Atomic Structure Theory Note

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 Date of Distribution: 03-Feb 2021

Atomic Structure Theory Note

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Planck's Quantum theory:
(1) Max Planck (1900) to explain the phenomena of 'Black body radiation' and 'Photoelectric
effect' gave quantum theory. This theory extended by Einstein (1905).

(2) If the substance being heated is a black body (which is a perfect absorber and perfect radiator
of energy) the radiation emitted is called black body radiation.

(3) Main points

(i) The radiant energy which is emitted or absorbed by the black body is not continuous but
discontinuous in the form of small discrete packets of energy, each such packet of energy is called a
'quantum'. In case of light, the quantum of energy is called a 'photon'.

(ii) The energy of each quantum is directly proportional to the frequency (  ) of the
radiation, i.e.

hc
E or E  hv 

where, h  Planck's constant = 6.62×10–27 erg. sec. or 6.62 1034 Joules sec .

(iii) The total amount of energy emitted or absorbed by a body will be some whole number quanta.
Hence E  nh , where n is an integer.

(iv) The greater the frequency (i.e. shorter the wavelength) the greater is the energy of the
radiation.

E1 1  2
 
thus,
E 2  2 1

(v) Also E  E1  E 2 ,

hc hc hc 1 1 1
   
hence,  1  2 or
 1  2 .

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Bohr’s atomic model:
(1) This model was based on the quantum theory of radiation and the classical law of physics.
It gave new idea of atomic structure in order to explain the stability of the atom and emission
of sharp spectral lines.
(2) Postulates of Bohr theory are :
(i) The atom has a central massive core nucleus where all the protons and neutrons are present. The
size of the nucleus is very small.
(ii) The electron in an atom revolve around the nucleus in certain discrete orbits. Such orbits are known
as stable orbits or non – radiating or stationary orbits.
(iii) The force of attraction between the nucleus and the electron is equal to centrifugal force of the
moving electron.
Force of attraction towards nucleus = centrifugal force
(iv) An electron can move only in those permissive orbits in which the angular momentum (mvr) of the
h
electron is an integral multiple of h / 2. Thus, mvr  n
2
Where, m = mass of the electron, r = radius of the electronic orbit, v = velocity of the electron in its
orbit.
h 2h 3h nh
(v) The angular momentum can be , , ,...... . This principal is known as
2 2 2 2
quantization of angular momentum. In the above equation ‘n’ is any integer which
has been called as principal quantum number. It can have the values n=1,2,3, -------
(from the nucleus). Various energy levels are designed as K(n=1), L(n=2), M(n=3) --
----- etc. Since the electron present in these orbits is associated with some energy,
these orbits are called energy levels.
(vi) The emission or absorption of radiation by the atom takes place when an electron jumps from
one stationary orbit to another.

E1 E1

E1 – E2 = h E1 – E2 = h
E2 E2
Emission Absorption

(vii) The radiation is emitted or absorbed as a single quantum (photon) whose energy
h is equal to the difference in energy E of the electron in the two orbits involved.
Thus, h  E Where ‘h’ =Planck’s constant,   frequency of the radiant energy. Hence the
spectrum of the atom will have certain fixed frequency.

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 Advantages of Bohr’s theory
(i) Bohr’s theory satisfactorily explains the spectra of species having one electron, viz. hydrogen
 2
atom, He , Li etc.

 Calculation of radius of Bohr’s orbit: According to Bohr, radius of orbit in which

electron moves is

 h2  n2
r   2 2 .
 4 me k  Z

 
where, n =Orbit number, m =Mass number 9.1 1031 kg , e =Charge on the electron 1.6  10 19 Z  
=Atomic number of element, k = Columbic constant 9 109 Nm2c2  
After putting the values of m,e,k,h, we get.

n2
rn   0.529 Å
Z

n2
or rn  r0
Z

(a) For a particular species [e.g., H, He+ or Li+2]

r  n 2 [Z = constant]
r1 n12
Thus we have  i.e., r1 : r2 : r3 ........... :: 1 : 4 : 9....... r1  r2  r3
r2 n 22

