Chapter 2

Atomic Structure

The University of Jordan

Chemical Engineering Department
First Semester 2022
Prof. Yousef Mubarak

1
Outline

1- Review of Atomic Structure

 Electrons, Protons, Neutrons.
 Atomic Bonding in Solids.
 Periodic Table.
 Primary Interatomic Bonds .
 Secondary Bonding (Van der Waals).
2- Molecules and Molecular Solids

2
Review of Atomic Structure

What are atoms?

 Atoms are the basic building blocks of
matter that make up everyday objects.
 Atoms are made out of three basic
particles:
1. Protons – carry a positive charge
2. Neutrons – carry no charge
 Protons and Neutrons join together to
form the Nucleus – the central part of the
atom
3. Electrons – carry a negative charge and
circle the nucleus
3
 The nucleus is the massive center of the atom. It was discovered in
1911, but it took scientists another 21 years of experimenting to
identify its parts.

4
5
Charges:
 Electron’s and Proton’s
charges are of the same
magnitude, 1.602 × 10-19
Coulombs.
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.

6
7
 Scientists thought there was
nothing smaller than the
proton in the nucleus of the
atom.

 Scientists discovered the

neutron in 1932. They
thought that there was
nothing smaller in the
atom’s nucleus?

8
 In 1968, scientists
discovered new particles
inside the proton. They
called these particles
quarks.

 There are three quarks in

each proton. The quarks
are held to each other by
other particles called
gluons.

9
 Electrons are extremely small and very
light.
 It is easy to strip off electrons of atoms
and use them for electrical power and in
devices like television sets.
 Electrons can be used to probe inside of
atoms. Higher energy electrons can
detect smaller features inside of atoms.
Scientists learn about the inside of atoms
by watching how electrons bounce off
the atom, and by how the atom changes
as a result of being hit by an electron.

10
Number of Atoms
 The number of atoms per cm3, n, for material of density d (g/cm3) and atomic
mass M (g/mol) is:
𝑁 𝑑
𝑛=
𝑀

where Nav is Avogadro’s number = 6.022  1023 atms/mol

 Mean distance between atoms

1
𝐿=
𝑛

Example:
Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol
n = (6 ×1023 atoms/mol × 3.5 g/cm3)/(12 g/mol)
= 17.5 × 1022 atoms/cm3
L = (1/(17.5 × 1022) )1/3 = 0.179 nm
11
Electrons in Atoms

 The electrons form a cloud around the nucleus, of radius of 0.05 – 2

nm.
 This “Bohr” picture looks like a mini planetary system. But
quantum mechanics tells us that this analogy is not Correct.

 Electrons move not in

circular orbits, as in popular
drawings, but in 'fuzzy'
orbits.

12
 One cannot tell how it moves, but only say what is the
probability of finding it at some distance from the nucleus.
 Valence electrons determine all of the following properties:
 Chemical.
 Electrical.
 Thermal.
 Optical.
 Each orbital at discrete energy level determined by quantum
numbers.

13
 The number of available electron states in some of the electron shells
and subshells
Principal Electrons
Shell Number Electrons
Quantum Subshells per
designation of States per Shell
number n Subshell
1 K S 1 2 2
2 L S 1 2
8
P 3 6
3 M S 1 2 18
P 3 6
D 5 10
4 N S 1 2
P 3 6
32
D 5 10
F 7 14
Subshells by energy:
1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,…

15
 Most elements: Electron configuration not stable.

16
Valence Electron

 Valence electrons – those in unfilled shells•

 Filled shells more stable.
 Valence electrons are most available for bonding and tend to
control the chemical properties.

