Chapter 2 Atomic Bonding

Chapter Outline
✓ Review of Atomic Structure
✓ Atomic Bonding in Solids
✓ Primary Interatomic Bonding
✓ Secondary Bonding
✓ Materials – The Bonding Classification

Understanding of interatomic bonding is the first step towards understanding/explaining materials properties... but
first… the structure within the individual atoms should be understood.

Atoms = nucleus (protons and neutrons) + electrons

✓ # of protons = determines the atomic number
✓ # of neutrons = defines isotope number when added to the #
of proton.
Masses:
✓ Protons and Neutrons have the same mass, 1.67 × 10 -27 kg.
✓ Mass of an electron is much smaller, 9.11 × 10-31 kg, and
can be neglected in calculation of atomic mass.
✓ The atomic mass (A) = mass of protons + mass of neutrons

Charges Figure 2-1 Schematic of the planetary model of a C12 atom

While chemical identification is done relative to the nucleus, atomic bonding involves electrons.
✓ Electrons and protons have negative and positive charges of the same magnitude, 1.6 × 10 -19 Coulombs;
Neutrons are electrically neutral; Therefore, atoms are electrically neutral.

Electrons in Atoms
Quantum Mechanics: A branch of physics that deals with atomic and subatomic systems; it allows only discrete
values of energy that are separated from one another.
Bohr Atomic Model: An early atomic model, in which electrons are assumed to revolve around the nucleus in
discrete orbitals. The electrons form a cloud around the nucleus, of radius of 0.05 – 2 nm.
This model looks like a mini planetary system but quantum mechanics tells us that this analogy is not correct:
Electrons move not in circular orbits, but in 'fuzzy‘ orbits. We cannot tell how it moves, but can only say the
probability of finding it at some distance from the nucleus.
Wave-mechanical model: electrons are considered to be wave-like and treat electron position in terms of a
probability distribution.

Quantum numbers: a set of four numbers, the values of which are used to label possible electron states. Three of
the quantum numbers (n, l, m1) are integers, which also specify the size, shape, and spatial orientation of an
electron’s probability density; the fourth number (m2) designates spin orientation.
Electron state (level): One of a set of discrete, quantized energies that are allowed for electrons. In the atomic case,
each state is specified by four quantum numbers.

n (principal quantum number)

✓ sometimes designated by the letters K, L, M, N O, and so on, corresponding to n = 1, 2, 3, 4, 5...
✓ associated with the Bohr model
✓ is related to the distance of an electron from the nucleus, or its position.
l (second quantum number)
✓ signifies the subshell and is related to the shape of the electron subshell.
✓ is denoted by a lowercase letter – an s, p, d, or f
✓ the number of these subshells is restricted by the magnitude of n.
ml (third quantum number)
✓ determines the number of energy states for each subshell
 ✓ 1, 3, 5 and 7 states exist for s, p, d and f subshells, respectively.
ms (fourth quantum number)
✓ is related to the spin moment which is oriented either up or down.
✓ Two values are possible (+1/2 and -1/2), one for each of the spin orientations.

The number of available electron states in some of the electron shells and subshells Fig. The relative energies of the electrons
for the various shells and subshells.
Features of the diagram:
1) the smaller the principal quantum number, the lower the energy level; for example, the energy of a 1s state is less than
that of a 2s state, which in turn is lower than the 3s.
2) the energy of a subshell level increases with the value of the l quantum number. For example, the energy of a 3d state is
greater than a 3p, which is larger than 3s.
3) there may be overlap in energy of a state in one shell with states in an adjacent shell, which is especially true of d and f
states; for example, the energy of a 3d state is greater than that for a 4s.

Periodic Table of Elements

Periodic table of the elements indicating

atomic number and atomic mass (in amu).

Elements in the same column (Elemental Group) share similar properties. Group number indicates the number of
electrons available for bonding.
0: Inert gases (He, Ne, Ar...) have filled subshells - chemically inactive
IA: Alkali metals (Li, Na, K…) have one electron in outermost occupied s subshell - eager to give up electron -
chemically active
VIIA: Halogens (F, Br, Cl...) missing one electron in outermost occupied p shell - want to gain electron - chemically
active

Periodic Table: Electronegativity

The nature of the chemical bonds between atoms of the same element and atoms of different elements depends on the
transfer or sharing of electrons between adjacent atoms.
✓ Electronegativity - the ability of an atom to attract electrons to itself.
✓ Subshells with one electron - low electronegativity
 ✓ Subshells with one missing electron - high electronegativity
✓ Electronegativity increases from left to right
✓ Metals are electropositive (Lower values of electronegativity) – they can give up their few valence
electrons to become positively charged ions
✓ Non-metals – Higher values of electronegativity

Fig. The electronegativity

values for the elements.

Types of Bonding

Primary bonds (Chemical bond)

1) Ionic - involves electron transfer from one atom to another (Mutual ionization occurs); attractive force is
coulombic in nature; non-directional (e.g.:ceramics; insulator)
✓ Ion = charged atom, Anion = negatively charged atom, Cation = positively charged atom
✓ Coulomb attraction: The electrostatic force of attraction exerted by one charged particle on another charged
particle of opposite sign. a.k.a. electrostatic attraction.

