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ATOMIC STRUCTURE

Atomic Number of an Element

Total number of protons present in the nucleus = Total number of electrons present in the atom
Mass number of an element = Number of protons + Number of neutrons.
Mass number A Symbol
of the
element
Atomic number Z
23 35
e. g. , 11 Na , 17 Cl and so on.

Terms associated with elements

v Isotopes : Atoms having same number of protons but different mass number.
v Isobars : Elements having same mass number.
v Isotones : Elements having same number of neutrons ( A - Z ).
v Isoelectronic : Species/elements having same number of electrons.
v Isosters : Species having same number of atoms and electrons
v Isodiaphers : Elements having same number of| N - Z| or | A - 2 Z|
v Paramagnetic : Species having non-zero unpaired electron.
v Diamagnetic : Species having zero unpaired electron.

Rutherford’s Model
v Electrons, protons & neutrons are the most important fundamental particles of atoms of all
elements (Except hydrogen)
A
v Z X , Mass number ( A) = Atomic number ( Z ) + number of neutrons (n)
v R N = R 0 ( A) 1 3 , R 0 = 133
. ´ 10 -13 cm A = mass number, R N = Radius of nucleus

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1 q ´ q2
v m a v a2 = K 1 ; r = distance of closest approach , v a = Velocity of a a-particle
2 r
m a = mass of a-particle
q1 = charge on a-particle
q2 = charge on metal foil.
Size of the Nucleus
The volume of the nucleus is very small and is only a minute fraction of the total volume of the
atom. Nucleus has a diameter of the order of 10 -12 to 10 -13 cm and the atom has a diameter of the
order of 10 -8 cm.
Thus, diameter (size) of the atom is 1,00,000 times the diameter of the nucleus.
Electromagnetic Spectrum

"Gamma"
X-rays UV VISIBLE IR Micro-
radio
g-rays waves
wave

–11 –8 –6 –3 6
[Wavelength] 10m 10m 10m 10m 10m 10m

l increases
n decreases

Violet Blue Green Yellow Orange Red

Indigo
VISIBLE SPECTRUM
400nm 750nm

Light
v Photon is considered as massless bundle of energy.
v Energy of light E = mc 2 , where m = mass of light particle, c = speed of light
1240 eV . nm
v E Photon = hn = hc l = hc n @
l (nm)
where h = Planck constant, l = wavelength of photon, v = wave number.
no.of molecules reacting
v Quantum efficiency or Quantum Yield =
no.of quanta absorbed

Bohr’s Model
Kq1 q2 1
v Electrostatic force = 2
where K = = 9 ´ 10 9 N - m 2 C 2
r 4 pe 0

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Kq1 q2
v Potential energy due to electrostatic force =
r
q1 = charge of electron, q2 = charge of nucleus
KQ
v Potential due to a charge (Q ) particle at a distance ( r) =
r
h
v Bohr quantization rule mvr = n × = n. h
2p
v According to Newtons’ second law, in a uniform circular motion resultant of all the forces
mv 2
towards centre must be equal to .
r
Kq1 q2 mv 2
v = ,
r2 r
where q1 = charge of electron, q2 = charge of nucleus, m = mass of electron,
r = radius of Bohr’s orbit
v Total energy of electron in n th Bohr orbit
E 2 p 2me 4 K 2 2 -2 p 2me 4 K 2 Z 2
E n = 12 Z 2 = - Z ; E 1 =
n n 2h 2 h2
2
z
E n = -13.6 ´ 2 eV atom, where Z = atomic number of single electron atoms/ion,
n
n = principal quantum number of shell, E 1 = total energy of electron in I Bohr orbit.
h2 n2 n2 æ n2 ö
v Radius of n th Bohr orbit, rn = ´ = 0 .529 ´ Å = r1
ç ÷ Å,
4 p 2 e 2mK Z Z ç Z ÷
è ø
where r1 = radius of I Bohr orbit.
2 pe 2 K Z Z æZö
v Velocity of electron in n th Bohr orbit, v n = ´ = 2 .18 ´ 10 6 ´ m s = v 1 ç ÷ m s
h n n ènø
where v 1 = velocity of electron in I Bohr orbit.
æ Z2 ö
v Revolutions per sec = v 2 pr = 0.657 ´ 10 16 ç 3 ÷
çn ÷
è ø
æ n3 ö
v Time for one revolution = 2 pr v = 152 . ´ 10 -16 ç 2 ÷
çZ ÷
è ø
v Energy difference between n 1 and n 2 energy level.
æ 1 1 ö æ 1 1 ö
DE = E n2 - E n1 = 13.6 Z 2 ç 2 - 2 ÷ eV atom = IE ´ ç 2 - 2 ÷
çn ÷ çn ÷
è 1 n2 ø è 1 n2 ø
where IE = ionization energy of single electron species.
v Ionization energy = E ¥ - E G .S. = E G .S. ; E G .S. = Energy of electron in ground state
v Total energy of electron in terms of kinetic energy (KE) and potential energy (PE)
PE
E n = KE + PE = - KE =
2

