Chapter 1

Compositions of Atoms and

Periodic Table
1.1. History of atomic
composition
• In the fifth century the Greek philosopher Democritus expressed
his belief
• All matter consists of very small and indivisible particles, named
atoms
• The Democritus was not accepted by contemporaries

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 In 1808, John Dalton (English scientist school teacher)
proposed his atomic theory. Danton’s work marked the
beginning of modern era of chemistry
• All matter consists of extremely small and
indivisible particles called atoms
• All atoms of a given element are identical,
having the same size, mass and chemical
properties
• Atoms of one element are different from
atoms of other elements
• Atoms cannot be destroyed

He had no idea about what an atom

is really like, and no attempt to
describe the structure or John Dalton (1766-1844)
composition of atoms 7|8
From the beginning of 1850s to the 20th century a
series of investigations were performed

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Atomic Theory Timeline

Scientist Information Model

John All matter is made of atoms.

Dalton Atoms are too small to see,
(1808) indivisible and
indestructible. All atoms of a
given element are identical.
Atomic Theory Timeline

 From these results, Rutherford explained that

+ Most  particles passed through the gold foil
(undeflected), the atoms are mostly open space
+ The large deflections of few  particles could be caused
by a center of concentrated positive charge that
contains most of the atom’s mass.
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Atomic Theory
Atomic TheoryTimeline
Timeline

Scientist Information Model

Ernest Discovered the nucleus of an atom
Rutherford and named the positive particles in
(1911) the nucleus “protons”. Concluded
that electrons are scattered in empty
space around the nucleus.
Atomic Theory Timeline
Atomic Theory Timeline
Scientist Information Model
Neutrons

James Discovered that neutrons were also

Chadwick located in the nucleus of an atoms and
(1932) that they contain no charge.
 Atomic Theory Timeline
Atomic Theory Timeline

Scientist Information Model

Neils Concluded that electrons are

Bohr located in planet-like orbits
(1913) around the nucleus in certain
energy levels.
Atomic Theory Timeline

Scientist Information Model

(Many Scientists!) Electrons do not orbit the
The Modern
Atomic Theory nucleus in neat planet-like
orbits but move at high
speeds in an electron cloud
around the nucleus.
1.2. Composition of atoms
• Atoms actually possess internal structure
• Atoms consist of three fundamental particles called
subatomic particles: electrons, protons and neutrons
• Atoms are electrically neutral and contain an equal number
of positive and negative charges.

Particle Mass (g) Charge, C

Electron 9.1x10-28 ≈ 0.055u -1.6x10-19
Proton 1.672x10-24 ≈ 1u +1.6x10-19
Neutron 1.674x10-24 ≈ 1u 0
• u (unified atomic mass unit); 1u=1/(12 M(12C))

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 Atomic number, mass number
•The number of protons in the nucleus (of each
atom) is equal to the number of electrons.
•The number of protons is a basic property of an
element, called atomic number and assigned to Z
•The mass number (A) is the total number of
neutrons and protons present in the nucleus of an
atom. Except for hydrogen (one proton, no
neutron)

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1.3. Theory of atoms composition

1.3.1. Bohr Theory

(1) Electrons in an atom can only occupy
certain orbits (corresponding to certain
energies).
(2) Electrons in permitted orbits have
specific, “allowed” energies;

RH RH- Rydberg constant

En   2 (RH = 2.18x10-18 J)
n
The energy of the electron only depends on n
The energy receives only the discrete values
n=1, electron in the ground state or ground
level
1.3.1. Bohr Theory
(3) Energy is only absorbed or emitted in
such a way as to move an electron from
one “allowed” energy state to another.
When an electron is promoted from a
lower energy to a higher one it absorbs a
definite amount of energy. When it falls
back to the lower energy level, it emits
the same amount of energy. The energy
absorbed or emitted depends on the
frequency of the radiation:
E = E2-E1 = hν = h.C/λ (1.1)’
Where: C - velocity of light
h - constant of Planck (6.626x10-34 J.s)
The subscripts 1 and 2 denote the initial and
final state

