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Tri 3, 2017/18
Atomic Structure
• Each atom consists of a very small nucleus composed of protons
and neutrons, which is encircled by moving electrons.
• Electron - a negatively charged particles. (mass = 9.11 × 10−31 kg)
• Proton - a positively charged particles in the nucleus. Nucleus is a
dense central core within the atom. (mass = 1.67 × 10−27 kg)
• Neutron - an electrically neutral particles having a mass slightly
greater than that of protons.
Mass Number A
ZX
Element Symbol
Atomic Number
235 238
92 U 92 U
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Atomic Mass
The atomic mass (A) - the sum of the masses of protons and neutrons
within the nucleus.
The atomic weight of an element corresponds to the weighted average
of the atomic masses of the atom’s naturally occurring isotopes.
The atomic mass unit (amu) may be used for computations of atomic
weight.
A scale has been established whereby 1 amu is defined as 1/12 of the
atomic mass of the most common isotope of carbon, carbon 12 (12C)
(A = 12.00000).
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Atomic Mass
Setting the atomic mass of carbon-12 at 12 amu provides the standard
for measuring the atomic mass of the other elements.
For example:
• Experiments have shown that, on average, a hydrogen atom is only
8.400 percent as massive as the carbon-12 atom if the mass of one
carbon-12 atom is exactly 12 amu, the atomic mass of hydrogen must
be 0.084 × 12.00 amu or 1.008 amu.
• Similar calculations show that the atomic mass of oxygen is 16.00 amu
and that of iron is 55.85 amu.
Thus, although we do not know just how much an average iron atom’s
mass is, we know that it is approximately 56 times as massive as a
hydrogen atom.
• Referring to the periodic table, the atomic mass for a carbon is not
12.00 amu but 12.01 amu.
• Reason for the difference: carbon has more than one isotope.
• When measuring the atomic mass of an element, the average mass of
the naturally occurring mixture of isotopes must be considered.
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The Mole
• The atomic weight of an element or the molecular weight of a
compound may be specified on the basis of amu per atom
(molecule) or mass per mole of material.
Wave-Mechanical Model
An electron is no longer treated as a
particle moving in a discrete orbital.
Position is described by a probability
distribution or electron cloud.
Comparison of the (a) Bohr and (b) The first three electron
(b) wave-mechanical atom models energy states for the
in terms of electron distribution. Bohr hydrogen atom. 10
Quantum Numbers of an Atomic Orbital
Three quantum numbers are required to describe the
distribution of electrons in hydrogen and other atoms.
They are called the principle quantum number, the angular
momentum quantum number, and the magnetic quantum
number.
These quantum numbers will be used to describe atomic
orbitals and to label electrons that reside in them.
A fourth quantum number – the spin quantum number –
describes the behavior of a specific electron and
completes the description of electron in atoms.
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Schrodinger Wave(n,Equation
Quantum Numbers l, ml, ms)
Principal Quantum Number, n
n = 1, 2, 3, 4, …. (n can have integral values 1, 2, 3, and so forth)
The larger n is, the greater the average distance of an electron in the
orbital from the nucleus and therefore the larger the orbital.
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Quantum numbers: (n, l, ml, ms)
Angular Momentum Quantum Number, l
for a given value of n, l = 0, 1, 2, 3, … n–1
l=0 s orbital
n = 1, l = 0
l=1 p orbital
n = 2, l = 0 or 1
l=2 d orbital
n = 3, l = 0, 1, or 2
l=3 f orbital
The angular momentum quantum number (l) tells us the “shape” of the
orbitals.
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15
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Quantum Numbers of an Atomic Orbital
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4d
4p N-shell n = 4
3d
4s
Energy 3p M-shell n = 3
3s
2p L-shell n = 2
2s
1s K-shell n = 1
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Electron Configuration
• For many-electron atoms, we must know the electron configuration
of the atom, that is, how the electrons are distributed among the
various atomic orbitals, in order to understand electronic behavior.
• For this discussion, recall that the number of electrons in an atom is
equal to its atomic number Z.
• The electron in a ground-state hydrogen atom must be in the 1s
orbital, so its electron configuration is 1s1 :
Electron Configuration
• The electron configuration can also be represented by an orbital
diagram that shows the spin of the electron:
The upward arrow denotes one of the two possible
spinning motions of the electron.
Alternatively, we could have represented the electron
with a downward arrow.
The box represents an atomic orbital.
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The Pauli Exclusion Principle
For many-electron atoms we use the Pauli exclusion principle to
determine electron configurations.
This principle states that no two electrons in an atom can have the
same set of four quantum numbers.
If two electrons in an atom should have the same n, l, and ml values
(that is, these two electrons are in the same atomic orbital), then
they must have different values of ms.
Only two electrons may occupy the same atomic orbital, and these
electrons must have opposite spins.
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• Diagrams (a) and (b) are ruled out by the Pauli exclusion principle.
