Chemistry: for

Engineering Students

Chapter 7: Chemical Bonding and Molecular Structure

7.1 INSIGHT INTO Materials for Biomedical Engineering
7.2 The Ionic Bond
7.3 The Covalent Bond
7.4 Electronegativity and Bond Polarity
7.5 Keeping Track of Bonding: Lewis Structures
7.6 Orbital Overlap and Chemical Bonding
7.7 Hybrid Orbitals
7.8 Shapes of Molecules

Mar-16 Chapter-7 1
 Chemistry: for
Engineering Students
INSIGHT INTO Materials for Biomedical Engineering

3D design

Engineering biomaterials Strength

for medical applications
Durability Chemical bonding
and polarity are
Biocompatibility major factors
bone replacements, determining
optical lenses biocompatibility
heart valves and arteries
…

Mar-16 Chapter-1 2
 Chemistry: for
Engineering Students The Ionic Bond

The simplest example of chemical bonding is found in an ionic bond, formed

through the electrostatic attraction of two oppositely charged ions.
Ex.: Ca3(PO4)2

Why do metals form cations and non-

metals form anions?

To gain a better understanding How does the energy of attraction

of ionic compounds, we must between ions compensate for the energy
answer a few questions costs of ion formation?

How does the ionic radius affect the strength

of the bond between an anion and a cation?

Mar-16 Chapter-7 3
 Chemistry: for
Engineering Students The Ionic Bond
Metals Formation of Ions Non-metals

1s2 2s2 2p6 3s1 IE1= 495 kJ/mol 1s2 2s2 2p63s2 3p5 EA= −349 kJ/mol

Na( g ) → Na(+g ) + e − NaCl Cl( g ) + e − → Cl(−g )

1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6

The ionization energy of metals is Gaining extra-electrons is energetically

relatively low. The valence shell of the favored for non-metals. The valence
most stable cations is filled or half-filled. shell of the most stable anions is filled.

Na+ ·····Cl−
The balance between electrostatic attractions and repulsions among
ions determines the stability of extended ionic structures,

Mar-16 Chapter-7 4
 Chemistry: for
Engineering Students The Ionic Bond

The lattice energy of an ionic compound

collects the Coulombic energy of all
pairwise interactions. For the sake of
stability, first-neighbors of cation in the lattice
structure must be anions and viceversa.

Ion-ion interactions are rather

strong. Hence, the ionic bonding
energy amounts to hundreds of
kcal/mol and ionic solids melt at
high temperatures. (700-2000 oC).

Crystalline
solid
NaCl Compact
Tm=801 oC packaging

Mar-16 Chapter-7 5
 Chemistry: for
Engineering Students The Ionic Bond
Lattice Energies (in kJ/mol) for Some Ionic Compounds

Compound Lattice Energy Compound Lattice Energy

LiF -1030 MgCl2 -2326
LiCl -834 SrCl2 -2127
LiI -730
NaF -910 MgO -3795
NaCl -788 CaO -3414
NaBr -732 SrO -3217
NaI -682
KF -808 ScN -7547
KCl -701
KBr -671 ZnS -3620
CsCl -657
CsI -600

Mar-16 Chapter-1 6
 Chemistry: for
Engineering Students The Ionic Bond
Properties of Ionic Compounds
NaCl (table salt)

Cl−
r=1.81 Å
Two lattices of Na+
and Cl- ions
intercalated
Na+
r=0.95 Å

Each unit cell type

ensures maximum
space filling for the Melting point: 801 oC
•Can ionic compounds
corresponding coord. index (Cl−)=6
ratio of charges coord. index (Na+)=6
conduct electricity when
and ionic radii they are in their solid
phase or when they are
molten?

Mar-16 Chapter-7 7
 Chemistry: for
Engineering Students The Ionic Bond
Ionic radii

(data in pm)
From the knowledge of
crystal structures of ionic
materials, it is possible to
derive the ionic radii of
the elements, which
clearly show that atoms
shrink or expand
significantly upon
losing or gaining
valence electrons.

