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Koya University
Faculty of Science and Health
Department of Chemistry

Lectures of
Atomic structure
First stage
2nd semester

Lecturer: Rezhna Hassan

[email protected]

Atomic Theory

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subatomic particles

Particle Grams Charge

Electron 9.109535×10-28 1-
Proton 1.672649×10-24 1+
Neutron 1.674954×10-24 0

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∆E =E2 - E1
Light is absorbed by an atom when the electron transition is from
lower n to higher n (nf > ni). In this case, ∆E will be positive.

Light is emitted from an atom when the electron transition

is from higher n to lower n (nf < ni). In this case,
∆E will be negative.

An electron is ejected when nf = ∞.

This spectrum consist of several lines which can be grouped into five series.
(emission spectrum of hydrogen)
•Lyman series: Discovered by lyman in 1915 which appears in the ultraviolet region.
This series are obtained when the electron jumps from 2nd, 3rd, 4th levels ….. to 1st level.

•Balmer series: Discovered by Balmer in 1835 which appears in the visible region.
This series are obtained when the electron jumps from, 3rd, 4th,5th,levels ….. to2nd level.

•Paschen series: Discovered by paschen in 1896which appears in the near infrared region.
This series are obtained when the electron jumps from, 4th, 5th, 6th, levels ….. to3rd level.

•Brackett series: Discovered by Brackett in 1922 which appears in the far infrared region.
This series are obtained when the electron jumps from 5th, 6th levels ….. to4th level.

•Pfund series: Discovered by pfund in 1925 which appears in the far infrared region.
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This series are obtained when the electron jumps from 6th, 7th, levels ….. to5th level.

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Properties of wave-wave parameters

1. Wave length(λ): Is defined as the distance
between two successive crests of a wave. It’s units:
1Ǻ=10-10m ,=10-8cm
1µm=10-6m
1nm=10-9m

2. Frequency (ʋ): Is defined as the number

of waves or cycles which pass a given point
on the wave in one second.
It’s unit: 1/s = s-1 = Hz

3. Velocity (C): Is defined as the distance travelled by the wave in one

second. It’s units: cm.s-1 or m.s-1
 It’s value has found to be constant for all types of electromagnetic
radiation and equal to 3×1010cm.s-1 or 3×108 m.s-1 and is equal to the
velocity of light.
ʋ = C/λ or C = λʋ

4. Wave number (ῡ): Is defined as the

number of wavelength per meter or centimeter.
It’s units: cm-1 or m-1
ῡ = 1/λ , λ=C/ʋ so: ῡ = ʋ/C

Visible light: is the portion of the electromagnetic radiation that is

visible to (can be detected by) the human eyes and its wavelength
between (380-750nm). 10

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Dual nature of electromagnetic radiation

1- Max Planck was able to explain light by assuming that light energy is quantized.
That quantum of light energy was later named a photon.

The energy E associated with each

quantum or photon of a given radiation
is proportional to the frequency.
E =hʋ so E = hc/λ
H= Plank’s constant = 6.624×10-34j.s

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2-Photoelectric effect
A photoelectric effect is any effect in which light energy is converted to
electricity. First explained by Albert Einstein in 1905

Study of the photoelectric effect led to

important steps in understanding the
quantum nature of light and influenced the
formation of the concept of wave–particle
duality of nature

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The principles of modern atomic theory

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Wave properties of matter (Louis de Broglie 1923)

Proving : For a photon that has both wave and particle

characteristics:
E = h = hc/ (recall c= )
E = mc2
mc2 = hc/ or  = h/mc
• Since mc is the momentum of a photon, can we replace this with
the momentum of a particle?
 = h/mv 14

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• If matter has wave properties, why are they not

commonly observed?
– The de Broglie relation shows that a baseball
(0.145 kg) moving at about 60 mph (27 m/s) has a
wavelength of about 1.7 x 10-34 m.
2
6.63  10 34 kgsm
 ( 0.145 kg )( 27 m / s )  1.7  10  34 m
– This value is so incredibly small that such waves
cannot be detected.
– Electrons have wavelengths on the order of a few
picometers (1 pm = 10-12 m).