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Spectral Lines
1 é 1 1ù
v Rydberg’s Equation = n = R H ê 2 - 2 ú ´ Z 2 ; R H @ 109700 cm -1 = Rydberg constant
l êë n 1 n 2 úû
v For First line of a series n 2 = n 1 + 1
v Limiting spectral line (series limit) means n 2 = ¥
v H a line means n 2 = n 1 + 1 ; also known as line of longest l , shortest n, least E
v Similarly H b line means n 2 = n 1 + 2
v When electrons de-excite from higher energy level (n) to ground state in atomic sample, then
n(n - 1)
number of spectral lines observed in the spectrum =
2
v When electrons de-excite from higher energy level (n 2 ) to lower energy level (n 1 ) in atomic
(n - n 1 )(n 2 - n 1 + 1)
sample, then number of spectral line observed in the spectrum = 2
2
v When electron de-excites from higher energy level (n 2 ) to lower energy level (n 1 ) in isolated
atom, then number of spectral line observed in the spectrum = (n 2 - n 1 )
n=6
v
Pfund series
n=5

n=4
Brackett
series
n=3
Paschen
series
n=2
Balmer
series
n=1
Hg H H
b a

Lyman
series

Photoelectric Effect
v When radiation with certain minimum frequency (n 0 called threshold frequency), strikes the
surface of a metal, electrons (called photoelectrons) are ejected from the surface.
v Kinetic energy of photoelectron = hn - w = hn - hn 0
where w = work function
n 0 = Threshold frequency
v If n ³ n 0 , then photoelectric effect takes place.
1
v Accelerating potential = eV = KE = mv 2
2

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de-Broglie Hypothesis
v All material particles possess wave character as well as particle character.
v l = h mv = h p
v The circumference of the n th orbit is equal to n times of wavelength of moving electron i . e. ,
2prn = nl
Number of waves = n = principal quantum number
150
v Wavelength of electron (l) @ Å
V ( volts)
v Wave nature of electron was confirmed by Davisson and Germer experiment.

Heisenberg Uncertainty Principle

v According to this principle, “it is impossible to measure simultaneously the position and
momentum of a microscopic particle with absolute accuracy”.
If one of them is measured with greater accuracy, the other becomes less accurate.
h l2
v Dx × Dp ³ h 4p or ( Dx)( Dv ) ³ or ( Dx)( Dl) ³
4pm 4p
where Dx = Uncertainty in position, Dp = Uncertainty in momentum.
Dv = Uncertainty in velocity, Dl = Uncertainty in wavelength.
m = mass of microscopic particle, l = Wavelength of microscopic particle
v Heisenberg replaced the concept of orbit by that of orbital.