Example: O (atomic number = 8)

17
The Periodic Table

 Electrons that occupy the outermost filled shell (the valence electrons)
they are responsible for bonding.
 Electrons fill quantum levels in order of increasing energy (due to
electron penetration).
 Example: Iron, Fe = 26: 1s22s22p63s23p63d64s2• 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.
18
19
The Electronegativity Values

 Electronegativity - a measure of 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 in the
periodic table.
 Metals are electropositive – they can give up their few
valence electrons to become positively charged ions.
 Electronegativity ranges from 0.7 to 4.0

20
21
22
 To calculate Pauling electronegativity for an element, it is
necessary to have data on the dissociation energies of at least
two types of covalent bond formed by that element.
 The difference in electronegativity between atoms A and B is
given by:

where:
The dissociation energies, Ed, of the A–B, A–A and B–B bonds are
expressed in electron volts, the factor (eV)−1/2 being included to
ensure a dimensionless result.

23
Example:

Calculate the difference in Pauling

electronegativity between hydrogen and
bromine if the dissociation energies: H–Br,
3.79 eV; H–H, 4.52 eV; Br–Br 2.00 eV.

Solution:

Note that 1 kcal/mol = 4.3363 10-2 eV

4.52 + 2.00
𝜒 − 𝜒 = 1.602 × 10 3.79 − × 1.602 × 10
2

𝜒 −𝜒 =0.728

24
Types of Bonding
Ionic

Primary Covalent

Metallic

Fluctuating induced dipole

Secondary Permanent dipole bond

Polar molecule-induced dipole

25
26
Ionic Bonding

Formation of ionic bond:

1- Mutual ionization occurs by electron transfer (remember
electronegativity table)
 Ion = charged atom
 Anion = negatively charged atom
 Cation = positively charged atom
2- Ions are attracted by strong columbic interaction
 Oppositely charged atoms attract
 An ionic bond is non-directional (ions may be attracted to
one another in any direction

27
Ionic Bonding

28
29
Ionic Bonding

 Electron transfer reduces the energy

of the system of atoms, that is,
electron transfer is energetically
favorable.
 Note relative sizes of ions: Na
shrinks and Cl expands

30
Ionic Bonding

31
Potential Energy

 In order for molecules to exist in aggregates in gases, liquids, or

solids, there must be forces that attract the molecules together.

𝐸 = 𝐸 +𝐸

32
Potential Energy
 When the repulsive and attractive forces are equal the
potential net energy is at a minimum and the system is stable.
Repulsive Forces
 The force is repulsive when the molecules are brought close
enough together that the outer charge clouds of the molecules
touch, and this causes the molecules to repel each other.
 The repulsive forces are necessary so that the molecules do not
destroy each other
Attractive Forces
 The forces that bring molecules together are called forces of
attraction.

33
Covalent Bonding

 A covalent bond is formed when electrons are shared between

atoms.
 Covalent bonds are between non-metals and non-metals or
hydrogen and non-metals.
 They share electrons so that both of them can have a stable octet.
 Covalent bonds are HIGHLY directional bonds.
 There are two types of covalent bonds:
1. Non-polar: result when two exact non-metals equally share
electrons.
2. Polar: result when two different non-metals share electrons.

34
Covalent Bonding

35
Covalent Bonding

36
Examples of Covalent Bonding

37
Naming Covalent Compounds

 Covalent compounds are much easier to name

than ionic compounds; Examples: No of Prefix
atoms
 P2O5 - diphosphorus pentoxide
1 Mono-
 CO - carbon monoxide 2 Di-
 CF4 - carbon tetrafluoride 3 Tri-
 Some important exceptions to this naming 4 Tetra-
scheme occur, examples: 5 Penta-
6 Hexa-
 H2O is "water"
7 Hepta-
 NH3 is "ammonia"
 CH4 is "methane“

38
What are the properties of covalent compounds

 Covalent compounds generally have much lower melting and

boiling points than ionic compounds.
 Covalent compounds are soft and squishy (compared to ionic
compounds).
 Covalent compounds tend to be more flammable than ionic
compounds.
 Covalent compounds don't conduct electricity in water.
 Like dissolves like. This means that compounds tend to dissolve in
other compounds that have similar properties (particularly
polarity).
 Since water is a polar solvent and most covalent compounds are
fairly nonpolar.
39
Metallic Bonds

 Metallic bonding occurs in metallic substances.