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Problem 1) what is the wavelength of an electron traveling at 5.31×106

m/s? (mass = 9.11×10-31Kg).

J=Kg. m2/s2

Problem 2) what is the wavelength in meter of a proton traveling at 2.55×108 m/s?

( which is 85% of the speed of light), assume the mass of the proton to be
1.67×10-27 kg).
85 100
X 3x108 m/s x=2.55x108 m/s

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Example:
What is the de Broglie wavelength (in nm) of a molecule
of buckminsterfullerene (C60), moving at a speed of 100.0 m/s?
Solution:
1) We need the mass of one C60 molecule in kilograms:
a) calculate molar mass:
60 x 12.011 = 720.66 g/mol
b) calculate mass of one molecule:
720.66 g/mol divided by 6.022 x 1023 molecules/mol = 1.1967 x
10¯21 g/molecule
c) convert to kilograms:
1.1967 x 10¯21 g/molecule divided by 1000 g/kg = 1.1967 x 10¯24 kg
2)
λ = h/mv
λ = 5.5369 x 10¯12 m
3) Convert to nm:
5.5369 x 10¯12 m times 109 nm / m = 5.537 x 10¯3 nm

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Heisenberg's Uncertainty Principle (probability)

It is impossible to measure simultaneously the exact position and exact momentum of

a sub atomic particle such as electron.

∆x.∆p≥h/4π
∆X= uncertainly in the position
∆P= uncertainly in momentum
∆X and ∆p are inversely proportional to each other, so
If the position of the particle is measured accuracy, so ∆x=0, means ∆p will be large and
vice versa.
On putting ∆p=∆v.m in the uncertainly relation we get:
∆X .∆v.m≥h/4π 19

– When m is large (for example, a baseball) the

uncertainties are small, but for electrons, high
uncertainties disallow defining an exact orbit.
The main reason behind this is that the energy of photon is
enough to alter the position and momentum of electron or
other microscopic particles. This is not sufficient for bigger
bodies

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Problem :

Calculate the uncertainly in the position of an electron if ∆v is 0.1%.

velocity of electron=2.2×106m.s-1. m=9.1 x10-31 Kg 22

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Quantum mechanics or Wave Mechanics

According to wave property of electron we cannot precisely define an
electron’s orbit( as a bohr proposed), we can obtain the probability of
finding an electron at a given point around the nucleus.
– Erwin Schrodinger defined this
probability in a mathematical
expression called a wave
function, denoted y (psi).

– The square of the wavefunction

y 2 is the probability density for
finding the particle at that
E. Schrodinger location
1887-1961

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The Results of Quantum Mechanicsof the atom and schrodinger

wave equation:
This model described the electron as a three dimensional wave x,y,z and called
schrodinger's wave equation.
This equation can be written as below:

•This equation shows relation between energy of system and wave function.

•For solution of schredinger's equation should change Cartesian (x,y,z) to

Spherical Polar Coordinates (r,θ,Φ).
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The solution of the Schrodinger equation for the hydrogen atom is a

formidable mathematical problem, but is of such fundamental importance that
it will be treated in outline here. The solution is managed by separating the
variables so that the wavefunction is represented by the product:

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Comparing between Bohr and modern atomic theory

• Instead of being located in orbits, the electrons are located in orbitals.

• An orbital is a region around the nucleus where there is a high probability 27
of finding an electron.

