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CHEMISTRY

Atomic Structure

Atomic Structure

ATOMIC STRUCTURE
1. LAWS OF CHEMICAL COMBINATIONS
Law of conservation of mass: Laws of conservation of mass states that in a chemical reaction the weight of
products is always equal to the weight of reactants.
Law of definite proportions: Law of definite proportions states that the elemental composition of a compound
always remains same if it is analysed form various sources e.g. water from a river or ditch or pond either in India
or in USA would always give H : O ratio as 2 : 1.
Law of Multiple Proportions: Law of multiple proportion states that elements combine in simple whole number
ratios to form various types of compounds e.g. The ratio of N : O is 1: 1, 1 : 2 and 2 : 1 in NO, NO2 and N2O.
respectively.
2. DALTONS THEORY OF ATOM
John Dalton developed his famous theory of atom is 1803. The main postulates of his theory were :

Atom was considered as a hard, dense and smallest indivisible particle of matter.

Each element consists of a particular kind of atoms.

The properties of elements differ because of differences in the kinds of atoms contained in them.

This theory provides a satisfactory basis for the law of chemical combination.

Atom is indestructible i.e. it cannot be destroyed or created.


Drawbacks

It fails to explain why atoms of different kinds should differ in mass and valency etc.

The discovery of isotopes and isobars showed that atoms of same elements may have different atomic
masses (isotopes) and atoms of different kinds may have same atomic masses (isobars).

The discovery of various sub-atomic particles like X-rays, electrons, protons etc. during the 19th
century lead to the idea that the atom was no longer an indivisible and smallest particle of the matter..
3. DISCOVERY OF ELECTRON
William Crookes found that certain rays come out of cathode and gain lots of energy because of high acceleration
potential before colliding with a gas molecule. This happens especially when the gas pressure is low. These rays
are known as cathode rays.
High Voltage
Gas at very low pressure
Cathode

Cathode

Anode
Suction pump

Fig. Cathode ray Tube experiment

Detailed study of cathode rays by J.J. Thomson led to the discovery of electrons. He observed that
1.Cathode rays always travel in straight lines
2.They are negatively charged. Cathode rays turn towards positively charged plates.
3.Charge on particles constituting rays was determined by Oil
Drop experiment by Millikan as 1.6 10 19 coulomb.
4.Specific charge (e/m) does not change when the gas inside discharge tube was changed indicating that electron
is fundamental particle.
e/m for electron = 1.758 1011 Coulombs / kg .
5.Value of charge on electron = 1.6 10 19 Coulombs
6.Mass of the electron = 1.9 10 31 kg .
4. ANODE RAYS (DISCOVERY OF PROTON)
It is well-known fact that the atom is electrically neutral. The presence of negatively-charged electrons in the
atom amphasized the presence of positively-charged particles.
To detect the presence of positively-charged particles, the discharged tube experiment was carried out, in which
a perforated cathode was used. Gas at low pressure was kept inside the tube. On passing high voltage between
the electrodes it was observed that some rays were emitted from the side of the anode. These rays passed through

Atomic Structure
the holes in the cathode and produced green fluorescence on the opposite glass was coated with ZnS. These rays
consist of positively-charged particles known as protons.
Perforated
cathode

ZnS
Coating

H2 gas inside
at low pressure

For anode rays, e/m is not fundamental property as different gases used have different mass on C-12 scale.
Highest e/m is for hydrogen gas.
5. DISCOVERY OF NEUTRON
After the discovery of electrons and protons, Rutherford (1920) had predicted the existence of a neutral fundamental
particle. In 1930, Bethe and Becker reported from Germany that if certain light elements, like beryllium, were
expoesd to alpha rays from the naturally radioactive polonium, a very highly penetrating radiation was obtained.
Similar results were obtained by Irene Cureia dn F. Jolit (1932). Chadwick (1932) demonstrated that this mysterious
radiation was a stream of fast moving particles of about the same mass as a proton but having no electric charge.
Because of their electrical neutrality, these particles were called neutron.
The lack of charge on the neutron is responsible for its great penetraing power.
Thus, a neutron is a sub-atomic fundamental particle which has a mass 1.675 10 24 g (approximately 1 amu),
almost equal to that of a proton or a hydrogen atom but carrying no electric charge. The e / m value of a neutron
is thus zero.
6. CONSTITUENTS OF ATOM
Some of the well known fundamental particles present in an atom are-protons, electrons and neutrons. Many
others were discovered later viz positron, neutrinos etc.
Subatomic
Symbol
Unit Charge
Unit Mass
Charge in
Mass in AMU
particles
Coulomb
Proton

p1

Neutron

Electron

e0

1.007825

1.60 1019
0

Negligible

1.602 1019

5.489 104

+1

0
1

1.008665

Do you Know?
Chandwick in 1932 discovered the neutron by bombarding elements like beryllium with fast moving -particles.
He observed that some new particles were emitted which carried no charged and had mass equal to that of
proton.
7. THEORIES OF ATOM
After the discovery of electrons, protons and neutrons several theories were proposed by various scientists such
as
1.Plum Pudding Model (Thomson Model of Atom)
2.Rutherfords Model of Atom
3.Plancks quantum theory
4.Bohrs Atomic Model
Thomson Model of Atom
According to this model, electrons are embedded in uniform sphere of positive charge to confer electrical neutrality.
This model was satisfactory to the extent that the electrostatic forces of repulsion among the electron cloud is
balanced by the attractive forces between the positively charged mass and the electron. How ever, this model
fails to explain the results of ionisation and scattering experiment and is, therefore discarded.
Rutherford Model of Atom
When -particles are bombarded on thin foils ( 4 105 cm thick) of metals like gold, silver, platinum or copper,,

Atomic Structure
most of them are passed through the metal foil with little or no deviation. However a small proportion of particles are scattered through large angles and even bounced back i.e. deflected through 1800. From these
observations, Rutherford drew the following conclusions:
Reflected -particles

Gold foil

Lead block

Lead plate

Zinc sulphide
screen

Fig. Rutherford's Experiment

(a) As most of the -particles passed through the foil without undergoing any deflection, there must be sufficient
empty space within the atom.
(b) As -particles are positively charged, deflected by large angle there must be heavy small positively charged
body present in the atom, which is called Nucleus.
From these observations, Rutherford proposed the following model of atom:
(a) Atom is composed of a positively charged nucleus where the whole mass of the atom is concentrated and the
electrons are present in relatively large volume around the nucleus. The total positive charge carried by nucleus
must be equal to the total negative charge carried by electrons and electroneutrality of atom is maintained.

positive sphere

electron

Fig: Thomson Model

(b) Electron are constantly moving around the nucleus in different orbits.
The centrifugal force arising from this motion balances the electrostatic attraction between the nucleus and the
electron. Therefore the electron dont fall into the nucleus.
Drawbacks in Rutherford Model
(a) The most fundamental objection arises from the electromagnetic theory of radiation which predicts that when
a charged body moves in a circular path, it should radiate energy continuously. As the electron is a negatively
charged particle revolving around the nucleus, it should radiate energy continuously. As a result, the electron
should fall into the nucleus.
(b) As the electron is continuously radiating energy, the spectra should be continuous. Actually, the spectra of
atom is a line spectra.
8. ATOMIC NUMBER OF AN ELEMENT
= Total number of protons present in the nucleus
= Total number of electrons present in the atom
* Atomic number is also known as proton number because the charge on the nucleus depends upon the number
of protons.
* Since the electrons have negligible mass, the entire mass o the atom is mainly due to protons and neutrons only.
Since these particles are present in the nucleus, therefore they are collectively called nucleons.
* As each of these particles has one unit mass on the atomic mass scale, therefore the sum of the number of
protons and neutrons will be nearly equal to the mass of the atom.
Mass number of an element = No. of protons + No. of neutrons.
* The mass number of an element is nearly equal to the atomic mass of that element. However, the main difference
between the two is that mass number is always a whole number whereas atomic mass is usually not a whole
number.
* The atomic number (Z) and mass number (A) of an element X are usually represented alongwith the symbol
of the element as

Atomic Structure
Mass Number

Atomic Number

e.g.

