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Energetics 6Born-Haber Cycle

Chemistry, pp.472 - 476
Reference: Higher Level

Body Level One

Body Level Two
Body Level Three
Body Level Four
Body Level Five
Essential Idea: A Born–Haber cycle is an application of Hess’s law, used to
show energy changes in the formation of an ionic compound .
Title Text

Body Level One

Body Level Two
Body Level Three
Body Level Four
Body Level Five
 Lattice
First, Enthalpy
a word about- words
Review...

Definition (for IB
and AP)
Lattice enthalpy is the enthalpy
Body Level One change that occurs when one mole
of a solid ionic crystal breaks into its
Body Level Twoions in the gaseous state (at standard
temperature and pressure).
Body Level Three
Chemical
Body Level Four Equation and ∆H Notation
MX(s) → M+(g) + X– ∆H = ∆Holattice
Body Level Five
(g)reaction
endothermic positive
value
The lattice enthalpy in an ionic compound is
influenced by:
Product of the charges on the positive and negative ions (proportional)
Sum of the ionic radii of the positive and negative ions (inversely
proportional)
 Born-Haber Cycles
Lattice enthalpy cannot be determined directly by experiment.

Instead, it can be found indirectly from other known enthalpy changes

by applying Hess’s Law.

Body Level One + –

M+(g) + X–(g)
∆HA = ∆HB + ∆HC + – ions in the
Body Level Two
+
–
– gaseous state
+
Body Level Three
A several reactions and lattice enthalpy C
several ∆H values ∆Holattice
Body Level Four
standard
M(s) + 1/2X2(g) Body Level Five enthalpy of
formation MX(s)
elements
∆Hof solid
in their
ionic crystal
standard state
B
 Born-Haber Cycles - Individual Reactions
A

2
1 elements to gaseous ions: many reactions and many ∆H values

Body Level One

Body Level Two
1. solid metal to gaseous metal atoms
M(s) → M(g)Body
∆H = Level
enthalpy Three
of atomization (or enthalpy of vaporization)

Body Level
endothermic Four(+ ∆H)
reaction
+
gaseous metal atomsBody
to ions Level Five
+ +
2. + + +
+ +

M(g) → M+(g) + 1e– ∆H = first ionization energy (IE1) (Table 9)

endothermic reaction (+ ∆H)
 Born-Haber Cycles - Individual Reactions
A

4 elements to gaseous ions: many reactions and many ∆H values

3

Body Level One

Body Level Two
3. non-metal molecules to gaseous atoms
Body∆HLevel
1/2X2(g) → X(g) Three
= 1/2 bond enthalpy (Table 12)
endothermic
Body Levelreaction
Four (+ ∆H)

4. Body
gaseous non-metal atoms Level Five
to ions
–
–

X(g) + 1e– → X–(g) ∆H = first electron affinity (EA1) (Table 9)

exothermic reaction (– ∆H)
 Born Haber Cycles - Individual Reactions

4. ELECTRON AFFINITY DEFINITIONS and

NOTES
First electron affinity (EA1) is the energy released when one mole of gaseous
atoms accepts one mole of electrons to form ions with a 1- charge.
Body Level One
X(g) + 1e → X (g) ∆H = first electron affinity (EA ) (Table 9)
– –
1

Body Level Twois exothermic (negative ∆H).

This reaction

Body Level Three

Second electron affinity (EA2) is the energy absorbed when one mole of
gaseous ions with aBody Level
1- charge Four
accepts one mole of electrons to form ions
with a 2- charge.
Body Level Five
X–(g) + 1e– → X2–(g) ∆H = second electron affinity (EA2) (Table 9)
This reaction is endothermic (positive ∆H).
 Born-Haber Cycles - Individual Reactions

B elements in their standard state

form 1 mole of ionic compound

M(s) + 1/2 X2(g) → MX(s) ∆H = ∆Hoformation = standard enthalpy of formation

Body Level One
exothermic reaction (– ∆H)
Body Level Two
(true for ionic compounds, but not necessarily others)

Body Level Three

C solid ionic crystal dissociates into gaseous ions
Body Level Four
MX(s) → M+(g) + XBody
–
(g) ∆H = lattice
Level enthalpy
Five
endothermic reaction (+∆H)
 Constructing Born-Haber Cycles
Example 1:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle
to find the lattice enthalpy for sodium chloride.

Bodyof Level
enthalpy One
atomization of Na(s) = +107 kJ
mol–1
Body
enthalpy LevelofTwo
of formation NaCl(s) = -411 kJ
mol–1
Bodyenergy
first ionization Levelfor Three
sodium +496 kJ
= mol-1
Body Level Four
bond enthalpy for the Cl-Cl bond x 1/2 1/2 (242) = +121
= kJ
BodyforLevel
first electron affinity Five-349 kJ
chlorine
= mol-1
lattice enthalpy for sodium chloride =
?
 Constructing Born-Haber Cycles
Example 1 continued:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle
to find the lattice enthalpy for sodium chloride.