Radial distribution function P(r)

P(r)dr is the probability of finding the electron in a shell of
radius r and thickness dr
Number of nodes = n-l-1 1s=1-0-1=0 node
2s=2-0-1=1 node
3s=3-0-1=2 node

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The 2p orbital is on average

closer to the nucleus, but note
the 2s orbital’s high probability of
being

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With solve the schrodinger's equation, four quantum numbers of

an electron are:

n the principal quantum number - a positive integer

l the angular momentum quantum number - an integer from 0 to n-1
ml the magnetic moment quantum number - an integer from -l to +l
ms = spin quantum number +1/2 or -1/2
An atomic orbital is specified by above three quantum numbers.

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Principal Quantum Number (Shell)

Y  fn(n, l, ml, ms)
principal quantum number = n

distance of e- from the nucleus

n = 1, 2, 3, 4, ….

n=3
n=1 n=2

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Angular Momentum Quantum Number (Subshell)

Y = fn(n, l, ml, ms)
angular momentum quantum number l
for a given value of n, l = 0, 1, 2, 3, … n-1
n = 1, l = 0 l=0 s orbital
n = 2, l = 0 or 1 l=1 p orbital
n = 3, l = 0, 1, or 2 l=2 d orbital
l=3 f orbital

Shape of the “volume” of space that the e- occupies

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Magnetic Quantum Number

Y = fn(n, l, ml, ms)
magnetic quantum number ml
for a given value of l
ml = -l, …., 0, …. +l
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space

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Sample Problem Determining Quantum Numbers for an Energy Level

PROBLEM: What values of the angular momentum (l) and magnetic (ml)
quantum numbers are allowed for a principal quantum number (n) of
3? How many orbitals are allowed for n = 3?

PLAN: Follow the rules for allowable quantum numbers found in the text.
l values can be integers from 0 to n-1; ml can be integers from -l
through 0 to + l.

SOLUTION: For n = 3, l = 0, 1, 2

For l = 0 ml = 0
For l = 1 ml = -1, 0, or +1

For l = 2 ml = -2, -1, 0, +1, or +2

There are 9 ml values and therefore 9 orbitals with n = 3.

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Sample Problem Determining Sublevel Names and Orbital Quantum

Numbers
PROBLEM: Give the name, magnetic quantum numbers, and number of orbitals
for each sublevel with the following quantum numbers:
(a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3

PLAN: Combine the n value and l designation to name the sublevel.

Knowing l, we can find ml and the number of orbitals.

SOLUTION:
n l sublevel name possible ml values # of orbitals

(a) 3 2 3d -2, -1, 0, 1, 2 5

(b) 2 0 2s 0 1
(c) 5 1 5p -1, 0, 1 3

(d) 4 3 4f -3, -2, -1, 0, 1, 2, 3 7

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Spin Quantum Number

One electron while moving in an orbital around nucleus also rotates around own axis (self-
rotation) either in a clockwise direction or in an anti-clockwise direction.
Y = fn(n, l, ml, ms)

spin quantum number ms

ms = +½ or -½

ms = +½ ms = -½
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7.6

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Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p
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7.8

Electronic configuration of atoms:

The distribution of electrons in various shell, subshells and orbitals of an atom is
called, according to Aufbaudiagram, that indicates the relative order of energy of
various orbitals of an atom.

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Rule(n+l): The orbital having the lowest value of (n+l) has the lowest energy and
will be filled up first with electrons.For example 2s, 2p.
Note: when two or more orbitals have the same value of (n+l), the orbital with
lower value of n is lower in energy and will be filled up first with electrons, for
example 3d, 4p.

Pauli's exclusion principle:

It is impossible for two electrons residing in the same orbital of a given poly
electron atom to have the same values of all four quantum numbers, for example,
1s2, 2s2 2p6.

Hund's rule of maximum multiplicity:

The distribution of electrons in a set degenerate orbitals like p or d, take place in such
away as to give the maximum number of unpaired electrons and these electrons must
have the same direction of their spins.

Problem : write the electronic configuration for below elements:

17Cl ,24Cr, 29Cu, 35Br,42Mo, 57La 41

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• The horizontal rows are called periods and the vertical columns are groups.

