Atomic Structure and Interatomic

Bonding
• Atomic Structure
• Electron Configuration
• Periodic Table
• Primary Bonding
• Ionic
• Covalent
• Metallic
• Secondary Bonding or van der Waals Bonding
• Three types of Dipole Bonding
• Molecules
REVIEW OF ATOMIC STRUCTURE
ATOMS = (PROTONS+NEUTRONS) + ELECTRONS
NUCLEUS BONDING
Atomic Structure
• Valence electrons determine all of the following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
BOHR ATOM
orbital electrons:
n = principal
quantum number
n=3 2 1

Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A ≈ Z + N

2
ELECTRON ENERGY STATES
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4p
Increasing energy

n=4 3d
4s
n=3 3p
3s
n=2 2p
2s
n=1 1s

3
l ml ms = ±½
 Electrons fill quantum levels in order of increasing
energy ( only n and l make significant differences
in energy configurations).

1s, 2s, 2p, 3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,….

When all electrons are at the lowest possible

energy levels => ground state

Excited states do exist such as in glow discharges

etc…

Valence electrons occupy the outermost filled shell.

Valence electrons are responsible for all bonding !
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
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 4 6 (stable)

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

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STABLE ELECTRON CONFIGURATIONS
Stable electron configurations...
• have complete s and p subshells
• tend to be unreactive.

Z Element Configuration
2 He 1s 2
10 Ne 1s 2 2s 2 2p 6
18 Ar 1s 2 2s 2 2p 6 3 s 2 3p 6
36 Kr 1s 2 2s 2 2p 6 3 s 2 3p 6 3d 10 4 s 2 4p 6

4
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
THE PERIODIC TABLE
• Columns: Similar Valence Structure, Similar Properties
give up 1e

inert gases
give up 2e

accept 2e
accept 1e
Metal
give up 3e
Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg S Cl Ar
K Ca Sc Se Br Kr
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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Periodic Table

Draft of the first periodic table, Mendeleev, 1869

ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons; reactivity
Metals like to give up, halogens like to acquire electrons !
H He
2.1 -
Li Be F Ne
1.0 1.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Smaller electronegativity Larger electronegativity

7
Atomic Bonding in Solids
• Start with two atoms infinitely
separated
• Attractive component is due to
nature of the bonding (minimize
energy thru electronic configuration)
• Repulsive component is due to Pauli
exclusion principle; electron clouds
r tend to overlap
• Essentially atoms either want to give
up (transfer) or acquire (share)
electrons to complete electron
configurations; minimize their energy
• Transfer of electrons => ionic bond
• Sharing of electrons => covalent
• Metallic bond => sea of electons
IONIC BONDING (I)
• Occurs between + and – ions (anion and cation).
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: Na+ Cl-

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]
IONIC BONDING (II)

Oppositely charged ions attract, attractive force is coulombic.

Ionic bond is non-directional, ions get attracted to one another in any direction.
Bonding energies are high => 2 to 5 eV/atom,molecule,ion
Hard materials, brittle, high melting temperature, electrically and thermally insulating

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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

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

Give up electrons Acquire electrons

COVALENT BONDING (I)
• Requires shared electrons
• 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

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COVALENT BONDING (II)

Diamond, sp3
Covalent bonds are formed by sharing of the valence
electrons
Covalent bonds are very directional
Covalent bond model: an atom can have at most 8-N’
covalent bonds, where N’ = number of valence electrons

Covalent bonds can be very strong, eg diamond, SiC, Si,

etc, also can be very weak, eg Bismuth
Polymeric materials do exhibit covalent type bonding. 10
EXAMPLES: COVALENT BONDING
H2 O

column IVA
H2 F2
C(diamond)
H He
2.1
Si C - Cl 2
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 GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA) 11
METALLIC BONDING
• Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).
Ion cores in the “sea of
electrons”.

Valance electrons belong

no one particular atom but
drift throughout the entire
metal.

“Free electrons” shield

+’ly charged ions from
repelling each other…

• Primary bond for metals and their alloys

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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 bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer second

a ry b o n secondary bonding
d i ng
Bonding energy
• 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

Attractive energy EA
Bonding Energy
The bonding energy of two atoms, Eo corresponds to
the energy at this minimum point; it represents the
energy that would be required to separate these two
atoms to an infinite separation
Bonding Energies
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
 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”
PROPERTIES FROM BONDING: E
• Elastic modulus, E cross
sectional
length, Lo
area A o
Elastic modulus
undeformed F L
L =E
Ao Lo
deformed F

• E ~ curvature at ro
Energy

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

larger Elastic Modulus 16

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

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

Eo
smaller 

Eo larger 
 Summary: Primary 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 e co n d
ary b o
n di ng
small E
large 
ANNOUNCEMENTS (I)
Reading: Chapter 2 and 3
http://www.fen.bilkent.edu.tr/~uner/chem201/fenis.html

Core Problems: 2.5,2.7, 2.11,2.12, 2.14,2.15, 2.19

Due February 21,2008, please hand in during the
lecture. SS

SELF STUDY
1- solve the BASIC QUESTIONS on the next page
2- Why does the volume of water expand when it freezes,
explain in your words (max 100 words) ?
3- 2.22

0
Basic Questions
• What should be the wavelength of a photon, when
absorbed, to break the bond between the N and H atoms
forming the N-H molecule ? Energy of the bond = 93.5
Kcal/mol.

• Energy of the 1s state in the W atom is -70000eV. Assume

that a high energy electron beam causes one of the two 1s
electrons to break away from the atoms. If this empty state
is filled by a 2p electron, W atom emits a photon of
wavelength 0.21 Angstroms. Find the energy level of the 2p
electron in the W atom.

• Find the weight of a single Al atom.

• How many Al atoms are there in per unit volume (density = 2.7
gm/cm3)
ANNOUNCEMENTS (II)
Midterm 1: March 27th, 2008, 6:00 pm (rooms and seating
arrangement are TBD)

Midterm 2: April 22th, 6:00 pm (rooms and seating

arrangement are TBD)