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Born-Haber cycles

Posted on 10/08/2014 by secondaryscience4all

Examples of Born-Haber energy cycles

1.Calculating the la ice dissociation enthalpy of sodium chloride.

ΔH⦵L.E (NaCl) = –ΔH⦵f (NaCl) + ΔH⦵at (Na) + ΔH⦵1st I.E. (Na) +ΔH⦵at (Cl) +ΔH⦵1st E.A.(Cl)
ΔH⦵L.E (NaCl) = –(−411) + 108 + 498 + 121 + (−351)
ΔH⦵L.E (NaCl) = +787 kJ mol−1

NB. ΔH⦵at Atomisation ½Cl2 to form one mole Cl atoms = ½ × ΔH⦵B.E. Bond Enthalpy (Cl−Cl)

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2.Calculating the la ice dissociation enthalpy of silver chloride

⦵
ΔH L.E (AgCl) = –ΔH f (AgCl) + ΔH
⦵ ⦵ ⦵ ⦵ ⦵
⦵ at (Ag) + ΔH 1st I.E. (Ag) +ΔH at (Cl) +ΔH 1st E.A.(Cl)
ΔH L.E (AgCl) = –(−127) + 289 + 732 + 121 + (−364)
⦵
ΔH L.E (AgCl) = +905 kJ mol
−1

⦵ ⦵
NB. ΔH at Atomisation ½Cl2 to form one mole Cl atoms = ½ × ΔH B.E. Bond Enthalpy (Cl−Cl)

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3.Calculating the la ice dissociation enthalpy of magnesium oxide.

ΔH
⦵ ⦵ ⦵ ⦵ ⦵ ⦵ ⦵
L.E= –ΔH (MgO) +ΔH at (Mg)+ΔH
⦵ f (O) 1st I.E. (Mg)+ΔH 2nd I.E.(Mg)+ΔH at (O)+ΔH 1st
(O)+ΔH
E.A.⦵ 2nd E.A.
ΔH L.E= –(−602) + 150 + 736 + 1450 + 248 +(−142) + 844
⦵
ΔH L.E (MgO) = +3888 kJ mol
−1

⦵ ⦵
NB. ΔH at Atomisation ½O2 to form one mole O atoms = ½ × ΔH B.E. Bond Enthalpy (O=O)

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4.Calculating the la ice dissociation enthalpy of calcium sulfide.

⦵ ⦵
ΔH L.E= –ΔH f (CaS) +ΔH at (Ca)+ΔH
⦵ ⦵ ⦵ ⦵ ⦵
⦵ 1st I.E. (Ca)+ΔH 2nd I.E.(Ca)+ΔH at (S)+ΔH 1st E.A.
(S)+ΔH 2nd E.A.(S)
⦵
ΔH L.E= –(−482) + 178 + 590 + 1145 + 279 +(−200) + 539
⦵
ΔH L.E (CaS) = +3013 kJ mol
−1

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Examples of calculations using Hess’ Law and Born-Haber cycles.

Q1. Methanol can be regarded as a carbon-neutral fuel because it can be synthesised from carbon
dioxide and hydrogen. Calculate the standard enthalpy change for this reaction using the data given
below.

CO2(g)+ 3H2(g) ⇌ CH3OH(g) + H2O(g)

⦵ –1
ΔH f /kJ mol : H2O(g) −242 CH3OH(g) −201 H2(g) 0 CO2(g) −394
⦵ ⦵ ⦵ –1
ΔH for reaction: = Σ ΔH f (products) −ΣΔH f (reactants)=(−242+(−201))−(−394+0)= −49 kJ mol

Q2. Use the data below to determine the standard enthalpy change for the formation of one mole of
calcium fluoride in its standard state, from its constituent elements in their standard states, under
standard conditions.
ο –1
ΔH / kJ mol

Ca(s) → Ca(g) +193

+ –
Ca(g) → Ca (g) + e +590
+ 2+ –
Ca (g) → Ca (g) + e +1150
F2(g) → 2F(g)
⦵ ⦵
+158 (ΔH B.E. (F−F) = 2 × ΔH at of fluorine)
– –
F(g) + e → F (g) –348
2+ –
CaF2(s) → Ca (g) + 2F (g) +2602
Ca(s) + F2(g) → CaF2(s) ?
⦵ ⦵ ⦵ ⦵ ⦵
ΔH dissociation L.E= –ΔH f (CaF2) +ΔH at (Ca)+ΔH 1st I.E. (Ca)+ΔH 2nd I.E.
⦵ ⦵
(Ca)+2×ΔH at (F)+2×ΔH 1st E.A.(F)
⦵
2602 = –ΔH f (CaF2) + 193 + 590 + 1150 + 158 + 2(−348)
⦵ 1
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Thus, ΔH
⦵ −1
f (CaF2) = −1207 kJ mol
Q3. Use the data below to calculate a value for the electron affinity of chlorine.

ΔHο / kJ mol–1

Ba(s) → Ba(g) +180

+
Ba(g) → Ba (g) + e – +503
+ 2+ –
Ba (g) → Ba (g) + e +965
Cl2(g) → 2Cl(g)
⦵ ⦵
+244 (ΔH B.E. (Cl−Cl) = 2 × ΔH at of chlorine)
– –
Cl(g) + e → Cl (g) ?
2+ –
BaCl2(s) → Ba (g) + 2Cl (g) +2056
Ba(s) + Cl2(g) → BaCl2(s) −859

ΔH⦵dissociation L.E= –ΔH⦵f (BaCl2) +ΔH⦵at (Ba)+ΔH⦵1st I.E. (Ba)+ΔH⦵2nd I.E.(Ba)+

⦵ ⦵
ΔH B.E. (Cl2)+2×ΔH 1st E.A.(Cl)
2056 = –(−859) + 180 + 503 + 965 + 244 + 2(ΔH⦵1st E.A. for Cl2)

Thus, ΔH⦵1st E.A. (Cl2) = −347.5 kJ mol−1

1.8 Thermodynamics
Born-Haber cycles

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