Cationic radii are about half the Anions expand almost twofold
atomic radii of the neutral atoms. with respect to the neutral atoms.

Both cationic and anionic radii increase downwards a group

Mar-16 Chapter-7 8
 Chemistry: for
Engineering Students The Ionic Bond
Properties of Ionic Compounds
• Why the melting point of the blende phase of zinc sulfide (1700 oC) is
much higher than that of sodium chloride (801 oC) ?
ZnS (zinc sulfide, blende phase)

S2− FCC lattice of S2-

Highly anions with Zn2+
r=1.84 Å
dissimilar cations occupying
ions Zn2+ half the tetrahedral
r=0.76 Å holes.

• Although ionic materials are hard, they’re brittle! Explain this.

Mar-16 Chapter-7 9
 Chemistry: for
Engineering Students The Covalent Bond

In a covalent bond
valence electrons
are shared rather
than transferred. Bond energy and
bond distance are
the fundamental
properties of a
A single covalent covalent bond.
bond is formed by the
sharing of 2 valence
e- between 2 atoms.

A covalent bond is
represented by a line
Lewis
Structure
Mar-16 Chapter-7 10
 Chemistry: for
Engineering Students The Covalent Bond
Bond energies and bond distances
BE are chemical properties. For example: a reaction will be energetically favored if
the energy required to break bonds is less than that released in making new bonds

A-B D0 dA-B A-B D0 dA-B A-B D0 dA-B A-B D0 dA-B

C-H 413 1.10 N-H 391 1.01 O-H 463 0.96 F-F 155 1.26
C-C 348 1.50 N-N 163 1.47 O-O 146 1.48
C-N 293 1.44 N-O 201 1.36 O-F 190 1.27 Cl-F 253 1.66
C-O 358 1.40 N-F 272 1.31 O-Cl 203 1.67 Cl-Cl 242 2.07
D0 in kJ/mol C-F 485 1.39 N-Cl 200 1.71 O-I 234 2.03
dA-B in Å C-Cl 328 1.79 N-Br 243 1.86 Br-F 237 1.82
C-Br 276 1.95 S-H 339 1.34 Br-Cl 218 2.22
C-I 240 2.15 H-H 436 0.74 S-F 327 1.68 Br-Br 193 2.37
C-S 259 1.81 H-F 567 0.98 S-Cl 253 2.09
H-Cl 431 1.38 S-Br 218 2.24 I-Cl 208 2.42
Si-H 323 1.49 H-Br 366 1.54 S-S 266 2.02 I-Br 175 2.57
Si-Si 226 2.33 H-I 299 1.74 I-I 151 2.77
Si-C 301 1.88
Si-O 368 1.63

Mar-16 Chapter-7 11
 Chemistry: for
Engineering Students The Covalent Bond

• Some biomaterials such as a Teflon (polytetrafluoroethylene, PTFE) are

intended to replace or strengthen tissues. Clearly it is important that these
materials not be consumed by metabolic reactions in the body. Explain the
resistance to chemical reactivity of PTFE by comparing the combustion of CH4
and CF4.

Mar-16 Chapter-7 12
 Chemistry: for
Engineering Students The Covalent Bond

The Lewis model predicts the electronic structure of covalent molecules. Its
fundamental
1
principle is the Octet rule: Atoms share electron pairs until they fill18
their valence
1
shell (8 e− for second and third-row elements, 2 e− for H). 2
1
Hidróg Helio
eno
He
H 4.0026
1.0079

2 If a neutral atom has a filled 13 14 15 16 17

2 3
Litio
4
Berilio
valence shell then it is a noble 5
Boro
6
Carbono
7
Nitróg
8
Oxígen
9
Flúor
10
Neón

gas and its electron configuration

eno o
Li Be B C F Ne
6.941 9.012 10.811 12.0112 N O 18.998 20.179
2 14.006 15.999 4
is highly stable 7 4