• Elements having similar outer electronic configurations in their atoms are

arranged in vertical columns.
• The period indicates the value of n for the outermost or valence shell. The period
is equal to the number of shells present in an atom.
• To find a period, the No. of shells = No. of periods.

• To determine the group, we need to understand some rules:

1. If the element is in s block, then the group number is equal to the number of
valence electrons.
Example: Mg

2. If the element is in the p block, then the number of the group can be determined
by the formula: (Number of valence electrons + 10)
Example:

3. If the element is in the d block, then the number of the group can be determined
by the formula: Number of electrons in(n−1)d subshell + (Number of electrons in (n)s
subshell).
Example

4. If the element is in the f block, then the number of the group is always 3. 43
Example: Cerium (58) belongs to 3rd group

General characteristics of group:

•Number of valence electrons: on moving down a given group, the number of valence
electrons does not change means remain same. Li, H.
•Properties of elements: All of elements of a given group possess very similar physical and
chemical properties.
The reactivity of halogens decreases as we pass from F to I.
•Size of atoms: increases on descending a group.
Li<Na<K<Rb<Cs
•Metallic character: increases in moving from top to bottom in group.
•Number of electron shells: increases on descending a group and ultimately becomes equal
to number of the period, Na, K.

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General characteristics of periods:

•Number of valence electrons: increases when we proceed from left to right in a period.
•Size of atoms: decreases from left to right in a period.
•Metallic character: decreases on moving from left to right in a period.
•Number of shells: remains the same and the number of a period correspond to the number
of the shells found in the elements of that period.

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Effective nuclear charge (Z*):

Is defined as the actual nuclear charge(Z) minus the shielding effect caused by the
electrons intervening between the nucleus and outer electrons.

Z* = Z – S(б)
Shielding effect: the decrease in the attractive force exerted by the nucleus on the
valence shell electron, which is obviously due to the presence of the electrons lying
between the nucleus and valence shell electrons is called shielding effect.

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Factors effecting the magnitude of shielding effect:

•Number of inner-shells: with move down a group, the number of inner-shell
increase and hence the shielding effect also increase.
•Type of the orbital occupied by the electron: the peneteration power of s orbital is
greater than that of an p orbital, and the peneteration power of p orbital is greater
than that of an d orbitals according to below order:

(more closer to nucleus) Peneteration of s orbital > p > d > f

That means s-electrons are more tightly bound with nucleus than p-electrons and
so so.

Based upon, the decreasing order of shielding effect including: s > p > d > f

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Calculation of effective nuclear charge by slater's rules:

According to this rule we write down the complete electronic configuration of the element
in order of shells and divide the electrons into the following orbital groups.
1s,2s 2p,3s 3p 3d,4s 4p 4d 4f,...
In order to calculation of shielding effect(S) use the shielding constant according the below
ruls:

•For s and p orbitals:

•All electrons in groups outside the electron chosen→0

•All electrons in the asked shell(s, p)→0.35 (or 0.3 for 1s electron)
•All electrons in shell immediately inside(n-1)→0.85
•All electrons in further inside (n-2)→1
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Examples:

•Calculate the effective nuclear charge of the last electron in fluorine atom?
(1s2)(2s2,2p5)
0.35 * 6 + 0.85 * 2 = 3.8
Z* = 9 – 3.8 = 5.2 for a valence electron

•Calculate the effective nuclear charge of the last electron in carbon atom?

Z* = 6-(2*0.85)-(3*0.35)= 3.25

•Calculate the effective nuclear charge of the electron of 4s in Cu atom?

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•For d and f orbitals:

•All electrons in groups outside the electron chosen→0

•All electrons in the asked shell(d, f)→0.35
•All electrons in left side of group(d, f) complete shielding→1

Examples:

•Calculate the effective nuclear charge of the electron of 3d in Cu atom?

•Calculate the effective nuclear charge of the electron of 4s and 3d in Co atom?

