Lecture 20 (04.20.

2023)
General Concepts of Chemical Bonding
Reading for today: Chapter 13.1-13.6, 13. 8
Reading for Lecture #21: Chapter 13.9-13.13
Homework #8 Due 4/21 (Friday); Homework #9 Due 5/3

Today’s Topics:
Types of chemical bonds
Ionic bond
Lattice energies of ionic solids
Covalent bonds: bond energies and DH°
Polar bonds and electronegativity
Experimental Determination of
ionization energies and electron affinities

Photoelectron spectroscopy
(photoelectric effect)
hn
M M+ + e- (Ke)
Photoionization

hn = IE + Ke
IE = hn - Ke

hn
A− A + e− (Ke)
photodetachment

hn = |EA| + Ke
|EA| = hn - Ke
Bottom Line:

1. Elements tend to lose/gain electrons to attain a filled outer

level (a noble gas configuration). isoelectronic- same # of
electrons & same e- configuration. (F−, Ne, Na+)

2. Reactive metals (columns 1A and 2A) have low IE so they

typically become cations.

3. Reactive nonmetals (columns 6A and 7A) have high |EA| so

they typically become anions.

4. Noble gases (column 8A) high IE and low EA so they do not lose
or gain electrons.

Important information to understand bonding

 Chemical bonds
Chemical bonds form when the arrangement of nuclei
and electrons of the bonded atoms results in a lower
energy (more negative) than for the separate atoms

Types of chemical bonds:

• Ionic bonds
• Covalent bonds
• Polar Covalent bonds
General Concepts of Chemical Bonding
Three types of Chemical Bonding

Diamond
 Ionic bonds
Ionic bonds involve the complete transfer of one or
many electrons between two atoms.

Bonding results from electrostatic attraction

between the cation and anion.

For examples:
e
NaCl (Na+ ̶ Cl-)
MgCl2 (Mg2+ ̶ 2Cl-)
CdSe (Cd2+ ̶ Se2-) +
Electrical Conductance and Ion Mobility
 Electrostatic Forces and
the Brittleness of Ionic Compounds
Ionic Bonding: all ionic bonding compounds exist as solid

Lattice Energy for Ionic Compounds

The enthalpy change when separated gaseous ions are packed
together to form an ionic solid:
Na+(g) + Cl−(g) → NaCl(s) ΔH°rxn = Lattice Energy

Lattice energy is difficult to measure experimentally, but it can

be calculated by Born-Haber Cycle (application of Hess’s Law):

NaCl(s) → Na(s) + ½ Cl2(g) reverse of formation rxn: -ΔH°f = 411 kJ

Na(s) → Na(g) heat of sublimation: ΔH°sub = +108 kJ
Na(g) → Na+(g) + e− ionization energy: IE1 = +496 kJ
½ Cl2(g) → Cl(g) ½ (Bond Energy) = +½(243) kJ
Cl(g) + e− → Cl−(g) electron affinity: EA1 = −349 kJ
NaCl(s) → Na+(g) + Cl−(g) DH = +788 kJ (/mol)

Lattice energy = -788 kJ/mol, very large value

 Trends in Lattice Energy (kJ)

F− Cl− Br− O2−

Li+ -1036 -853 -807 -2925
Na+ -923 -788 -747 -2695
K+ -821 -715 -682 -2360

Lattice energy depends on two factors:

LEµ (q+q−)/d = (cation charge)x(anion charge)/(r++r−)

• Increase in ion size → Decrease in magnitude of lattice energy

• Increase in ion charge → Increase in magnitude of lattice energy

Greater Lattice energy → Greater m.p. and b.p.

Greater lattice energy → smaller solubility

 TopHat Question #1

Arrange these compounds in order of increasing

lattice energy: KCl, CaO, CaS.

A. CaO < CaS < KCl

B.
B. KCl <<CaS
KCl CaS< CaO
< CaO
C. CaO < KCl < CaS
D. CaS < CaO < KCl
E. KCl < CaO < CaS
charge ↓ → lattice energy ↓ → KCl the lowest (K+ & Cl-)
ionic size ↑ → lattice energy ↓ → CaS the next lowest (S2- > O2-)
 Covalent bonds
Covalent bond: a pair of electrons shared between two
atoms
For examples: e e
H2 , O2

Polar covalent bond:

e
An unequal sharing of electrons e
between two atoms with
different electronegativities (0.4
< Δχ < 1.7)
For examples:
CO, OH, NH
Covalent Bond Formation in H2 (H:H)
A B
Bond Energy

Bond Length

Covalent bonding is really quantum mechanical in nature. The simple electrostatic

argument does not produce a bound state.
 Com

Wh

____
A2
Wh

B2

Which bond is stronger? B2

Which
III. bond length isto)
(Introduction LEWISBSTRUCTURES
shorter? 2
Covalent bonds are strong
Bond Energy: Energy required to break a bond
Average bond energies:
the same bond in different molecules may have different bond strength

Process Energy required (kJ/mol)

CH4(g) à CH3(g) + H(g) 435
CH3(g) à CH2(g) + H(g) 453
CH2(g) à CH(g) + H(g) 425
CH(g) à C(g) + H(g) 339
CH4(g) à C(g) + 4H(g) Total = 1652
Average C-H bond energy = 1652/4 = 413 kJ/mol in CH4
Average C-H bond energy in C2H6 is 410 kJ/mol

HCF3(g) à CF3(g) + H(g) 430 kJ/mol

HCCl3(g) à CCl3(g) + H(g) 380 kJ/mol
HCBr3(g) à CBr3(g) + H(g) 380 kJ/mol
Bond Order:
(pairs of e- shared) As bond order increases,
Single bond = 1 bond length decreases and
Double bond = 2 bond strength increases
Triple bond = 3
 What is the origin of ΔH°rxn?
The heat released or absorbed during a chemical change is due
to differences between reactant bond energies and product bond
energies
Using bond energies to calculate ΔH°rxn
for reactions in the gas phase.

