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CHEMISTRY
ATOMIC STRUCTURE
LECTURE # 1 TO 10
Lecture : 1
Atomic structure
1.
Introduction :
STRUCTURE OF ATOM
Rutherford's Model
Bohr's Model
Daltons concept of the indivisibility of the atom was completely discredited by a series of experimental
evidences obtained by scientists. A number of new phenomena were brought to light and mans idea about
the natural world underwent a revolutionary change. the discovery of electricity and spectral phenomena
opened the door for radical changes in approaches to experimentation. It was concluded that atoms are
made of three particles : electrons, protons and neutrons. These particles are called the fundamental particles
of matter.
2.
In 1859 Julius Plucker started the study of conduction of electricity through gases at low pressure
(104atm) in a discharge tube When a high voltage of the order of 10,000 volts or more was impressed across
the electrodes, some sort of invisible rays moved from the negative electrode to the positive electrode these
rays are called as cathode rays.
Path of travelling is straight from the cathode with a very high velocity as it produces shadow of an
object placed in its path.
(ii)
Cathode rays produce mechanical effects. If small paddle wheel is placed between the electrodes,
it rotates. This indicates that the cathode rays consist of material part.
(iii)
When electric and magnetic fields are applied to the cathode rays in the discharge tube. The rays
are deflected thus establishing that they consist of charged particles. The direction of deflection
showed that cathode rays consist of negatively charged particles called electrons.
(iv)
They produce a green glow when strike the glass wall beyond the anode. Light is emitted when they
strike the zinc sulphide screen.
(v)
Cathode rays penetrate through thin sheets of aluminium and metals.
(vi)
They affect the photographic plates
(vii)
The ratio of charge(e) to mass(m) i.e. charge/mass is same for all cathode rays irrespective of the
gas used in the tube. e/m = 1.76 1011 Ckg1
Thus, it can be concluded that electrons are basic constituent of all the atoms.
Page # 1
Discovery of Neutron :
Later, a need was felt for the presence of electrically neutral particles as one of the constituent of
atom. These particles were discovered by Chadwick in 1932 by bombarding a thin sheet of Beryllium
with -particles, when electrically neutral particles having a mass slightly greater than that of the
protons were emitted. He named these particles as neutrons.
9
4 Be
1
24He 12
6 C 0n
The NUCLEUS :
Electrons, protons & neutrons are the fundamental particles present in all atoms,(except hydrogen)
Particles
Symbol
Electron
0
1e
or
Mass
9.1096 x 10-31 kg
0.000548 amu
Proton
Neutron
1
1H
1
0n
Charge
1.602 x l019
Coulombs
4.803 1010 esu
1.6726 x 1027 kg
+ 1.602 x 1019
Coulombs
1.00757 amu
1.6749 x 1027 kg
1.00893 amu
1 amu 1.66 1027 kg
neutral
0
Discoverer
J.J. Thompson
Stoney Lorentz 1887
Goldstein
Rutherford1907
James Chadwick
1932
Page # 2
Lecture : 2
ATOMIC MODELS :
(A)
1.
2.
3.
Most of the -particles passed straight through the gold foil without suffering any deflection from
their original path.
A few of them were deflected through small angles, while a very few were deflected to a large extent.
A very small percentage (1 in 100000) was deflected through angles ranging from 90 to 180.
2.
This was not according to the classical theory of electromagnetism proposed by maxwell. According
to this theory, every accelerated charged particle must emit radiations in the form of electromagnetic
waves and loses it total energy.
Since energy of electrons keep on decreasing, so radius of the circular orbits should also decrease
and ultimately the electron should fall in nucleus.
It could not explain the line spectrum of H-atom.
Page # 3
PROPERTIES OF CHARGE :
1.
2.
Q = ne ( charge is quantized)
Charge are of two types :
(i) positive charge
(ii) Negative Charge
e = 1.6 x 1019
p = + 1.6 x 1019C
This does not mean that a proton has a greater charge but it implies that the charge is equal and opposite.
Same charge repel each other and opposite charges attract each other.
3. Charge is a SCALAR Qty. and the force between the charges always acts along the line joining the
charges.
The magnitude of the force between the two charge placed at a distance r is given by
FE
(electrical force)
1
4 0
q1q2
r2
4. If two charge q1 and q2 are sepreated by distance r then the potential energy of the two charge system is
given by.
The magnitude of the force between the two charge placed at a distance r is given by
1
4 0
q1q2
r
5. If a charged particle q is placed on a surface of potential V then the potential energy of the charge is
q x V.
P.E.
An -particle is projected from infinity with the velocity V0 towards the nucleus of an atom having atomic
number equal to Z then find out (i) closest distance of approach (R) (ii) what is the velocity of the -particle at
the distance R1 (R1 > R) from the nucleus.
3
Sol.
m
R
R1
0+
R=
1
K( Ze)(2e)
m V2=
+0
2
R
4KZe 2
m V
0+
K( Ze)(2e)
1
1
m V2=
+
m V2
R1
2
2 1
Page # 4
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 of 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.
e.g.
1.
23
35
11 Na, 17 Cl
and so on.
sotopes : Such atoms of the same element having same atomic number but different mass numbers
are called isotopes.
1
2
1H, 1 H
2.
and 13H and named as protium, deuterium (D) and tritium (T) respectively. Ordinary hydrogen
is protium.
Isobars : Such atoms of different elements which have same mass numbers (and of course different
atomic numbers) are called isobars
e.g.
3.
Isotones : Such atoms of different elements which contain the same number of neutrons are called
isotones
e.g.
4.
Example.
40
40
40
18 Ar, 19 K, 20 Ca.
14
15 16
6 C, 7 N, 8 O.
Isoelectronic : The species (atoms or ions) containing the same number of electrons are called
isoelectronic.
For example, O2, F, Na+, Mg2+, Al3+, Ne all contain 10 electrons each and hence they are
isoelectronic.
Complete the following table :
Particle
Nitrogen atom
Calcium ion
20
20
Oxygen atom
16
Bromide ion
45
36
Page # 5
Sol.
Ex. (NCERT)
Sol.
In this case,
80
35 Br
80
35 Br
The number of electrons, protons and neutrons in a species are equal to 18, 16 and 16 respectively.
Assign the proper symbol to the species.
The atomic number is equal to number of protons = 16. The element is Sulphur (S).
Mass number = number of protons + number of neutrons = 16 + 16 = 32
Species is not neutral as the number of protons is not equal to electrons. It is anion (negatively
charged) with charge equal to excess electrons = 18 16 = 2. Symbol is
32 2
16 S .
Page # 6
LECTURE : 3
Electromagnetic wave radiation :
The oscillating electrical/magnetic field are electromagnetic radiations. Experimentally, the direction of oscillations
of electrical and magnetic field are prependicular to each other.
7.
Wavelength of a wave is defined as the distance between any two consecutive crests or troughs. It is
represented by (lambda) and is expressed in or m or cm or nm (nanometer) or pm (picometer).
1 = 10 8 cm = 1010 m
1 nm = 10 9 m, 1 pm = 1012 m
Frequency of a wave is defined as the number of waves passing through a point in one second. It is
represented by (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 (read as nu bar).
Page # 7
c 3.00 10 8 ms 1
=
= 219.3 m
1368 10 3 s 1
Ex. (NCERT)
The wavelength range of the visible spectrum extends from violet (400 nm) to red (750 nm). Express these
wavelengths in frequencies (Hz). (1 nm = 109 m)
Sol.
c 3.00 10 8 ms 1
= 7.50 1014 Hz
400 10 9 m
c 3.00 10 8 ms 1
= 4.00 1014 Hz
750 10 9 m
The range of visible spectrum is from 4.0 1014 to 7.5 1014 Hz in terms of frequency units.