23
11

Symbol of the
element

35
Na , 17
Cl and so on.

1.Isotopes:
Such atoms of the same element having same atomic number but different mass numbers are called isotopes.
1
1

H , 12 H and 13 H and named as protium, deuterium (D) and tritium (T) respectively. Ordinary hydrogen is
protium.

2. Isobars:
Such atoms of different elements which have same mass numbers (and of course different atomic numbers) are
called isobars.
e.g.

40
18

Ar ,

40
19

K,

40
20

Ca .

3. Isotones:
Such atoms of different elements which contain the same number of neutrons are called isotones.
e.g.

14
6

C,

15
7

.
K , 16
8 O

4. Isoelectronics:
The species (atoms or ions) containing the same number of electrons are called isoelectronic.
For Example, O 2 , F , Na , Mg 2 , Al 3 , Ne all contain 10 electrons each and hence they are isoelectronic.
Illustration.
Complete the following table:
Particle
Mass No.
Atomic No.
Protons
Neutrons
Electrons
Nitrogen atom

7
7
Calcium ion

20

20

Oxygen atom
16
8

Bromide ion

45
36
Solution.
For nitrogen atom.
No. of electron = 7
(given)
No. of neutrons = 7
(given)
No.
of
protons
=
Z
=
7
( atom is electrically neutral)

Atomic number = Z = 7
Mass No. (A) = No. of protons + No. of neutrons = 7 + 7 = 14
For calcium ion.
No. of neutrons = 20
(given)
Atomic No. (Z) = 20
(given)
No. of protons = Z = 20;

No. of electrons in calcium atom = Z = 20


But in the formation of calcium ion, two electrons are lost from the extranuclear part according to the equation
Ca Ca 2 2e but the composition of the nucleus remains unchanged.
No. of electrons in calcium ion = 20 2 = 18
Mass number (A) = No. of protons + No. of neutrons = 20 + 20 = 40.

For oxygen atom.


Mass number (A) = No. of protons + No. of neutrons = 16
Atomic No. (Z) = 8
No. of protons = Z = 8,

(Given)
(Given)

Atomic Structure
No. of electrons = Z = 8
No. of neutrons = A Z = 16 8 = 8
Some important characteristics of a wave:

Crest

Crest

a
Trough

Trough

Wavelength of a wave is defined as the distance between any two consecutive crests or troughs. It is represented
by and is expressed in or m or cm or nm (nanometer) or pm (picometer).
1 10 8 cm 1010 m
1 nm 109 m, 1 pm 10 12 m

Frequency of a wave is defined as the number of waves passing through a point in one second. It is represented
by v (nu) and is expressed in Hertz (Hz) or cycles/sec or simply sec1 or s1.
1 Hz = 1 cycle/sec
Velocity of a wave is defined as the linear distance travelled by the wave in one second. It is represented by v and
is expressed in cm/sec or m/sec (ms1).
Amplitude of a wave is the height of the crest or the depth of the trough. It is represented by a and is expressed
in the units of length.
Wave number is defined as the number of waves present in 1 cm length. Evidently, it will be equal to the
reciprocal of the wavelength. It is represented by v (read as nu bar).
1
v

If is expressed in cm, v will have the units cm1.


Relationship between velocity, wavelength and frequency of a wave. As frequency is the number of waves
passing through a point per second and is the length of each wave, hence their product will give the velocity
of the wave. Thus,

v v
Cosmic rays < - rays < X-rays < Ultraviolet rays < Visible < Infrared < Micro waves < Radio waves.
9. PLANCKS QUANTUM THEORY (1901)
It states
1.Radiant energy is emitted or absorbed discontinuously in the form of tiny bundles of energy called Quanta.
2.Each quantum is associated with a definite amount of energy E which is proportional to frequency of radiation.

E hv
Where,

h = Plancks constant = 6.626 10 34 Joule sec .


v = Frequency of the light radiation

3.A body can emit or absorb radiations only in whole multiples of quantum i.e. E nhv
where n 1, 2,3......

where

c = velocity of light

= wavelength

Atomic Structure

hc

9(a). Some Important Formulae


1.A = Z + N (Number of neutrons)
2.dynamic mass of particle m m0 /[1 (v / c) 2 ]1/ 2
3.Radius of nucleus R R0 ( A)1/ 3 , R0 1.2 10 15 m
4. c v

5.wave number = v 1/
6. E hv hc / hcv
q1 q2
1
9
2
2
7. F K r 2 ; K 4 9.0 10 Nm / C
0

8. E hv E2 E1
Illustration 1.
Calculate number of photon coming out per sec. from the bulb of 100 watt. If it is 50% efficient and wavelength
coming out is 600 nm.
Solution.
energy = 100 J
energy of one photon =

no. of photon =

hc 6.625 1034 3 108 6.625

1019

600 109
2

100
1019 15.09 1019
6.625

Illustration 2.
Certain sun glasses having small of AgCl incorporated in the lenses, on exposure to light of appropriate wavelength
turns to gray colour to reduce the glare following the reactions:
hv
AgCl
Ag (Gray ) Cl

If the heat of reaction for the decomposition of AgCl is 248 kJ mol1, what maximum wavelength is needed to
induce the desired process?
Solution.
Energy needed to change = 248 10 3 J / mol
If photon is used for this purpose, then according to Einstein law one molecule absorbs one photon. Therefore,

NA

hc
248 103

6.625 1034 3.0 108 6.023 1023


4.83 107 m .
248 103

10. BOHRS ATOMIC MODEL


The postulates of Bohrs atomic theory regarding stability of electrons of an atom are as follows:
(i) The electrons is an atom revolve around the nucleus only in certain selected circular orbits. These orbits are
known as energy levels or stationary states. An electron can be excited from a lower state to higher state with the
absorption of a quantum of energy, or can come down from a higher to lower state with emission of a radiation
of energy (as shown in figure) equal to energy to quantum E E2 E1 hv . E2 and E1 are energies of the
electron associated with stationary orbits.

Atomic Structure
Emission of
radiation with energy
Absorption of E

E(E2 E1 )

E1
+

Fig. Bohr's Atomic Model

(ii) The stability of the circular motion of an electron requires that the electrostatic force (due to the attraction
between the nucleus and the electron) provides the necessary centripetal force for the motion of electron.
1 ( Ze) e
.
mv 2 / r
4 0 r 2

where

... (i)

Z atomic number
e charge on electron

0 permittivity of the charge in vacuum


r distance between positive charge & electron
(iii) Angular momentum of electron is quantised i.e. electron can revolve only in those orbits where its angular
momentum is an integral multiple of h / 2
... (ii)

mvr nh / 2
where,

v velocity of electron

m mass of electron
h Plancks constant

n 1, 2, 3........ are known as Principal quantum number..