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1.3.1. Bohr Theory
Bohr’s theory allows to explain the line spectrum of
the hydrogen
- When an hydrogen electron in an excited state with
n = 2, 3, 4,… falls back to a lower energy level, it
gives off energy as a photon of light
- This transition process is called emission
- Each transition of the electron from a higher energy
level to a lower gives one line corresponding a
specific wavelength of light in the emission
spectrum of hydrogen

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The application of Bohr’s theory
 The application of Bohr’s theory
Tab 1.2. The various series in atomic hydrogen
emission spectrum

Series nf ni Spectrum
region
Lyman 1 2,3,4, … Ultraviolet

Balmer 2 3, 4, 5,… Visible and

ultraviolet
Paschen 3 4, 5, 6,… Infrared
 The results and limitations of the atomic
theory of Bohr’s

1. The Bohr theory satisfactorily explained the

spectra of hydrogen and other species having one
electron (He+, Li2+)
2. Could not explain the spectra of more complex
species
3. The theory of Bohr’s could not mention in wave
nature of the electron, so the Bohr assumption of
circular orbits of the electron in the atom was failed
 The classical mechanics could not solve a problem
with small particles. To deal with this problem, it is
necessary to use a new physics, quantum mechanics
1.3.2. The principles of quantum mechanics
1. Wave- particle duality of matter and radiation
1887-1927 experiments were done.
Light as a wave
Light (electromagnetic radiation) is the periodic
variation of an electric field
An electromagnetic wave can be characterized by
means of:
- Wavelength (): the distance between two
adjacent identical points of the wave
- Frequency (υ): the number of wave crests passing
a given point per unit time (1/s)
1.3.2. The principles of quantum mechanics

For a wave, traveling at some speed, the wavelength and the

frequency are related to each other by:
υ= c= 2.997x108 m/s
1.3.2. The principles of quantum mechanics
Light as a particle
The photoelectric effect
A beam of light hitting a metal surface can eject electrons
Ei < ϕ Ei ≥ ϕ K.E = Ei - ϕ

Metal

The energy of an incoming photon (Ei) must be equal or greater

than the work function of the metal in order to eject an electron)

Einstein taught us that both descriptions (wave and particle) can

coexist without a contradiction
1.3.2. The principles of quantum mechanics
2. The wave nature of the electron
 In 1924 Louis De Brogie (PhD thesis, Nobel Prize
1929) postulated that just as light has wave-like and
particle-like properties, matter (electrons) must also
be both wave-like and particle-like properties
 The motion of any microparticle can be regarded
as a wave process with a certain wavelength:

h
λ  (1.2)
mv
1.3.2. The principles of quantum mechanics
Later the prediction of de Broglie was confirmed by
Clinton Davisson and Lester Germer (Found the diffraction
of electrons by a Ni crystal)
Similar diffraction experiments have been observed with
other micropartilces: protons and neutrons
- Whether the de Broglie equation is true for every moving
particle or not ?
* Calculate the wavelength of an electron traveling at
1.24x107 m/s. me = 9.1x10-31 kg (λ = 5.87x10-11m)
* Calculate the wavelength of a baseball of mass 149g
traveling at 41.3m/s (λ = 1.08x10-34m)
* Wave properties of macroparticles can be rejected
- Electrons have both wavelike and particlelike properties
- If particles like e have wave properties what is the
equation of the motion of an e?
1.3.2. The principles of quantum mechanics
3. The uncertainty principle
One of the underlying principles of quantum mechanics
Given in 1927 by Heisenberg that is consistent with the
experimental observations
Statement:
It is impossible to determine accurately both the position
and the velocity of an electron (or any other small particle)
simultaneously. The mathematical expression is:

h
Δx.Δvx  (1.3)
m
1.3.2. The principles of quantum mechanics
4. The quantum mechanics picture of the atom
a. Wave function
The wave function is different for various points of
atomic space. Mathematically it is written as the
equality  = (x,y,z), Where x, y, z are the co-ordinates
of a point
+ Its square 2 characterises the probability of
finding the electron at a definite point in atomic space
+ The value of 2 dV is the probability of finding the
electron in an element of volume dV
1.3.2. The principles of quantum mechanics
b. Schrodinger equation
1927 Erwin Schrodinger wrote an equation of motion
for particles (like electrons) that account for their
wave-like properties.