3 11 12 13 14 15 16 17 18
Sodio Magn Alumin Silicio Fósfor Azufre chloro Argón
esio io o
Na Si S Cl Ar
22.989 Mg Al 28.086 P 32.064 35.453 39.948

Tend to5 lose Tend to gain

24.30 26.981 30.973
5
3 4 6 7 8 9 10 11 12 5 8

4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Scelectrons Ga electrons
Potasi Calcio Escandio Titanio Vanadio Cromo Mangan Hierro Cobalt Níquel Cobre Cinc Galio Germanio Arséni Seleni Bromo Kriptón
o eso o co o
Ca Ti V Cr Mn Fe Ni Cu Zn Ge Br Kr
K Co As Se
Transition
40.08 44.956 47.90 50.942 51.996 55.84 58.71 63.546 65.38 69.723 72.59 79.904 83.80
39.098 54.938 7 58.953 74.922 78.96

5 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

metals
Rubidi Estron Ytrio Circonio Niobio Molibd Tecne Ruteni Rodio Paladio Plata Cadmi Indio Estaño Antimo Telurio Iodo Xenón
o cio eno cio o o nio
Y Zr Nb Rh Pd Ag In Sn Te I Xe
Rb Sr 88.905 91.22 92.906 Mo Tc Ru 102.90 106.4 107.86 Cd 114.82 118.69 Sb 127.60 126.90 131.30
85.468 87.62 95.94 (99) 101.0 5 8 112.40 121.75 4
7

6 55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cesio Bario Lantan Haf Tantalio Wolfra Renio Osmio Iridio Platino Oro Mercur Talio Plomo Bismut Poloni Astato Radón
o nio mio io o o
Cs Ba Ta Re Os Ir Pt Au Tl Pb At Rn
132.90 137.3 La Hf 180.948 W 186.2 190.2 192.2 195.09 196.96 Hg 204.37 207.19 Bi Po (210) (222)
5 4 138.91 178. 183.85 7 200.59 208.98 (209)
49 0

7 87 88 89 ** 10 105 105 107 108 109 110 111 112

Franci Radio Actinio 4 Hahnio Seabo Nielsb Hassi Meitne
o rgio orio o rio
Ra Ac Ruthe
rfodio Ha
Fr (226) (227)
Rf (262) Sg Ns Hs Mt
(223) (263) (261) (265) (266)
Mar-16 (26
1)
Chapter-7 13
 Chemistry: for
Engineering Students The Covalent Bond

Element # valence
Lewis Lewis dot symbols keep track of
e-
Symbol valence electrons, making it easier
to predict bonding in molecules
H 1
H with the help of Lewis structures
He 2 He
Single
Li 1 Li bond
Be 2 +
Be

B 3 B Lone Bonding
C 4 C pairs pair
N 5 N Double
O 6 bond
O

F 7 +
F

Mar-16 Chapter-7 14
 Chemistry: for
Engineering Students The Covalent Bond
• Both distance and binding energy are fundamental properties of a covalent bond. For
example, it is known that the C-C distances are 1.54, 1.33 and 1.19 Å, for ethane,
ethylene and acetylene, respectively. Explain the relationship between the Lewis
structures of these molecules and their C-C bond distances and energies.

H H
H C C H
1.54Å
H H
1.33Å

1.19Å
H C C H
 Chemistry: for
Engineering Students Electronegativity and Bond Polarity

Covalent bonds A−B between two different atoms are polar bonds

HF dipole moment
r
0.92 Å
F H

q(H)= +0.50 e
q(F)= −0.50 e

μ = q r = 1.94 D

Dipole moment Electrostatic potential

(vector quantity) represented over
1 Debye = 3.34·10-30 C m the molecular surface
Mar-16 Chapter-7 16
 Chemistry: for
Engineering Students Electronegativity and Bond Polarity

The polarity of the A-B covalent bond can be interpreted

in terms of the electronegativities (χ’s) of A and B

χ of an element A is a numerical index that

expresses the ability of A to attract
bonding electrons to itself.
The electronegativity of an atom in a molecule is related
to the atom’s ionization energy and electron affinity.

