Chemical

Bonding V:

Ionic
Bonds
Li F  Li F
Not stable

Li F Li F
Not stable Not stable
•Not enough e- to share
•Electronegativity difference too high (>2.0)
•Can not form stable compound via covalent bonds
 The Ionic Bond
+ -
Li F
Electrostatic Attraction
holds ions together
LiF
next
Ionic compounds form
crystalline solids

Each ion has multiple ionic

bonds

Lattice
Arrangement of cations
and anions maximizes
electrostatic attractions
and minimizes repulsions
 Lattice Energy (LE)
• a measure of the strength of bonds in
an ionic compound
• Two definitions:
1) the enthalpy of formation of one mole
of solid ionic compound from gaseous
ions
(lattice energy is exothermic)
2) the energy required to completely
separate one mole of a solid ionic
compound into gaseous ions
(lattice energy is endothermic)
Lattice energy is the enthalpy of formation of one
mole of solid ionic compound from gaseous ions
Ionic bond strength is governed by Coulomb’s Law:
kQ1Q2 kQ1Q2
F= 2
and E = Fd =
d d
Q1= cation charge
Q2= anion charge
d = radial distance between ions
Charles-Augustin de
• Large Q → strong attraction → larger E Coulomb
• Large d → charge felt less → smaller E (1736 – 1806)

• As E (and F) increases, Lattice Energy increases

Electrostatic (Lattice) Energy due to Coulomb’s Law

kQ1Q2 kQ1Q2
F= 2
and E = Fd =
d d
Compound Lattice Energy Why?
(kJ/mol)
MgF2 2957 Q: +2,-1
MgO 3938 Q: +2,-2

LiF 1036
d F- < d Cl-
LiCl 853
Lattice energy dependence
on ionic sizes
LiCl 834
kJ/mol
NaCl 787
kJ/mol
KCl 701
kJ/mol
CsCl 657
kJ.mol
Lattice energy dependence
on ionic charges
NaF 910
kJ/mol
CaO 3414
kJ/mol

Larger charge (Q) is usually more

significant than smaller ionic size (d)
(radial distance)
 Larger charge (Q) is usually more
significant than smaller ionic size (d)
(radial distance)
 Ionic Solids Have High Melting Points
Compou Lattice Melting
nd Energy Point
(kJ/mol) (°C)
LiF 1017 845
LiCl 834 610 In an ionic lattice,
MgCl2 2527 714 many bonds must be
weakened in order to
MgO 3890 2800
melt the solid

As Fattraction between ions increases according to

Coulomb’s Law
• More energy is required to weaken bonds
• Melting Point temperature increases
 Formation of Ionic
•
Compounds
Get elements as
atoms (generally
requires energy)
• Form ions (anions
are energetically
favorable, cations
are unfavorable)
• Bring ions together
(favorable)
• Condense to solid
phase (favorable)
 Energetics of NaCl
Formation
Step ∆ H (kJ/mol) Comment
Na(s) →Na(g) +107.3 Sublimation
Na(g) → Na+ + 1e− +495.8 1st I.E. (I1)
½ Cl2(g) → Cl (g) +122 Bond Dissociation (B.E.)
1e− + Cl(g) → Cl−(g) −348.6 Electron Affinity (E.A.)
Na+(g) + Cl−(g) → NaCl(s) −787Lattice Energy
======================================
===========
Na(s) + ½ Cl2(g)  NaCl(s) −411 ∆ Hf° (formation)

All these steps are part of a Born-Haber Cycle

Born-Haber Cycle of NaCl
Mg + Cl2  MgCl2 ∆ H°f = -642
kJ/mol
Mg + Br2  MgBr2 ∆ H°f = -561
kJ/mol
Why are they different?
 Born-Haber Cycle
• Born-Haber cycles are used to calculate lattice
energy of ionic compounds
• Compares ∆ Hf° to the enthalpy required to make
gaseous ions from the elements
• An application of Hess's Law

Max Born (1882-1970) Fritz Haber(1868-1934)

Ex: Calculate the lattice energy of LiF(s).
 Write the lattice energy rxn for LiF(s)
Li+(g) + F−(g) → LiF(s) ∆ HLE = ?
 Write the standard formation equation for LiF(s)

Li(s) + ½ F2(g)  LiF(s) ∆ Hf°= - 594.1

 Write ∆ Hf° for LiF(s) from a givenkJ/mol
∆ Hf°
table
 Write rxn steps to produce gaseous ions from elements
Li(s) Li(g) 155.2 kJ/mol (Sublimation)
Li(g)  Li+(g) + 1e− 520 kJ/mol (I1)
½ F2(g)  F (g) 75.3 kJ/mol (½ Bond E.)
1e− + F(g)  F−(g) -328 kJ/mol (E.A.)
 Write ∆ H° for each step from appropriate (given) tables
Ex: Calculate the lattice energy of LiF(s).
 Use
 WriteHess’s
the lattice
Lawenergy rxnforfor∆ LiF(s)
to solve HLE
Li+(g) + F−(g) → LiF(s) ∆ HLE = ?
 Write the standard formation equation for LiF(s)

Li(s) + ½ F2(g)  LiF(s) ∆ Hf°= - 594.1 kJ/mol

 Write ∆ Hf° for LiF(s) from a given ∆ Hf°
table
 Write rxn steps to produce gaseous ions from elements
Li(s) Li(g) 155.2 kJ/mol (Sublimation)
Li(g)  Li+(g) + 1e− 520 kJ/mol (I1)
½ F2(g)  F (g) 75.3 kJ/mol (½ Bond E.)
1e− + F(g)  F−(g) -328 kJ/mol (E.A.)
 Write ∆ H° for each step from appropriate (given) tables
Ex: Calculate the lattice energy of LiF(s).

Li+(g) + F−(g) → LiF(s) ∆ HLE = ?

Li(s) + ½ F2(g)  LiF(s) - 594.1 kJ/mol

Li(s) Li(g) 155.2 kJ/mol
Li(g)  Li+(g) + 1e− 520 kJ/mol
½ F2(g)  F (g) 75.3 kJ/mol
1e− + F(g)  F−(g) - 328 kJ/mol

Li+(g) + F−(g) → LiF(s) -1017 kJ/mol =

∆ HLE
∆H o
overall = ∆H + ∆H + ∆H + ∆H + ∆H
o
1
o
2
o
3
o
4
o
5

∆H = ∆H
o
f
o
sub + ∆H o
BE + ∆H + ∆H
o
IE
o
EA + ∆H o
LE
Chemistry In Action:
Sodium Chloride: A
Common and Important
Compound

Mining Salt Solar Evaporation for Salt

Ionic Vs. Covalent Bonding

next
 BREAK
HW: p. 404 # 40 - 45

Important Equations:
kQ1Q2 kQ1Q2
F= 2
and E = Fd =
d d
 Q2 Mid-Term Exam
• (12/4/09)
24 Multiple Choice Q’s
- 28 min
- NO CALCULATOR
- -0.25 point penalty
for incorrect answer
• 5 FRQ’s
- 55 min
- Calculator OK Get Ready!
• Thermochem, Atomic Structure, Periodicity,
Molecular Structure & Polarity, VSEPR, History
of Atomic Theory