(1.4)

E is the full energy of the electron;

H is Hamiltonian operator
Ψ- wavefunction (describes the particles)
For the H atom, where the potential energy is a function of
one distance variable, r

It simplifies the equation to use the spherical polar coordinates.

The wavefunction of the electron in an H is written as a function
of r, θ , Ф: ψ (r, θ , Ф)
1.3.3. The quantum mechanics picture of the atom
1.3.3. The solution of the Schrodinger equation for
H atom
1. The binding energy En of the electron to the nucleus
for H atom:

(J) = -13.6/n2 (eV)

n – integer, 1, 2, 3…

Key idea: binding energy can be quantized

The principle quantum number n, come out of
solving the Schrödinger equation.
Note:
- All binding energies are negative
- Negative energy means that the electron is
bound to the nucleus.
- At n= , En = 0, the e- is free from the nucleus
- The lowest (most negative) energy is called
the ground state
+ The ground state is the most stable state
+ The ground state is the n =1 state
2. The 2nd result is wave function

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3. The meaning of quantum numbers
• According to quantum mechanics, each electron is
described by four quantum numbers:

• 1. Principal quantum number (n)

• 2. Angular momentum quantum number (l)
• 3. Magnetic quantum number (ml)
• 4. Spin quantum number (ms)

• The first three define the wave function for a

particular electron. The fourth quantum number
refers to the magnetic property of electrons.
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7 | 40
a. Principal Quantum Number, n
•This quantum number is the one on which
the energy of an electron in an atom
primarily depends. The smaller the value of
n, the lower the energy and the smaller the
orbital.

•The principal quantum number can have any

positive value: 1, 2, 3, . . ., ∞

•Orbitals with the same value for n are said to

be in the same shell (each value of n indicate
the shell of electron in the atom).

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• Shells designated by uppercase letters:

Shell K L M N O P Q ...
n 1 2 3 4 5 6 7

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b. Angular Momentum Quantum Number, l
• This quantum number distinguishes orbitals of a
given n (shell) having different shapes.

• It can have values from 0, 1, 2, 3, . . . to a maximum

of (n – 1).

• For a given n, there will be n different values of l, or

n types of subshells.

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• Subshells are sometimes designated by lowercase letters:

l 0 1 2 3 ...
Subshell s p d f

•Orbitals with the same values for n and l are said to be

in the same shell and subshell.

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c. Magnetic Quantum Number, ml

•The magnetic quantum number depends on

the value of l and can have any integer value
from –l to 0 to +l. Each different value
represents a different orbital. For a given
subshell (l), there will be (2l + 1) values of ml,
and therefore (2l + 1) orbitals.
•This quantum number distinguishes orbitals of
a given n and l—that is, of a given energy and
shape but having different orientations.

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•Let’s summarize:
•When n = 1, l has only one value, 0.

•When l = 0, ml has only one value, 0.

•So the first shell (n = 1) has one subshell,
an s-subshell, 1s. That subshell, in turn,
has one orbital.

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•When n = 2, l has two values, 0 and 1.

- When l = 0, ml has only one value, 0. So

there is a 2s subshell with 1 orbital (2s).

-When l = 1, ml has only three values, -1, 0,

+1. So there is a 2p subshell with three
orbitals.
- So, the shell L (n=2) has 1+3=4 orbitals (4
AO)
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•When n = 3, l has three values, 0, 1, and 2 (there
are 3 subshell in this shell: 3s, 3p, and 3d).

- When l = 0, ml has only one value, 0. So there is 1

subshell (3s) with 1 orbital.
- When l = 1, ml has three values, -1, 0, +1. So there
is a 3p subshell with three orbitals.
- When l = 2, ml has only five values, -2, -1, 0, +1, +2.
So there is a 3d subshell with five orbitals.