Mar-16 Chapter-7 17
 Chemistry: for
Engineering Students Electronegativity and Bond Polarity
1 1 2 13 14 15 16 17
Hydrogen
H Pauling χ
2.1

2 3 4 5 6 7 8 9
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0

3 11 12 13 14 15 16 17
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0

4 19 20 31 32 33 34 35
Potassium Calcium Gallium Germanium Arsenic Selenium Bromine
K Ca Ga Ge As Se Br
0.8 1.0 1.6 1.8 2.0 2.4 2.8

5 37 38 49 50 51 52 53
Rubidium Strontium Indium Tin Antimony Tellurium Iodine
Rb Sr In Sn Sb Te I
0.8 1.0 1.7 1.8 1.9 2.1 2.5

6 55 56 81 82 83 84 85
Cesium Barium Thallium Lead Bismuth Polonium Astatine
Cs Ba Tl Pb Bi Po At
0.7 0.9 1.8 1.9 1.9 2.0 2.2
Mar-16 Chapter-7 18
 Chemistry: for
Engineering Students Nº Rule Example
0 Pick up the central atom (the least
electronegative) and place around the rest
of the atoms
1a Draw the bond skeleton characteristic
Keeping of the molecule. O C O
track of 2ª Obtain the total number of valence
electrons (For ionic species consider
bonding: also the total charge q)
Lewis
Structures 3ª Assign 2 e to each covalent bond

4ª Distribute the rest of e− in such a way

that the octet rule is satisfied (the last
e are assigned to the central atom)
H accommodates only 2 e−.

5ª If there are not enough valence

electrons, convert some single bonds
into multiple bonds.

Mar-16 Chapter-7 19
 Chemistry: for
Engineering Students Keeping track of bonding: Lewis Structures

• Draw the Lewis structures for the following compounds:

F2 O2 N2 OH−

fluorine oxygen nitrogen hydroxide anion

CO NO HCCH S8

carbon nitrogen acetylene sulfur

monoxide monoxide

Mar-16 Chapter-7 20
 Chemistry: for
Engineering Students Keeping track of bonding: Lewis Structures
•Draw the Lewis structures for the following compounds:
N 2O BF3 SF6 H 2 O2

dinitrogen oxide boron Sulfur Water peroxide

trifluoride hexafluoride

PO43− CH3CH2OH H2Se [Al(H2O)6]3+

Phosphate ethanol Hydrogen hexaaquoaluminium

selenide cation
anion
Mar-16 Chapter-7 21
 Chemistry: for
Engineering Students Keeping track of bonding: Lewis Structures

Resonance structures:
Sometimes a single Lewis structure cannot describe the arrangement of
the valence electrons. In this case, several Lewis structures (called
resonance structures) must be used to describe the intermediate
character of the chemical bonds.

Oxygen O3 ozone Water peroxide

O O
O O O O H
O O O O
H
r=1.21 Å r=1.28 Å r=1.49 Å
C6H6 benzene
cyclohexene cyclohexane

r=1.34Å r=1.53 Å
r=1.39 Å
Mar-16 Chapter-7 22
 Chemistry: for
Engineering Students Shapes of Molecules
ABn Molecular Shapes
Linear Angular or bent Trigonal planar Trigonal
pyramidal
F 120o
180o
100o N

O C O
O O B F H
H
H

107o
S

Ej.: CO2, N2, C2H2 Ej.: SO2, H2O, O3 Ej; BF3, SO3 NH3
Tetrahedral Squared planar Trigonal Octahedral
bipyramidal
H
F
Cl F
o 90o
109.5o 90 90o
F F
F
P F S
C
Cl Pt Cl F F
H
o F
120 o
H
H
90

Cl F
F

Ej.: CH4, CF2Cl2 PtCl42− PF5 SF6

Mar-16 Chapter-7 23
 Chemistry: for
Engineering Students Shapes of Molecules

How to predict the shape of ABn molecules ?

