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Chapter 2
Atomic Structure & Bondingin Solids
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Issues to address
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?
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Fundamental ConceptAtom
Basic Unit of an ElementDiameter : 10 –10 m.
Neutrally Charged
NucleusDiameter : 10 –14 m
Positive ChargeAccounts for almost
all mass
Electron CloudMass : 9.109 x 10 –28 g
Charge : -1.602 x 10 –9 CAccounts for all volume
ProtonMass : 1.673 x 10 –24 g
Charge : 1.602 x 10 –19 C
NeutronMass : 1.675 x 10 –24 g
Neutral Charge
atomic structure
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Fundamental Concept
atomic structure
Periodic table of the elements
O
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
ClS
Li Be
H
Na Mg
BaCs
RaFr
CaK Sc
SrRb Y
Atomic number, ZAtomic weight, A Cu
29
63.54
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Electron Principle
atomic structure
Principle
classical mechanic
s
quantum mechanics
Bohr
ato
mic
m
odel
Wave
mech
anic
al
ato
m m
odel
electron structure
electron energy
electron configuration
electron position
electronnucleus
Atomic structure
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Electron Principle
atomic structure
Bohr atomic model Wave mechanical atom model
electron structure & position
▣ structure: assume electrons as particle-like & revolve around the atomic nucleus in discrete paths.
▣ position: in terms of its orbital in discrete path.
▣ limitation: inability to explain several phenomena involving electron.
▣ further refined from Bohr model.
▣ structure: assume electrons as particle-like & wave-like.
▣ Position: in terms of probability distribution (various location around the atomic nucleus).
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Electron Principle
atomic structure
Bohr atomic model Wave mechanical atom model
electron energy
▣ Energy are quantized.
▣ Electrons are permitted to have only specific values of energy
(have energy levels @ states).▣ Each adjacent orbital/state are separated by finite energies.▣ Electron may change energy by make a quantum jump.▣ Energy is absorbed to move to higher energy level.▣ Energy is emitted during transition to lower level.
Both model assume:
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Electron Principle
atomic structure
Bohr atomic model Wave mechanical atom model
electron energy
emit energy(photon)
absorb energy(photon)
energy levels
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Electron Principle
atomic structure
Bohr atomic model Wave mechanical atom model
electron energy
n=1
n=2
n=3
▣ electron in its orbital (position) & separate by energy levels.
▣ Each orbital at discrete energy levels separate into electron subshells & quantum numbers dictate the number of state within each subshell.
4. Spin quantum number, ms. (spin)
3. Magnetic quantum number, ml. (state).
2. Subsidiary quantum number, l. (orbital/subshell).
1. Principle quantum number, n. (energy level/shell).
▣ Every electron characterized by 4 quantum numbers.
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Electron Principle
atomic structure
Bohr atomic model
electron energy
Bohr atomic model
orbitaln=1
n=2
n=3
s orbital (l=0)
p orbital(l=1)
s orbital (l=0)
Energy level
n=2n=1
Energy level/shell
Orbital/subshell
Wave mechanical atom model
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Electron Principle
atomic structure
electron energy Wave mechanical atom model
-1.5
-3.4
-13.6 K-shell n = 1
L-shell n = 2
M-shell n = 3
N-shell n = 4
Energ
y
1s
2s2p
3s3p
3d4s
4p4d
Orbital/ subshell
State Energy level/shell
eV
Electron energy level
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Electron Principle
atomic structure
Bohr atomic model
electron configurations Wave mechanical atom model
◈ Electron Configuration: lists the arrangement of electrons in orbital.
◈ Maximum number of electrons in each atomic shell is given by 2n2.
n # of electrons 1 2 2 8 3 18 4 32◈ Apply Pauli exclusion principle: Each electron state can hold no more than 2 electrons which
must have opposite spin.◈ Electrons have discrete energy state & tend to occupy lowest
energy state.◈ Atomic size (radius) increases with addition of shells.