Bohrs Atomic Radius
from (i) &(ii) we have from (i)

v 2 ze 2 /(4 0 ) mr

... (iii)

v 2 n 2 h 2 / 4 2 m2 r 2
Equating (iii) and (iv),
we have
& from (ii)

... (iv)

Ze 2 /(4 0 ) mr n 2 h 2 / 4 2 m 2 r 2

or,

(4 0 )n2 h 2
4 2 mZe 2

r is called Bohrs radius.


Where h, , e, m and 0 are constants, Thus, r K (n 2 / Z )
Putting the values of h, , e, m and 0 , r (5.297 10 11 m) ( n 2 / Z )
Illustration 1.
For hydrogen atom Z 1 , therefore radius of the first orbit = (5.297 10 11 m) (12 /1)
For He ion Z 2 , therefore radius of the first orbit = (5.297 10 11 m) (12 / 2)
2.649 10 11 m

Solution.
Velocity of electrons in various orbits

Atomic Structure
Substituting value of r in equation no. (ii)
v

2 Ze 2
K ( Z / n)
4 0 nh

The energy of an electron in an orbit


Ze 2
1 2
E = Kinetic energy + Potential energy = mv
(4 0 ) r
2

Putting ( mv ) 2 from equation (i), we have


Ze 2
Ze 2
Ze 2

2(4 0 ) r (4 0 ) r
2(4 0 ) r

Now, putting the value of ' r ' , we have


E

2 2 mZ 2 e 4
K ( Z 2 / n2 ) (2.18 10 18 J ) ( Z 2 / n2 )
2 2 2
(4 0 ) n h

The energy difference between two energy levels n2 and n1 is given by


E En2 En1

1
2 2 mZ 2 e 4
1/ n12 1/ n22

(4 0 ) 2
h2

1 1
(2.18 1018 J ) Z 2 2 2
n1 n2

It terms of wave-number, we have


v RH Z 2 1/ n12 1/ n22

10(a). Bohrs Model for Hydrogen like Atoms:


1. mvr n

2. En

E1

h
2

E1 2
z2
z2
z 2.178 1018 2 J / atom 13.6 2 eV
2
n
n
n

2 2 me 4
n2

3. rn

n2
h2
0.529 n 2
2 2

Z 4 e m
Z

4. v

2 ze 2 2.18 106 z

m/s
nh
n

5.Revolutions per sec = v / 2 r

0.657 Z 2 1016
n3

6.Time for one revolution = 2 r / v

1.52 1016 n3
Z2

7. En K .E. P.E.( P.E. 2 K .E.)


2
8. K .E. 1/ 2mv , P.E.

1 ze 2
4 0 r

Atomic Structure
Illustration 1.
What is the principal quantum number of H atom orbital is the electron energy is 3.4 eV? Also report the
angular momentum of electron.
Solution.
E1 for H = 13.6 eV
E1
n2

Now,

En

3.4

n=2

13.6
n2

Now, Angular momentum (mur) = n.

h 2 6.626 1034

2.1 1034 J sec 1 .


2
2 3.14

Illustration 2.
Calculate the energy, velocity and radius of electron in Li2+ ion.
Solution.
For Li2+ ion, z = 3, n = 1, then
radius = 0.529

n2
z

1
0.529 0.1763
3

8
velocity = 2.18 10 cm / sec

z
3 2.18 108 cm / sec.
n

6.54 108 cm / sec.

Energy

13.6 ev

z2
9
13.6 ev
2
n
1

122.4 ev .
11. DEFINITION VALID FOR SINGLE ELECTRON SYSTEM :
(i) Ground state:
lowest energy state of any atom or ion is called ground state of the atom.
Ground state energy of H-atom = 13.6 eV
Ground state energy of He+ ion = 54.4 eV
(ii) Excited state:
State of atom other than the ground state are called excited states:
n=2
first exited state
n=3
second exited state
n=4
third exited state
n=n+1
nth exited state
(iii) Ionisation energy (IE) :
Minimum energy required to move an electron from ground state to
n is called ionisation energy of the atom or ion.
Ionisation energy of H-atom = 13.6 eV
Ionisation energy of He+ ion = 54.4 eV
Ionisation energy of Li+2 ion = 122.4 eV
(iv) Ionisation Potential (I.P):
Potential difference through which a free electron must be accelerated from rest, such that its kinetic energy
becomes equal to ionisation energy of the atom is called ionisation potential of the atom.
I.P. of H atom = 13.6 V
I.P of He+ Ion = 54.4 V

10

Atomic Structure
(v) Excitation Energy:
Energy required to move an electron from ground state of the atom to any other state of the atom is called
excitation energy of that state.
excitation energy of 2nd state = excitation energy of 1st state = 1st excitation energy = 10.2 eV.
(vi) Excitation Potential:
Potential difference through which an electron must be accelerated from rest to so that its kinetic energy become
equal to excitation energy of any state is called excitation potential of that state.
excitation potential of third state = excitation potential of second excitate state = seconds excitations potential =
12.09 v.
(vii) Binding Energy or Separation Energy:
Energy required to move an electron from any state to n is called binding energy of that state.
Binding energy of ground state = I.E. of atom or Ion.
Illustration.
A single electron system has ionisation energy 11180 kJ mol1. Find the number of protons in the nucleus of the
system.
Solution.
I.E. =

Z2
21.69 1019 J
n2

11180 103 Z 2

21.69 1019
6.023 1023 I 2
Z=3

12. HYDROGEN SPECTRUM:


1. Study of Emission and Absorption Spectra:
An instrument used to separate the radiation of different wavelengths (or frequencies) is called spectroscope or
a spectrograph. Photograph (or the pattern) of the emergent radiation recorded on the film is called a spectrogram
of simply a spectrum of the given radiation. The branch or science dealing with the study of spectra is called
spectroscopy.
Emission Spectra
When the radiation emitted from some source e.g. from the sun or by passing electric discharge through a gas at
low pressure or by heating some substance to high temperature etc, is passed directly through the prism and then
received on the photographic plate, the spectrum obtained is called Emission spectrum.
Depending upon the sources of radiation, the emission spectra are mainly of two types:
(i) Continuous spectra:
When white light from any source such as sun, a bulb or any hot glowing body is analysed by passing through a
prism it is observed that it splits up into seven different wide bound of colours from violet to red. These colours
are so continuous that each of them merges into the next. Hence the spectrum is called continuous spectrum.
White light

R
O
Y
G
B
I
V

Beam
Slit

Prism

Photographic
Plate

(ii) Line Spectra:


When some volatile salt (e.g., sodium chloride) is placed in the Bunsen flame or an electric discharge is passed
through a gas at low pressure light emitted depends upon the nature of substance.
Platinum wire
Beam

5896
Two yellow lines
5890

Slit
Prism

Photographic
Plate

11

Atomic Structure
It is found that no continuous spectrum is obtained but some isolated coloured lines are obtained on the
photographic plate separated from each other by dark spaces. This spectrum is called Line emission spectrum
or simply Line spectrum.
2. Absorption spectra:
When white light from any source is first passed through the solution or vapours of a chemical substance and
then analysed by the spectroscope, it is observed that some dark lines are obtained in the otherwise continuous
spectrum. These dark lines are supposed to result from the fact that when white light (containing radiations of
many wavelengths) is passed through the chemical substance, radiation. of certain wavelengths are absorbed,
depending upon the nature of the element.
White light

R
O
Y}
G
B
I
V

NaCl
Solution

Slit

Prism

Photographic
Plate

Dark lines in yellow region of


continuous spectrum

Beam
Slit
Prism

Photographic
Plate

EMISSION SPECTRUM OF HYDROGEN:


12(a). H-Atom Spectrum
When an electric discharge is passed through hydrogen gas at low pressure, a bluish light is emitted. When a ray
of this light is passed through a prism, discontinuous line spectrum of several isolated sharp lines is obtained as
shown in figure.

n=
6
5

Pfund series

Bracket series

Paschen series

Energy
2

n=1

Balmer series

Lymann series
Energy levels of H-atom

All these lines observed in the hydrogen spectrum can be classified into the series as is tabulated in the table.
The hydrogen Spectrum
Region
Spectral lines
n1
n2
UV
Lyman series
1
2,3,4,.....
Visible
Balmer series
2
3,4,5,.....
IR
Paschen series
3
4,5,6,.....
far-I.R
Brackett series
4
5,6,7,.....