1. Lewis Structure Count the

number of electron groups
around the central atom A.

Valence shell electron 2. ABn adopts the shape that

pair repulsion (VSEPR) minimizes the repulsion among
the electron groups around A.

3. Label the resulting geometry

ignoring the non-bonding electron
pairs.

Key element of the VSEPR model

Mar-16 Chapter-7 24
 Chemistry: for
Engineering Students Shapes of Molecules

Lewis # of e- Arrangement of Bond Geometry

Structure groups minimum repulsion Angle

2 180o Linear 180o linear

O C O

F 3 120o Trigonal 120o Trigonal

B planar
F F

H 4 Tetrahedral 109.5o Tetrahedral

H C H
H
4 109.5o Tetrahedral < 109.5o Trigonal
H N H pyramid
H
4 Tetrahedral < 109.5o Angular
O
H H
Mar-16 Chapter-7 25
 Chemistry: for
Engineering Students Shapes of Molecules

Lewis # of e- Arrangement of Bond Geometry

Structure groups minimum repulsion Angle

90o
5 Trigonal 120o Trigonal
Cl
Cl bipyramidal 90o bipyramidal
Cl P
Cl
Cl 120o

F 6 90o Octahedral 90o octahedral

F
F S F 1800
F 90o
F
 Chemistry: for
Engineering Students Shapes of Molecules
Practice VSEPR….
Lewis # of e- Arrangement of Bond Geometry
Structure groups minimum repulsion Angle

Mar-16 Chapter-7 27
 Chemistry: for
Engineering Students Shapes of Molecules

Dipole moment is a vector quantity

μ bond = qrbond

μ total = ∑μ
bond
bond

A molecule with µtotal≠0 is a polar molecule

A molecule with µtotal=0 is a non polar molecule

Mar-16 Chapter-7 28
 Chemistry: for
Engineering Students Shapes of Molecules
q(O)= -0.82 μ2
μ1
μ1 μ2
1.17Å

0.96Å

q(O)= -0.33 q(C)= 0.66 q(O)= -0.33

q(H)= 0.41
μ = μ1 + μ 2 = 0 μ = 2.2D

q(Cl)= -0.16
q(Cl)= -0.09

1.79Å 1.81Å
q(C)= 0.36

q(CH3)= 0.16
1.09Å

μ = 2.04D
Mar-16 μ=0 Chapter-1 29
 Chemistry: for
Engineering Students Shapes of Molecules

General Situation: Polyhedra with shared vertices

H H
H C C O
H H H
Tetrahedral C Tetrahedral C
Lewis structure for ethanol 3D model for ethanol

Mar-16 Chapter-7 30
 Chemistry: for
Engineering Students Shapes of Molecules

General Situation: Polyhedra with shared vertices

CH3(CH2)16COOH

OH

Stearic acid

Molecules with
linear or
branched
chains are
usually quite
flexible at room
temperature
Mar-16 Chapter-7 31
 Chemistry: for
Engineering Students Shapes of Molecules
SO2, sulfur dioxide: Bonding, Geometry and Polarity
# valence e- Lewis structure # e- groups Least repulsion
around arrangement
central atom

Central Two resonant structures

atomS: 1x6e− are needed. The Lewis Trigonal
formula of SO2 is 3
O: 2 x 6 e − isoelectronic with that of O3 (two S-O Planar
bonds and 120o
18 e − one LP)

Geometry Polarity
The S-O bonds are polar
ANGULAR bonds. The angular geometry of
the molecule results in a net
δ+ dipole moment.
δ- 1.43Å
S δ- μ = 1.62 D ≠ 0
O O
119o

