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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Relative size of an atom

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 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
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 Isotopes are variants of a particular chemical element which differ in neutron number,
although all isotopes of a given element have the same number of protons in each atom.
They have similar chemical properties.

Can be stable or un-stable (radioactive)--> decay

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 Some units (Freshman Phy.)

What is the unit of mass ?

What is the unit of weight ? By the way what is weight ?

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In1932 by Irène Joliot-Curie and Frédéric
Joliot showed the existence of an unknown particle
that they suggested was a gamma ray.

Majorana was the first to interpret correctly the

experiment as requiring a new particle that had a
neutral charge and a mass about the same as
the proton; this particle is the neutron.

Fermi told him to write an article, but Majorana didn't

bother. James Chadwick proved the existence of the
neutron by experiment later that year, and he was 8
awarded the Nobel Prize for this discovery.
 Atomic Structure

• Valence electrons determine all of the

following properties

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

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 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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 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

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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 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• Why? Valence (outer) shell usually not filled completely.

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 Electron Configurations
• Valence electrons – (for main-group elements) are the electrons in the outermost shell of
the atom.

• BUT for a transition metal it is different. Transition metals can use the electrons in their ‘d’
subshells as valence electrons.
Hint -> count electrons that reside outside a noble-gas core.

• 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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 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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 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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 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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 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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 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

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

[Ne] 3s2

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

[Ne] [Ne]

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 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms

electrostatic attraction /
potential energy
Q1*Q2
EN = EA + ER = k
r

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 The system becomes more stable (the energy of the system
decreases) as two hydrogen atoms move toward each other
from r = ∞, until the energy reaches a minimum at r = r0 (the
observed internuclear distance in H2 is 74 pm). Thus at intermediate
distances, proton–electron attractive interactions dominate, but as
the distance becomes very short, electron–electron and proton–
proton repulsive interactions cause the energy of the system to
increase rapidly.

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• Calculate the amount of energy released when 1 mol
of gaseous Li+F− ion pairs is formed from the
separated ions. The observed internuclear distance in
the gas phase is 156 pm.

• Calculate the amount of energy released when 1 mol

of gaseous MgO ion pairs is formed from the
separated ions. The internuclear distance in the gas
phase is 175 pm.
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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-, from carbon atom
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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Metallic Bonding

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 Mixed Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (X A X B )2 
% ionic character =   4

1
 e x (100%)
 
 
where X & X are Pauling electronegativities
A B

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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 Secondary Bonding
• Secondary bonds are due to electrostatic attractions of
electric dipoles in atoms or molecules.
• Dipoles are created when positive and negative
charge centers exist.
• Basically there two types of secondary bonds:
i) fluctuating, ii) permanent

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I) Fluctuating Dipole

natural oscillation of
atoms leading to
momentary
breakdown of charge
symmetry and
temporary dipoles

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 I- Fluctuating - (a) Induced Dipole
Ion-Induced Dipole Forces Dipole-Induced Dipole Forces

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 I.(a) Induced Dipole  Van der Waals

• driven by induced electrical

interactions between two or more
atoms or molecules that are very
close to each other.

• Van der Waals interaction is the

weakest of all intermolecular
attractions

• Stronger for more polarizable molecules so larger

molecules (atoms),. e.g. Ar > He
 MSE 501 – Fall 2016

I.(a) Induced Dipole  Van der Waals

Van der Waals forces can be categorized, on the ground of
the molecules involved in the interaction, to:

Keesom: two polarized molecules interact due to the inherent

difference in charge distribution

Debye: a molecule with a permanent dipole induces charge

redistribution to neighboring molecules with no dipole
moments.

London (dispersion): No permanent dipoles, i.e. fluctuations

on the e- cloud  charge redistribution to neighbours.

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II) Permanent Dipole

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II) Permanent Dipole

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II.(a) Hydrogen 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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 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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 Properties From Bonding : 
• Coefficient of thermal expansion, 
length, Lo coeff. thermal expansion
unheated, T1
L L
= (T2 -T1)
heated, T2 Lo

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

Eo
larger 

Eo smaller 
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 Summary: Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
s eco n d
a ry b o
ndi n g
small E
large 

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