Class 3 Class 3 General Review of General Review of Class 3 Class 3 General Review of General Review of

Atomic Bonding Atomic Bonding Atomic Bonding Atomic Bonding

READING
Chapter 2 in DeGraef and McHenry, pp. 38-48.
HANDOUT from Chapter 2 of R.J.D. Tilley, Understanding Solids: The Science of Materials HANDOUT from Chapter 2 of R.J.D. Tilley, Understanding Solids: The Science of Materials
(Wiley, New York, 2004).
ADDITIONAL REFERENCES:
Chapter on bonding from any Introduction to Materials book.
Prof. M.L. Weaver
Chapter 1 in Rohrer
Chapter 8 in Bloss
The next 16 viewgraphs are a g p
review of the previous lecture.
Prof. M.L. Weaver
Atomic Structure (Freshman Chem.) Atomic Structure (Freshman Chem.)
atom electrons 9.11 x 10
-31
kg
protons
} 6
27
k
p
neutrons
atomic number = # of protons in nucleus of atom
}1.67x10
27
kg
= # of electrons of neutral species
A[=] atomic mass unit = amu = 1/12 mass of
12
C A [ ] atomic mass unit amu 1/12 mass of C
Atomic wt = wt of 6.022 x 10
23
molecules or atoms
1 amu/atom = 1g/mol
C 12.011
Prof. M.L. Weaver
56
H 1.008 etc.
RECALL/REVIEW
AtomicStructure AtomicStructure
Valenceelectronsdetermineallofthefollowing
properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
57
RECALL/REVIEW
ImpactofBondingonProperties ImpactofBondingonProperties
TheBohrmodelshows
electronsrevolving
aroundthenucleusin aroundthenucleusin
discreteenergylevels
Quantummechanics
governhowthese
electronsfillthespecific
levelsandhowthey
interactwitheachother interactwitheachother Electrons revolve around the nucleus in discrete
energy levels. For an electron to change energy
levels it must either gain or lose specific
amounts of energy.
RECALL/REVIEW
F Q N b F Q N b FourQuantumNumbers FourQuantumNumbers
Principal Quantum Number (n) determines the energy of Principal Quantum Number (n) determines the energy of
the electrons.
Second Quantum Number* (l or l) determines the Second Quantum Number* (l or l) determines the
general shape of the electron cloud.
(*aka. Subsidiary or azimuthal quantum number)
Third Quantum Number** (m
l
or m
l
) indicates the
spatial orientation of the electron cloud.
(**aka. Magnetic quantum number)
Fourth Quantum Number*** (M
s
) represents the spin of
the individual electrons.
(***aka. Spin quantum number)
RECALL/REVIEW
PrincipalQuantumNumber PrincipalQuantumNumber
Innermostlevelisassigned
n=1,nextlevelisn=2,etc.
Lettersareassignedto
representtheindividual
h ll / bit l shells/orbitals
Kcorrespondston=1;
Lcorrespondston=2,
Klevel,n=1
Etc.
Llevel,n=2
Mlevel,n=3
Etc
RECALL/REVIEW
S d Q N b S d Q N b SecondQuantumNumber SecondQuantumNumber
Someoftheenergylevels
splitintosublevels
(orbitals/suborbitals)
Thesublevelsareassignedas Thesublevelsareassignedas
follows
First=s(l =0)
Second p(l 1) Second=p(l =1)
Third=d(l =2)
Fourth=f(l =3)
Etc
l =n1but:
Max.numberofsuborbitals=
principlequantumnumber
RECALL/REVIEW
ThirdQuantumNumber ThirdQuantumNumber
Indicatesthespatialorientationoftheelectroncloud.
RECALL/REVIEW
l = 0
ShapesoftheElectronOrbitals ShapesoftheElectronOrbitals
l 0
l = 1
m
l
= 0
m
l
= +1 m
l
= -1
l = 2
1 2
m
l
= 1 m
l
= 2
m
l
= -1 m
l
= -2
Differentshapes
correspondingtodifferent
m
l
= 0
Chapter1 TypesofMaterials,
ElectronEnergyBands,and
ChemicalBonds
suborbitals.
Veryimportantinbonding
FourthQuantumNumber FourthQuantumNumber
Thefourthquantumnumber(spin)hasno
relationshiptotheotherthree.
ThetwopossiblevaluesareM
s
=+or
Electronswiththesamevaluehaveparallelspins
whilethoseofoppositevalueshaveoppositespins
ThePauli exclusion principle showsthatnotwo
l h h f f electronscanhavethesamesetoffourquantum
numbers.Nomorethantwoelectronswithopposite
spinscanoccupyeachorbital spinscanoccupyeachorbital.
RECALL/REVIEW
Electron Energy States gy
have discrete energy states
tend to occupy lowest available energy state.
Electrons...
4p
4d
