Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chapter 2 Outline
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Review of Atomic Structure
Electrons,
Protons,
Neutrons,
Quantum
mechanics, Electron states, The Periodic Table

Interatomic bonding
First step in understanding material properties
Atomic Bonding in Solids
Energies vs. Forces
Periodic Table
Primary Interatomic Bonds
Ionic
Covalent
Metallic
Secondary Bonding (Van der Waals)
Molecules and Molecular Solids
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Review of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons
Charges:
Electrons (-): protons(+) 1.6 10-19 Coulombs.
Neutrons are electrically neutral.

Masses:
Protons and Neutrons ~1.67 10-27 kg.
Electron 9.11 10-31 kg

Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons
chemical identification of element
Isotope number # neutrons
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic mass units. Atomic weight.

Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).
The atomic mass of

C atom is 12 amu.

12

Atomic weight: A
Weighted average of atomic masses of naturally
occurring isotopes.
Atomic weight of carbon is 12.011 amu.
Atomic weight is often in mass per mole.
A mole
Amount of matter with mass in grams equal to
the atomic mass in amu
(A mole of carbon has a mass of 12 grams).
One Mole contains Avogadros number of atoms,
Nav = 6.023 1023.
Nav = 1 gram/1 amu.
Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Some simple calculations

Number density, n: (number of atoms per cm3)
Mass density, (g/cm3)
Atomic mass, A (g/mol):
n = Nav / A
Graphite (carbon): = 2.3 g/cm3, A = 12 g/mol
n = 61023 atoms/mol 2.3 g/cm3 / 12 g/mol
= 1.15 1023 atoms/cm3
Diamond (carbon): = 3.5 g/cm3, A = 12 g/mol
n = 61023 atoms/mol 3.5 g/cm3 / 12 g/mol
= 1.75 1023 atoms/cm3
Water (H2O) = 1 g/cm3, A = 18 g/mol
n = 61023 molecules/mol 1 g/cm3 / 18 g/mol
= 3.3 1022 molecules/cm3
SIZE of a Atom or Molecule
If n = 6 1022 atoms/cm3
Mean separation between atoms L = (1/n)1/3 = 0.25 nm.
scale of atomic structure in solids a fraction of 1 nm
or a few Angstroms
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (I)

Electrons form a cloud
around the nucleus
Radius ~ 0.05 1nm.
Picture looks like a mini
planetary system.
But
Quantum Mechanics says
this analogy is not correct

Electrons orbits are 'fuzzy

Can only discuss probability of finding it at some distance
from the nucleus.
Only certain orbits or shells are allowed.
Shells identified by principal quantum number n,
n related to size of radius (and energy)
n = 1, smallest; n = 2, 3 .. are larger.
Second quantum number l, defines subshells.
Two more quantum numbers characterize states within
subshells.
University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (II)

Quantum Numbers came from solution of
Schrodingers equation
Pauli Exclusion Principle: only one electron can
have a given set of the four quantum numbers.
Maximum Number of Electrons in Shells and Subshells
Principal
Q. N., n
1 (l=0)
2 (l=0)
2 (l=1)
3 (l=0)
3 (l=1)
3 (l=2)
4 (l=0)
4 (l=1)
4 (l=2)
4 (l=3)

Subshells
s
s
p
s
p
d
s
p
d
f

Number
of States
1
1
3
1
3
5
1
3
5
7

Number of Electrons
Per Subshell Per Shell
2
2
2
8
6
2
18
6
10
2
32
6
10
14

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (III)

Subshells by energy: 1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,

Electrons fill levels in order of increasing energy

(only n, make a significant difference).
Example: Iron, Z = 26: 1s22s22p63s23p63d64s2
Outermost shell the valence electrons
responsible for bonding.
University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table

Elements in same column share similar properties.

Group number number of electrons available
for bonding
0: Inert gases (He, Ne, Ar...) filled subshells: chem. inactive
IA: Alkali metals (Li, Na, K) one electron in outer shell
eager to give up electron chem. active
VIIA: Halogens (F, Br, Cl...) missing one electron in outer
shell - want to gain electron - chem. active
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table - Electronegativity

Figure 2.7 from text

Electronegativity - how willing atoms are to
accept electrons
Subshells with one electron - low electronegativity
Subshells with one missing electron -high
electronegativity
Electronegativity increases from left to right
Metals are electropositive can give up their few
valence electrons to become positively charged ions
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Energies and Forces

Potential Energy, E

repulsion

0
attraction
equilibrium

Typical potential between two atoms

Repulsion when they are brought close together
Related to Pauli principle
(As electron clouds overlap energy increases)
Attractive part: at large distances
(Depends on type of bonding)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Energies and Forces

Potential Energy

a0

Ut=Ur+Ua

E0

a0

E0 bond energy
F= dE/da
a0 equilibrium distance
at a0, dE/da = 0, Fa = Fr

Force

Tensile
(+)

Compressive
(-)

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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

The electron volt (eV)

Energy unit convenient for atomic bonding
Electron volt
energy lost / gained when an electron is taken
through a potential difference of one volt.