12

Atomic Structure
far-I.R.
P fund series
5
6,7,8,.....
Illustration
Calculate the highest wavelength of line spectra of H-atom when the electron is situated in 3rd excited state.
Solution.
Highest wavelength means lowest energy difference of electronic transition from one energy level to other
energy level.
Hence, lowest energy transition will be n 4 to n 3 .
E4 13.6 ev

1
16

0.85 ev

E3 13.6 ev

1
9

1.54 ev

E E4 E3

(0.85 1.54)ev

hc
0.69ev 0.69 1.6 10 19 J

6.626 1034 3 108


m
0.69 1.6 1019

18 107 m

13. DE-BROGLIE RELATIONSHIP


According to de-Broglie matter has dual character i.e. wave as well as particle, if the wavelength of matter be
having mass m moving with velocity v , then,

h
mv

where h is Plancks constant (6.626 10 34 Joul sec) .

wave in phase
Case - I

wave out of phase


Case - II

For electron moving around a nucleus in a circular path, two possible waves of different wavelengths are possible.
In case I, the circumference of the electron orbit is an integral multiple of wavelength.
In case II, wave is destroyed by interference and hence, does not exist.
Therefore, the necessary condition for a stable orbit of electron of radius r is, 2 r n
when n 1, 2,3, etc .
As

2 r

h
mv

nh
mv

or ,

mvr

nh
2

This is simply the original Bohr condition for a stable orbit. Hence, the Bohrs model of H-atom is justified by
de-Broglie relationship.
13.(a)
De-Broglie Relations:

h
h

mc p

13

Atomic Structure
de-Broglie pointed out that the same equation might be applid to material particle by suing m for the mass of the
particle instead of the mass of photon and replacing c, the velocity of the photon, by v, the velocity of the
particle.

mv

h
2m( K .E.)

From the de-Broglie equation it follows that wavelength of a particle decreases with increase in velocity of the
particle. Moreover, lighter particles would have longer wavelengths than heavier paticles, provided the velocity
is equal.
If a charged particle Q is accelerated through potential difference V from rest then de-broglie wavelength is
h

2mQV

de-Broglie concept is more isgnificant for microscopic or sub-microscopic particles whose wavelength can be
measured.
The circumference of the nth orbit is equal to n times the wavelength of the electron.
2 rn n
Wavelength of electron is always calculated using De-broglie calculation.
Illustration. 1
Calculate the wavelength of a body of mass 1 kg moving with a velocity of 10 m sec1.
Solution.

We know,

h
mv

Substituting the values, m = 1, mg = 106 kg, v = 10 m sec1.


h 6.625 10 34 kg m 2 s 1

and

6.625 1034
6.625 1029 m
106 10

Illustration. 2
13.6 eV is needed for ionisation of a hydrogen atom. An electron in a hydrogen atom in its ground states absorbs
1.50 times as much energy as the minimum energy required for it to escape from the atom. What is the wavelength
of the emitted electron? ( me 9.109 10 31 kg , e 1.602 10 19 coulomb, h 6.63 10 34 J .s )
Solution.
1.5 times of 13.6 eV, i.e., 20.4 eV, is absorbed by the hydrogen atom out of which 6.8 eV (20.4 13.6) is
converted to kinetic energy.
KE = 6.8 eV = 6.8 ( 1.602 10 19 coulomb ) (1 volt) = 1.09 10 18 J .
Now,

KE

1
mv 2
2

or,

2 KE
2(1.09 10 18 J )

1.55 10 6 m / s.
m
(9.109 10 31 kg )

h
(6.63 10 34 J .s)

4.70 10 10 metres.
mv (9.109 10 31 kg )(1.55 10 6 m / s )

14. HEISENBERGS UNCERTAINTY PRINCIPLE (1927):


If subatomic particles have wave nature then we cant pinpoint where exactly a particle is. The idea was defined
by Heinsenberg as - There is a limit to the precision to which the position and momentum of a particle may be
determined simultaneouslyx p h / 4

14

Atomic Structure
Where

x uncertainty in position of an electron.

p uncertainty in momentum of an electron, i.e., when we try to determine position for a subatomic
particle correctly, uncertainly in momentum will be very large or when we try to determine the momentum
correctly then uncertainly in position will be large.
ORIGIN OF QUANTUM THEORY
When solid body heated it emit radiations in the forms of waves. The wave nature of light can be explained by
diffraction interference etc. But some other observable properties such as photoelectric effect, compton effect
could not be explained from wave nature. Hence a different theory is needed to explain these facts.
Illustration.
Calculate the uncertainty in the velocity of a wagon of mass 2000 kg whose position is known to an accuracy of
10 m .
Solution.
Uncertainty in position,

x 10 m

Mass of the wagon,

m 2000 kg

According to Heinsenbergs principle,


x.m v

h
4

h
6.626 10 34 kgm 2 s 1

2.64 10 39 ms 1 .
4 m.x 4 3.14 2000 kg 10 m

14(a). Black Body Radiation


When radiation falls on an object, a part of it is reflected, a part is absorbed and the remaining part is transmitted
because no object is a perfect absorber. But the black body (e.g., a metallic hollow sphere with a small hole,
blackened on the inside surface) absorbs completely all the radiations falls on it by successive reflections inside
the enclosure.
T1
energy

T2
T3

T1>T2>T3

Wave length

The black body is not only a perfect absorber of radiation energy, but also an ideal radiation, i.e., when the black
body is heated, it radiates the maximum amount of energy. The energy which is radiated is dependent on the
temperature of the black body and is independent of the nature of the interior material.
The curves represent the distribution of radiation from a black body at different temperatures. The shape of the
curves couldnt be explained on the basis of classical electromagnetic theory in which it was assumed that the
body radiates energy continuously. So, the intensity of radiation should increase continuously without limits as
the frequency increases. But the experimental observations are contrary to the classical view. For each temperature,
there is a maximum in the curve corresponding to a particular wavelength, indicating the maximum radiation of
energy. At higher temperature, the position of the maximum in the curve shifts towards shorter wavelength and
becomes more pronounced. To explain this black body radiation, Max Planck put forward new quantum theory.
Planck Quantum Theory
(a) Radiation energy is not emitted or absorbed continuously but discontinuously in the form of tiny bundles of
energy, called quanta.
(b) Each quanta is associated with a defined amount of energy (E) which proportional to the frequency of
radiation i.e, E v or, E hv where h is Plancks constant

(6.626 10 34 J sec) .