(b) For particular orbit of different species

1 r Z
r [Z =constant] Considering A and B species, we have A  B
Z rB Z A

Thus, radius of the first orbit H, He  , Li 2 and Be 3 follows the order :

H  He   Li 2  Be 3

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 Calculation of velocity of electron:

1/2
2e 2 ZK  Ze 2 
Vn  , Vn   
nh  mr 
2.188  108
For H atom, Vn  cm. sec 1
n

(a) For a particular species [H, He+ or Li+2]

1 V n
V [Z = constant] Thus, we have, 1  2
n V2 n 1
1 1
The order of velocity is V1  V2  V3 ......... or V1 : V2 : V3 .......... :: 1 : : ........
2 3

(b) For a particular orbit of different species

V  Z [n =constant] Thus, we have H  He   Li 2

(c) For H or He+ or Li+2, we have

V1 : V2  2 :1; V1 : V3  3 : 1; V1 : V4  4 :1

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  Calculation of energy of electron in Bohr’s orbit
kZe 2 kZe 2 kZe 2
Total energy of electron = K.E. + P.E. of electron   
2r r 2r
 22 mZ 2 e 4 k 2
Substituting of r, gives us E  Where, n=1, 2, 3………. 
n 2h 2
Putting the value of m, e, k, h,  we get
12 Z2 19 Z2
E  21.8  10  2 erg per atom  21.8  10  2 J per atom (1J  107 erg )
n n
Z2 Z2
E  13.6  eV per atom (1eV  1.6  10 -19
J )  313.6  kcal. / mole
n2 n2
(1 cal = 4.18J)

1312 2
or 2
Z kJmol 1
n

(a) For a particular species [H, He+ or Li+2]

1 E1 n22
E   2 [Z =constant] Thus, we have 
n E 2 n12
The energy increase as the value of n increases
(b) For a particular orbit of different species
2
E   Z 2 [n =constant] Thus, we have E A  Z A
2
EB ZB

For the system H, He+ , Li+2, Be+3 (n-same) the energy order is H  He   Li 2  Be 3
The energy decreases as the value of atomic number Z increases.
When an electron jumps from an outer orbit (higher energy) n 2 to an inner orbit
(lower energy) n1 , then the energy emitted in form of radiation is given by

22 k 2 me 4 Z2  1 1   1 1 
E  E n 2  E n1  2
 2  2   E  13.6Z2  2  2  eV / atom
h  n1 n 2   n1 n 2 
1 E 22 k 2 me 4 Z2  1 1
Since E  h , c   and    ,   2  2 
 hc ch 3
 n1 n 2 
1  1 1  22 k 2 me4
This can be represented as    RZ 2  2  2  where, R 
  n1 n 2  ch3

1
R is known as Rydberg constant. Its value to be used is or  912 Å
R

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 Quantisation of energy of electron

(i) In ground state: No energy emission. In ground state energy of atom is minimum and
st
for 1 orbit of H-atom, n = 1.
E1  13.6eV.

(ii) In excited state: Energy levels greater than n1 are excited state. i.e. for H-atom n2 , n3, n4
are excited state. For H- atom first excitation state is  n 2

(iii) Excitation potential: Energy required to excite electron from ground state to any
excited state.
Ground state  Excited state
Ist excitation potential = E 2  E1  3.4  13.6  10.2 eV.
IInd excitation potential = E 3  E1  1.5  13.6  12.1 eV.

(iv) Ionisation energy\: The minimum energy required to relieve the electron from the
binding of nucleus.
2
Z eff.
Eionisation  E   En  13 .6 2 eV .
n

E ionisation
(v) Ionisation potential: Vionisation 
e
(vi) Separation energy: Energy required to excite an electron from excited state to infinity.
S.E. = E   E excited .

(vii) Binding energy: Energy released in bringing the electron from infinite to any orbit
is called its binding energy (B.E.).

13.6
Note : Principal Quantum Number 'n' = .
(B.E.)

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Atomic spectrum - Hydrogen spectrum.
Atomic spectrum
(1) Spectrum is impression produced on a photographic film when the radiation (s) of particular wavelength
are analyzed through a prism or diffraction grating. It is of two types, emission and absorption.

