical magnitude of standard
enthalpy change of hydration of bromide ion to compare with that of
chloride ion.

∆H
hyd
(anion) ·
÷
÷
r
q

- Ionic radius of Cl

< Br


- Charge density of Cl

> Br


- Strength of interaction with water molecules : Cl

> Br


- I AH
hyd
I : Cl

> Br








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