(c) A body can emit or absorb energy only in whole number multiples of quanta i.e. E nhv where n 1, 2,3 etc.
15. PHOTOELECTRIC EFFECT
Sir J.J. Thomson has discovered this phenomenon of ejection of electron from the surface of a metal when light
of suitable frequency of strikes on it.

15

Atomic Structure
Only few metals show this effect under the action of visible light, but many more show it under the action of
more energetic u.v. light. For every metal, there is a minimum frequency of incident radiation necessary to eject
electron from that metal surface, is known as Threshold frequency ( v0 ). This v0 varies metal to metal.
The number of ejected electrons from the metal surface depends upon the intensity of the incident radiation.
Greater the intensity, the larger is the number of ejected electrons.
Hence, according to quantum theory, when a photon of light of frequency (v v0 ) strikes on an electron in a
metal, it imparts it entire energy to the electron. Then some of its energy (equal to binding energy of electron with
the nucleus) is consumed to separate the electron from the metal and the remaining energy will be imparted to the
ejected electron.
1
1
hv hv0 mv 2 where hv0 is the binding energy of work function of the electron and mv 2 is the kinetic
2
2
energy of electron. Alkali metals are mainly used for photoelectric effect. Cesium, amongst alkali metals, has
lowest threshold energy and used largely in photoelectric cell.
16. SHAPES OF ORBITALS
s-orbital: they do not have directional character. They are spherically symmetrical. The s-orbital of higher
energy levels are also spherically symmetrical. They are more diffused and have spherical shells within them
where probability of finding the electron is zero.
y
Node
z

2s orbital

In the s-orbital, number of nodes is (n 1)


p-orbital: p orbital has a dumb-bell shape and it has a directional character.
The two lobes of a p-orbital are separated by a plane that contains the nucleus and is perpendicular to the
corresponding axis. Such plane is called a nodal plane because there is no probability of finding the electron.
y

z
z

+
x

z
+
x

px

py

pz

In the absence of an external electric or magnetic field, the three p-orbitals of a particular energy level have same
energy and are degenerate. In the presence of an external magnetic field or electric field this degeneracy is
removed.
d-orbitals: For d-orbitals five orientations are possible viz., dxy, dyz, dxz, d x2 y 2 , d z 2 . All these five orbitals in the
absence of magnetic field are equivalent in energy and are degenerate.
The shapes of the orbitals are as follows:

16

Atomic Structure
x

dxy

dxz

dyz

These three d orbitals are similar. The maximum probability of finding the electron is in lobes which are
directed in between the axes. Nodal region is along the axes.
z

dz2

dx2-y2

These two d-orbitals are similar. Probability of finding the electron is maximum along the axes and the nodal
region is in between the axes.
17. QUANTUM NUMBERS
These are used to determine the region of probability of finding a particular electron in an atom.
(a) Principal quantum number (n):
This denotes the energy level or the principal or main shell to which an electron belongs. It can have only
integral values 1, 2, 3 etc. The letter K, L, M ..... are also used to designate the value of n. Thus, an electron in the
K shell has n = 1, that is L shell has n = 2 and so on.
Illustration. 1
The principal quantum number of 2s-electron is
Solution.
n=2
(b) Azimuthal quantum numbers (l):
This denotes the orbital (Sub-level) to which an electron belongs. It gives an idea about the shape of the orbital.
l can have any value from 0 to (n 1), for a given value of n,
i.e. l = 0, 1, 2, ..... (n 1)
Value of l
0
1
2
3
Sub Shell
s
p
d
f
The value of orbital angular momentum of the electron for a given value of l is

l (l 1)

h
2

(c) Magnetic quantum number (m):


It gives us the idea about the orientations an orbital can have in space in the presence of magnetic field. The
values of m depends on l orbital quantum number.
Total value of m = (2l + 1) and it varies l to +l.
For example, for l = 0 the value of magnetic quantum number m is also equal to zero, i.e. s-orbital can have
only one orientation in space in presence of magnetic field.
(d) Spin quantum number (s):
The electron while moving round the nucleus in an orbit also rotates or spins about its own axis either in a

17

Atomic Structure
clockwise direction or in an anticlockwise direction. Its value is

1
1
or corresponding to clockwise or
2
2

anticlockwise spin.
(1) The value of spin angular momentum for a given value of s is

s( s 1)

h
2

(2) The spin magnetic moment of electron (excluding orbital magnetic momentum) is given by

effective n(n 2) BM (Where n = Number of unpaired electrons).


18. DISTRIBUTION OF ELECTRONS IN AN ATOM
The filling up of orbitals with electrons takes place according to certain rules which are given below:
(i) The maximum number of electrons in a main shell is equal to 2n 2, where n is the principal quantum number.
(ii) The maximum number of electrons in a sub-shell like s, p, d, f is equal to (2l + 1), where l is the azimuthal
quantum number for the respective orbitals. Thus s, p, d, f can have a maximum of 2, 6, 10 and 14 electrons
respectively.
(a) Afbau Principle
According to the principle, Electrons are added progressively to the various orbitals in the order of increasing
energy.
What does the word Afbau mean?
Afbau is a German term which means building up or construction.
The energy of various orbitals increase in the order given below:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p < 8s < ......

(i) A new electron enters the orbitals for which (n + l) is minimum, e.g. if we consider 3d and 4s orbitals, the
electron will first enter 4s-orbitals in preference to 3d.
This is because the value of (n + l) for 4s-orbitals is less (4 + 0 = 4) than that for 3d-orbital (3 + 2 = 5)
(ii) In case where (n + l) values are the same, the new electron enters the orbitals for which n is minimum, e.g.
in a choice between 3d and 4p for which (n + l) values are same (3 + 2 = 5, 4 + 1 = 5), the electron will prefer to
go to the 3d-orbital, since n is lower for this orbital.
(b) Paulis Exclusion Principle
It states that it is impossible for two electrons in a given atom to have same set of quantum numbers.
Example:
(a)
n = 2, l = 0,
m = 0, s = +1/2
n = 2, l = 0,
m = 0, s = 1/2
(b)
n = 2, l = 1,
m = 0, s = +1/2
n = 2, l = 1,
m = 0, s = 1.2
n = 2, l = 1,
m = +1, s = +1/2
n = 2, l = 1,
m = +1, s = 1/2
n = 2, l = 1,
m = 1, s = +1/2
n = 2, l = 1,
m = 1, s = 1/2
(c) Hunds Rule of Maximum Multiplicity
According to this rule, electrons enter the orbitals (e.g. s, px, py, pz ...) in the same sub-level in such a way as to

18

Atomic Structure
give maximum number of unpaired electrons. In other words it means that pairing begins with the introduction of
the second electron in the s-orbital, the fourth in p, etc.
What is the electronic configuration of Cu (Z = 29)?
1s2 2s2 2p6 3s2 3p6 3d10 4s1
Exceptional Electronic Configuration
Some atoms such as copper and chromium exhibit exceptional electronic configuration.
For example:
Cr(Z = 24) has an electronic configuration
1s2 2s2 2p6 3s2 3p6 3d5 4s1
It is because of the extra stability associated with the half-filled and completely filled orbitals.
CONCEPT BUILDING EXAMPLES
Example 1.
Find out the energy of the electron in the first excited state in an H-atom.
Solution.
Energy of an electron in H-like atom is given by
Z2
E (2.18 108 J ) 2 ; where z is the number of protons and n is
n

number of shell in which electron is present.