4s = 3.9 3d= 6.9

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•Calculate the effective nuclear charge of the electron of 4s in potassium atom?

S= 8*0.85 +10*1 = 16.8

Z *= 19-16.8 =2.2

•Calculate the effective nuclear charge of the last electron in Sulfur atom?

S =5 *0.35 + 8*0.85+ 2*1 =10.55

Z*=16-10.55=5.45

What is the effective nuclear charge of 3d electron of Bromine?

(1s)2 (2s, 2p)8 (3s, 3p)8 (3d)10 (4s2, 4p5)
S= 9(0.35)+18(1.00)
S = 21.15
Bromine's atomic number is 35.
Z*=35-21.15=13.85=Zeff

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Calculate Z* for a 6s electron in Platinum.

(1s2)(2s2,2p6)(3s2,3p6) (3d10) (4s2,4p6) (4d10) (4f14) (5s2,5p6) (5d8) (6s2)
0.35 · 1 + 0.85 · 16 + 60 · 1.00 = 73.95
Z* = 78 – 73.95 = 4.15 for a valence electron.
Calculate effective nuclear charge on one of 6s electron in tungsten.
(At. No. =74)Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p6)(4s2, 4p6) (3d10)
(4f14) (5s2, 5p6)(5d4), (6s2)
• σ = (0.35 × 1) + (0.85 × 12) + (1 × 60) = 70.55
• Z* = Z – σ = 74 – 70.55 =3.45

• Calculate effective nuclear charge in Zinc for 4s electron & for 3d

electron.
Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p6)(3d10)(4s2). For 4s
electron,
σ = (0.35 × 1) + (0.85 × 18) + (1 × 10) = 25.65
Z* = Z – σ = 30 – 25.65 = 4.35
Fo r 3d electron,
σ = (0.35 × 9) + (1 × 18) = 21.15
Z* = Z – σ = 30 – 21.15 = 8.85
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• Sn A.N =50 Z*of p electron =5.65

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Variation of shielding effect (S) in periodic table

1) On moving down a group, the value of S will be increased.

Each atom has another energy level(more shielding)

2) When we proceed from left to right, the value of S will be increased.

the next element has one more valence electron therefore greater shielding

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Variation of effective nuclear charge in periodic table

1) On proceeding from left to right, the value of effective nuclear charge is increased.
Because when we proceed from left to right across a period the atomic
number(nuclear charge) increase by one electron at each element and the next
element has one more valence electron with its shielding equal to 0.35 and
therefore the Z* increase by 1-0.35=0.65 from member to member
.Consequently the Z*of each next atom is greater by 0.65than the previous atom.

Effective nuclear charge on 3d orbital is greater than 4s orbital. But shielding effect is vice versa.
Q1) If effective nuclear charge on 3d orbital is greater than 4s orbital, why 4s orbital will be filled
up of electrons first?
This can be explained by the following: •
s electrons penetrate closer to the nucleus than p
p electrons penetrate closer to the nucleus than d
d electrons penetrate closer to the nucleus than f •
Thus, the attraction between the the electron and the
nucleus decreases in the order:
ns > np > nd > nf
The result is that the ns orbitals are lower in energy 54
then the (n-1)d orbitals.

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Q2) removing of electron take place in which orbitals first, 4s or 3d?

Eg: Calculate Z* for a 4s and a 3d electron in Zn
(1s)2(2s, 2p)8(3s, 3p)8(3d)10(4s)2
For a 4s electron:
S = (1 x 0.35) + (18 x 0.85) + (10 x 1.00) = 25.65
Z*= Z‐S = 30‐25.65 = 4.35
For a 3d electron:
S = (9 x 0.35) + (18 x 1.00) = 21.15
Z*= Z‐S = 30‐21.15 = 8.85
From this example, you can see that the 3d electrons experience a much greater positive
charge than the 4s electron and would be held more tightly. Thus, the 4s electrons will be
the first removed when Zn is ionized.