Ex. (NCERT)
Calculate (a) wavenumber and (b) frequency of yellow radiation having wavelength 5800 .
Sol.
1
1
c
3 10 8 m s 1
= 5.172 1014 s1
5800 10 10 m
the nature of emission of radiation from hot bodies (black - body radiation)
(ii)
ejection of electrons from metal surface when radiation strikes it (photoelectric effect)
Page # 8
The above experimental results cannot be explained satisfactorily on the basis of the wave theory of light.
Planck suggested that atoms and molecules could emit (or absorb) energy only in discrete quantities and
not in a continuous manner.
hc
(c - speed of light)
( - wavelength)
Order of magnitude of Eo =
10 34 10 8
10 10
= 1016 J
One electron volt (e.v.) : Energy gained by an electron when it is accelerated from rest through a potential difference
of 1 volt.
Note : Positive charge always moves from high potential to low potential and ve charge always. moves from low
potential to high potential if set free.
K.E. =
1
mVf2
2
1
mVf2 = e(1 volt)
2
Page # 9
If a charge q is accelerated through a potential dirrerence of V volt then its kinetic energy will be increased by q.V.
Ex. (NCERT)
Sol.
Calculate energy of one mole of photons of radiation whose frequency is 5 1014 Hz.
Energy (E) of one photon is given by the expression E = h
h = 6.626 10 34 J s
= 5 1014 s1 (given)
E = (6.626 1034 J s) (5 1014 s1) = 3.313 1019 J
energy of one mole of photons = (3.313 1019 J) (6.022 1023 mol1) = 199.51 KJ mol1
Ex. (NCERT)
Sol.
A 100 watt bulb emits monochromatic light of wavelength 400 nm. Calculate the number of photons emitted per
second by the bulb
Power of the bulb = 100 watt = 100 J s1
Energy of one photon E = h = hc/=
Ex.
Sol.
Ex.
Sol.
6.626 10 34 J s 3 10 8 m s 1
100 J s 1
4.969 10 19 J
400 10 9 m
= 4.969 1019 J
= 2.012 1020 s1
If a charged particle having charge of 2e on being accelerated by 1 volt, its K.E. will be increased by ?
K.E. = (2e) . (1V)
= 2 x 1eV
= 2 x 1.6 x 1019 J
= 3.2 x 1019 J
A charged particle having a charge +3e is projected towards +ve plate, from ve plate with K.E.i = 12eV What
is the minimum potential that should be applied between the plates so that the charged particle cannot strike
the +ve plate ?
K.E.i + P.E.i = P.E.f + K.E.f
(+3e) 0 + 12eV = 3e(V) + 0
Ex.
12eV
= 4Volts
s
3e
Number of photons emitted by a bulb of 40 watt in 1 minute with 50% efficiency will be approximately
( = 6200 , hc = 12400 eV )
(A) 7.5 1020
(B) 3.75 1020
(C) 3.75 1019
(D*) 3.75 1021
Sol.
E =
Ex.
Sol.
hc
x NA = 194 x 103
V=
12400
= 2eV..
6200
194 x 10 3
1
= = 6.63 x 10 34 x 10 8 x 6 x 10 23
~ 1.62 x 106 m1
Page # 10
h.c
E = h =
E = mc2
or
h
mc
h
mc
Which is same as de - Broglie relation.
This was experimentally verified by Davisson and Germer by observing diffraction effects with an electron
beam.
Let the electron is accelerated with a potential of V then the K.E. is
or
1
mv2 =eV
2
m2v2 = 2emV
mv =
2emV = p (momentum)
h
2emV
If we associate Bohrs theory with de - Broglie equation then
2r = n
or
2r
n
h
mv
so, mvr =
therefore
h
2r
=
mv
n
nh
2
m = dynamic mass =
m0
v
1
c
Page # 11
K.E. =
1
mv2
2
1 2 2
m v multiplied by mass on both side
2
m (K.E.) =
m.v. =
2m(K.E.)
h
=
2m(K.E.)
If a charge q is accelerated through a potential difference of V volt from rest then K.E. of the charge is equal
to : q.V
h
150 2
=
V
mvr = n
2m(q.V )
h
2m e (eV )
1
12.3
(V in volt)
h
2
h
mv
mv =
h
nh
putting this in mvr =
2
2r
h
nh
r=
n de Broglie wavelength
Ex. (NCERT)
What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s1 ?
Sol.
According to de Broglie equation
=
(6.626 10 34 Js)
h
=
(0.1 kg) (10 m s 1 )
mv
Page # 12
The mass of an electron is 9.1 1031 kg. If its K.E. is 3.0 1025 J, calculate its wavelength.
Sol.
Since K.E. =
1
mv2
2
1
2 3.0 10 25 kg m 2 s 2
2 K.E. 2
v=
=
9.1 10 31 kg
m
2
= 812 m s1
6.626 10 34 Js
h
=
mv
(9.1 10 31kg) (812 m s 1 )
Find the wavelength associated with a dust particle of mass 5 mg. moving with velocity 200 m/s.
=
6.62 10 34
6.62 10 34
h
=
=
= 6.62 1031 m
mv 5 10 6 200
1000 10 6
Note : Since order of the wavelength is extremely small, therefore de-Broglie wavelength calculation for daily life
particle has no physical significance
Ex.
Find the wavelength associated with the electron moving with the velocity 106 m/s.
=
6.62 10 34
6.62 10 9
h
=
=
mv
9.1
9.1 10 31 10 6
Note
Since wavelength associated with the electron has considerable value therefore we can conclude that
electron has more of wave nature and less of particle nature.
Ex.
Calculate ratio of wavelength for an particle & proton accelerated through same potential difference.
Sol.
p
Ex.
h
2 q m V
qpmp
q .m
1 1
.
2 4
h
2 qpm p V , m = 4mp ,
q = 2qp
1
1
Ans.
8 2 2
(a) Hydrogen sample is in st excited state A photon of energy 8eV is used to excite the hydrogen sample.
Find the de-Broglie wavelength of the electron.
(a)
n=2
K.E. of electron = 8 3.4 = 4.6 eV
=
150
4 .6
A = 5.71
OR
1
mv2 = 4.6 1.6 1019
2
v = 1.27 106 m/sec
(m = 9.1 10 31 kg)
6.626 10 34
9.1 10 31 1.27 10 6
h
, we get :
mv
5.7
Page # 13
Ex.
Ans.
An electron having Initial K.E. of 6eV is accelerated through a potential difference of 4V find the wavelength
of associated with electron
Total K.E. = 6eV + 4eV = 10eV
1
150
=
10
150 2
=
=
10
15 = 3.87
Ex.
De-Broglie wavelength of electron in second orbit of Li2+ ion will be equal to de-Broglie of wavelength of
electron in
(A) n = 3 of H-atom
(B*) n = 4 of C5+ ion
(C) n = 6 of Be3+ ion
(D) n = 3 of He+ ion
Sol.
h
mv
Now
z
v
n
so
n
z
4
2
n = 4 of C5+ ion, =
3
6
for
Ex.
2
3
An electron, practically at rest, is initially accelerated through a potential difference of 100 volts. It then has
a de Broglie wavelength = 1 . It then get retarded through 19 volts and then has a wavelength 2 .