For the first excited state, n 2
12
E (2.18 1018 J ) 2
2
E 5.45 10 19 J

Example 2.
The K.E. of a moving electron is 5 10 25 J ; Calculate its velocity and the wavelength.
Solution :
K .E.

1 2
mv
2

velocity v

2( K .E )

Now, wavelength

2 5 10 25 J
1.048 103 ms 1
9.1 10 31 kg

h
mv

6.626 10 34 Js
6.949 10 7 m
3
1
(9.1 10 kg ) (1.048 10 ms )
31

Example 3.
If the electron of the hydrogen atom has been excited to a level corresponding to 10.2 electron volts, what is the
wavelength of the line emitted when the atom returns to its ground state?
Solution.
E E2 E1
hc

E hv

E 10.2 eV

E 10.2 1.6 10 19 J

19

Atomic Structure

6.624 1034 3 108


m
10.2 1.6 1019

6.624 1034 3 108 109


nm
10.2 1.6 1019

121.8nm .
Example 4.
An electron jumps from fourth excited state to the ground stable in Li+2 -ion and the energy released in the form
of photon is allowed to strike a metal ( x ) surface whose work function ( ) is 1 10 18 J . What is the K.E. &
velocity of the electron ejected.
Solution.
The amount of energy released is given by
1
1
E (2.18 1018 J ) z 2 2 2 where z is the atomic number of H-like atom.
n1 n2

E (2.18 1018 J ) (3) 2 1 1.23 1018 J


16
Now, hv K .E.
K .E. (1.23 1018 1 10 18 J )

1 2
mv 2.3 10 18 J
2

2 2.3 10 19
ms 1 7.11 105 ms 1
9.1 10 31

Example 5.
Ionisation energy of hydrogen atom is 13.6 eV. What will be the ionisation energy of He+ and Li++ ions?
Solution.
As we know ionisation energy for one electron system is given by

I .P. 13.6 eV

z2
n2

For hydrogen atom, z = 1, n = 1,


For He+ ion z = 2 and n = 1.

So, I.P = 13.6 eV

So, I.P = 13.6 13.6 (2) 2


i.e., I .P. 54.4 eV For Li2+, z = 3 & n = 1; I.P. = 13.6 (3) 2
i.e., I .P 122.4 eV .
Example 6.
A hydrogen like atom (atomic number Z) is in a higher excited state of quantum number n . This excited atom
can make a transition to the first excited state by successively emitting two photons of energies 10.2 eV and 17
eV respectively. Alternatively, the atom from the same excited state can make a transition to the second excited
state by successively emitting two photons of energy 4.25 eV and 5.95 eV respectively. Determine the values of
n and z (ionisation energy of hydrogen atom = 13.6 eV).
Solution.
Total energy liberated during transition of electron from nth shell to first excited state (i.e., 2nd shell)

10.2 17 17.2 eV
27.2 1.602 10 12 erg

20

Atomic Structure

hc
1 1
RH Z 2 hc 2 2

2 n

1 1
27.2 1.602 1012 RH Z 2 hc 2 2
2 n

... (i)

Similarly, total energy liberated during transition of electron from nth shell to second excited state (i.e. 3rd shell):

4.25 5.95 10.2eV


10.2 1.602 10 12 erg

1 1
10.2 1.602 1012 RH Z 2 hc 2 2
3 n

... (ii)

Dividing eq. (i) by eq. (ii) n 6


On substituting the value of n in eqns. (i) or (ii) Z 3 .
Example 7.
1 mol of He+ ion excited. Spectral analysis showed the existence of 50% ions in 3rd level, 25% in 2nd level and
remaining 25% in ground state. Ionisation energy of He+ is 54.4 eV; calculate total energy evolved when all the
ions return to ground state.
Solution.
25% of He+ ions are already in ground state, hence energy emitted will be from the ions present in 3rd level and
2nd level.
1 1
E ( IP )2 2 2 per ion or atom.
n1 n2

E 31 (54.4)

N0
2

1 1
N0
ions falling to ground state
12 32 for

54.4

N 1 1
4 N0
N
eV and E 21 (54.4) 0 2 2 for 0 ions falling to ground state.
4 1 2
9
4

54.4

3 N0
eV
16

4 3
Hence total energy = 54.4 N 0
9 16
54.4 6.023 10 23

91
eV
144

54.4 6.023 10 23

91
1.6 1019 J
144

331.13 10 4 J

Example 8.
Estimate the difference in energy between the 1st and 2nd Bohr orbit for a hydrogen atom. At what minimum
atomic number, would a transition from n = 2 to n = 1 energy level result in the emission of X-rays with

3.0 108 m . Which hydrogen atom like species does this atomic number correspond to?
Solution.
For hydrogen atom, the expression for energy difference between two energy level is,
1 1
E RH hc 2 2
n2 n2

21

Atomic Structure

1
7
34
8
So, E E2 E1 1.09677 10 6.626 10 3 10 1
4
1.635 10 8 J

For hydrogen like species, the same expression is


1 1
1
z 2 RH 2 2

n2 n2

So,

or,

1 1
1
z 2 RH 2 2

n1 n2

1
3
z 2 (1.09677 107 ) or, z = 2
8
3 10
4

So, the species is He+ because z = 2.


Example 9.
What is the degeneracy of the level of the hydrogen atom that has the energy
(a) RH,
(b) RH/9
Solution.
En RH / n 2

(a)

E RH ,

n 1

The level is degenerate.

(b)

E RH / 9

n3

when n 3 ,

when

l 0,

me 0 (3s-orbital)

when

l 1,

me 1, 0,1 (3p-orbital)

when

l 2,

me 2, 1, 0,1, 2 (3d-orbitals)

when n 1 ,

me 0

l 0,

l 0,1, 2

This is 1 + 3 + 5 = 9 states in all. The degeneracy is 9.


Example 10.
Calculate the uncertainty in the velocity of a ball of mass 150g if uncertainty in this position is
1 ( h 6.6 10 34 Js )

Solution.
From Heisenberg uncertainty principle we know that
xp

h
4

or

xm v

h
4

or

h
4 mx

Substituting value: m 150 g 0.15 kg , x 1 1010 m

6.6 1034
4 3.14 1010 0.15

v 3.499 10 24 ms 1 .

Subjective Solved Examples


Exampe1. 11
Calculate the waelength and wave number of the spectral line when an electron in H-atom falls from higher
energy state n 3 to a state n 2 . Also determine the energy of a photon to ionise this atom by removing the
electron from 2nd Bohrs orbit. Compare it with the energy of photon required to ionise the atom by removing
the electron from the ground state.
Solution.

22

Atomic Structure
Photon absorbed

n=1

+e

n=2

n=3

+1e

n=
n=2

Photon emitted

First calculate the energy (E ) between the

To ionise the atom from n 2 , the

Bohr orbits n 3 and n 2 using:

responsible transition will be n 2 n .

1 1
E 2.18 1018 Z 2 2 2 J
n1 n2

1
1
E(2 ) 2.18 1018 12 2 2 J
2

1 1
E(32) 2.18 1018 (1) 2 2 2 J (Z 1)
2 3

5.45 10 19 J

3.03 10 19 J

To ionise the atom from ground state

Now this energy difference is the energy of the

(n 1) , the transition is 1 .

photon emitted.

