01-Oct-17

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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Atomic Structure

• atomic number (Z) = # of protons in nucleus of atom = # of

electrons of neutral or complete atoms

• atomic mass (A) = mass of protons + neutrons within the

nucleus.
•Isotopes
–A ≅ Z + N

• average atomic weight = weighted average of the atomic

mass of the atom’s naturally occurring isotopes.
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Atomic Structure
• In 1 mole of a substance there are Avogadro’s number (NA)
of atoms or molecules.

• 12 g of the pure material 12C contains 1 mol of 12C atoms.

• Atomic wt of an element or molecular wt of a compound= wt

of 6.022 x 1023 molecules or atoms:

1 amu/atom = 1g/mol

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Example 2.1

Chapter 2 - 4

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Atomic Models
Objective: to understand the behavior and position of electrons
in atoms

1) Bohr model: electron is a particle which is assumed to

revolve around the atomic nucleus in discreet circular
orbits. Electron energy quantized into shells

Nucleus: no. of Proton & no. of Neutron

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Atomic Models

2) Wave-mechanical model:
Electrons have wavelike and
particle-like characteristics.
– Means that electrons are in orbitals
–Electron position is defined in terms
of a probability distribution at various
locations around the nucleus.
–Electron energy quantized into both
shells and subshells

Fig 2.3 (a) Bohr and (b) wave-mechanical atom models in terms of electron distribution of
hydrogen atom

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Atomic Models
•Both models allow electrons to only be at particular
energy levels: have discrete energy states.
•Using wave mechanics: each orbital at discrete
energy level is determined by four parameters, called
quantum numbers:

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

ex: The electrons having n = 1 are said to form the K-shell of the atom; electrons
in the n = 2 state form the L-shell and so on
ex: A state with l = 0 is called an s-state; a state with l = 1 is called a p-state and so
on. 7

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Question

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Relation among the quantum n,l, m and

number of orbital & Electron
Table 2.1

Nucleus: no. of Proton & no. of Neutron 9

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Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state
• smaller the principal quantum number, the lower the energy level

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

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Question
Allowed values for the quantum numbers of electrons are as follows:

n = 1, 2, 3, . . . 1
l = 0, 1, 2, 3, . . . , n –1 ms = 
2
ml = 0, ±1, ±2, ±3, . . . , ±l

The relationships between n and the shell designations are noted in


Table 2.1. Relative to the subshells,
l = 0 corresponds to an s subshell
l = 1 corresponds to a p subshell
l = 2 corresponds to a d subshell
l = 3 corresponds to an f subshell

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Electron Configurations for Some of the Common

Elements
• Most elements: Electron configuration not stable

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

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

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

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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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Atomic Structure

• Valence electrons determine all of the

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

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Periodic Table
• Classification of materials: due to electronic configuration
• Columns: Similar Valence Structure
give up 3e-

Figure: 2.8
Electropositive elements: Electronegative elements:
Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
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Electronegativity
• Measure of the tendency of an atom to attract a
bonding pair of electrons.
• Ranges from 0.9 to 4.1
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

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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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Ionic Bonding
Ionic bond – metal + nonmetal
donates accepts
electrons electrons

• Occurs between + and – ions & Requires electron transfer

• Greater the difference in electronegativity, the greater the tendency to form
an ionic bond.
• Consider magnesium and oxygen with electronegativities of 1.31 and 3.44.
• Here’s what happens when Mg and O come near one another:

Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

electron(s)
(Ne + 3s2) (Ne – 2p2)
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6
(Ne) (Ne) + -
cation anion Coulombic 19
Attraction

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Example: NaCl

• Cation (+ charge) is attracted not only by the nearest anions, but to a

lesser extent by those farther away
• Similarly, it is repelled by all other cations
• Sum of the energy due to all attractions and repulsions is known as
the Madelung Energy
• Approximately 60% greater than the energy of attraction for isolated
ions the same distance apart as in the lattice

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Ionic bonding between one cation (+)

and one anion (-)
Energy balance of attractive and repulsive terms

-
A +
B
EN = EA + ER =
Repulsive energy ER r rn
A, B, and n are constants
whose values depend on
Interatomic separation r the particular ionic system.
The value of n is
Net energy EN approximately 8.