Its further retardation through 32 volts changes the wavelength to 3, What is
(A)
20
41
(B)
h
Sol.
1 =
2mq (100)
10
63
k
, =
10 2
(C*)
h
2mq(81)
k
=
9 3
20
63
3 2
1 ?
(D)
10
41
k
2mq( 49) = 7
2k
k k
3 2
20
63
7 9
=
=
=
1
k
63
k
10
10
so the required answer.
Page # 14
LECTURE : 4
Photoelectric Effect :
When certain metals (for example Potassium, Rubidium, Caesium etc.) were exposed to a beam of light
electrons were ejected as shown in Fig.
The phenomenon is called Photoelectric effect. The results observed in this experiment were :
(i)
The electrons are ejected from the metal surface as soon as the beam of light strikes the surface, i.e., there
is no time lag between the striking of light beam and the ejection of electrons from the metal surface.
(ii)
(iii)
For each metal, there is a characteristic minimum frequency, 0 (also known as threshold frequency)
below which photoelectric effect is not observed. At a frequency > 0, the ejected electrons come out with
certain kinetic energy. The kinetic energies of these electrons increase with the increase of frequency of the
light used.
When a photon of sufficient energy strikes an electron in the atom of the metal, it transfers its energy
instantaneously to the electron during the collision and the electron is ejected without any time lag or delay.
Greater the energy possessed by the photon, greater will be transfer of energy to the electron and greater the
kinetic energy of the ejected electron. In other words, kinetic energy of the ejected electron is proportional to
the frequency of the electromagnetic radiation. Since the striking photon has energy equal to h and the
minimum energy required to eject the electron is h0 (is also called work function, W 0) then the difference in
energy (h h0) is transferred as the kinetic energy of the photoelectron. Following the conservation of
energy principle, the kinetic energy of the ejected electron is given by the equation
h = h0 +
1
m 2
2 e
where me is the mass of the electron and v is the velocity associated with the ejected electron.
Example 1.
The threshold frequency 0 for a metal is 6 1014 s1. Calculate the kinetic energy of an electron emitted when
radiation of frequency = 1.1 1015 s1 hits the metal.
Sol.
K.E. =
1
m V2 = h ( 0)
2 e
Page # 15
Example 2.
When electromagnetic radiation of wavelength 310 nm fall on the surface of Sodium, electrons are emitted
with K.E. = 1.5 eV. Determine the work function (W 0) of Sodium.
Sol.
h =
12400
= 4 eV
3100
1
m V2 = 1.5 eV
2 e
h0 = W 0 = h
1
m V2 = 4 1.5 = 2.5 eV
2 e
Ex. (NCERT)
When electromagnetic radiation of wavelength 300 nm falls on the suface of sodium, electrons are emitted
with a kinetic energy of 1.68 105 J mol1. What is the minimum energy needed to remove an electron from
sodium ? What is the maximum wavelength that will cause a photoelectron to be emitted ?
Sol.
6.626 10 34 J s 3.0 10 8 m s 1
300 10 9 m
= 6.626 1019 J
The energy of one mole of photons
= 6.626 1019 6.022 1023
= 3.99 105 J mol1
The minimum energy needed to remove a mole of electrons from sodium = (3.99 1.68) 105 J mol1
= 2.31 105 J mol1 The minimum energy for one electron =
2.31 10 5 J mol 1
6.022 10 23 electrons mol 1
= 3.84 1019 J
This corresponds to the wavelength
6.626 10 34 J s 3.0 10 8 m s 1
hc
=
= 517 nm.
3.84 10 19 m
E
According to Einsteins equation Kinetic energy - 1/2 mev2 = h( 0) = (6.626 1034 J s) (1.0 1015 s1 7.0
1014 s1) = (6.626 1034 J s) (3.0 1014 s1) = 1.988 1019 J
Page # 16
Lecture : 5
BOHRS ATOMIC MODEL
Bohrs model is applied only on one electron species like H, He+, Li++, Be+++ etc.
The important postulates of Bohr model of an atom are
(a) Electron revolves around the nucleus in a fixed circular orbit of definite energy. As long as the electron
occupy a definite energy level, it does not radiate out energy i.e. it does not lose or gain energy. These orbits
are called stationary orbits.
(b) Electron revolves only in those orbits whose angular momentum (mvr) is an integral multiple of the factor
h/2(where h is Planks constant)
mvr = n
h
2
where :
m = mass of the electron
v = velocity of the electron
n = number of orbit in which electron revolves i.e. n = 1, 2, 3 ........
r = radius of the orbit.
(c) The energy is emitted or absorbed only when the electron jumps from one energy level to another. It may
jump from higher energy level to a lower level by the emission of energy and jump from lower to higher energy
level by absorption of energy.
This amount of energy emitted or absorbed is given by the difference of the energies of the two energy levels
concerned.
KZe 2
r
1
where : K = constant = 4 = 9 x 109 Nm2/C2
0
mv 2
r
For the stable orbit of an electron both the forces are balanced.
and the centrifugal force F =
i.e
KZe 2
mv 2
=
r
r2
then
v2 =
KZe 2
mr
......... (i)
Page # 17
nh
2
v2 =
On squaring
v=
nh
2mr
n 2h 2
........ (ii)
4 2m 2r 2
From equation (i) and (ii)
n 2h 2
KZe 2
=
4 2m 2r 2
mr
On solving, we will get
n 2h 2
r=
4 2mKZe 2
On putting the value of e , h , m, the radius of nth Bohr orbit is given by :
rn = 0.529 x
n2
Ex.
Calculate radius ratio for 2nd orbit of He+ ion & 3rd orbit of Be+++ ion.
Sol.
22
nd
32
r1
0.529 2 2 / 2
8
Therefore r =
=
2
0.529 3 / 4
2
9
Ex.
If the radius of second orbit of Li2+ ion is x then find the radius of Ist orbit of He+ in terms of x.
Sol.
22
= x (given)
3
... (i)
3x
3x 1
12
=
=
8
4 2
2
nh
2
nh
2mr
put the value of r in the equation (iii)
v=
then,
v=
......... (iii)
nh 4 2mZe 2K
2mn 2h2
Ze 2K
nh
on putting the values of , e-, h and K
v=
vn = 2.18 x 106 x
Z
m/sec
n
vZ
1
n
Page # 18
2r
v
v
2 r
1
mv2
2
Hence, T.E. =
KZe 2
r
1
KZe 2
mv2
2
r
KZe 2
mv 2
KZe 2
2 =
=
or
mv
r
r
r2
substituting the value of mv2 in the above equation :
we know that,
T.E. =
KZe 2 KZe 2
KZe 2
=
2r
r
2r
KZe 2
2r
substituting the value of r in the equation of T.E.
So, T.E. =
4 2 Ze 2m
2 2 Z 2 e 4 m K 2
KZe 2
x
=
2 2
2
n h
n 2h 2
Thus, the total energy of an electron in nth orbit is given by
Then
T.E. =
2
2 2 me 4 k 2 z
T.E. = En =
n2
h2
... (iv)
Putting the value of m,e,h and we get the expression of total energy
En = 13.6
Z2
n2
eV / atom
n T.E.
; Z T.E.
1
P.E.
2
T.E. = K.E.
T.E. =
Page # 19
Ex. (NCERT)
What are the frequency and wavelength of a photon emitted during a transition from n = 5 state to the n = 2
state in the hydrogen atom ?
Sol.
Since ni = 5 and nf = 2, this transition gives rise to a spectral line in the visible region of the Balmer series.