1 1
E 2.18 1018 12 2 2
1
hc
hcv

EPhoton hv

hc
3.03 10 19 6560.3

and

2.18 10 18 J

1
1.52 10 6 m 1

Example 12
A hydrogen atom in the ground state is hit by a photon by a photon exciting the electron to 3rd excited state.
The electron then drops to 2nd Bohr orbit. What is the frequency of radiation emitted and absorbed in the
process?
Solution.
Energy is absorbed when electron moves from ground state (n 1) to 3rd excited state (n 4) .
Photon absorbed
n=1
n=4
+e

n=1

n=2

First calcuate the energy difference btween n 1 and n 4 .


1
1
Use: E(1 4) 2.18 10 18 Z 2 2 2 .
n
n
1
2

23

Atomic Structure
Here,

Z 1, n1 1, n2 4

1 1
18
2
E(14) 2.18 10 1 12 42

Put n1 2 and n2 4 in the expression of E , to get:

1 1
E(4 2) 2.18 1018 12 2 2
2 4

2.04 10 18 J

This is the energy of the photon absorbed.

4.08 10 19 J

This is the energy of the photon emitted.

Use:

EPhoton hv 2.04 10 18 J to get: Use:

EPhoton hv 4.08 1019 J

v 3.08 1015 Hz

v 6.16 1014 Hz

Similarly, when electron jumps from


n 4 to n 2 , energy is emitted and is given by the same relation.
Example 13

A hydrogen like ion, He (Z 2) is exposed to electromagnetic waves of 256.4 . The excited electron gives
out induced radiations. Find the waelength of the indicated radiations, when electron de-excites back to the
ground state. R = 109677 cm1.
Solution:
He+ ion contains only one electron, so Bohrs
medhot is applicable here. It absorbs a photon of

From n 3 , the electron can fall back to the


ground state in three possible ways (transitions)

3 1, 3 2, 2 1

wavelength 256.4 . Assume the electron to


be in ground state initially. Let it jumps to an
excited state n2.
v

Hence three possible radiations are emitted.


Find the wavelengths corresponding to these

1
1
1
RZ2 2 2

n1 n2

transitions.

Substitute for 256.4 256.4 10 8 cm ,

The wavelength ( ) for transition, 3 1 will


be same i.e., 256.4 . Find for 3 2 and
2 1 using the same relation.

R 109677, Z 2 for He+ ion,

(3 1) 256.4 , (3 2) 1641.3

n1 1 and find n2 .

(2 1) 303.9
n=3
n=2

1 1
1
109677 107 (2)2 2 2 n 3
2
256.4 108
11 n2
n=1

Example 14
Hydrogen gas when subjected to photon-dissociation, yields one normal atom and one atom possessing 1.97
eV more energy than normal atom. The bond dissociation energy of hydrogen moleucle into normal atoms is
103 kcals mol1. Compute the wave length of effective photon for photon dissociation of hydrogen molecule in
the given case.
Solution:
H2 H H

where H is normal H -atom and H * is excited H-atom. So the energy requird to dissociate H 2 in this
manner will be greater than the usual bond energy of H 2 molecule.
E (absorbed) = dissociation energy of H 2 extra energy of excited atom.
Energy required to dissociated in normal manner

24

Atomic Structure
3

(given)

103 10 cal per mol

103 103 4.18


7.17 1019 J / atom
6 1023

The extra energy possessed by excited atom is 1.97 eV


1.97 1.6 10 19 J 3.15 10 19 J

E (absorbed) = 7.175 10 19 3.15 10 19 J


1.03 10 18 J

Now calculate the wavelength of photon corresponding to this energy.


EPhoton

hc
1.03 1018 1930

Example 15
An electron in the first excited state of H-atom absorbs a photon and is further excited. The de Broglie wavelength
of the electron in this state is found to 13.4 . find the wavelength of photon absorbed by the electron in .
Also find the longest and shortest wavelength emitted when this electron de-excites back to ground state.
Solution:
Note: The energy state n 1 is known as Ground State
The energy state n 2 is known as First Excited State
The energy state n 3 is known as Second excited
State and so on.

n=n
+e
n=2

Photon

The electron from n 2 absorbs a photon and is further excited to a higher energy level (let us say n ).
The electron in this energy level ( n ) has a de Broglie wavelength ( ) 13.4

h
me ve

and

vn 2.18 106

Z 1
ms
n

[vn is the velocity of e in nth Bohr orbit]

6.626 10 34
h
1
2.18 106
(13.4 1010 ) (9.1 10 31 )
m
n

2.18 10 6

1
n4
n

Now find the wavelength of the photon responsible for the excitation from n 2 to n 4 .
Using the relation :
1 1
E 2.18 1018 Z 2 2 2 4.09 10 19 J [n =2, n =4, Z=2]
1
2
n1 n2

(2 4)

(2 4)

hc
4.09 10 19 4863.1

The Longest wavelength emitted when this electron

25

E(4 3) 1.06 1019

Atomic Structure
E EPhoton

(from n 4 ) falls back to the ground state will corresponds

hc
1.06 10 19 J

to the minimum energy transition.

18752.8

The transition corresponding to minimum energy will

Shortest wavelength : 4 1

1 1
E(4 1) 2.18 1018 12 2 2
1 4

be 4 3 .

2.04 10 18 J

Note: The transition corresponding to maximum energy

E(4 1) EPhoton

will be 4 1 .
E( Energy diff .) EPhoton

Photon

hc
hv

hc

973.2

or E vPhoton

1
18 2 1
Using the same relation : E(43) 2.18 10 Z n2 n 2
1
2

[n1 3, n2 4, Z 2]

Example 16
A single electorn orbits around a stationary nucleus of charge Ze , where Z is a constant and e is the
magnitude of electronic charge. It requires 47.2 eV to excite the electron from second Bohr orbit to the third
Bohr. Find :
(a)
the value of Z
(b)
(c)
(d)
(e)
Solution.

the energy required to excite the electron from n 3 to n 4 .


the wavelength of radiation required to remove electron from 2nd Bohrs orbit to infinity
the kinetic energy, potential energy and angular momentum of the electron in the first orbit.
the ionisation energy of above one electron system in eV.

Since the nucleus has a charge Ze , the


atomic number of the ion is Z .
(a) The transition is n1 2 n2 3 by absorbing a photon of energy 47.2 eV .

E 47.2eV
Using the relation:
1 1
E 13.6Z 2 2 2 eV
n1 n2

1 1
47.2 13.6Z 2 2 2 Z 5
2 3

(b) The required transition is n1 3 n2 4 by absorbing a photon of energy E .


1
2 1
Find E by using the relation: E 13.6Z 2 2 eV
n1 n2

1 1
E 13.6(5)2 2 2
3 4

eV

E 16.53 eV

(c) The required transition is n1 2 n2 by absorbing a photon of energy E .