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Note

•The number of subshells in a shell = n

•The number of orbitals in a subshell = (2l+1)
•The number of orbitals in a shell = n2

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• We could continue with n =4 and 5. Each would gain an additional
subshell (f and g, respectively).

• In an f subshell, there are seven orbitals; in a

g subshell, there are nine orbitals.

• Table 7.1 gives the complete list of permitted values for n, l, and ml
up to the fourth shell. It is on the next slide.

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7 | 51
• The figure shows
relative energies
for the hydrogen
atom shells and
subshells; each
orbital is
indicated by a
dashed-line.

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d. Spin Quantum Number, ms
•This quantum number refers
to the two possible
orientations of the spin axis of
an electron.
•It may have a value of either
+1/2 or -1/2.
•Describes magnetic field
vector of electron

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Example

Which of the following are permissible sets

of quantum numbers?
• n = 4, l = 4, ml = 0, ms = ½
• n = 3, l = 2, ml = 1, ms = -½
• n = 2, l = 0, ml = 0, ms = ³/
²
• n = 5, l = 3, ml = -3, ms = ½

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(a) Not permitted. When n = 4, the maximum
value of l is 3.

(b) Permitted.

(c) Not permitted; ms can only be +½ or –½.

(b) Permitted.

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4. Atomic Orbital Shapes
a. AO s (l=0)
When l=0, → ml=0. There is only 1 value of ml,
so there is 1 AO s
• An s orbital is spherical.
b. AO p (l=1)
l=1, → ml=-1, 0, +1. There are 3 AO p (px, py, pz)
• A p orbital has two lobes along a straight line
through the nucleus, with one lobe on either
side.
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4. Atomic Orbital Shapes

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• The cross-sectional
view of a 1s orbital
and a
2s orbital highlights
the difference in the
two orbitals’ sizes.

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• The cutaway
diagrams of the 1s
and 2s orbitals give a
better sense of them
in three dimensions.

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• The next slide illustrates p orbitals.

• Figure A shows the general shape of a p

orbital.

• Figure B shows the orientations of each of the

three p orbitals.

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7 | 61
• The complexity of the d orbitals can be seen
below

dzx

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1.4. Electron configuration
1.4.1. Orbital energy levels in a many- electron atom
The Schrodinger equation is much more
complicated for many electron atoms
To solve this equation for this case we must use
symplying approximations
The solution of the Schrodinger is wave functions
and the corresponding energies
* The orbitals resemble the atomic orbitals of
hydrogen. Each electron also is described by the
same combinations of four quantum numbers (n, l,
ml, ms)
1.4.1. Orbital energy levels in a many- electron atom

* Energies of the orbitals are different from that in

hydrogen. The energy is dependent on two quantum
numbers: n and l (no phenomena is so-called
degeneration in energy)
* The energy of the orbitals increases with increasing
value of n. For a given value of n, energy increases
with increasing value of l
That means, within a main shell, the s subshell is
lowest in energy, the p subshell is the next lowest
then the d, f and so on
Within a given value of n, sublevels increase in
energy in the order:
Ens< Enp < End< Enf
1.4.1. Orbital energy levels in a many- electron atom

The energies of orbitals

are closer together at
higher energies

The largest energy gap is

between 1s and 2s

Orbital energy levels in a many-electron atom

1.4.2. The shielding effect in many electron atoms
According to the uncertainty principle, an electron
can be present at any point in atomic space, but with
different probability:
+ an outer electron can spend time existing nearly
the nucleus. The phenomenon is called penetrating and
resulting in shielding phenomenon
+ The penetrating decreases as the principle
quantum number n increases. The electron with the
large value of n will have less penetrating as compared
to the electron with small n and will be more shielded
+ For the same principle quantum number n, the
penetrating effect decreases and the shielding effect
increases as l increases by the order: ns> np > nd > nf
1.4.3. The general rules for arranging electrons in
atomic orbitals