N-shell n = 4
py gy
3d
4s
3s
3p
M-shell n = 3
Energy
Adapted from Fig. 2.4,
2s
2p
L-shell n = 2
p g ,
Callister & Rethwisch 8e.
Chapter 2 - 65
1s
K-shell n = 1
RECALL/REVIEW
SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Electron configuration
Atomic # Element
1s
1
1 Hydrogen
(stable)
1 Hydrogen
1s
2
2 Helium
1s
2
2s
1
3 Lithium
1s
2
2s
2
4 Beryllium
1s
2
2s
2
2p
1
5 Boron
Adapted from Table 2 2
...
1s 2s 2p
5 Boron
1s
2
2s
2
2p
2
6 Carbon
...
1s
2
2s
2
2p
6
(stable)
10 Neon
1s
2
2s
2
2p
6
3s
1
Adapted from Table 2.2,
Callister & Rethwisch 8e.
...
1s
2
2s
2
2p
6
3s
1
11 Sodium
1s
2
2s
2
2p
6
3s
2
12 Magnesium
1s
2
2s
2
2p
6
3s
2
3p
1
13 Aluminum
...
Wh ?
1s
2
2s
2
2p
6
3s
2
3p
6
(stable)
...
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
(stable)
18
...
36
Argon
...
Krypton
Chapter 2 - 66
Why? Valence (outer) shell usually not filled completely.
RECALL/REVIEW
Electron Configurations g
Valence electrons those in unfilled shells
Filled shells more stable Filled shells more stable
Valence electrons are most available for
bonding and tend to control the chemical g
properties
l C ( t i b 6) example: C (atomic number = 6)
1s
2
2s
2
2p
2
p
valence electrons
Chapter 2 - 67
RECALL/REVIEW
Electronic Configurations g
ex: Fe - atomic # = 26 1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
valence
electrons
3d
4p
4d
N-shell n = 4
3
M h ll 3
3d
4s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2
3s
3p
M-shell n = 3
Energy
1s
2s
2p
K shell n = 1
L-shell n = 2
Chapter 2 - 68
1s
K-shell n = 1
RECALL/REVIEW
Review Review
Aufbau Principle Aufbau Principle
Review Review
Aufbau Principle Aufbau Principle pppp
Energy levels of quantum shells dont fill in strict
numerical order. Thus there are deviations.
The Aufbau principle is a graphical device used to
predict deviations from expected ordering.
K (2)
SHELL (# e
--
)
L (8)
M(18)
N (32)
See this website for a good review
( )
O (50)
P (72)
Q (98)
Prof. M.L. Weaver
2011CengageLearningEngineering.AllRightsReserved.
g
http://www.avogadro.co.uk/light/aufbau/aufbau.htm
Q (98)
s
2
p
6
d
10
f
14
g
18
h
22
i
26
RECALL/REVIEW
Aufbau Example Aufbau Example Aufbau Example Aufbau Example pppp
IRON (atomic number 26)
1
2
2
2
2
6
3
2
3
6
4
2
3d
6
(M 26 l t )
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
6
(Means 26 electrons)
Principal quantum numbers are arranged from lowest
to highest when writing electronic structure. This we
usually write IRON as: usually write IRON as:
1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
NOTE: the magnetic behavior of iron is caused by
the unfilled 3d level (remember d has five orbitals
Prof. M.L. Weaver
(
space for 10 electrons)
See this website for a good review
http://www.avogadro.co.uk/light/aufbau/aufbau.htm
RECALL/REVIEW
Aufbau Example Aufbau Example contd contd Aufbau Example Aufbau Example contd contd pppp
Electrons will usually occupy every orbital singly
before the orbitals are doubly occupied before the orbitals are doubly occupied.
NITROGEN ( t i b 7) NITROGEN (atomic number 7):
1s
2
2s
2
2p
3
Each of the three p orbitals in the L shell contains one
l t d t bit l t i i electron as opposed to one orbital containing one
electron and one containing zero electrons.
Prof. M.L. Weaver
See this website for a good review
http://www.avogadro.co.uk/light/aufbau/aufbau.htm
RECALL/REVIEW
The Periodic Table of Elements
Arrangement based on electron
configuration configuration.
Columns have similar valence structure
K
VIII
L
M
N
O
F ll
O
P
Q
Full
Q
Chapter 1 - Types of Materials, Electron Energy Bands, and Chemical Bonds -
72
Interactionsbetweenatoms Interactionsbetweenatoms
Electronsintheoutermostlevels(valenceelectrons)
interactfirst.
Wh h h ll fill d i l Whentheoutershellsareunfilled,atomsgain,lose,or
borrowelectronswhichisthebasisofbonding.
Exampleofanionicbondbtw.Cl