1
1
E = 2.18 1018 J 2 2 = 4.58 1019 J
2
5
It is an emission energy
The frequency of the photon (taking energy in terms of magnitude) is given by
4.58 10 19 J
E
=
h
6.626 10 34 Js
= 6.91 1014 Hz
=
3.0 108 ms 1
c
=
= 434 nm
6.91 1014 Hz
Ex. (NCERT)
Calculate the energy associated with the first orbit of He+. What is the radius of this orbit?
Sol.
En =
(2.18 10 18 J) Z 2
n2
For He+, n = 1, Z = 2
atom1
(2.18 10 18 J)
= 8.72 1018 J
12
The radius of the orbit is given by equation
E1 =
52 .9 (n 2 )
(0.0529 nm) n2
pm =
Z
Z
Since n = 1, and Z = 2
rn =
rn =
Ex.
Sol.
(0.0529 nm )12
= 0.02645 nm
2
Calculate energy ratio for 3rd orbit of Li++ ion & 2nd orbit of Be+++ ion.
E1 for 3rd orbit of Li++ ion
= 13.6
32
ev/atm
32
E2 for 2nd orbit of Be+++ ion
= 13.6
42
22
ev/atm
E1 1
E 2 4 Ans.
Page # 20
Ex.
Sol.
Radius of two different orbits in a H like sample is 4R and 16R respactively then find out the ratio of the
frequency of revolution of electron in these two orbits.
0.529 n12
r1
4R
r2 = 0.529 n22 = 16 R
n12
n 22
1
4
or
n1
1
n2 = 2
Now,
3
n32
n2
v1 / 2r1
2
f1
=
= 3 = = =8:1
v 2 / 2r2
n1
f2
1
n1
Lecture : 6
Energy Level Diagram :
(i)
(ii)
Orbit of lowest energy is placed at the bottom, and all other orbits are placed above this.
The gap between two orbits is proportional to the energy difference of the orbits.
0 eV
-0.85 eV
-1.51eV
-3.4eV
n=
n=4
n=3
n=2
12.1eV
-13.6eV
10.2eV
n=1
Page # 21
Sol.
I.E.H = E E1
= 0 ( 13.6) = + 13.6 ev/atom
E Z2
I.E for Li++ = (ZLi++)2 IEH = 9 13.6 = 122.4 ev Ans.
Ex.
Sol.
22
32
ev = 6.04 ev
Ans.
Binding Energy of H like system corresponding to second excited state is given by 13.5 eV. then
(a) Identify the sample
(b) Ionisation energy of sample
(c) Energy of photon required to cause the transition from 2nd state to 3rd excited state.
(d) Wavelength of the emitted photon when electron fall from 1st excited state to ground state.
(A)
1.5 Z2 = 13.5
Z2 =
13.5
=9
1 .5
Z=3
Ans. Li++
(B)
(C) n = 2 to n = 4
4
3
2
1
22.95 eV
(d) (E)2 1 = 10.2 Z2
10.2 32 = 10.2 9 = 91.8 eV
=
12400
= 135.1
91.8
Page # 22
Ex.
Sol.
If st excitation potential of H like sample is 15V, find : The .E. and nd excitation potential of sample.
st excitation energy 15 eV (E)
E=
E1 =
E2 =
13.6 Z 2
n2
13.6 Z 2
1
13.6 Z 2
22
E1 = E0
E2 =
E0
4
E0
= 15eV
E = E2 E1 = E0
4
3E o
= 15
4
Eo =
15 4
= 20eV
3
IE = 20eV
E1 =
E3 =
13.6Z 2
1
13.6Z 2
32
(E)1 3 = Eo
Eo
9
8
E
9 o
8
20 = 17.75 eV..
9
2nd excitation potential = 17.75 V.
HYDROGEN SPECTRUM :
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 or simply a spectrum of the given radiation The branch or science dealing with the study of
spectra is called spectroscopy.
Spectrum
Based on
Nature
Based on
origin
Discrete
Continuous
Band
Spectrum
Absorption
spectrum
Emission
spectrum
Line
Spectrum
Page # 23
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 source of radiation, the emission spectra are mainly of two type :
(a) 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 band 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.
Dark space
Band
Band spectrum contains colourful continuous bands sepearted by some dark space.
Generally molecular spectrum are band spectrum
(2)
Line Spectrum :
This is the ordered arrangement of lines of particular wavelength seperated by dark space eg. hydrogen
spectrum.
Line spectrum can be obtained from atoms.
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 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, radiations of certain wavelengths are
absorbed, depending upon the nature of the element.
Page # 24
When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on passing electric
discharge is examined with a spectroscope, the spectrum obtained is called the emission spectrum of
hydrogen.
Line Spectrum of Hydrogen :
Line spectrum of hydrogen is observed due to excitation or de-excitation of electron from one stationary orbit
to another stationary orbit
Let electron make transition from n2 to n1 (n2 > n1) in a H-like sample
13.6 Z
n
2
2
13.6 Z2
n1
eV
n2
eV
n1
photon
= (E)n2
=
13.6Z
n 22
n1
13.6Z 2
n12
1
1
= 13.6Z2 2 2
n2
n1
hc
= ( E)
n 2 n1
=
hc
1
1
13.6Z 2 2 2
n
n
2
1
(13.6)z 2
1
=
hc
1
1
n 2 n 2
2
1
Page # 25
Wave number,
1
1
1
= = RZ 2 2 2
n
1 n2
13.6eV
; R ch = 13.6 eV
hc
Ex.1
Calculate the wavelength of a photon emitted when an electron in H- atom maker a transition from n = 2 to n = 1
Sol.
1
1
1
= RZ2 2 2
n 2
n1
1
1
1
= R(1)2 2 2
2
1
1
4
3R
=
or
3R
4
Lecture : 7
SPECTRA LINES OF HYDROGEN ATOM :
LYMAN
*
*
*
SERIES
It is first spectral series of H.
It was found out in ultraviolet region in 1898 by Lyman.
Its value of n1 = 1 and n2 = 2,3,4 where n1 is ground state and n2 is called excited state of electron present
in a H - atom.
1
1
1
= RH 2 2 where n2 > 1 always.
n 2
1
n12
for all series. So for lyman series = R .
RH
H
Page # 26
12400
12400
A
13.6 lyman 10.2
12400
Longest line : longest wavelength line longest or max. = ( E)
min
12400
Shortest line : shortest wavelength line shortest or min = ( E)
max
*
*
Series limit :
t is the last line of any spectral series.
Wave no of st line of Lyman series
=
1
1
1
= = R 12 2 2
2
1
4 1
2
= R 1 4
=
R3
3R
=
4
4
3R
=R
For Lyman series,
longest =
12400
, shortest
( E)2 1
12400
E 1
BALMER SERIES :
* It is the second series of H-spectrum.
* It was found out in 1892 in visible region by Balmer.
* Its value of n1 = 2 and n2 = 3,4,5,.............
* The wavelength of marginal line of Balmer series =
1
1
1
= RH 2 2
n2
4
n12
22
=
= R
RH
RH
H
balmer
12400
1. 9
1
1
5R
( ) 1st line = R 1 2 2 =
36
3
2
1
1
R
( ) last line = R 2 2 =
2
4
PASCHEN SERIES :
(a) It is the third series of H - spectrum.
(b) It was found out in infrared region by Paschen.
(c) Its value of n1 = 3 and n2 = 4,5,6 ........
(e)
9
n12
32
=
= R .
