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Chapter 2: Atomic Structure &

Atomic Structure (Freshman Chem.)
Interatomic Bonding
• atom – electrons – 9.11 x 10-31 kg
protons
ISSUES TO ADDRESS...
}
neutrons 1.67 x 10 kg
-27

• atomic number = # of protons in nucleus of atom

• What characteristics of atoms/molecules = # of electrons in neutral species
promote interatomic/intermolecular bonding?
• atomic mass unit = amu = 1/12 mass of 12C
• What types of interatomic/intermolecular
bonds exist ? A = Atomic wt = wt of 6.022 x 1023 molecules or atoms
• What properties of materials depend on the 1 amu/atom = 1 g/mol
magnitude of interatomic/intermolecular bonds ?
C 12.011
H 1.008
etc.
Chapter 2 - 1 Chapter 2 - 2

Atomic Structure (cont.) Electronic Structure

• Electrons have wave-like and particle-like
• Some of the following properties are
characteristics.
determined by an atom's electronic structure:
• Two wave-like characteristics are
1) Chemical – Electron position in terms of probability density
2) Electrical – shape, size, orientation of probability density
3) Thermal determined by quantum numbers
4) Optical
– Quantum # Designation/Values
n = principal (shell) K, L, M, N, O (1, 2, 3, 4, etc.)
l = azimuthal (subshell) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic (no. of orbitals) 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

Chapter 2 - 3 Chapter 2 - 4

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Electron Energy States SURVEY OF ELEMENTS

Electrons... • Most elements: Electron configurations not stable.
• have discrete energy values Element Atomic # Electron configuration
• tend to occupy lowest available energy states Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
4d Lithium 3 1s 2 2s 1
4p N-shell n = 4 Beryllium 4 1s 2 2s2
Boron 5 1s 2 2s 2 2p 1
3d Carbon 6 1s 2 2s 2 2p 2
... ...
4s Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
3p M-shell n = 3 Magnesium 12 2 2
1s 2s 2p 3s 6 2
Energy
3s 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)
2p L-shell n = 2 ... ... ...
2s Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

1s
• Why not stable? Valence (outer) shell usually not
K-shell n = 1
completely filled.
Chapter 2 - 5 Chapter 2 - 6

Electron Configurations Electronic Configurations (cont.)

ex: Fe (atomic # = 26)
• Valence electrons – those in outer unfilled
shells Electron configuration 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
• Filled shells are more stable – require more 4d
energy to gain or lose electrons 4p N-shell n = 4 valence
• Valence electrons available for bonding and 3d
electrons

tend to determine an atom’s chemical properties 4s

– example: C (atomic number = 6) Energy 3p M-shell n = 3

3s

1s2 2s2 2p2 2p L-shell n = 2

valence electrons 2s

1s K-shell n = 1
Chapter 2 - 7 Chapter 2 - 8

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The Periodic Table Electronegativity

• Elements in each column: Similar valence electron structure • Ranges from 0.7 to 4.0,

inert gases
give up 1e-

• Large values: tendency to acquire electrons.

give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Smaller electronegativity Larger electronegativity

Electropositive elements: Electronegative elements:
Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
Chapter 2 - 9 Chapter 2 - 10

Ionization Process Ionic Bonding

• Occurs between + and - ions.
metal atom + nonmetal atom • Requires electron transfer.
• Large difference in electronegativity required.
donates accepts • Example: NaCl
electrons electrons
Na (metal) Cl (nonmetal)
Dissimilar electronegativities unstable unstable
ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4 electron
[Ne] 3s2
Na (cation) + - Cl (anion)
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6 stable stable
Coulombic
[Ne] [Ne] Attraction

Chapter 2 - 11 Chapter 2 - 12

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Ionic Bonding (cont.) Ionic Bonding (cont.)