Schrodinger Equation
v Schrodinger equation is central equation of wave mechanics according to following equation.
¶ 2y ¶ 2y ¶ 2y 8 p 2m
+ + + (E - V ) y = 0
¶x 2 ¶y 2 ¶z 2 h2
y = Wave function = f( x , y , z )
E = Total energy of particle
V = Potential energy of particle.
v A Schrodinger equation leads to infinite solutions.
v Most of the solution are not realistic (or acceptable). Only few solution can be accepted.
v Each solution - y ( x , y , z ) correspond to a definite energy state which depends on quantum
number n , l & m.
By proper mathematical manipulation the main equation is broken in two parts and solved
separately.
(i) Radial part contain only ‘ r’, depends on quantum numbers n & l.
(ii) Angular part contain q and f, depends on quantum numbers l & m.
Each value of y contain all the information about that particular quantum state.
v Atomic Orbital : This is a three dimensional space around the nucleus within which the
probability of finding the electron is maximum.
v Degenerate Orbital : Orbitals with same value of n and l of same subshell are degenerate
orbitals, which have same energy.
For example, 2 p x , 2 p y , 2 p z etc.

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v Radial Probability Density = 4 pr 2 R 2( r)
It is the probability of finding electron in the region between r and r + dr
v Radial Node : It is zero electron density region. R 2( r) = 0 or R( r) = 0
v Nodal Point : It is a point ( r = 0) where electron density is zero.
v Nodal Planes : It is plane by which two lobes are separated and electron density is zero
here.

Quantum Number
There are four of quantum number which are required in order to explain e - in atom.
v Principal quantum number ( n) : It determines the size of an orbital. Each value of n
represents a shell of orbital. Possible values of n = 1, 2, 3, 4,............
v Azimuthal quantum number (l ) : It determines shape of an orbital. Each value of l
represents a subshell of an orbital. Possible values of l = 0,1, 2, ....... (n - 1)
v Magnetic quantum number (m ) : It decides orientation of orbital in space.
Possible values of m = -l , - l + 1, ....... 0, 1, 2, l
Total (2l + 1) values are possible form for each value of l.
v Spin quantum number ( s) : It is intrinsic property of an electron. The electron has two
1 1
spin states. Possible values of s = + , -
2 2
Shell, sub-shells and orbitals
Shell (n) Sub-shells (l) Orbitals (m )
1 0 0
0ü 0 ü
2 ý ý
1þ ±1, 0 þ
0ü 0ü
ï ï
3 1ý ±1, 0 ý
2 ïþ ±2 , ± 1, 0 ïþ

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Various Curves

Important Points on Quantum Number

h
v Orbital angular momentum = l (l + 1)
2p
h
v Spin angular momentum = S( S + 1)
2p
v Spin Magnetic moment (m) = n(n + 2) B.M. ; n = number of unpaired electron
v Maximum number of electrons in a shell = 2n 2
v Maximum number of electrons in a subshell = 2 (2l + 1)
v Maximum number of electrons in an orbital = 2
v Total number of orbitals in a subshell = 2l + 1
v Number of subshells in a shell = n
v Number of orbitals in a shell = n 2
v Radial Nodes = (n - l - 1)
v Angular nodes = l
v Total nodes = (n - 1)
v Azimuthal quantum number 0 1 2 3 4
Name of sub-shell s p d f g

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Pauli’s Exclusion Principle
No two electrons in an atom can have the same set of all the four quantum numbers, i . e. , an
orbital cannot have more than 2 electrons because three quantum numbers (principal, azimuthal
and magnetic) at the most may be same but the fourth will be different, i . e. , spins will be in opposite
directions.
Aufbau Principle
Electrons are filled in various orbitals in order of their increasing energies. An orbital of lowest
energy is filled first. The sequence of orbitals in order of their increasing energy is :
1s, 2 s, 2 p , 3 s, 3 p , 4 s, 3 d , 4 p , 5s, 4 d , 5 p , 6 s, 4 f , 5d , 6 p , 7 s, 5 f , 6d ,......
The energy of the orbitals is governed by (n + l) rule.
Hund’s Rule
No electron pairing takes place in the orbitals in a sub energy shell until each orbital is occupied
by an electron with parallel spin. Exactly half filled and fully filled orbitals make the atoms more
stable, i . e. , p 3 , p 6 , d 5 , d 10 f 7 and f 14 configurations are more stable.

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