RH
RH
H
1
1
1
= RH 2 2 where n2 > 3 always.
n2
BRACKETT SERIES :
(a) It is fourth series of H - spectrum.
(b) It was found out in infrared region by Brackett.
(c) Its value of n1 = 4 and n2 = 5,6,7 ..............
(d) The wavelength of marginal line of brackett series =
(e)
16
n12
42
=
= R
RH
RH
H
1
1
1
= RH 2 2 where n2 > 4 always.
n2
PFUND SERIES :
(a) It is fifth series of H- spectrum.
(b) It was found out in infrared region by Pfund.
(c) Its value of n1 = 5 and n2 = 6,7,8 ............... where n1 is ground state and n2 is excited state.
25
n12
52
=
= R
RH
RH
H
1
1
1
= RH 2 2 where n2 > 5 always.
n2
5
HUMPHRY SERIES :
(a) It is the sixth series of H - spectrum.
(b) It was found out in infrared region by Humphry.
(c) Its value of n1 = 6 and n2 = 7 , 8 , 9 ...................
(e)
(e)
1
= RH
36
n12
62
=
= R
RH
RH
H
1
1
2 2 where n2 > 6.
n2
6
Ex.
Sol.
1
1
1
R(2)2 2 2
n1 n2
n1 = 2
n2 = 4
1
1
1
R( 2 2 ) 2 2
4
2
Page # 28
1 3R
14.
4R
Ans.
3
n ( n 1)
, where n = n2 n1
2
In case of single isolated atom if electron make transition from n th state to the ground state then max.
number of spectral lines observed = (n-1)
Ex.
If electron make transition from 7th excited state to 2nd state in H atom sample find the max. number of
spectral lines observed.
n = 8 2 = 6
6 1
7
= 6
= 21
spectral lines = 6
2
2
Ex.
An electron in isolated hydrogen atom is in 4th excited state, then, upon de excitation:
(A) the maximum number of possible photons will be 10
(B) the maximum number of possible photons will be 6
(C) it can emit two photons in ultraviolet region
(D*) if an infrared photon is generated, then a visible photon may follow this infrared photon.
Ex.
In a hydrogen like sample, ions are in a particular excited state, if electrons make transition upto 1st
excited state, then it produces maximum 15 different types of spectral lines then electrons were in
(A) 5th state
(B) 6th state
(C*) 7th state
(D) 8th state
Sol.
Ex.
Sol.
n n 1
= 15
2
n = 5
n2=5
n=7
In a Hydrogen like sample, all the ions are in a particular excited state. When electron make transition up to
ground state, then 6 diff. types of photons are observed. If second excitation potential of the sample is 193.64
V, then :
(a) dentify the sample
(b) Find the excited state of sample
(c) Find ionisation energy
(d) Find binding energy of 3rd state
(e) Shortest and longest wavelength belonging to above transition
(f) Series limit of Brackett series (wavelength) (in terms of R)
(g) Find the diff between the wave number of 2nd line of Lyman series and st line of Balmer series
(h) If 2nd line of Balmer series of this sample is used to excite the He+ ion already in ground state, then find
the final excited state of He+
(i) Find the no of lines not in visible range.
(j) If single isolated atom is considered in the above sample then find the max. number of spectral lines
observed in the above transition
(a) Second excitation energy = 193.6 eV.
12.1 Z2 = 193.6 eV
Page # 29
Z2 =
193 .6
= 16
12.1
Z2 = 16
Z = 16 = 4
Hence sample is Be3+
n(n 1)
6
=
2
1
(b)
n=4
Hence sample is in 3rd excited state or 4th state
13.6 16
eV
218 .6
(c)
.E. = 13.6 Z2 =
(d)
(e)
12400
12400
=
longest = ( E)
(1.5 0.85 ) 4 2
43
12400
shortest = ( E)
4 1
1
1
1
2 2
=
R
2
4
(f)
1
1
= R, = R
(g)
1
1
8R
128R
Lyman series 1 = R 42 2 2 =
16 =
9
9
3
1
1
1
R 80
20R
( 2 ) balmer = R 42 2 2 =
=
36
9
3
2
1 2 =
128R
20R 128R 20R
108 R
=
=
9
9
9
9
3
2
-3.4 eV
(h)
-13.6 eV
n=1
-3.4 eV
6
5
4
3
2
-13.6 eV
++
n=1
Li
Page # 30
Note : Let electron make transition from n2 to n1 in a Hydrogen like sample having atomic number Z1 and n3 n4
transition in a sample having atomic no z2 then,
(E) n n = (E) n n
2
1
4
3
1
1
13.6 Z12 2 2
n2
n1
Z12
n12
Z12
Z22
n2 2
2
= 13.6 Z2
n3 2
1
1
n 2 n 2
4
3
Z22
n4 2
On comparing,
2
Z1
2
n1
Z12
&
n2
Z2
n3
Z22
n4
Z1 Z 2
n1
Z
n1 n3
n3 Z 2
n2
Z1
n Z
4
2
n1
n2
Z1
=
=
n3
n4
Z2
H4
2
4
1
n3 = n 4 = Z 2
n3 = 2Z2, n4 = 4Z2
nd line of Balmer series = 4 2
n1 = 2 , n2 = 4,
Z1 = 4, Z2 = 2.
2
4
4
n3 = n 4 = 2
n3 1
n 2
4
(i)
Page # 31
0.65 16
10.40eV
1.55 eV E 3.1 eV
There are no lines in visible range all the lines are lie in the ultraviolet region.
4
3
2
(j)
3+
Be
where,
x . (mv)
h
4
x = uncertainty in position
p = uncertainty in momentum
h = Planks constant
m = mass of the particle
v = uncertainty in velocity
p
But,
p=
h
p.x
(multiplied & divided by t)
4
h
P
t . x
t
4
F.x.t
h
4
E . t
h
4
P
= rate of change in momentum = F)
t
E uncertainty in energy
t uncertainty in time
Page # 32
In terms of uncertainty in energy E, and uncertainty in time t, this principle is written as,
E.t
h
.
4
Ex. (NCERT)
A golf ball has a mass of 40 g, and a speed of 45 m/s. If the speed can be measured within accuracy of 2%,
calculate the uncertainty in the position.
Sol.
2
= 0.9 m s1.
100
6.626 10 34
h
=
= 1.46 1033 m
4m v
4 3.14 40 10 3 (0.9 m s 1 )
This is nearly ~ 1018 times smaller than the diameter of a typical atomic nucleus. As mentioned earlier for
large particles, the uncertainty principle sets no meaningful limit to the precision of measurements.
Ex.
A microscope using suitable photons is employed to locate an electron in an atom within a distance of 0.1:
What is the uncertainty involved in the measurement of its velocity?
[Mass of electron = 9.1 x 1031 kg and Plancks constant (h) = 6.626 x 1034Js)
Sol.
x p =
v =
h
h
or x mv =
4
4
6.626 10 34 J s
h
=
= 0.579 107 ms1 (1J = 1 kgm2s2)
4 3.14 0.1 10 10 m 9.1 10 31kg
4 x m
Sol.
1
m
(B)
1
2m
(C*)
1
2m
h
(D) 4 m
h
2
x = 2p
Now x. p
h
4
2p2
h
;
4
2(mv)2
h
4
1
2m
h
2
Lecture : 8
THE SCHRODINGER EQUATION :
The de Broglie wave relation is the basis for predicting the behavior of freely moving particles. Shortly after it
was proposed, Erwin Schrodinger demonstrated that the de Broglie expression could be generalized so as
to apply to bound particles such as electrons in atoms. The heart of Schrodinger's theory is that the allowed
energies of physical systems can be found by solving an equation which so resembles the equations of
classical wave theory that it is called the wave equation. For the motion of one particle in one (the x)
direction, the Schrodinger wave equation is
h2
d2
8 m dx 2
+ V = E .