• Energy – minimum energy most stable Predominant bonding in Ceramics
Examples:
– Net energy = sum of attractive and repulsive energies NaCl
– Equilibrium separation when net energy is a minimum MgO
EN = EA + ER = - A + Bn CaF 2
r r CsCl
Repulsive energy ER

Interatomic separation r

Net energy EN
Fig. 2.10(b), Callister &
Rethwisch 5e.
Give up electrons Acquire electrons
Attractive energy EA

Chapter 2 - 13 Chapter 2 - 14

Covalent Bonding Covalent Bonding: Bond Hybrization

• Similar electronegativities  share electrons
• Carbon can form sp3 hybrid
• Bonds involve valence electrons – normally s and p orbitals
orbitals are involved
• Example: H2
H2

Each H: has 1 valence e-,

needs 1 more
H H
Electronegativities
are the same.
shared 1s electron shared 1s electron
from 1st hydrogen from 2nd hydrogen Fig. 2.14, Callister & Rethwisch 5e.
atom atom (Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Fig. 2.12, Calliser & Rethwisch 5e.

Fig. 2.13, Callister & Rethwisch 5e.
Chapter 2 - 15 Chapter 2 - 16

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Covalent Bonding (cont.) Metallic Bonding

Hybrid sp3 bonding involving carbon • Electrons delocalized to form an “electron cloud”

Example: CH4
C: each has 4 valence electrons,
needs 4 more
H: each has 1 valence electron,
needs 1 more

Electronegativities of C and H
are similar so electrons are
shared in sp3 hybrid covalent
bonds.
Fig. 2.15, Callister & Rethwisch 5e.
(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with Fig. 2.19, Callister & Rethwisch 5e.
permission of John Wiley and Sons, Inc.)

Chapter 2 - 17 Chapter 2 - 18

Mixed Bonding Secondary Bonding

• Most common mixed bonding type is Covalent-Ionic Arises from attractive forces between dipoles
mixed bonding • Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2
% ionic character = x (100%)
+ - + - H H H H
secondary secondary
where XA & XB are electronegativities of the two bonding bonding
elements participating in the bond
• Permanent dipoles
Ex: MgO XMg = 1.3 secondary
XO = 3.5 -general case: + - bonding
+ -

æ -
(3.5-1.2)2 ö
-ex: liquid HCl H Cl
secondary
H Cl
% ionic character = çç1- e 4 ÷ x (100%) = 73.4%
÷
bonding
è ø
-ex: polymer
linear polymer molecule
Chapter 2 - 19 Chapter 2 - 20

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Properties Related to Bonding I: Properties Related to Bonding II:

Melting Temperature (Tm) Coefficient of Thermal Expansion (αl)
• Coefficient of thermal expansion, αl
• Bond length, r • Melting Temperature, Tm length, L o ΔL
Energy = αl (T2 -T1)
unheated, T1 Lo
r ΔL
heated, T 2
• Bond energy, Eo ro
r The smaller Eo, the larger αl.
Energy smaller Tm
unstretched length • Increase in bond length is due to

Energy
unstretched length ro asymmetry of the E vs. r curve. This
ro larger Tm
r r results in an increase in al.
Eo = larger αl • As E0 increases this asymmetry
The larger Eo, the higher Tm. E
decreases.
“bond energy” o
E smaller αl
Chapter 2 - 21 o Chapter 2 - 22

Summary: Properties Related to

Bonding Type and Bonding Energy SUMMARY
• A material’s chemical, electrical, thermal, and optical
Ceramics Large bond energy properties are determined by electronic configuration.
(Ionic & covalent bonding): high Tm • Valence electrons occupy the outermost unfilled
large E
small αl
electron shell.
• Primary bonding types include covalent, ionic, and
Metals Variable bond energy metallic bonding.
(Metallic bonding): moderate Tm • Secondary or van der Waals bonds are weaker than
moderate E the primary bonding types.
moderate αl
• The percent ionic character of a covalent-ionic mixed
bond between two elements depends on their
Polymers Weak bond energy (between chains) electronegativities.
(Covalent & Secondary): Secondary bonding responsible for
most physical properties
low Tm
small E
large αl
Chapter 2 - 23 Chapter 2 - 24