Body LevelEAOne
=- 1
349
Body Level
1/2BE = Two
+121 ∆Hlattice = x
Body Level Three
IE1 =
+496
∆Hat = +107
Body Level Four
Body Level
∆H = -Fivef
411
Calculate the lattice enthalpy for NaCl: (107 + 496 + 121 + (-349) ) = (-411) + x
x=
786
∴ ∆Hlattice = 786 kJ mol-1
 Constructing Born-Haber Cycles
Example 2:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle
to find the lattice enthalpy for magnesium chloride.

enthalpy
Body of atomization
Level One of Mg(s) = + 147 kJ
mol –1

enthalpy of formation
Body Level of MgCl2(s) = -641 kJ
Two
mol–1
first ionization
Bodyenergy
Level for Three +738 kJ
magnesium = mol-1
second ionization
Body energy
Level for Four
magnesium = +1451 kJ
mol-1
bond enthalpy Body Level
for the Cl-Cl Five+242-1 kJ
bond
= mol
first electron affinity for chlorine 2 x -349 kJ mol-1 = -698
= kJ
lattice enthalpy for magnesium chloride =
?
 Constructing Born-Haber Cycles
Example 2 continued:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle
to find the lattice enthalpy for magnesium chloride.

Mg2+(g) + 2Cl–
(g)
Body Level2 x One
EA = -698 1

Mg2+(g) +
2Cl(g)
Body Level
BE Two
=
+242
∆Hlattice = x
Body
IE =Level Three
+1451
2

Body Level Four

IE1 =
+738
∆Hat = +147
Body Level Five
∆Hf = -
641
Calculate the lattice enthalpy for MgCl2: (147 + 738 + 1451 + 242 + (-698) ) = (-641) + x
x= ∴ ∆Hlattice = +2521 kJ mol-1
2521
 Constructing Born Haber Cycles
Example 3:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle for
calcium oxide and find the second ionization energy for calcium.

enthalpy of atomization of Ca(s) = +178 kJ

molBody
–1 Level One
enthalpy of formation of CaO(s) = -635 kJ
mol–1 Body Level Two
first ionization energy for calcium +590 kJ
= Body Level Three mol-1

second ionization energy for calcium

=?
Body Level Four
bond enthalpy for the O=O bond x 1/2 1/2 (498) = +249 kJ
= mol-1
BodyforLevel
first electron affinity oxygenFive
-141 kJ
= mol-1
second electron affinity for oxygen +753 kJ
= mol-1
lattice enthalpy for calcium oxide = +3499 kJ
mol-1
 Constructing Born-Haber Cycles
Example 3 continued:
Use the following data, plus values from the data booklet, to construct a Born-Haber cycle for
calcium oxide and find the second ionization energy for calcium.

EA2 =
Body Level One +753
EA1 = -
Body Level Two 141
1/2 BE =
∆Hlattice = +3499
Body Level Three
+249
IE2 =
x
IE1 = Body Level Four
+590
∆Hat = +178 Body Level Five
∆Hf = -
635
Calculate IE2 for calcium: (178 + 590 + x + 249 + (-141) + 753) = (-635) + 3499

x= ∴ IE2 = +1235 kJ
-1
 Alternate Styles for Born-Haber Cycles
Many Born-Haber cycles use an “enthalpy diagram” style to show the enthalpy changes for
each step, and show endothermic and exothermic reactions more accurately:

Example: Born-Haber cycle for lithium fluoride

Body Level One

Body Level Two
Body Level Three
Body Level Four
Body Level Five

http://commons.wikimedia.org/wiki/File:Born-haber_cycle_LiF.svg
 Alternate Styles for Born-Haber Cycles
Convert the Born-Haber cycle for calcium oxide from Example 3 to the enthalpy diagram style.
Annotate each enthalpy change.

gaseous ions

Body Level One

Body Level Two
Body Level Three
en
th Body Level Four
START here
al
with the p
y
elements in their
Body Level Five
standard state

solid ionic
compound
 Alternate Styles for Born-Haber Cycles
Convert the Born-Haber cycle for calcium oxide from Example 3 to the enthalpy diagram style.
Annotate each enthalpy change.

Ca2+(g) + O2-
(g)
gaseous ions

Body Level One Ca2+(g) + O(g)

EA2 = +753
1/2 BE = +249
Body Level
Ca + Two
1/2 O
2+
(g) 2(g)
EA1 = -141

IE2 = Ca2+(g) + O-
Body Ca
Level
+1235 Three
+ 1/2 O
1+
(g) 2(g)
(g)

IE1 = +590
en
th Body Level
Ca + 1/2 O
(g)
Four2(g)

START here
al
∆Hat =
with the p
y
elements in their
Body
+171 Level
Ca + 1/2 O
(s)
Five
2(g)
∆Hlattice = +3499

standard state

∆Hf
=-
solid ionic 635
compound CaO(s