Page # 33
The "knowns" in this equation are m, the mass of the particle, and V, its potential energy expressed as a
function of x. The "unknowns" to be found by solving the equation are E, the quantized or allowed energies of
the particle, and , which is called the wave function. The quantity d2/dx2 represents the rate of change of
d/dx, the rate of change of . When this equation is applied to real systems such as the hydrogen atom, it
is found that it cannot be solved unless E takes on certain values which are related by integers. Thus
quantized energy and quantum numbers are an automatic consequence of the Schrodinger theory, and do
not have to be tacked on to Newtonian mechanics as was done by Bohr.
What is ? By itself, it has no physical meaning. However, the square of the absolute value of , 2, does
have an important physical interpretation. It is a mathematical expression of how the probability of finding a
particle varies from place to place. Thus the exact trajectories of Newtonian mechanics and the Bohr theory
do not appear in the results of the Schrodinger quantum mechanics; this, according to the Uncertainty
Principle, is as it should be.
A similar analysis is possible for the other 2p-functions. The px function has the yz-plane as an angular node,
since the function is proportional sin cos and cos = 0 everywhere in the yz-plane. The maximum values
of 1 for sin and cos occur along the positive x-axis. The py function, proportional to the sin sin ,
vanishes in the xz-plane, where sin = 0, and has a maximum along the positive y-axis, where both sin
and sin are unity.
Orbital Wave Functions, Probability Distribution and Shape of Orbitals
(a) Wave function () provides several useful informations about an electron. These are :
(i) enegy of electron in an orbital.
(ii) position of electron in space in a particular allowed energy state.
(b) On the basis of values of ||2, i.e., probability of finding electron, electron clouds may be drawn and the
region where they are dense shows region of high probability.
(c) The plane and point where ||2 is zero (i.e., no probability) is called nodal plane or nodal point respectively.
(d) Orbital wave function is the product of two functions, radial function and angular function i.e.,
= (r). ( )
(r) is the function of distance (r) from the nucleus while (, ) is the function of two sphereical
co-ordinates and as shown in figure.
(e) (r) i.e. radial part of wave function depends upon quantum number n and l and decides the size of an
orbital.
(f) Angular part of wave function ( ), depends upon quantum numbers l and m and describes the
shape of orbital. For the sake of convenience the (r) vs. r and ( ) vs. angle are plotted seperately.
Page # 34
Note : The figure and reveal that the boundary surfaces of 2 and are similar, however, the main
difference lies in the fact that values may have negative sign whereas 2 is always positive.
(ii) The distance (i.e., value of r), where value of 2 is high shows the area of high probability of finding
electron.
(iii) On the other hand, the distance at which 2 is zero, shows node (i.e., area of zero probability of
finding an electron).
(iv) In 1s orbital, there is not node while in 2s and 3s, there are one and two radial nodes repsectively.
The distance of node is at r where 2 is zero.
(v) Graphs plotted 2 vs r, represents the variation of 2 with distance from nucleus and are knwon as
probability distribution curves. (figure)
Page # 35
(vi) The function 2 is a measure of probability of finding an electron in unit volume around a particullar
point, so it is also referred as probable density.
(3) By plotting (r) vs r :
(i) Plots (r) vs. r are shown in figure. The distance at which (r) is zero or negative show the distance of zero
electron probability.
Variation of (a) (r)1s with r nucleus; (b) (r) 2s vs. r from the nucleus; (c) (r)3s vs. r
(ii) These plots differs from plots of 2 in that value of may be negative but 2 is always positive.
(B) The p-orbitals :
(i) p-orbitals are not spherically symmetrical and have dumb-bell shape.
(Ii) p-subshell is constituted by three p-orbitals px, py and pz named with respect to axis, along which its
electron density lies.
Page # 36
(iv) Lobes of dxy, dyz, and dxz lie between the axes, while dx2y2 and dz2 lie on the axes.
(v) dz2 has two lobes on z-axis and doughnut in xy-plane. It looks like baby soother.
(vi) All the d-orbitals belonging to a subshell have same energy and so are degenerate (five fold degeneracy).
Although dz2 appers different in shape, it also has same energy as that of other d-orbitals.
(D) The f-orbitals :
(i) For f-subshell l - 3 and thus m will have seven values m = 3, 2, 1, 0, + 1, + 2, + 3. For l = 3, minimum
value of n must be four thus if, 2f of 3f have no existence and f-orbitals starts from n = 4 (i.e., 4f).
(ii) In a f-subshell, there are seven f-orbitals. Their contour diagram which are 3-D, are difficult to draw on
paper.
(iii) The seven f-orbitals are :
fx(x2 y2), fy(x2 y2), fz(x2 y2), fxyz, fz3, fyz2 and fxz2.
Note :
1. Sometimes an orbital is represented in terms of n, l, m also. Usually for m = 0, z axis is chosen.
e.g., 420 reveals that n = 4, l = 2, and m = 0, thus it is 4dz2 y310 reveals that n = 3, l = 1, m = 0 thus it 3pz.
2. For an orbital (or subshell) as the value of n increases, the size of orbital increases i.e., 1s < 2s < 3s etc.
3. As r approaches to 0, also approaches zero except s-orbital. It concludes that only s-electron can
penetrate through nucleus and has probability to be found at nucleus.
4. For one electron system (e.g., H, He+, Li2+, Be3+ etc.), energy of orbital depends only on value of n and
not on l, thus all hte subshells belonging to same shell will have same energy.
5. There is no unique way of representing the angular dependence functions of all seven f-orbitals. An
alternative way may be as fz3, fxz2, fyx2, fzy2, fx(x2 3y2)fy(y2 3z2) and fz(z2 3x2).
Page # 37
Radial probability density for some orbitais of the hydrogen atom. Ordinate is proportional to
4 r2 R2, and all distributions are to the same scale.
Orbital :
An orbital may be defined as the region of space around the nucleus where the probability of finding an
electron is maximum (90% to 95%)
Orbitals do not define a definite path for the electron, rather they define only the probability of the electron
being in various regions of space around the nucles.
4.
5.
6.
Orbitals
1.
Page # 38
s- orbital :
Shape spherical
s- orbital is non directional and it is closest to the nucleus, having lowest energy.
s-orbital can accomodate maximum no. of two electrons.
d - Orbital :
Page # 39
f - orbital :
Page # 40
(3-fold degenerate)
d-subshell :
(5-fold degenerate)
Lecture : 9
QUANTUM NUMBERS :
The set of four numbers required to define an electron completely in an atom are called quantum numbers.
The first three have been derived from Schrodinger wave equation.
(i) Principal quantum number (n) :
(Proposed by Bohr)
It describes the size of the electron wave and the total energy of the electron. It has integral values
1, 2, 3, 4 ...., etc., and is denoted by K, L, M, N. ..., etc.
*
Number of subshell present in nth shell = n
n
subshell
1
s
2
s, p
3
s, p, d
4
s, p, d, f
*
The maximum number of electrons which can be present in a principal energy shell is equal to 2n2.