Emission spectrum: A substance gets excited on heating at a very high temperature or by giving
energy and radiations are emitted. These radiations when analyzed with the help of spectroscope,
spectral lines are obtained. A substance may be excited, by heating at a higher temperature, by passing
electric current at a very low pressure in a discharge tube filled with gas and passing electric current
into metallic filament.

Emission spectra is of two types:

(A) Continuous spectrum: When sunlight is passed through a prism, it gets dispersed into continuous
bands of different colors. If the light of an incandescent object resolved through prism or
spectroscope, it also gives continuous spectrum of colors.
(B) Line spectrum: If the radiations obtained by the excitation of a substance are analyzed with help of
a spectroscope a series of thin bright lines of specific colors are obtained. There is dark space in
between two consecutive lines. This type of spectrum is called line spectrum or atomic spectrum.
(C) Band Spectrum: If the radiations obtained by the excitation of a substance are analyzed with help of
a spectroscope and series of band or strips of different wavelength are obtained, its called band
spectrum.

(3) Absorption spectrum: When the white light of an incandescent substance is passed through any substance,
this substance absorbs the radiations of certain wavelength from the white light. On analyzing the
transmitted light we obtain a spectrum in which dark lines of specific wavelengths are observed. These
lines constitute the absorption spectrum. The wavelength of the dark lines corresponds to the
wavelength of light absorbed.

Atomic spectrum of Hydrogen

(1) Hydrogen spectrum is an example of line emission spectrum or atomic emission spectrum.
(2) When electric discharge is passed through H-gas at low pressure, light is emitted.
(3) This light shows discontinuous line spectrum of several isolated sharp lines through prism.
(4) All these lines of H-spectrum have Lyman, Balmer, Paschen, Barckett, Pfund and Humphrey series.
These spectral series were named by the name of scientist discovered them.
(5) To evaluate wavelength of various H-lines Ritz introduced the following expression,

1  1 1
   R 2  2 
 c  n1 n 2 
Where R is universal constant known as Rydberg’s constant its value is 109, 678 cm 1 .
1
A more useful value is  912 Å .
R

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 Spectral evidence for quantization (Explanation for H spectrum on the basis of Bohr atomic model)

(i) The light absorbed or emitted as a result of an electron changing orbits produces characteristic
absorption or emission spectra which can be recorded on the photographic plates as a series of lines, the
optical spectrum of hydrogen consists of several series of lines called Lyman, Balmar, Paschen,
Brackett, Pfund and Humphrey. These spectral series were named by the name of scientist who
discovered them.

(ii) To evaluate wavelength of various H-lines Ritz introduced the following expression,

1  1 1
   R 2  2 
 c  n1 n 2 
22 me 4
where, R is =  Rydberg's constant
ch 3

It's theoretical value = 109,737 cm–1 and It's experimental value = 109,677.581cm 1

This remarkable agreement between the theoretical and experimental value was great
achievement of the Bohr model.

(iii) Although H- atom consists only one electron yet it's spectra consist of many spectral
lines as shown in fig.

n=8
n=7
n=6 Humphrey series
n=5 Pfund

n=4 series
Brackett
series
Energy level

n=3
Paschen

series
n=2
Balmer
series

n=1
Lyman

series

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 Comparative study of important spectral series of Hydrogen

