Chapter 2

Atomic Structure

IMPORTANT DEFINITIONS
Proton (mP)/anode Neutron (mn) Electron (me)
rays /cathode rays
mass = 1.67 × 10–27 kg mass = 1.67 × 10–27 kg mass = 9.1 × 10–31 kg
mass = 1.67 × 10–24 g mass = 1.67 × 10–24 g mass = 9.1 × 10–28 g
mass = 1.00750 amu mass = 1.00850 amu mass = 0.000549 amu
e/m value is dependent e/m of electron is found
on the nature of gas to be independent
taken in discharge tube. of nature of gas &
electrode used.

REPRESENTATION OF AN ELEMENT
Mass number A Symbol
X of the
Atomic number Z element

Terms associated with elements:

● Atomic Number (Z): = No. of protons
Electron = Z ± C (charge on atom)
● Mass number (A) = Total number of neutron and proton present
A = Number of proton + Number of Neutrons
● Isotopes: Same atomic number but different mass number
Example: 6C12, 6C13, 6C14
● Isobars: Same mass number but different atomic number
Example: 1H3, 2He3
● Isodiaphers: Same difference of number of Neutrons & protons
Example: 5B11, 6C13
 ● Isotones: Having same number of neutron
3 4
Example: 1H , 2He
● Isosters: They are the molecules which have the same number of
atoms & electrons
Example: CO2, N2O
● Isoelectronic: Species having same no. of electrons
–
Example: Cl , Ar

ATOMIC MODELS
● Thomson: An atom considered to be positively charged sphere
–
where e is embedded inside it.
● Drawback: Cannot explain stability of an atom.
● Rutherford Model of an Atoms:
Electron is revolving around the nucleus in circular path.
RN = R0(A)1/3, R0 = 1.33 × 10–13 cm
[A = mass number, RN = Radius of nucleus]

SIZE OF 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
● RW → MW → IR → Visible → UV → X-ryas → CR (Radiowaves→
Microwaves → Infrared rays→Visible rays → Ultraviolet rays →
X-rays → Cosmic rays)
● Wavelength decreases →
● Frequency increases →
c 1 v
● c = vl λ= ν= =
v λ c
1 hc –34
T= =E = hv, h = 6.626 × 10 Js
v λ
12400
E(ev) = 
λ (A)
nhc
● Total amount of energy transmitted=E nhv
=
λ

Hand Book (Chemistry) 8

BOHR’S ATOMIC MODEL
Theory based on quantum theory of radiation and the classical laws of physics
K(Ze)(e) mv 2
● =
r2 r
● Electron remains in stationary orbit where it does not radiate its energy.
n2
● Radius:
= r 0.529 × Å
Z
Z
● Velocity:
= v 2.188 × 106 ms –1
n
Z2
● Energy (KE + PE) = Total energy = –13.6× 2 eV/atom
n
2 2 2
KZe –KZe KZe
● TE –=
= , PE = , KE
2r r 2r
PE = –2KE, KE = –TE, PE = 2TE
v
● Revolutions per sec =
2πr
2πr
● Time for one revolution =
v
● Energy difference between n1 and n2 energy level

 1 1  eV  1 1 
∆E = E n 2 – E n1 = 13.6Z2  2 – 2  = IE ×  2 – 2 
 n1 n 2  atom  n1 n 2 
where IE = ionization energy of single electron species.
● Ionization energy = E∞ – EG.S. = 0 – EG.S.
EG.S.= Energy of electron in ground state.
–12z2
E = 21.8 × 10 erg per atom
n2
2
–19 z
= –21.8 × 10 per atom
n2
z2
= –13.6 2 eV/atom
n
1 eV = 3.8 3 × 10–23 kcal
1 eV = 1.602 × 10–12 erg
1 eV = 1.602 × 10–19 J
z2
E = –313.6 2 kcal/mole (1 cal = 4.18 J)
n
2πkze 2
V=
nh