No energy shell in the atoms of known elements possesses more than 32 electrons.
nh
2
i.e.
h
2
( 1) =
( 1)
h
,
2
h
2
Page # 41
orbitals (px, py and pz), d-subshell five orbitals (d xy , d yz , d zx , d x 2 y 2 , dz 2 ) and f-subshell has seven orbitals.
s( s 1) or
h
2
s( s 1)
1
x No. of unpaired electron.
2
Ex. (NCERT)
What is the total number of orbitals associated with the principal quantum number n = 3 ?
Sol.
For n = 3, the possible values of are 0, 1 and 2. Tthere is one 3s orbital (n = 3, = 0 and m = 0) ; there are
three 3p orbitals (n = 3, = 1 and m= 1, 0, + 1) ; there are five 3d orbitals
(n = 3, = 2 and m= 2, 1, 0, + 1+, + 2).
Therefore, the total number of orbitals is 1 + 3 + 5 = 9
The same value can also be obtained byusing the relation; number of orbitals = n2, i.e. 32 = 9.
Ex. (NCERT)
Using s, p, d, f notations, describe the orbital with the following quantum numbers
(a) n = 2, = 1, (b) n = 4, = 0, (c) n = 5, = 3, (d) n = 3, = 2
Sol.
n
orbital
(a)
2
1
2p
(b)
4
0
4s
(c)
5
3
5f
(d)
3
2
3d
Ex.
Ans.
Find orbital angular momentum of an electron in (a) 4s subshell and (b) 3p subshell
(a) 0
(b)
Ex.
h
2
h
then find the maximum number
( 1)
h
=
2
( 1) = 2 5 =
( 1)
h
2
= 4.
h
5
20
1
2
(B) n = 2, l = 0, m = 0, s =
(C) n = 4, l = 2, m = 1, s = +
1
2
(D*) n = 4, l = 3, m = 4, s =
1
2
1
( m > is not possible)
2
Page # 42
Electronic configuration :
Paulis 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 must be different, i.e., spins must be in opposite directions.
Aufbau principle :
Aufbau is a German word meaning building up. The 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, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ....
The energy of the orbitals is governed by (n + ) rule.
n + Rule :
The relative order of energies of various sub-shell in a multi electron atom can be predicated with the help
of n + rule
The sub-shell with lower value of ( n + ) has lower energy and it should be filled first.
eg.
3d
4s
(n +) = 3 + 2 (n +) = 4 + 0
=5
=4
Since, (n + ) value of 3d is more than 4s therefore, 4s will be filled before 3d.
If two sub-shell has same value of ( n + ) then the sub-shell with lower value of n has lower energy and
it should be filled first.
eg.
3d
4p
(n +) = 3 + 2
=5
3d is filled before 4p.
=4+1
=5
MEMORY MAP :
1s
2s
2p
3s
3p
3d
4s
4p
4d
4f
5s
5p
5d
5f
6s
6p
1 s
2 s,p
3 s,p
4 s,d,p
5 s,d,p
6 s,f,d,p
6 s,f,d,p
7 s,f,d,p
Hunds rule :
No electron pairing takes place in the orbitals in a sub - shell until each orbital is occupied by
one electron with parallel spin. Exactly half filled and fully filled orbitals make the atoms more stable, i.e., p3,
p6, d5, d10, f7 and f14 configuration are most stable.
Ex.
Write the electronic configuration and find the no. of unpaired electrons as well as total spin for the following
atoms :
(1)
C
6
(2)
O
8
(3)
P
15
(4)
Sc
21
Page # 43
(5)
(6)
(i)
Fe
Ne
10
26
1s
2s
15
3p
Total spin =
21
2
2
or
2
2
3s
(iv)
2p
Total spin =
(iii)
2
2
or
2
2
3
3
or
2
2
or
4s
(v)
Total spin =
1
1
or
2
2
4s
3d
(vi)
10
Total spin =
4
4
or
2
2
Page # 44
EXCEPTIONS :
(1)
24
(2)
29
Ex.
Ans.
(i)
Find the electronic configuration of Fe2+ and Cr3+ and their magnetic moments.
Fe [Ar] 3d6, 4s2
Fe2+ [Ar] 3d6
3d
= 2 6
n(n 2) B.M. =
4( 4 2) B.M. =
4 6 B.M. =
24
B.M.
No of unpaired electrons = 3
Magnetic moment =
Ex.
n(n 2) B.M. =
3(3 2) B.M. =
3 5 B.M. =
15
B.M.
1
2
Lecture : 10
Stability of Nucleus
Nucleus of an atom contains all the protons and neutrons in it while all the electrons are in the outer sphere.
Nuclides can be grouped on the basis of nuclear stability, i.e., stable and unstable nucleus. The question
naturally arises why some nuclides are stable while others are unstable. The stability of atom has been
explained in terms of Coulombic forces of attraction and forces of motion. The stability of nucleus cannot be
explained in terms of these forces because of similar charged particles present in nucleus. No single rule
allows us to predict whether a particular nucleus is radioactive and how it might decay.
Note : (1) A common term nucleons is referred for the proton and the neutron.
(2) Generally nuclei are spherical but nuclei of Hf and Ta are reported to be oval shaped.
(3) Recall that nuclear density is of the order of 1017 kg/m3 and is approximately same for all nuclei.
Page # 45
1.
14.923 10 11 m
1.602 10 19
14.923 10 11 m
1.602 10 19 10 6
eV
MeV
(106 eV = 1 MeV)
Plot of nuclear binding energy per nucleon against the mass number for naturally occuring
nuclides.
Page # 46
Note : (1) The greater the binding energy per nucleon, the more stable is nucleus and thus
56
26 Fe
is most stable
nucleus.
C and 16
(2) Elements with mass number 4, 12 and 16 have high values of and B therefore, 24 He , 12
8 O are
6
stable nuclei.
Ex.
In a nuclear transition
19
16
8 O 8 O
( excited state )
Sol.
( ground state )
10 3
cal.
4.18
10 3
4.18
m = 0.49 102 gm
m ~ 5 103 gm.
The neutron to proton ratio n/Z
Neutrons apparently help to hold protons together within the nucleus. The number of neutrons necessary to
create a stable nucleus increases rapidly as the number of protons increases ; the number of neutron to
proton ratio of stable nuclei increases with increasing atomic number. The area within which all stable
nuclei are found is known as the belt of stability. The majority of radioactive nuclei occur outside this belt.
Note : (1) For elements mass number A < 40, Nature prefers the number of protons and neutrons in the nucleus
to be about the same to attain stability.
Page # 47
(2) For elements having A > 40, Nature prefers n > p to attain stability. As the number of protons increases,
the coulombic repulsive force increases and so the excess of neutrons which produce only attractive force
(nuclear force) is required for stability. It is therefore neutron vs. proton curves departs from n = Z line.
(3) Even in light nuclei n may exceed Z but except (in 1H and 32 He ) is never smaller e.g.,
11
6 C
11
5 B
is stable but
is not.
The type of radioactive decay that a particular radio isotope will undergo depends to a large extent on its
neutron to proton ratio compared to those of near by nuclei that are with in belt of stability.
(a) A nucleus whose high
n
n
ratio places it above the belt of stability emits a -particle in order to lower
p
p
e.g,
11p +
82
34 Se
0
1e
82
36 Kr
+ ( is Anti neutrino)
+ 2 01e
n
ratio places it below the belt of stability either emits positrons or undergo
p
electron capture. Both modes of decay decrease the number of protons and increase the number of neutrons
in the nucleus and thus, positron emission or electron capture results in an increase in
n
ratio. Positron
p
emission is more common than electron capture among the higher nuclei, however, electron capture becomes
increasingly common as nuclear charge increases. In such nuclides, the nucleus captures an electron from
the K-shell and thus also known as K-electron capture. The vacancy created in K-shell is filled by electrons
from higher energy levels giving rise to characteristic X-rays.