Fig 2.4 Ionic bonding between sodium and chlorine

Ionic bonds are very strong, nondirectional bonds. atoms. Electron transfer from Na to Cl creates a cation
Characteristics of ionic materials: Hard, Brittle, Electrically (Na+) and an anion (Cl−). The ionic bond is due to the
and thermally insulative. coulombic attraction between the ions of opposite charge.

2) Covalent - involves electron sharing between neighboring atoms to saturate the valency; highly directional (e.g.:
polymers; insulator). The simplest example is the H2 molecule, where the electrons spend more time in between the
nuclei than outside, thus producing bonding. (e.g.: polymers: insulator).

Fig. The covalent bond in a molecule of chlorine gas, Cl2,

is illustrated with (a) planetary model (b) the actual
electron density (c) an electron-dot schematic (d) a bond-
line schematic.
 Double bond: covalent sharing of
two pairs of valence electrons.

`
(a) (b) Polymeric molecules (structural basis of polymers)
Figure 2-14 (a) An ethylene molecule (C2H4) is compared with (b) a polyethylene molecule (C2H4) n that results
from the conversion of the C=C double bond into two C-C single bonds.

Fig. 2-D schematic of the “spaghetti-like” structure of solid polyethylene

- The straight lines between C and C and between C and H represent strong, covalent bonds.
- Only weak, secondary bonding occurs between adjacent sections of the long molecular
chains.
- It is this secondary bonding that is the “weak link” that leads to the low strengths and low
melting points for traditional polymers.

3) Metallic - involves electron sharing with all atoms in the material; non-directional; (e.g.: metals)
✓ The valence electron are said to be delocalized electrons.
✓ they have an equal probability of being associated with any of a large number of adjacent atoms.
✓ Valence electrons are detached from atoms, and spread in an 'electron sea' that "glues" the ions
together.  high electrical conductivity.

Figure 2-20 Metallic bond consisting of an electron

cloud, or gas. An imaginary slice is shown through the
front face of the crystal structure of copper, revealing
Cu2+ ion cores bonded by the delocalized valence
electrons.

Secondary Bonding (Physical bond)-van der Waals

It is possible to obtain some atomic bonding with substantially smaller bonding energies without electron transfer or
sharing
✓ Similar to ionic bonding (attraction of opposite charges) but no electrons are transferred
✓ Attraction depends on asymmetrical distributions of positive and negative charges within each atom or
molecular unit being bonded (Dipole)
✓ Bonding results from interaction of atomic or molecular dipoles
✓ Bonding is weak

• Dipole: a pair or equal yet opposite electrical charges that are separated by a small distance.

Hydrogen Bond: is a special type of secondary bonding. Hydrogen bonds are chemical bonds that form between
molecules containing a hydrogen atom bonded to a strongly electronegative atom (an atom that attracts electrons).
Because the electronegative atom pulls the electron from the hydrogen atom, the atoms form a very polar molecule,
meaning one end is negatively charged and the other end is positively charged. Hydrogen bonds form between these
molecules because the negative ends of the molecules are attracted to the positive ends of other molecules, and vice
versa. Hydrogen bonding makes water form a liquid at room temperature.
 Figure 2-23 Hydrogen bridge. This secondary bond is formed
between two permanent dipoles in adjacent water molecules.
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).

Secondary (van der Waals) bonding mechanisms

a) Fluctuating Induced dipole: Example: Argon (Noble gas): Does not tend to form primary bonds because it has a
stable, filled outer orbital shell. Weakest secondary bonding.
Isolated argon – has a perfectly spherical distribution of
negative electrical charge surrounding its positive nucleus.
When another argon atom is brought nearby, the negative
charge is drawn slightly toward the positive nucleus of the
adjacent atom. The degree of charge distortion related to
an induced dipole is small, the magnitude of the resulting
dipole is small, leading to a relatively small bond energy.
b) Polar Molecule-Induced dipole bond: Polar molecules: a polar molecule in which there is a permanent electric
dipole moment by virtue off the asymmetrical distribution of positively and negatively charged regions.
c) Permanent dipole bond: Permanent dipole moments exist in some molecules (called polar molecules) due to the
asymmetrical arrangement of positively and negatively charged regions (HCl, H 2O). Bonds between adjacent polar
molecules – permanent dipole bonds – are strongest among secondary bonds. (Pls. see hydrogen bond above)

Materials – The Bonding Classification

Bonding Character of the Four Fundamental Types of Engineering Materials
Material Type Types of Bonds Example
Metals Metallic Iron (Fe) and the ferrous alloys
Ceramics and Glasses Ionic/covalent Silica (SiO2): crystalline and noncrystalline
Polymers Covalent and Secondary Polyethylene (C2H4)
Semiconductors Covalent or covalent/ionic Silicon (Si) or cadmium sulfide (CdS)