9 Atomic Structure
 n2h2
r=
4π2 mkze 2
2π2 mz 2 e 4 k 2
E=
n2h2
HYDROGEN SPECTRUM
Rydberg’s Equation:
●
1 1 1
= v = R H  2 – 2  × Z2
λ  n1 n 2 
–1
RH ≅ 109700 cm = Rydberg constant
● For first line of a series n2 = n1 + 1
● Limiting spectral line (series limit) means n2 = ∞
● Ha line means n2 = n + 1; also known as line of longest l, shortest v,
least E
● Similarly Hb line means n2 = n1 + 2
● When electron de-excite from higher energy level (n) to ground
state in atomic sample, then number of spectral lines observed in the
n(n –1)
spectrum =
2
● When electrons de-excite from higher energy level (n2) to lower
energy level (n1) in atomic sample, then number of spectral line
(n – n1 )(n 2 – n1 + 1)
observed in the spectrum = 2
2
● No. of spectral lines in a particular series = n2 – n1.

Hand Book (Chemistry) 10

DE-BROGLIE HYPOTHESIS
● All material particles posses wave character as well as particle
character.
h h
● =
λ =
mv p
th
● The circumference of the n orbit is equal to n times of wavelength
of electron i.e., 2prn = nl
Number of waves = n = principal quantum number
150
● Wavelength of electron (l) ≅ Å
V(vols)
h
● λ=
2mKE

HEISENBERG UNCERTAINTY
● 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 h
● ∆x.∆p ≥ or ( ∆x)( ∆v) ≥
4π 4πm
where Dx = Uncertainty in position
Dp = Uncertainty in momentum
Dv = Uncertainty in velocity
m = mass of microscopic particle
● Heisenberg replaced the concept of orbit by that of orbital.

QUANTUM NUMBER
● Principal Quantum number (By Bohr)
⇒ Indicates = Size and energy of the orbit, distance of e– from nucleus
⇒ Values n = 1, 2, 3, 4, 5 …
h
⇒ Angular momentum = n ×
2π
⇒ Total number of e s in an orbit = 2n2
–

⇒ Total number of orbitals in an orbit = n2

⇒ Total number of subshell in an orbit = n

11 Atomic Structure
 ● Azimuthal/Secondary/Subsidiary/Angular momentum quantum
number (l)
⇒ Given by = Sommerfeld
⇒ Indicates = Sub shells/sub orbit/sub level
⇒ Values ⇒ 0, 1 … (n–1)
⇒ Indicates shape of orbital/Sub shell
Value of n Values of l [Shape] Initial from word
eg. l = 0 (s) [Spherical] Sharp
If n = 4 l = 1 [p] [Dumb bell] Principal
l = 2 [d] [Double dumb bell] Diffused
l = 3 [f] [Complex] Fundamental

⇒ Total no. of e–s in a suborbit = 2(2l + 1)

⇒ Total no. of orbital in a suborbit = (2l + 1)
h
⇒ Orbital angular momentum = l (l + 1) = l (l +1) h
h = Planck’s constant 2 π
⇒ For H & H like species all the subshells of a shell have same
energy.
i.e 2s = 2p 3s = 3p = 3d
● Magnetic Quantum number (m)
⇒ Given by Lande
⇒ Indicates orientation of orbital i.e. direction of electron density.
⇒ Value of m = –l ...........0.............+l
⇒ Maximum no of e’s in an orbital = 2
(with opposite spin)
m for p sub shell = px py pz
–1 +1 0

m for d sub shell =
dxy dyx dz2 dxz dx2–y2
–2 –1 0 +1 +2

● Spin Quantum Number (ms or s)

Given by Uhlenback & Goudsmit
Values of s = ±½
Total value of spin in an atom = ±½ × number of unpaired electrons
h
Spin Angular momentum = s(s + 1)
2π
Hand Book (Chemistry) 12
RULES FOR FILLING OF ORBITALS
● Aufbau principle: The electrons are filled up in increasing order of
the energy in subshells.
2 2 6 2 6 2 10 6 2 10 6 2 14 10 6 2 14 10
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d
● (n + l) rule: The subshell with lowest (n + l) value is filled up first,
but when two or more subshells have same (n + l) value then the
subshell with lowest value of n is filled up first.
● Pauli exclusion principle: Pauli stated that no two electrons in an
atom can have same values of all four quantum numbers.
● Hund’s rule of maximum multiplicity: Electrons are distributed
among the orbitals of subshell in such a way as to give maximum
number of unpaired electrons with parallel spin.
qqq

13 Atomic Structure