andNa
+
ions
OptimalDistancebetweenAtoms OptimalDistancebetweenAtoms
Interactionsareblendsof
attractiveandrepulsiveforces
Bothforcesareafunctionof
distance
Thepointatwhichthe
differencebetweenthe
attractive repulsiveforcesis
greatestrepresentsthe
optimaldistance p
Polarity Polarity
Whendifferentmolecules
interact,onehasagreater
affinityforelectronsthanthe y
other.
Th l t d it f Theelectrondensityofa
typicalpolarbondisshown
ontheright.
Electronegativity Electronegativity
Electronegativityistheabilityofanatomtoaccept
electrons.
RECALL/REVIEW
The Periodic Table
RECALL: Columns Similar Valence Structure
e

u
p

1
e
-
u
p

2
e
-
e
r
t

g
a
s
e
s
p
t

1
e
-
p
t

2
e
-
g
i
v
g
i
v
e

u
e

u
p

3
e
-
i
n
e
a
c
c
e
p
a
c
c
e
p
He H
Adapted from
Fig. 2.6,
Callister &
Rethwisch 8e
g
i
v
e
O
Se Br
Ne
Ar
Kr
F
Cl S
Li Be
Na Mg
Ca K Sc
Rethwisch 8e.
Te
Po At
I Xe
Rn Ba Cs
Ra Fr
Sr Rb Y
Electropositive elements:
Readily give up electrons
Electronegative elements:
Readily acquire electrons
Ra Fr
Chapter 2 - 77
Readily give up electrons
to become + ions.
Readily acquire electrons
to become - ions.
RECALL/REVIEW
Electronegativity
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.
g y
Smaller electronegativity Larger electronegativity
Chapter 2 - 78
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.
RECALL/REVIEW
Review Review
Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties
Review Review
Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties
Metallicity (electropositivity):
Tendency of an atom to donate electrons to metallic or
ionic bonds. This is opposite of electronegativity.
I t bi d it l l t ith d d Increases as an atom binds it valence electrons with reduced
strength (i.e., as valence electron-nucleus separation increases,
binding force decreases).
As you go from right to left on the periodic table, the valence
electron-nucleus separation is about the same, but nuclear charge
decreases (thus, binding force decreases).
Increases from top to bottom and from right to left of
periodic table.
Prof. M.L. Weaver
RECALL/REVIEW
Review Review
Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties
Review Review
Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties Periodic Trends in Atomic Properties
Size:
Same trends as metallicity (for the same reasons) Same trends as metallicity (for the same reasons).
REMEMBER that cations (+) are smaller than protons
(neutral), whereas anions (-) are larger.
Mass:
I ith t i b (I b t k h ) Increases with atomic number (I bet you know why).
Periodic trends are not absolute but we can still use Periodic trends are not absolute, but we can still use
these trends to predict bonding and properties.
Prof. M.L. Weaver
RECALL/REVIEW
Types of Bonding Types of Bonding Types of Bonding Types of Bonding
IONIC
0.9 3.0
METALLIC
Van der Waals
COVALENT
There are many models that describe
atomic bonding Ive condensed some
Prof. M.L. Weaver
2011CengageLearningEngineering.AllRightsReserved.
COVALENT
atomic bonding. I ve condensed some
information in the next two lecture
modules. Please read them.
RECALL RECALL
Paulings expression for Paulings expression for ionicity ionicity fraction of a bond fraction of a bond
RECALL RECALL
Paulings expression for Paulings expression for ionicity ionicity fraction of a bond fraction of a bond Pauling s expression for Pauling s expression for ionicity ionicity fraction of a bond fraction of a bond Pauling s expression for Pauling s expression for ionicity ionicity fraction of a bond fraction of a bond
( )
2
1
4
1
nm m
x x
f e