26

Atomic Structure
Find E by using the relation:

1
1
E 13.6(5) 2 2 2 E 85eV
2
Find of radiation corresponding to energy 85 eV..

hc 6.626 10 34 3 108

E
85 (1.6 10 19 )

146.16

(d) If energy of electron be En, then KE = En and PE = 2En

En

13.6 Z 2 13.6 52

340 eV
n2
12

KE (340eV ) 340 eV
PE 2(340 eV ) 680eV

h
Angular momentum (l ) n

6.626 1034
l 1
1.05 10 34 J s
2

(e) The ionisation energy (IE) is the energy required to remove the electron from ground state to infinity. So
the required transition is 1 . The ionisation energy
( IE ) E1 13.6( Z ) 2 eV

IE 13.6 52 340eV

Example 17
With what velocity should an alpha ( ) particle travel towards the nucleus of a copper atom so as to arrive at
a distance 1013 m from the nucleus of the copper atom?
Solution.
As -particle appraoches towards the Cu nucleus, it decelerates due to repulsion from it and finally its
velocity will become zero at point A (which is the turning point). After that, particle will move in the left
direction (and accelerating)
r0

-particle
V

A
V=0

Cu Nucleus
(+29e)

To arrive at a distance (r 0) from the nucleus, the kineticc energy of alpha particle should be equal to the
electrostaic potential energy of it, i.e., KE = EPE
Kq q
1
m v2 N
2
r0

m :

mass of -particle = 4 (1.67 1027 kg )

v :

velocity of -particle = ?
K 9 109 N m / C 2

27

Atomic Structure
q charge on -particle = 2 ( 1.6 10

19

C)

r0 = Minimum distance of approach


Note:

q 2e, m 4 m p [ -particle is He2+ ion or He Nucleus]

qN = charge in Cu nucleus = Ze = 29(+1.6 1019C)


d = distance from nucleus = 1013 m

2Kq qN
m r0

Substituting the given values, we get,


v 6.325 106 m / s.

Note:

This is a simple cases where velocity of -particle is directed towards the centre of the Cu-nucleus.

-particle

Cu

r0
V=0

Note: When there is a difference between the velocity vector of -particle and the Cu(target) nucleus, the
trajectory is more complicated.

-particle

Target

Example 18
Find the energy required to excite 1.22 litre of hydrogen atoms gas at 1.0 atm and 298 K to the first excited
state of atomic hydrogen. The energy requied for the dissociatio of H-H bonds is 436 kJ/mol. Also calculate
the minimum frequency of a photon to break this bond.
Solution.
Let us, first find the number of moles of hydrogne atoms.
nH 2

PV
1 1.22

0.05
RT 0.0821 298

Thus the energy required to break 0.05 moles of H2 (H-H bond) = 0.05 436 19.62 kJ .
Now calculate the energy needed to excite the H-atoms to first excited state i.e., to n 2 (First excited state is
referred to n 2 ).

1 1
E 2.18 1018 (1)2 2 2
1 2

J / atom

1.635 1018 J / atom

No. o H atoms = (No. of H2 molecules) 2


(0.05 6.02 10 23 ) 2 6.02 10 22

28

Atomic Structure
22

The energy required to excited the given number of H-atom = 6.02 10 1.635 10 18 J 98.43 kJ
So the total energy required
19.62 98.43 118.05 kJ
Now the energy required to break to single
H-H bond =

436 103
7.2381019
6.023 1023

= Energy supplied by the photon

7.328 10 19 hv 6.626 10 34 (v)

v 1.09 1015 Hz

Example 19
Estimate the differnce in energy between 1st and 2nd Bohrs orbit for a H-atom. At what minimum atomic
number (Z), a transition from n 2 to n 1 energy level would result in the emission of radiatio with wavelength

3.0 10 8 m ? Which hydrogen atom like species this atomic number corresponds to? How much ionisation
potential is needed to ionise this species? ( R 1.097 107 m 1 )
Solution.
The difference in energy is given by E :

1 1
E 2.18 1018 (1)2 2 2 J / atom
1 2
1.65 10 18 J 1.65 10 11 ergs 10.2eV

For a H-like atom, 3.0 108 m .

1 1
E 2.18 1018 Z 2 2 2
1 2

(2 1)

EPhoton

hc

Solve to get :
Z=2
Hence the H-like atom is He+ ion.
To ionise, He+ ion, ionisation energy (IE) = (E1)
IE (13.6 2 2 ) 54.4eV

The ionisation potential (IP) is the voltage difference required to generate this much energy.

IE qV e( IP ) 54.4 eV

IP (required) 54.4 Volt

Example 20
A stationary He+ ion emits a photon correspondings to the first line ( H ) of Lyman series. The photon thus
emitted, strikes a H-atom in the ground state. Find the velocity of the photoelectrons ejected out of the hydrogen
atom. The value of R 1.097 10 7 m 1 .
Solution.
The difference in energy (E ) will be equal to the energy of the photon emitted.
First line in Lyman series corresponds to the transition 2 1 .

1 1
E 2.18 1018 (2) 2 2 2
1 2

J / atom

6.54 10 18 J

29

Atomic Structure
The photon of this much energy strikes a H-atom in the ground state. Note that the ionisation energy of H-atom
is 2.18 10 18 J . This will be the work function of H-atom. Using the Einsteins photoelectric equation:
KE Ei W0

1
me ve2
2

[Ei = Incident energy]

ve

2( Ei W0 )
me

ve

2(6.54 10 18 2.18 1018 )


9.1 1031

ve 3.09 10 6 m / s

We can also calculate the wavelength of electron ejected out = 2.36 10 10 m 2.36

h
6.626 10 34

m 2.36
me ve 9.7 10 38 3.09 106

Example 21
An electron in a hydrogen like species, makes a transition from nth Bohr orbit to next outer Bohr ( n 1 ).
Find an approximate relation between the dependence of the frequency of the photon absorbed as a function of
n . Assume n to be large value ( n 1 ).
Solution.
1
1
E( energy difference ) hv 2.18 10 18 Z 2 2
J
(n 1) 2
( nn 1)
n

2n 1
hv 2.18 10 18 Z 2 2
J.
2
n ( n 1)

Since n 1 (given)

n 1 ~ n ; 2 n 1 2n

hv 2.18 10 18 Z 2

v n 3 .

2n
J
n4

30

Atomic Structure

M IND M AP
1. According to the quantum
theory, the radiant energy is
emitted by atoms & molecules
in small discrete amounts
(quanta)m rather than over a
continuous rante. The energy of
each quanta is given by E = hv.

2. According to Bohr model, the 3. The radius of an orbit is given


angular mometum of an electron by
The
r n 2 h 2 / 4 2 kZms 2 .
is an integral multiple of h / 2 . velocity of an electron in an orbit
Bohrs model is applicable single is given by v nh / 2 mr and the
electron species (hydrogen like energy of an electron in an orbit
species).
is given by E 2 pk 2 Z 2 ms 4 / n2h 2 .

9. In phot oelectric effect,


electrons are elected from the
surface of certain met al
exposed to light of at least a
certain minimum frequency.

4. In bohr model, an electron


emits a photon when it drops
from a higher energy state to a
lower energy state.

hv hv0 K .E .

8. Four quant um numbers


characterise each electron in an
atom. The principal quantum
number(n) indentifies the main
energy level, t he angular
quantum number (l) indicates
shapes of orbital, the magnetic
orientation of orbital in space
and the spin quant um
number(s) indicat es t he
direction of the electrons spin
on its axis.

ATOMIC
STRUCTURE

5. The emission spectra of


hydrogen is obtained when
electron from an ecited state is
deexcited to the ground state.
The release of specific amounts
of energy in the form of photons
accounts for the lines in the
hydrogen spectrum. v of each
line in the spectrum can be
given by
1/ Ryz 2(1/ n12 ) (1/ n22 )]

7. An orbital may be defined as


a region in space around the
nucleus where the probability
of finding the electron is
maximum.

6. De Broglie exended
Einsteins wave particle
descrition of light to all matters
in motion. The wavelength of
a moving particle of mass m
and velocity v is given by de
Broglie equation, h / mv.

31