Mar-16 Chapter-1 32
 Chemistry: for
Engineering Students Problems and Exercises
7.7 Why is the Na2+ ion not found in nature?
7.8 Why do nonmetals tend to form anions rather than cations
7.10 Arrange the members of each of the following sets of cations in order of increasing
ionic radii: (a) K+, Ca2+, Ga3+, (b) Ca2+, Be2+, Ba2+, Mg2+, (c) Al3+, Sr2+, Rb+, K+
7.11 Arrange the following sets of anions in order of increasing ionic radii: (a) Cl–, P3–,
S2, (b) S2–, O2–, Se2–, (c) Br–, N3–, S2–, (d) Br–, Cl–, I–.
7.12 Which pair will form a compound with the larger lattice energy: Na and F or Mg
and F? Why?
7.14 Use the concept of lattice energy to rationalize why sodium fluoride dissolves in
water, whereas calcium fluoride does not. Extending this reasoning, would you expect
magnesium fluoride to be soluble?
8.25 (TCS) The lattice energies of KBr and CsCl are nearly equal. What can you
conclude from this observation?

7.17 Sketch a graph of the potential energy of two atoms as a function of the distance
between them. On your graph, indicate how bond energy and bond distance are
defined.
7.18 When a covalent bond forms, is energy absorbed or released? Explain how your
answer is related
Mar-16
to the graph you sketched in the previous problem.
Chapter-7 33
 Chemistry: for
Engineering Students Problems and Exercises
7.21 If the formation of chemical bonds always releases energy, why don’t all
elements form dozens of bonds to each atom?

7.29 Distinguish between electron affinity and electronegativity.

7.34 Based on the positions in the periodic table of the following pairs of elements,
predict whether bonding between the two would be primarily ionic or covalent. Justify
your answers. (a) Ca and Cl, (b) P and O, (c) Br and I, (d) Na and I, (e) Si and Br.
7.36 Considering the trends in electronegativity shown in Figure 7.8, explain why
alloys that form between two or more transition metals are not ionic substances.
7.42 Draw a Lewis structure for each of the following molecules or ions: (a) CS2, (b)
BF4–, (c) HNO2 (where the bonding is in the order HONO), (d) OSCl2 (where S is the
central atom).
7.52 Identify what is incorrect in the Lewis
structures shown for BBr3 and SO2.
7.92 Both ozone and oxygen absorb UV light in the upper atmosphere. The ozone,
however, absorbs slightly longer wavelengths of UV light -wavelengths that would
otherwise reach the surface of the planet. How can Lewis structures help explain the
bonding difference between ozone and oxygen that gives rise to the difference in
the absorption wavelength?
Mar-16 Chapter-7 34
 Chemistry: for
Engineering Students Problems and Exercises
7.54 Chemical species are said to be isoelectronic if they have the same Lewis
structure (regardless of charge). Consider these ions and write a Lewis structure for a
neutral molecule that is isoelectronic with them. (a) CN–, (b) NH4+, (c) CO32–.

7.72 Predict the shape of each of the following molecules or ions: (a) PH4+, (b) OSF4,
(c) ClO2–, (d) I3–.

7.74 Give approximate values for the indicated bond angles:

(a) Cl-S-Cl in SCl2 , (b) N-N-O in N2O, (c) bond angles
1, 2, and 3 in vinyl alcohol.

7.84 Consider the Lewis structure below. Is this an ion? If so,

what is its charge?

8.51 (TCS) Write Lewis structures that obey the octet rule for each of the following, (a)
OCS, (b) SOCl2 (S is bonded to the two Cl atoms and to the O),(c) BrO3-, (d)HClO2 (H
is bonded to O).

8.55 (TCS) Predict the ordering of the bond lengths in CO, CO2, and CO32−.

8.59 (TCS) Does the octet rule apply to ionic as well as to covalent compounds?
Explain using examples as appropriate.
Mar-16 Chapter-7 35