E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt
1 eV = 1.6 x 10-19 J

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Types of Bonding
Primary Bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)
Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)
Covalent: electrons shared between the atoms.
Example - H2
Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material
Secondary Bonding: no e- transferred or shared
Interaction of atomic/molecular dipoles
Weak (< 100 KJ/mol or < 1 eV/atom)
Fluctuating Induced Dipole (inert gases, H2, Cl2)
Permanent dipoles (polar molecules - H2O, HCl...)
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (I)

Mutual ionization by electron transfer
(remember electronegativity table)
Anion = negatively charged atom
Cation = positively charged atom
Ions are attracted by strong coulombic interaction
Oppositely charged atoms attract
An ionic bond is non-directional

Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer
shell (Neon)
11 Protons Na 1S2 2S2 2P6 3S1
11 Protons Na+ 1S2 2S2 2P6

donates e10 e- left

Cl has 17 electron, 1 less than needed for a full outer shell

(Argon)
17 Protons Cl 1S2 2S2 2P6 3S2 3P5
17 Protons Cl- 1S2 2S2 2P6 3S2 3P6

receives e18 e-

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (II)

Na

e-

Cl

Na+

Cl-

Electron transfer reduces energy of the system

Na shrinks and Cl expands

Ionic bonds: very strong, nondirectional bonds

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (I)

Electrons shared between the atoms.

Valence electrons spend more time between
nuclei than outside bonding.
Covalent bonds- HIGHLY directional in direction of
greatest orbital overlap

Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5)
N = 7, 8 - N = 1 can form only one covalent bond

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (II)

Example: Carbon Zc = 6 (1S2 2S2 2P2)
N = 4, 8 - N = 4 can form up to four covalent
bonds
ethylene molecule:

polyethylene molecule:

ethylene mer

diamond:
(each C atom has four
covalent bonds with four
other carbon atoms)

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (III)

2-D schematic of the spaghetti-like structure
of solid polyethylene

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (IV)

Potential energy of system of

covalent bonds
P.E.=

Depend on distances between atoms

AND angles between bonds
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Metallic Bonding
Valence electrons are detached from atoms
Spread in an 'electron sea'
that "glues" the ions together
Metallic bond is non-directional atoms pack closely

Electron cloud from valence electrons

ion core

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (I)

Secondary = physical bond
(as opposite to chemical bond that involves e- transfer)
Interaction of dipoles
Is weak, ~0.1 eV/atom or ~10 kJ/mol.

-two dipoles attract

Permanent dipoles exist in some molecules

polar molecules: e.g. HCl, H2O
Due to asymmetry of positive and negative regions
Strongest among secondary bonds.
Polar molecule induces a dipole in adjacent non-polar
molecule.
Attraction between the permanent and induced dipoles.
Fluctuations of electron density distribution in one
atom A is felt by the electrons of an adjacent atom:
Mutual dipoles induced (van der Waals)
This bond is the weakest (He-Ne, H2 - H2).
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (II)

Example: hydrogen bond in water. The H end of the
molecule is positively charged and can bond to the
negative side of another H2O molecule (the O side of the
H2O dipole)

+
Dipole

Hydrogen bond secondary bond formed between

two permanent dipoles in adjacent water molecules.
University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (III)

Hydrogen bonding in liquid water
from a molecular-level simulation

Molecules: Primary bonds inside, secondary bonds

among each other
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Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (IV)

The Crystal Structures of Ice

Hexagonal Symmetry of Ice Snowflakes

Figures by Paul R. Howell

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (I)

Examples of bonding in Materials:

Metals: Metallic
Ceramics: Ionic / Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent / Ionic

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (II)

University of Virginia, Dept. of Materials Science and Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (III)
Make sure you understand language and concepts:

Atomic mass unit (amu)

Atomic number
Atomic weight
Bonding energy
Coulombic force
Covalent bond
Dipole (electric)
Electron state
Electronegative
Electropositive
Hydrogen bond
Ionic bond
Metallic bond
Mole
Molecule
Periodic table
Polar molecule
Primary bonding
Secondary bonding
Van der Waals bond
Valence electron

University of Virginia, Dept. of Materials Science and Engineering