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Electron Principleatomic structure
electron configurations Wave mechanical atom model
▣ The # of available electron states in some of the electron shells & subshells
1 K
2 L
3 M
Principle quantum number, n
shell/energy level
shell designation
Subsidiary quantum #, l
Magnetic quantum #, ml
subshells/orbital
sspspdspdf
1131351357
22262610261014
8
18
324 N
Number of states
Number of electrons
per subshell per shell
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Electron Principle
atomic structure
electron configurations Wave mechanical atom model
example: Fe (Z = 26)electron configuration is
n = 1
n = 2
n = 3
n = 4
En
erg
y
1s
2s2p
3s3p
3d
4s
4p4d
Low
est
energ
y
state
(gro
und
state
)
Hig
hest
energ
y s
tate
Principal Quantum Numbers
Orbital letters
# of electrons
1s2 2s2 2p6 3s2 3p63d 6 4s2
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Electron Principle
atomic structure
electron configurations Wave mechanical atom model
1s2s 2p3s 3p 3d4s 4p 4d 4f5s 5p 5d 5f
Method of arrangement:
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Electron Principle
atomic structure
electron configurations Wave mechanical atom model
Electron configuration
(stable)
...
... 1s2 2s2 2p6 3s2 3p6 (stable)... 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 (stable)
Atomic #
18...36
Element1s1 1Hydrogen1s22Helium1s2 2s1 3Lithium1s2 2s24Beryllium1s2 2s2 2p15Boron1s2 2s2 2p26Carbon
...1s2 2s2 2p6 (stable)10Neon1s2 2s2 2p6 3s111Sodium1s2 2s2 2p6 3s2 12Magnesium1s2 2s2 2p6 3s2 3p113Aluminum
...Argon...Krypton
Electron configuration of some elements
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Electron Principle
atomic structure
electron configurations Wave mechanical atom model
▣ Why? Valence (outer) shell usually not filled completely.
▣ Most elements: electron configuration not stable.
example: Carbon C
1s2 2s2 2p2
atomic number, Z = 6
valence electrons
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Electron Principle
atomic structure
Valence electron
▣ Electron that occupy the outermost (valence) shell.
▣ Valence electrons ▷ those in unfilled shells (most elements) not stable & filled shells (inert gases) more stable.
▣ Participate in the bonding (unfilled shell) between atoms to form atomic & molecular aggregates.▷ determine physical (optical, thermal & electrical) & chemical properties.
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Periodic Table
atomic structure
Electropositive & electronegative elements
O
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
ClS
Li Be
H
Na Mg
BaCs
RaFr
CaK Sc
SrRb YElectropositive elements
Electronegative elements
Inert
g
ases
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Periodic Table
atomic structure
electronegative elements
readily give up electrons to become cations (+ions).
metallic elements. smaller electro-
negativity.
readily accept electrons to become anions (-ions).
non-metallic elements.
higher electro-negativity.
unfilled valence shell. not stable electron configuration. assume stable by losing @ gaining valence electrons to form charge ions.
filled valence shell. stable electron configuration.
unreactive chemically.
electropositive elements
Inert gases
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Periodic Table
atomic structure
electronegativity
Smaller electronegativity Larger electronegativity
▣ Ranges from 0.7 to 4.0.▣ Large values: tendency to acquire electrons.
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atomic bonding
type
Secondary
bonding
Ionic
bondin
g
Covale
nt
bondin
g
Atomic bonding
Meta
llic
bondin
g
Primary bonding
Type of bonding
Fluct
uati
ng
dip
ole
s bond
Perm
anent
dip
ole
s bond
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Primary bonding
atomic bonding
Ionic bonding
▣ Strong atomic bonds due to transfer of electrons. ▣ It can form between metallic & nonmetallic
elements.▣ Electrons are transferred from electropositive to
electronegative atoms.▣ Large difference in electronegativity required.▣ Occurs between + & - ions.▣ Non Directional bonding.
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atomic bonding
Metal (electropositive
element) - unstable
Non metal (electronegative
atom) - unstable
electron transfer
Cation(+ve charge)
- stable
Anion(-ve charge)
- stable
Ionic bond
electrostaticattraction
donates electrons
accepts electrons
Primary bondingIonic bonding
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atomic bonding
Primary bondingIonic bonding
1s2 2s2 2p6 3s2 Mg O 1s2 2s2 2p4
[Ne] 3s2
Mg: X = 1.2, Z = 12
O: X = 3.5, Z = 8
1s2 2s2 2p6 Mg2+ O2- 1s2 2s2 2p6 [Ne]
[Ne]
Example: Magnesium oxide (MgO)
Metal (electropositive
element) - unstable
Non metal (electronegative
atom) - unstable
electron transfer
Cation(+ve charge)
- stable
Anion(-ve charge)
- stable
Ionic bond
MgO
electrostaticattraction
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atomic bonding
Primary bondingIonic bonding
Bonding Force
▣ due to electrostatic attraction.