S.No. Spectral Lies in the Transition n12n22 n12  max n2

max   min   2 2 2
(n22  n12 )R R  min n 2  n1
series region n2  n1

(1) Lymen Ultraviolet n1  1 n1  1 and n 2  2 n1  1 and n 2  

4
series region n 2  2,3,4....  4 1
 max   m in  3
3R R

(2) Balmer Visible n1  2 n1  2 and n 2  3 n1  2 and n2  

series region n 2  3,4,5....  36 4 9
 max   m in 
5R R 5

(3) Paschen Infra red n1 = 3 n1  3 and n 2  4 n1  3 and n 2  

16
series region n 2  4,5,6....  144 9
 max   m in  7
7R R

(4) Brackett Infra red n1  4 n1  4 and n2  5 n1  4 and n 2  

25
series region n 2  5,6,7....  16  25 16
max   m in  9
9R R

(5) Pfund Infra red n1  5 n1  5 and n 2  6 n1  5 and n 2  

36
series region n 2  6,7,8....  25  36 25
 max   min  11
11 R R

(6) Humphrey Far infrared n1  6 n1  6 and n 2  7 n1  6 and n 2  

49
series region n 2  7,8....  36  49 36
 max   m in  13
13 R R

(v) If an electron from nth excited state comes to various energy states, the maximum spectral lines obtained
n (n  1)
will be = . n= principal quantum number.
2
6(6  1) 30
as n = 6 than total number of spectral lines =   15.
2 2
 Failure of Bohr Model
(i) Bohr theory was very successful in predicting and accounting the energies of line spectra of hydrogen i.e.
one electron system. It could not explain the line spectra of atoms containing more than one electron.
(ii) This theory could not explain the presence of multiple spectral lines.
(iii) This theory could not explain the splitting of spectral lines in magnetic field (Zeeman effect) and in
electric field (Stark effect). The intensity of these spectral lines was also not explained by the Bohr
atomic model.
(iv) This theory was unable to explain of dual nature of matter as explained on the basis of de Broglies
concept.
(v) This theory could not accommodate uncertainty principle.
(vi) No conclusion was given for the concept of quantization of energy.

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 Examples
1
The velocity of electron in the ground state hydrogen atom is 2.18  10 ms .
8
Example:
Its velocity in the second orbit would be
(a) 1.09  108 ms 1 (b) 4.38  108 ms 1 (c) 5.5  10 5 ms 1 (d) 8.76  108 ms 1

Solution : (a) We know that velocity of electron in nth Bohr's orbit is given by
Z
v  2.18  10 6 m / s
n
for H, Z  1
2.18  106
 v1  m/s
1
2.18  106
 v2  m / s  1.09  106 m / s
2

Example: The ionization energy of the ground state hydrogen atom is 2.18  10 18 J.
The energy of an electron in its second orbit would be
(a) 1.09  1018 J
(b)  2.18  10 18 J
(c)  4.36  10 18 J
(d)  5.45  10 19 J

Solution : (d) Energy of electron in first Bohr's orbit of H-atom

 2.18  10 18 (
E 2
J ionization energy of H = 2.18  10 18 J )
n
 2.18  10 18
E2  J  5.45  10 19 J
22
1
Example: The wave number of first line of Balmer series of hydrogen atom is 15200 cm . What is the
3
wave number of first line of Balmer series of Li ion.
(a) 15200cm 1
(b) 6080 cm 1
(c) 76000cm 1
(d) 1,36800 cm 1

Solution : (d) For Li 3 v  v for H  z 2 =15200 ×9= 1,36800 cm 1

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Example: The Bohr orbit radius for the hydrogen atom (n = 1) is approximately 0.530Å.
The radius for the first excited state (n = 2) orbit is (in Å)
(a) 0.13
(b) 1.06
(c) 4.77
(d) 2.12

Solution : (d) The Bohr radius for hydrogen atom (n = 1) = 0.530Å

n2 (2) 2
The radius of first excited state (n = 2) will be = 0.530   0.530   2.120Å
Z 1

Example: How many chlorine atoms can you ionize in the process Cl  Cl  e  , by the energy liberated
from the following process :
Cl  e   Cl for 6  10 23 atoms
Given electron affinity of Cl  3.61eV, and IP of Cl  17.422 eV
(a) 1.24  10 23 atoms
(b) 9.82  10 20 atoms
(c) 2.02  1015 atoms
(d) None of these

Solution : (a) Energy released in conversion of 6  10 23 atoms of Cl  ions = 6  10 23 × electron affinity

= 6× 1023  3.61  2.166  10 24 eV.