H2(g) + F2(g) → 2 HF(g) ΔH°rxn= ?

H2(g) → 2H(g) D(H2)
F2(g) → 2F(g) D(F2)
2H(g) + 2F(g) → 2HF(g) −2D(HF)
H2(g) + F2(g) → 2 HF(g) ΔH°rxn= D(H2)+D(F2) −
2D(HF)
ΔH°rxn = S D(bonds broken) - S D(bonds formed)
reactants products
The weaker the reactant bonds, the more heat released. The stronger the product bonds, the more heat released.
Example,
2 H2(g) + O2(g) → 2 H2O(g)
2(H-H) + O=O → 2(H-O-H)
ΔH°rxn = 2(DH-H) + (DO=O) – 4(DO-H)

ΔH°rxn = 2(432) + (495) – 4(467) = –509 kJ

Appendix 4: ΔH°f [H2O(g)] = -242 kJ/mol

2 mole of H2O = -482 kJ

5% error, not bad for an estimate

Sources of error: DH = DE + PDV

Temp and pressure dependence of DH
 Three Methods for Determining DH°rxn
• Hess’s Law
The enthalpy change of an overall process is the sum
of the enthalpy changes of the individual steps

• Standard Heats of Formation

DH°rxn = SDH°f(products) – SDH°f(reactants)

• Bond Energies (for gas reactions) (estimate)

DH°rxn = SD(bonds broken) – SD(bonds formed)
Covalent solids form the
hardest materials, e.g,
quartz and diamond
 Polar bonds:
between two different atoms
Most bonds are not 100% ionic (e− completely transferred)
or covalent (e− shared equally). They are somewhere in
between. How ionic/how covalent depends on how well
each bonded atom attracts the shared electrons. The
measure of this attraction is known as electronegativity
(EN).

Linus Pauling developed a scale of relative electronegativities:

• F has the highest EN (4.0). It attracts the electrons in

a shared bond more tightly than any other element.
• Decreasing atomic size → increasing EN:
smaller atoms attract the electrons more strongly.
The Pauling Electronegativity Scale
When atoms form a bond, consider the ΔEN for the two atoms.
• ΔEN = 0 for bonding between two atoms of the same
element. Electrons are shared equally and the bond is
considered “nonpolar covalent”.
• ΔEN ≠ 0 when two different elements bond. Electrons
are not shared equally and the bond is considered
“polar covalent,” or “ionic” when ΔEN is large (>1.7).
• Increasing ΔEN → Increasing polarity of the bond

Ranges of ΔEN are arbitrary!

Important: EN is a relative quantity. There are other EN scales.

Classifying Ionic Character of Chemical Bonds

Polar molecules have dipole moments and

they can be oriented in electrical field.

µ = q.r (unit: C.m or Debye)

DEN
1.0
1.9
0.9
0.7
0.4
2.1
3.0
3.2
2.0
The polarity of H2O is important for many of its properties and
explains why it is the best solvent on earth.

ice

µ= 1.85 D

|DEN| = |3.5 – 2.1| = 1.4

Autoionization

H2O(l) H+(aq) + OH-(aq)

L. S. Wang, et al.
Journal of Chemical Physics
Vol. 113, p. 10837 (2000) SO42-(H2O)6
 TopHat Question #2
Arrange these atoms in order of increasing
electronegativity: Mg, K, S, F.

A. Mg < K < S < F

B. K < Mg < S < F
C. K < S < Mg < F
D. F < S < Mg < K
E. F < S < K < Mg

Decreasing size → Increasing electronegativity

Size: K > Mg > S > F
EN : K < Mg < S < F
 TopHat-Question #3

Choose the bond with the greatest polarity.

Electro- |DEN|
negativities A. N−H |3.0 – 2.1| = 0.9
H = 2.1 B. F−O |4.0 – 3.5| = 0.5
N = 3.0 C. O−C |3.5 – 2.5| = 1.0
O = 3.5 D. F − Br |4.0 – 2.8| = 1.2
F = 4.0
E. F−F |4.0 – 4.0| = 0, nonpolar
C = 2.5
Br = 2.8 To denote the negative end (high EN)
d- F – Br d+ and the positive end (low EN) of a polar
bond, either use an arrow with a plus on
one end or the symbols d- and d+.
 TopHat-Question#4
Which of the following molecules does not have a
dipole moment?

A. CO
B. CO2
C. H2O
D. NH3
E. SO2

The C=O bond is polar, but CO2 is linear, O=C=O, and the two
dipoles of the C=O bonds cancel each other