=
x
nm
is the electronegativity of the nonmetallic element
f e
x
m
is the electronegativity of the metallic element
Assume:
f > 0.5 (x > 1.7) ionic bonds
f 0.5 (x 1.7) covalent bonds f 0.5 (x 1.7) covalent bonds
Actual change from metallic to ionic/covalent is more
Prof. M.L. Weaver
complex. Thus we assign some elements as metalloid.
RECALL/REVIEW
Primary Bonding Primary Bonding Primary Bonding Primary Bonding
Metallic Bond -- delocalized as electron cloud
Ionic-Covalent Mixed Bonding
% ionic character =
%) 100 ( x
1e

(X
A
X
B
)
2
4
|


|
|
| % o c c a acte
where X
A
& X
B
are Pauling electronegativities
) (

\


.
|
|
Ex:MgO X
Mg
=1.2
X
O
=3.5
ionic 73.4% (100%) x e 1 character ionic %
4
) 2 . 1 5 . 3 (

2
=
|
|
|
.
|

\
|
=

Prof. M.L. Weaver

83
|
.

\
RECALL/REVIEW
Bonding Generalizations Bonding Generalizations
Based on Periodic Trends in EN Based on Periodic Trends in EN contd contd
RECAP
In ternary or more complex compounds, the fractional ionicity
can be determined by using stoichiometrically weighted averages
Based on Periodic Trends in EN Based on Periodic Trends in EN cont d cont d
y g y g g
for the values of x
m
and/or x
nm
, ex.: In
4
Sn
3
O
12

It must be emphasized that the change from metallic to It must be emphasized that the change from metallic to
nonmetallic character is continuous and complex, so much so
that many authors would refute the apparently arbitrary binary
i i d fi d h f categorization defined thus far.
It is more common to define a third class of elements, the ,
metalloids, which straddle the metalnonmetal boundary (e.g.:
B, Si, Ge, As, Te, and Se).
Prof. M.L. Weaver
RECALL/REVIEW
Bonding Bonding Property Interrelationships Property Interrelationships
However, a binary classification is nevertheless implemented because it has the
practical advantage of leading to a simple set of rules to determine bond types.
O th b d t i d fi d th t f t i t t d ti th t th Once the bond type is defined, the type of atomic structure and properties that the
solid might have can also be inferred.
This is illustrated schematically:
When crossing metal-nonmetal
b d ti h
Prof. M.L. Weaver
boundary, properties change
dramatically with variation in
bonding:
CovalentvsIonicBonding CovalentvsIonicBonding
Thepolarityofacovalent
bondisthepartialionic
character
Realbondsliesomewhere
b t i i d l t betweenionicandcovalent
Thedifferencein
electronegativitycorresponds
directlytothepercentionic
characterofthebond