1
1p
11
6 p
e.g.,
1
1p
e.g.,
133
56 Ba
0
1e
0
1e
1
0n
11
5 B
1
0n
0
1e
0
1e
(Positron emission)
+ X-ray
133
55 Cs +
(Electron capture)
X-ray
(K-electron)
Note : A positron has same mass as electron but carries opposite charge. The positron has a very short life
because it is annihilated when it collides with an electron, producing gamma rays. This phenomenon is
known as pair annihilation.
0
1e
0
1e
2 00
Similarly pair production occurs when a photon passes through the matter
h =
0
1e
0
1e
(c) The nuclei lying beyond the upper right edge (i.e., nuclei with atomic number > 83), outside the belt of
stability, undergo -emission. Emission of an -particle decreasing both the number of protons and neutrons
n
ratio.
p
238
92 U
Thus,
n
n
> 1.0, unstable nuclei ;
< 1.0, stable unclei
Z
Z
234
90 Th
234
90 Th
4
2 He
should undergo -decay on the basis of above guide line (c), whereas, it
undergoes -decay.
233
90 U
233
91 Pa
0
1e
Page # 48
(2) A few radioactive nuclei lie within the belt of stability, e.g.,
belt of stability but
147
60 Nd
146
60 Nd
and
148
60 Nd
Properties
Alpha
Fast moving He
nuclei
Beta
Nature
Notation
2He
Charge
2 unit (+ ve)
1 unit ( ve)
No charge
Typical source
Ra - 226
C14
Tc-99m
Velocity
1/10 of light
Same
waves
Nature of path
Straight line
Crooked
Waves
1 or
(0.01 mm of Al foil)
100 or
(0.1 cm of Al foil)
10,000 or
(8 m lead or 25
cm steel)
2-4 cm
200-300 cm
500 m
7
8
Relative
penetrating
power
Travel distance
in air
or
Gamma
High energy
radiations
1e
or
or
as
light
Tissue depth
0.05 mm
4-5 mm
50 cm or more
10
Shielding
Paper, clothing
Lead,
thick concrete
11
Mass g/particle
6.65 10
12
13
Relative ionising
power
Electrical
or magnetic
field's influence
-24
9.11 10
-28
10,000
100
Deflected towards
ve pole
Deflected towards
+ ve pole
Not deflected
Page # 49
Step I : An excited nucleus (a nucleus of low B.E. or higher energy level) tries to attain lower energy level
in order to attain stability. Therefore, -particles come out of nucleus as energy carrier.
Step II : During -decay no doubt that energy level comes down but
decrease
n
ratio increases and therefore to
p
n
ratio and attain stability, nucleus undergoes neutron decay or neutron transformation to show
p
emission of -particles.
1
0n
1
1
1p + 1e +
Step III : The resultant nucleus after , -emission still possesses higher energy level than required for its
stability, the difference of energy comes out in form of -rays. Thus gamma radiations are given off by nuclei
in an excited state.
Therefore, , -emission are primary emissions and -emissions are secondary emissions.
Note : (1) -particles originates in the nucleus; they are not orbital electrons.
(2) -radiations always accompany or -emissions and thus, are emitted after and -decay.
(3) In gamma decay neither the atomic number nor the mass number changes. Only the quantum state of
the nucleons change.
(4) , and -decay are collectively called radioactive decay ; the material showing radioactive decay is
called radioactive material and the emission of , - and - are collectively called nuclear radiations.
II gp
222
86 Rn
218
84 Po
0 gp
VI gp
(ii) A radioactive atom on decay of a -particles shows a gain in its atomic number by 1 unit whereas, mass
number remains same.
Thus, newly formed element occupied one position right to the parent element in periodic table.
214
82 Po
VI gp
Ex.
Sol.
23
214
83 Bi
V gp
VI gp
24
11 Na
24
n/p ratio of Na is 13/11 and thus greater than one. It will therefore decay following -emission.
0
24
11 Mg + 1e
Sol.
214
84 Po
Na is the most stable isotope of Na. Find out the process by which
24
11 Na
Ex.
ab
4
c X b Y +
a
d
ab
(B) d + 2 + c
c b
(C*) d + 2 a
b is :
dY
ab
(D) d + 2 c
m 24 He + n 01e
c = b + 4m
and
a = d + 2m n
by (i) & (ii)
......(i)
......(ii)
c b
n = d + 2 a.
Page # 50
Ex.
13
7 N
is :
(A)
13
8 O
0
1e
(C)
13
6 C
+ K electron capture
(B*)
13
6 C
0
1e
(D) 95 Be + 24 He
Sol.
13
7 N
Ex.
An element of group III with atomic number 90 and mass number 238 undergoes decay of one -particle.
The newly formed element belongs to :
(A) 1st group
(B) 13th group
(C) IInd group
(D) 14th group
The finally formed stable element for all three natural radioactive series is Pb belonging to group 14.
Sol.
Ex.
Sol.
A radioactive element X has an atomic numbers of 100. It decays directly into an element Y which decays
directly into an element Z. In both processes a charged particle is emitted. Which of the following statement
would be true?
(A) Y has an atomic number of 102.
(B) Z has an atomic number of 101.
(C) Z has an atomic number of 97.
(D*) Z has an atomic number of 99.
X and Y can decay one each or one each or X-decays, 1 , Y-decays 1 or X-decays 1 . In either case
(a), (b) and (c) cannot be true.
Radioactive Series
A series of nuclear reactions that begins with an unstable nucleus and terminates with a stable one is
known as radioactive series or a nuclear disintegration series.
About 42 radioactive nuclides with Z > 82 occur in nature. Systematic studies established that these
nuclides are the daughter products of the three natural decay series. The parent members of the series are
232
Th, 238U and 235U. An atom of these three elements undergoes a series of successive , -decay forming
intermediates eventually leading to the formation of a stable isotope of lead.
232
90 Th
238
92 U
208
82 Pb
206
82 Pb
235
92 U
207
4
0
82 Pb + 7 2 He + 4 1e (4n + 3 series)
The parent elements, intermediates and final stable element of 232Th series have masses which are integral
multiple of 4. That is why this series is known as 4n series. Similarly, 238U and 235U series are known as (4n
+ 2) and (4n + 3) series.
Nuclear Reactions
The phenomenon of interaction of nucleons giving rise to the formation of a new nucleus or a process in
which one nuclide in converted to another by interaction with another nuclide. The first ever nuclear
reaction in laboratory was carried out by Rutherford when the bombarded N atoms with -particles.
17
14
4
8
7 N 2He
O 11H Q
14
7 N (:
p).
Nuclear Fission :
(a) The phenomenon of splitting up of a heavy nucleus, on bombardment with slow speed neutrons, into two
fragments of comparable mass, with the release of two or more fast moving neutrons and a large amount of
energy, is known as nuclear fission.
(b)
236
235
1
92 U 0n 92 U
Page # 51
A loss in mass occurs releasing a vast quantity of energy ~ 2.041 1010 kJ per mol of 235U
(c) Fission of 1 mole g235 U releases energy =
20.41 10 9
kJ = 8.68 107 kJ
235
H 2 He 10 n ; (H = 17.6 MeV)
(b) Huge amount of energy of required to overpower the Coulombic forces of repulsion in between two nuclie
which is obtained by triggering on nuclear fission.
Page # 52