Let x Cl atoms are converted to Cl ion
Energy absorbed  x  ionization energy
x  17.422  2.166  10 24 ; x  1.243  10 23 atoms

Example: The binding energy of an electron in the ground state of the He atom is equal to 24eV. The
energy required to remove both the electrons from the atom will be
(a) 59eV
(b) 81eV
(c) 79eV
(d) None of these
Z2 22
Solution : (c) Ionization energy of He  2  13.6  2  13.6  54.4eV
n 1
Energy required to remove both the electrons
 binding energy + ionization energy
 24.6  54.4  79eV

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Example: The wave number of the shortest wavelength transition in Balmer series of atomic hydrogen will
be
(a) 4215 Å
(b) 1437Å
(c) 3942Å
(d) 3647Å

1  1 1   1 1 
Solution : (d)  RZ 2  2  2   109678  12   2  2 
 shortest  n1 n 2  2  
  3.647  10 5 cm  3647Å

Example: If the speed of electron in the Bohr's first orbit of hydrogen atom is x, the speed of the electron in
the third Bohr's orbit is
(a) x/9
(b) x/3
(c) 3x
(d) 9x

Solution : (b) According to Bohr's model for hydrogen and hydrogen like atoms the velocity of an electron in
2Ze 2 1
an atom is quantised and is given by v  so v  in this case n  3
nh n

Example: Of the following transitions in hydrogen atom, the one which gives an absorption line of lowest
frequency is
(a) n=1 to n=2
(b) n  3 to n  8
(c) n  2 to n  1
(d) n  8 to n  3

Solution : (b) Absorption line in the spectra arise when energy is absorbed i.e., electron shifts from lower to
higher orbit, out of a & b, b will have the lowest frequency as this falls in the Paschen series.

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Photoelectric effect

(1) When radiations with certain minimum frequency ( 0 ) strike the surface of a metal, the electrons
are ejected from the surface of the metal. This phenomenon is called photoelectric effect and the
electrons emitted are called photo-electrons. The current constituted by photoelectrons is known as
photoelectric current.

(2) The electrons are ejected only if the radiation striking the surface of the metal has at least a minimum
requency ( 0 ) called Threshold frequency. The minimum potential at which the plate photoelectric
current becomes zero is called stopping potential.

(3) The velocity or kinetic energy of the electron ejected depend upon the frequency of the incident radiation
and is independent of its intensity.

(4) The number of photoelectrons ejected is proportional to the intensity of incident radiation.

(5) Einstein’s photoelectric effect equation : According to Einstein, Maximum kinetic energy of the ejected
electron = absorbed energy – threshold energy

1 1 1 
mv 2max  h  h 0  hc   
2   0 

where,  0 and  0 are threshold frequency and threshold wavelength.

Note :  Nearly all metals emit photoelectrons when exposed to UV light. But alkali metals like lithium,
sodium, potassium, rubidium and cesium emit photoelectrons even when exposed to visible light.

U.V. light Metal Photo electrons

Visible light Metal other

than alkali No photo electrons
metals

Visible light Alkali

metals Photo electrons

 Cesium (Cs) with lowest ionization energy among alkali metals is used in photoelectric cell

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 Examples
Example: Photoelectric emission is observed from a surface for frequencies 1 and 2 of the incident
radiation (1>2). If the maximum kinetic energies of the photoelectrons in two cases are in
ratio 1:K then the threshold frequency 0 is given by
(A) (B) (C) (D)
K1   2 K 2  1 2  1
 2  1
K 1 K 1 K 1 K

Solution: KE1 = h1 – ho

KE2 = h2–ho
It is given that
KE1 1
KE2 = K
h 1  h o 1

h 2  h o K
K1   2   o K  1
K 1   2
o =
K 1
 (B)

Example: Atomic radius is the order of 10 8 cm, and nuclear radius is the order of 10 13 cm. Calculate what
fraction of atom is occupied by nucleus.

Solution : Volume of nucleus  (4 / 3) pr 3  (4 / 3) p  (10 13 ) 3 cm 3

Volume of atom  (4 / 3) pr 3  (4 / 3) p  (10 8 ) 3 cm 3
Vnucleus 10 39
   10 15 or Vnucleus  10 15  Vatom
Vatom 10 24

Example: Suppose 10 17 J of energy is needed by the interior of human eye to see an object. How many
photons of green light (  550 nm ) are needed to generate this
minimum amount of energy

(a) 14 (b) 28 (c) 39 (d) 42

hc 10 17   10 17  550  10 9

Solution : (b) n  10 17 ; n    27.6  28 photons
 hc 6.626  10 34  3  108

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