• In (a), both electrons have the same upward spin and would have the
quantum numbers (1, 0, 0, +½).
• In (b), both electrons have downward spins and would have the
quantum numbers (1, 0, 0, –½).
• Only the configuration in (c) is physically acceptable, because one
electron has the quantum numbers (1, 0, 0, +½) and the other has (1,
0, 0, –½).
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Hund’s Rule
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Electron Configurations
• Valence electrons – those that occupy the outermost shell, they
participate in the bonding between atoms to form atomic and
molecular aggregates.
• Filled shells more stable
• Valence electrons are most available for bonding and tend to control
the chemical properties
valence electrons
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Electronic Configurations
Example: Fe (Z = 26) 1s2 2s2 2p6 3s2 3p6 3d 6 4s2
4d
4p N-shell n = 4 valence
electrons
3d
4s
Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s
1s K-shell n = 1
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SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
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)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)
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accept 2e-
accept 1e-
give up 3e-
H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra
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Ionic Bonding
Ionic bond – metal + nonmetal
donates accepts
electrons electrons
Dissimilar electronegativities
Example: MgO
Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4
[Ne] 3s2
Na (metal) Cl (nonmetal)
unstable unstable
electron
Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
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Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
−
A +
B
EN = EA + ER =
r rn
Repulsive energy ER
Interatomic separation r
Net energy EN
Attractive energy EA
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Ionic Bonding
Ionic bonding is termed
nondirectional - the magnitude of
the bond is equal in all directions
around an ion.
For ionic materials to be stable, all
positive ions must have as nearest
neighbors negatively charged ions
in a three-dimensional scheme, and
vice versa.
Bonding energies is large and
generally range between 600 and
1500 kJ/mol.
Ionic solids have high melting
temperatures.
Hard, rigid, strong and brittle.
Excellent Insulators.
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Covalent Bonding
• Similar electronegativity ∴ share electrons
• Stable electron configurations are assumed by the sharing
of electrons between adjacent atoms.
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms
F + F F F F F
H
O + O O O O=O
N + N N N N N
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Metallic Bonding
• Found in metals and their alloys.
• Atoms in metals are closely packed in crystal structure.
• Loosely bounded valence electrons are attracted towards
nucleus of other atoms.
• Electrons spread out among atoms forming electron clouds.
• These free electrons are reason for electric conductivity and
ductility.
• Since outer electrons are shared by many atoms, metallic
bonds are Non-directional.
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Metallic Bonding
• Pure metals are significantly more malleable than ionic or
covalent networked materials.
• At room temperature, most metals and their alloys fail in a
ductile manner (fracture occurs after the materials have
experienced significant degrees of permanent deformation).
• Strength of a pure metal can be significantly increased
through alloying.
• Pure metals are excellent conductors of heat and electricity.
42 42
SECONDARY BONDING
• Secondary bond or van der Waals (physical) bond is weak in
comparison to the primary (chemical) bonds, with lower bonding
energy.
• Secondary (or intermolecular) bonds are possible between atoms or
groups of atoms, which themselves are joined together by primary (or
intramolecular) ionic or covalent bonds.
• 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 induced dipoles, between induced
dipoles and polar molecules (which have permanent dipoles), and
between polar molecules.
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Hydrogen bonding in
hydrogen fluoride (HF).
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Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Ionic-Covalent Mixed Bonding
• The degree of either bond type depends on the relative
positions of the constituent atoms in the periodic table or the
difference in their electronegativities.
• The greater the difference in electronegativity, the more ionic is
the bond.
• Percent ionic character (% IC) of a bond between elements A
and B (A being the most electronegative) can be approximated:
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Mixed Bonding
Example: MgO XMg = 1.2
XO = 3.5
−
( 3.5 −1.2 )2
% ionic character = 1 − e 4
x (100%) = 73.4% ionic
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Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Metallic-Covalent Mixed Bonding
• Commonly found for some elements in Groups IIIA, IVA, and VA
of the periodic table (viz., B, Si, Ge, As, Sb, Te, Po, and At).
• These materials are called the metalloids or semi-metals, and
their properties are intermediate between the metals and
nonmetals.
• For Group IV elements, there is a gradual transition from
covalent to metallic bonding as one moves vertically down this
column (bonding in carbon (diamond) is purely covalent,
whereas for tin and lead, bonding is predominantly metallic).
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Mixed Bonding
• Mixed bonding are found for many real materials, the atomic
bonds are mixtures of two or more bonding types.
Metallic-ionic Mixed Bonding
• Usually for compounds composed of two metals when there is
a significant difference between their electronegativities.
• Some electron transfer is associated with the bond inasmuch as
it has an ionic component.
• The larger this electronegativity difference, the greater the
degree of ionicity.
• For example, there is little ionic character to the titanium–
aluminum bond for the intermetallic compound TiAl3 because
electronegativities of both Al and Ti are the same (1.5).
• A much greater degree of ionic character is present for AuCu3;
the electronegativity difference for copper and gold is 0.5.
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