 We must know electron configuration for many-

electron atoms (how the electrons are distributed
among the various atomic orbitals)
 The arrangement of electrons in an atom will obey
three following rules:
1. The Pauli exclusion principle
2. The stable principle
3. Hund’s rule
1.4.3. The general rules for arranging electrons in
atomic orbitals
1. The Pauli exclusion principle
Statement:
No two electrons in an atom may have the same set
of four quantum numbers.
In other words, 4 values of 4 quantum numbers: n, l,
ml, ms can characterize only one electron.
 Two electrons can be presented in one orbital with
ms=+1/2 and ms=-1/2 (because if 2 electrons are in one
orbital, these electrons have the same 3 values of 3
quantum numbers: n, l, ml => then they must have
different values of ms.)
No more than two electrons can be placed in each
orbital.
 1. The Pauli exclusion principle
• If in an atom, 2 electron have:
- Same n: In the same shell
- Same l: In the same subshell
- Same ml: In the same orbital
According to Pauli principle, these 2 e must have
ms different
In the other hand, there are only 2 value of ms
(+1/2, -1/2)
No more than two electrons can be placed in each
orbital.
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 2

The maximum number of electrons that an subshell can have:

s subshell (1 orbital) 2e maximum (s2)

p subshell (3 orbitals) 6e maximum (p6)

d subshell (5 orbitals) 10e maximum (d10)

f subshell (7 orbitals) 14e maximum (f14)

1.4.3. The general rules for arranging electrons in
atomic orbitals
2. The stable principle
In a multi-electron atom, electrons are first filled with orbitals
in the lowest energy level by the order as follows:
1s < 2s < 2p < 3s < 3p < 4s  3d < 4p < 5s  4d < 5p < 6s 4f 
5d < 6p < 7s, ….
Kleskowski’s rule will help you to write electron
configuration:
+ Electrons are assigned to subshells in order of
increasing value of (n+l)
+ For subshells with the same value of (n+l), electrons are
assigned first to the subshell with lower n.
n

7 7s 7p

6 6s 6p 6d 6f

5 5s 5p 5d 5f

4 4s 4p 4d 4f

3 3s 3p 3d

2 2s 2p

1 1s
1.4.3. The general rules for arranging electrons in
atomic orbitals
3. Hund’s rule
Statement:
The most stable arrangement of electrons in
subshells is the one with the greatest number of
parallel spins
1s 2s
 According to Hund’s rule: The most stable
arrangement of electrons in subshells is the
one that the number of unpaired electrons is
maximum and these unpaired electrons must
have the same values of ms.
 Hund’s Rule
(of maximum multiplicity)

“For degenerate orbitals,

the lowest energy is
attained when the number
of electrons with the same
spin is maximized.”
NOT:
1.4.4. Write the electron configuration of an atom
Remember two principles and one rule:
1. The Pauli exclusion principle
2. The stable principle
3. The Hund’s rule
To write electron configurations have to know:
- The total number of electrons in the atom (the
atomic number Z)
- Place electrons in orbitals according to the stable
principle (the energy order of orbitals)
- Know the maximum number of electrons in a
subshell: 2e -s subshell, 6e- p subshell; 10e –d; 14e- f
Electron Configurations
• Distribution of all
electrons in an atom
• Consist of
– Number denoting the
energy level
Electron Configurations
• Distribution of all
electrons in an atom
• Consist of
– Number denoting the
energy level
– Letter denoting the type of
orbital
Electron Configurations
• Distribution of all
electrons in an atom.
• Consist of
– Number denoting the
energy level.
– Letter denoting the type of
orbital.
– Superscript denoting the
number of electrons in
those orbitals.
1.4.4. Write the electron configuration of an atom
To write orbital diagram, you should:
- Firstly, write electron configuration
- Write orbital diagram and for an outer unfilled
subshell electron will be placed based on the Hund’s
rule
* For example:
N (Z=7): 1s22s22p3

Note: When electrons are placed to orbitals obeying

the principles and Hund’s rule, the atom in its ground
state with the lowest energy.
Electron configurations