Q3) According to effective nuclear charge rule ,Explain removing electron from 4s orbital
of vanadium not 3d orbital .
2) On descending a group, the value of effective nuclear charge can increase (transition metal)
and can remain same (main elements).

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Investigation some properties of periodic table

Atomic radius (r)
The atomic radius of a chemical element is a measure of the size of its atoms, usually
the mean or typical distance from the nucleus to the boundary of the surrounding
cloud of electrons.
•Atomic radius of elements decreases on moving horizontally from left to right
•As you go L to R, e- are put into the same orbital, but more p+ and e- total (more
attraction = smaller size)
•while increases on moving down the groups.
•As you go down, e- are filled into orbitals that are farther away from the nucleus
(attraction not strong)
Ionization energy (I)
The ionization energy of an atom or molecule is defined as the amount of energy
required to remove an electron from that atom or molecule in the gas phase.(I)
M(g) →M+(g) + e- 56

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In atomic physics the ionization energy is typically reported in the unit electron volt
(eV). Large atoms or molecules typically have a low ionization energy, whereas small
molecules tend to have higher ionization energies.

The ionization energy may be an indicator of the reactivity of an element. Elements

with a low ionization energy tend to be reducing agents and form cations, which in turn
combine with anions to form salts.
Generally the (n+1)th ionization energy is Lower than the nth ionization energy.
Always, the next ionization energy involves removing an electron from an orbital closer
to the nucleus. Electrons in the closer orbitals experience greater forces of electrostatic
attraction; thus, their removal requires increasingly more energy.
Ionization energy of elements increase on moving horizontally from left to right .
Because as radius decreases across a period, the electron you are removing is closer
to the nucleus and harder to remove.
while decrease on moving down the groups ,because outer electron are farther
from the nucleus and easier to remove. 57

Some values for elements of the third period are given in the following table:
Successive molar ionization energies inkJ/mol
(96.485 kJ/mol = 1 eV/particle)
Element First Second Third Fourth Fifth Sixth Seventh
Na 496 4,560
Mg 738 1,450 7,730
Al 577 1,816 2,881 11,600
Si 786 1,577 3,228 4,354 16,100
P 1,060 1,890 2,905 4,950 6,270 21,200
Cl 1,256 2,295 3,850 5,160 6,560 9,360 11,000
Ar 1,520 2,665 3,945 5,770 7,230 8,780 12,000
S 999.6 2,260 3,375 4,565 6,950 8,490 27,107

M(g) + I1 →M+(g) + e- I1
M+(g)+ I2→M2+(g) + e-I2
M2+(g)+ I3→M3+(g) + e- I3

Ionization energy are in the order: I1< I2< I3

Second ionization energy defined the required energy to remove one more electron
from the gaseous cation to get M2+(g). 58

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Mg Al Si P
Atomic radius(Aº) 1.36 1.18 1.11 1.06
I (Kj/mol) 737.7 577.9 786.5 1011.8

Electronegativity

Electronegativity, symbol χ, is a chemical property that describes the tendency of an

atom or a functional group to attract electrons (or electron density) towards itself.

Electronegativity increases on passing from left to right along a period, and

decreases on descending a group.

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Electro Affinity (Eea)

The electron affinity of an atom or molecule is defined as the amount of energy

released when an electron is added to a neutral atom or molecule to form a negative ion.

X + e − → X−

This property is measured for atoms and molecules in the gaseous state only, since in
the solid or liquid states their energy levels would be changed by contact with other
atoms or molecules.

For any reaction that releases energy, the change in energy, ΔE, has a negative value
and the reaction is called an exothermic process.

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O(g) + e- → O-(g) E1 = -141 Kj/mol exothermic

O-(g) + e- → O2-(g) E2 = 921 Kj/mol endothermic E2 >E1

O(g) + 2e- + absorbed energy (E2-E1)→ O2-(g)

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