 Atoms of metals are held together in this structure by the
sharing effect of the electrons amongst all of the atoms.
 This forms a "sea" or a "cloud" of free electrons that floats
around the surface of metals.
 The crystal lattice of metals consists of ions NOT atoms
surrounded by a 'sea of electrons' forming another type of giant
lattice.

40
Metallic Bonds

 A metallic bond is non-directional (bonds form in any direction) →

atoms pack closely

41
Properties of Metallic Bonds
 The strong bonding generally results in dense, strong materials with
high melting and boiling points.
 Metals are good conductors of electricity because these 'free' electrons
carry the charge of an electric current when a potential difference
(voltage) is applied across a piece of metal.
 Metals are also good conductors of heat. This is also due to the free
moving electrons.
 Typical metals also have a silvery surface, but remember this may be
easily tarnished by corrosive oxidation in air and water.
 Unlike ionic solids, metals are very malleable, they can be readily bent,
pressed or hammered into shape. The layers of atoms can slide over
each other without fracturing the structure . The reason for this is the
mobility of the electrons
42
Secondary bonding - Intermolecular Forces

 Secondary, Van der Waals, or physical bonds are weak in comparison to the
primary bonds.
 Secondary bonding exists between virtually all atoms or molecules, but its
presence may be obscured if any of the three primary bonding types is present.
 Secondary bonding forces arise from atomic or molecular dipoles.
 An electric dipole exists whenever there is some separation of positive and
negative portions of an atom or molecule.
 The bonding results from the Coulombic attraction between the positive end of
one dipole and the negative region of an adjacent one
 Dipole interactions occur between:
1- Fluctuated induced dipoles.
2- Permanent dipole bond.
3- Polar molecule-induced dipole
43
Fluctuating induced dipoles

 Very weak electric dipole bonding can take place among atoms
due to an instantaneous asymmetrical distribution of electron
densities around their nuclei.
 This type of bonding is termed fluctuation since the electron
density is continuously changing.

44
Permanent dipoles

 Coulombic forces also exist between adjacent polar molecules.

 Weak intermolecular bonds are formed between molecules which
possess permanent dipoles.
 A dipole exists in a molecule if there is asymmetry in its electron
density distribution.

45
Polar molecules - induced dipole

 Polar molecules (with

asymmetric arrangement
of positively and
negatively charged
regions) can induce
dipoles in adjacent
nonpolar molecules

46
Hydrogen bonding

 Hydrogen bonding, a special type of secondary bonding, is found to exist

between some molecules that have hydrogen as one of the constituents.
 An intermolecular attraction between a partially positively charged hydrogen in
one molecule and a partially negatively charged oxygen, nitrogen, or fluorine in
a nearby molecule

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)

47
Type Bond Energy Comments
Ionic Large Nondirectional
(ceramics)

Covalent Variable Directional

Large-Diamond (semiconductors,
Small-Bismuth ceramics, polymer chains)

Metallic Variable Nondirectional

Large-Tungsten (metals)
Small-Mercury

Secondary Smallest Directional

Inter-chain
(polymer)
Inter-molecular

48
Bonding and materials properties

 Materials with large bonding energies usually have high melting

temperatures.
 There is a correlation between the magnitude of the bonding energy
and the state of materials
Solids have large bonding energies
Liquids tend to have relatively lower energies
 The expansion/contraction during heating/cooling of materials is
related to the shape of its E(r) curve.
 A deep and narrow ‘trough,’ which typically occurs for materials
having large bonding energies, usually imply a low coefficient of
thermal expansion.

49
Properties From Bonding: Tm

50
Properties From Bonding: Tm

51
Properties From Bonding: α

52
Example

For a K+ - Cl- ion pair, attractive and repulsive energies EA and ER,
respectively, depend on the distance between the ions r, according to

1.436 5.8 × 10
𝐸 =− and 𝐸 =
𝑟 𝑟
For these expressions, energies are expressed in electron volts per K+ -
Cl- pair, and r is the distance in nanometers. The net energy EN is just
the sum of the two expressions above. Determine:
(i) The equilibrium spacing r0 between the K+ and Cl- ions.
(ii) The magnitude of the bonding energy E0 between the two ions.

53