Attractive energy EA

Stable at minimum energy E0 for radius r0. r0

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Force = dE/dr = 0 at r0

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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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Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e -, CH 4
from carbon atom
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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Examples: Covalent Bonding

H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9
Adapted from, Callister 8e. GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA)

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Bond Hybridization
• Mixing of two or more atomic orbitals to
form a new set of hybrid orbitals
• Carbon can form sp3 hybrid orbitals
• Ground state of carbon reveals a pair of
electrons in the 2s and two single
electrons in the 2p
• Need 4 hybrid orbitals, so 4 atomic
orbitals are required as follows: (s + p +
p + p) = sp3

Fig. 2.14, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
Fig. 2.13, Callister & Rethwisch 9e. 25
permission of John Wiley and Sons, Inc.)

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Covalent Bonding: Carbon sp3

• Example: CH4

C: has 4 valence e-,

needs 4 more
H: has 1 valence e-,
needs 1 more

Covalent bonds are formed by:

a. Overlap of hybrid orbitals with
other atomic orbitals/hybrid
orbitals
Fig. 2.15, Callister & Rethwisch 9e.
(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

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Ionic-Covalent Mixed Bonding

% ionic character = {1-exp[ - (0.25)(XA – XB)2]} x 100

XA and XB are electro-negativities for the respective

elements
KEY POINT: Larger electronegativity difference more ionic

Ex: MgO XMg = 1.2 XO = 3.5

 ( 3.5 -1.2 ) 
2
- (0.25)
% ionic character  1 - e  x (100%)  73.4% ionic
 
 

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Example 2.3

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Metallic Bonding
• Delocalized as electron cloud
Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom)

• Primary bond for metals and

their alloys
Attraction between the positively
charged metal ions and the
electron cloud
Non directional
These “conduction” electrons
carry electric current and heat

http://mypchem.com/myp9/myp9c/myp9c_swf/metal_vib.htm

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Question

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Secondary Bonding
Arises from interaction between dipoles generates van der
waals forces
Dipoles fluctuates rapidly
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary Adapted from Fig. 2.20, secondary
bonding Callister & Rethwisch 9e.
bonding
• Permanent dipoles-molecule induced
secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl
Within an organic molecule the bonding is
-ex: polymer mostly covalent, while between molecules
the bonding is mostly van der Waals.
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Hydrogen bonds
• Between hydrogen atoms and the nearby negative end of a
molecular dipole, to strongly electronegative atoms such as O, H , F
or N.
• Partly covalent and partly electrostatic
• Much stronger than van der Waals bonds.
• Determines the unusual properties of water liquid and solid.
• Also occurs with other molecules, and even between parts of
complex molecules such as proteins.

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Bonding Energy & Melting Temperature of

various Substances Tm

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Properties From Bonding: Tm

Interaction energy E
• Melting Temperature, Tm
versus atomic separation r
Energy
• Bond length, r

r
ro
r
• Bond energy, Eo
smaller Tm
Energy
larger Tm
unstretched length
ro
r Tm is larger if Eo is larger.
Eo =
“bond energy”
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PROPERTIES FROM BONDING: E

• Elastic modulus, E
Elastic modulus

F L
=E
Ao Lo

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

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Properties From Bonding : a

• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
L L
= a(T2 -T1)
heated, T2 Lo
a  measures the fractional change in
length per degree change in temperature
• a ~ symmetric at ro at a constant pressure

Energy
unstretched length
ro
r a is larger if Eo is smaller.

E
larger a
o
E smaller a
o 36

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Summary: Bonding

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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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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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Solve the questions

Q 2.2

Silicon has three naturally occurring isotopes: 92.23% of 28Si,

with an atomic weight of 27.9769 amu; 4.68% of 29Si, with an
atomic weight of 28.9765 amu; and 3.09% of 30Si, with an
atomic weight of 29.9738 amu. On the basis of these data,
confirm that the average atomic weight of Si is 28.0854 amu.

Q 2.8
For the K shell, the four quantum numbers for each of the two
electrons in the 1s state, in the order of nlml ms , are 100(1/2)
and 100( - 1/2). Write the four quantum numbers for all of the
electrons in the L and M shells, and note which correspond to
the s, p, and d subshells.
.
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Q 2.11

Without consulting Figure 2.8 or Table 2.2, determine whether

each of the following electron configurations is an gas, a
metal, or non metal. Justify your choices.

(a) 1s22s22p63s23p5
(b) 1s22s22p63s23p63d24s2
(c) 1s22s22p63s23p64s1
(d) 1s22s22p63s2

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