Chapter 2: Atomic Structure &

Interatomic Bonding

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

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Chapter 1-
Atomic Structure (Freshman Chem.)
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons }
1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.
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Chapter 1-
AVAGADRO’S NUMBER = 6.022 x 1023 = NA

ATOMIC OR MOLECULAR WEIGHT =

NA x WEIGHT PER ATOM.

number of neutrons = N
number of protons = Z
A= Z + N

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Chapter 1-
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

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Chapter 1-
BOHR ATOM

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Chapter 1-
 Electronic Structure
• Electrons have wavelike and particulate properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level is determined by
quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

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Chapter 1-
 Electron Configurations

• Valence electrons – those in unfilled shells

• Filled shells more stable
• Valence electrons are most available for bonding
and tend to control the chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

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Chapter 1-
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
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Chapter 1-
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
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Chapter 1-
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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Chapter 1-
Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

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Chapter 1-
 Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

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Chapter 1-
Prof. S. Karthiyayini, BITS Pilani, Dubai Campus 13
Chapter 1-
FORCES AND ENERGIES

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Chapter 1-
Equilibrium exists when

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Chapter 1-
Prof. S. Karthiyayini, BITS Pilani, Dubai Campus 16
Chapter 1-
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - +
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.

Attractive energy EA
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Chapter 1-
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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Chapter 1-
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals dominate
bonding
• Example: CH4
shared electrons
H from carbon atom
C: has 4 valence e-, CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister & Rethwisch 8e.

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Chapter 1-
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A -X B )2 
 - 
% ionic character = x (100 %)
4

1- e
 
 
where XA & XB are Pauling electronegativities
Ex: MgO XMg = 1.2
XO = 3.5

 ( 3.5-1.2 )2 
 - 
% ionic character  1 - e 4
 x (100%)  73.4% ionic
 
 
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Chapter 1-
METALLIC BONDING

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Chapter 1-
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
bonding
Callister & Rethwisch 8e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

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Chapter 1-
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
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Chapter 1-
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”
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Chapter 1-
 Properties From Bonding : a
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T 1
DL DL
= a(T2 -T1 )
heated, T 2 Lo

• a ~ symmetric at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

Eo
larger a

Eo smaller a
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Chapter 1-
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large a

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Chapter 1-
 Chapter 2:
Atomic Structure & Interatomic
Bonding

Tutorials

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Chapter 1-
 Bonding Forces and Energies

2.13 Calculate the force of attraction

between a K+ and an O2- ion the centers of
which are separated by a distance of ro
=1.5 nm.

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Chapter 1-
 Solution
The attractive force between two ions FA is just the
derivative with respect to the interatomic separation
of the attractive energy expression,

 A 
d- 
dEA  r  A
FA = = =
dr dr r2
valences of the K+ and O2- ions, (Z1 and Z2) are +1
and -2, respectively, Z1 = 1 and Z2 = 2, then

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Chapter 1-
 (Z1e) (Z 2 e)
FA =
40r 2

(1)(2)(1.602  10-19 C) 2
=
(4)() (8.85  10 -12 F/m) (1.5  10-9 m) 2

= 2.05  10-10 N



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Chapter 1-
Prof. S. Karthiyayini, BITS Pilani, Dubai Campus 31
Chapter 1-
 (a) Differentiation of Equation (2.11) yields
dEN A nB
= - = 0
dr r(1 + 1 ) r(n + 1 )
(b) Now, solving for r (= ro)
A nB 1/(1 - n)
 A 
= or ro =  
ro 2 ro(n + 1 ) nB 

(c) Substitution for ro into Equation (2.11) and solving for E (= Eo)
A B
Eo = - +
ro ron
A B
= - +
1/(1 - n ) n/(1 - n )
 A   A 
   
nB  nB 
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Chapter 1-
Ex.2.14. For a Na+ - Cl- ion pair, attractive and repulsive energies EA and
ER respectively depend on the distance between the ions r according
to
EA = - 1.436/r
ER = 7.32 x 10-6/r8
For these expressions, energies are expressed in electron volts per
Na+ -Cl- pair, and r is the distance in nanometers. The net energy EN is
just the sum of the two expressions above.
(a)Superimpose on a single plot EN, ER, EA versus r up to 1.0 nm.
(b)On the basis of this plot, determine (i) the equilibrium spacing r0
between the Na+ and Cl- ions and (ii) magnitude of the bonding
energy E0 between the two ions.
(c)Mathematically determine the r0 and E0 values.
Prof. S. Karthiyayini, BITS Pilani, 33
Chapter 1-
Dubai Campus
(a) Curves of EA, ER, and EN are shown on the plot below

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Chapter 1-
 (b) From this plot ro = 0.24 nm
Eo = -5.3 eV
(c) From for EN

A = 1.436

B = 7.32 x 10-6
1/(1 - 8 )
n=8 1/(1 - n)  
 A 
  
1.436
Thus, ro =    0.236 nm
nB   (8)

 
7.32 x 10 -6 

 
1.436 7.32 x 10 -6
and Eo = - 1/(1 - 8)
+ 8/(1 - 8)
= - 5.32 eV
   
 1.436   1.436 
(8) 7.32 x 10-6  (8) 7.32 x 10 -6 
     
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Chapter 1-
 Ex 2.19
2.19 Compute the percents ionic character of
the interatomic bonds for the following
compounds: TiO2, ZnTe and CsCl.

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Chapter 1-
 Solution
For TiO2, XTi = 1.5 and XO = 3.5, and therefore,
 (- 0.25)(3.5-1.5) 2 
%IC = 1 - e   100 = 63.2%
 
For ZnTe, XZn = 1.6 and XTe = 2.1, and therefore,

 (- (2.1-1.6) 2 
 %IC = 1 - e 0.25)
  100 = 6.1%
 

For CsCl, XCs = 0.7 and XCl = 3.0, and therefore,

  (- 0.25)(3.0- 0.7) 2 
%IC = 1 - e   100 = 73.4%
 

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Chapter 1-
Thank you

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Chapter 1-