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atomic bonding
Primary bondingIonic bonding
Bonding Energy ▣ Energy – minimum energy most stable
▷ Energy balance of attractive & repulsive terms
Attractive energy EA
Net energy EN
Repulsive energy ER
Interatomic separation r
rA
nrBEN = EA + ER = __
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atomic bonding
Primary bondingIonic bonding
Bonding Energy
Eo =
“bond energy”
Energy
r o r
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atomic bonding
Primary bondingIonic bonding
▣ Predominant bonding in Ceramics
Give up electrons Acquire electrons
NaClMgO
CaF2CsCl
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Primary bonding
atomic bonding
Covalent bonding
▣ share valence electrons.
▣ similar @ small differences in electronegativity.
▣ bonds determined by valence – s & p orbitals dominate bonding.
▣ Directional bonding.
overlapping electron clouds
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Primary bonding
atomic bonding
Covalent bonding
Example: Methane (CH4)
C: X = 2.5, Z = 6
H: X = 2.1, Z = 1
shared electrons from carbon atom
shared electrons from hydrogen atoms H
H
H
H
C
C: 1s2 2s22p2
H: 1s1
4 valence electrons
1 valence electron
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Primary bonding
atomic bonding
Ionic & Covalent bonding
Percent ionic character
▣ Ionic-Covalent Mixed Bonding
▣ % ionic character = where
XA = electronegativity value for element A
XB = electronegativity value for element B
4
2
1)XX(
BA
e %)100( x
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Primary bonding
atomic bonding
Ionic & Covalent bonding
Example: Magnesium oxide (MgO)
XMg = 1.3 XO = 3.5
4
2
1)XX(
BA
e %)100( x % ionic character =
= 70.2 % ionic
Percent ionic character
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Primary bonding
atomic bonding
Metallic bonding
▣ Atoms in metals are closely packed in crystal structure.
▣ Loosely bounded valence electrons are attracted towards nucleus of other atoms.
▣ Electrons spread out among atoms forming electron clouds.▷ these free electrons are reason for a good electric conductivity & ductility.
▣ Non-directional bonding▷ outer electrons are shared by many atoms.
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Primary bonding
atomic bonding
Metallic bonding
positive ion
valence electron charge cloud
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Secondary bonding
atomic bonding
Fluctuating dipoles bond
▣ Arises from interaction between dipoles.▣ Very weak electric dipole bonds due to
asymmetric distribution of electron densities.
asymmetric electron clouds
+ - + -secondary
bonding
HH HH
H2H2
secondary bonding
example: liquid H2
▣ general case:
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Secondary bonding
atomic bonding
Permanent dipoles bond
▣ Also, arises from interaction between dipoles.▣ Weak electric dipole bonds due to molecule
induced.
Example 1: liquid HCl acid
Example 2: polymer
+ - + -
secondary bonding
▣ general case:
secondary bonding
H Cl H Clsecondary bonding
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Summary bonding
atomic bonding
Primary bonding Secondary bonding
TypeIonic
Covalent
Metallic
Secondary
Bond EnergyLarge
Variablelarge-Diamondsmall-Bismuth
Variablelarge-Tungstensmall-Mercury
smallest
CommentsNondirectional (ceramics)
Directional(semiconductors, ceramicspolymer chains)
Nondirectional (metals)
Directionalinter-chain (polymer)inter-molecular
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Summary bonding
atomic bonding
Primary bonding Secondary bonding
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Properties from bonding
atomic bonding
Melting temperature
Tm is larger if bonding energy, Eo is larger.
ro r
Energy
larger Tm
smaller Tm
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Properties from bonding
atomic bonding
Coefficient of thermal expansion
= α (T2-T1)LLo
coeff. thermal expansion
L
length, Lo
unheated, T1
heated, T2
a is smaller if Eo is larger.ro
r
smaller α
larger α
Energy
unstretched length
Eo
Eo
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atomic bonding
Summary
Properties from bonding
Ceramics
(Ionic & covalent bonding):
Large bond energylarge Tm
large Esmall α
Metals(Metallic bonding):
Variable bond energymoderate Tm
moderate Emoderate α
Polymers(Covalent & Secondary):
Directional PropertiesSecondary bonding dominates
small Tm
small E large α
secondary bonding
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End of Chapter
2