Chapter 2
Chapter 2
Chapter 2
60
Chapter
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Structure of atom
John Dalton 1808, believed that matter is made (ii) Cathode rays produce mechanical effect, as
up of extremely minute indivisible particles, called
atom which can takes part in chemical reactions. These
can neither be created nor be destroyed. However,
modern researches have conclusively proved that atom
ID they can rotate the wheel placed in their
path.
(iii) Cathode rays consist of negatively charged
particles known as electron.
is no longer an indivisible particle. Modern structure of
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(iv) Cathode rays travel with high speed
atom is based on Rutherford’s scattering experiment on approaching that of light (ranging between
atoms and on the concepts of quantization of energy. 10 9 to 10 11 cm/sec)
Composition of atom
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subatomic particles and others are non-fundamental they ionize the gas through which they pass.
particles. (ix) The cathode rays produce scintillation on the
Electron (–1eo) photographic plates.
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(1) It was discovered by J.J. Thomson (1897) and (x) They can penetrate through thin metallic
is negatively charged particle. Electron is a component sheets.
particle of cathode rays. (xi) The nature of these rays does not depend upon
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60
Name of constant Unit Electron(e–) Proton(p+) Neutron(n)
Amu 0.000546 1.00728 1.00899
–31 –27
Mass (m) Kg 9.109 × 10 1.673 × 10 1.675 × 10–27
Relative 1/1837 1 1
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Coulomb (C) – 1.602 × 10–19 +1.602 × 10–19 Zero
–10 –10
Charge(e) Esu – 4.8 × 10 +4.8 × 10 Zero
Relative –1 +1 Zero
Specific charge (e/m) C/g 1.76 × 108 9.58 × 104 Zero
Density
Gram / cc
ID 2.17 10 17
The atomic mass unit (amu) is 1/12 of the mass of an individual atom of
Negative mu meson
– – 4.8029 0.1152 Anderson (1937)
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(iv) Anode rays may get deflected by external (viii) These rays produce flashes of light on ZnS
magnetic field. screen.
(v) Anode rays also affect the photographic plate. Neutron (on1, N)
(vi) The e/m ratio of these rays is smaller than (1) Neutron was discovered by James Chadwick
that of electrons. (1932) according to the following nuclear reaction,
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(ii) It was determined by Moseley as,
1
s whole number (on atomic weight scale), weight is not
a(Z b) or aZ ab necessarily a whole number.
Z
Where, X ray’s frequency Fig. 2.1
(ii) The atom of an element X having mass
number (A) and atomic number (Z) may be represented
Z= atomic number of the metal a&b are
by a symbol, XA.
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constant. Z
Isotopes
(Soddy)
(ii) No. of protons
(iii) No. of electrons
(iv) Electronic configuration
(v) Chemical properties
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(ii) No. of neutrons
(iii) Physical properties
(ii)
(iii)
16 17
35
17
18
8 O, 8 O, 8 O
37
Cl , 17 Cl
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(vi) Position in the periodic
table
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14
(iv)
P 3 , S 2 , Cl , Ar , K and Ca 2 (18 e )
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(iii) Physical and chemical
Isosters (iii) HCl and F2
properties.
(iv) CaO and MgS
(v) C6 H 6 and B3 N 3 H 6
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denoted by the symbol (nu) and is expressed in terms
Electromagnetic radiations of cycles (or waves) per second (cps) or hertz (Hz).
(1) Light and other forms of radiant energy distance travelled in one second = velocity =c
propagate without any medium in the space in the form c
of waves are known as electromagnetic radiations.
These waves can be produced by a charged body
moving in a magnetic field or a magnet in a electric
field. e.g. rays, rays, cosmic rays, ordinary light
rays etc.
ID (iii) Velocity : It is defined as the distance
covered in one second by the wave. It is denoted by the
letter ‘c’. All electromagnetic waves travel with the
same velocity, i.e., 3 10 10 cm / sec .
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(2) Characteristics
c 3 10 10 cm / sec
(i) All electromagnetic radiations travel with the
velocity of light. (iv) Wave number : This is the reciprocal of
wavelength, i.e., the number of wavelengths per
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nearest crests or nearest troughs is called the the letter ‘A’. It determines the intensity of the
wavelength. It is denoted by (lambda) and is radiation.
measured is terms of centimeter(cm), angstrom(Å), The arrangement of various types of
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micron( ) or nanometre
Crest (nm).
Wavelengt electromagnetic radiations in the order of their
h increasing or decreasing wavelengths or frequencies is
Vibrating
source known as electromagnetic spectrum.
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Atomic spectrum
Spectrum is the impression produced on a
photographic film when the radiation (s) of particular (2) This model failed to explain the line spectrum
wavelength (s) is (are) analysed through a prism or of an element and the scattering experiment of
diffraction grating. Rutherford.
Types of spectrum Rutherford's nuclear model
(1) Emission spectrum : Spectrum produced by
(1) Rutherford carried out experiment on the
the emitted radiation is known as emission spectrum.
bombardment of thin (10–4 mm) Au foil with high speed
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This spectrum corresponds to the radiation emitted
(energy evolved) when an excited electron returns back positively charged particles emitted from Ra and
to the ground state. gave the following observations based on this
(i) Continuous spectrum : When sunlight is passed experiment,
through a prism, it gets dispersed into continuous bands (i) Most of the particles passed without any
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of different colours. If the light of an incandescent object deflection.
resolved through prism or spectroscope, it also gives
(ii) Some of them were deflected away from their
continuous spectrum of colours.
path.
(ii) Line spectrum : If the radiation’s obtained by
(iii) Only a few (one in about 10,000) were
the excitation of a substance are analysed with help of
returned back to their original direction of
a spectroscope a series of thin bright lines of specific
colours are obtained. There is dark space in between
two consecutive lines. This type of spectrum is called
line spectrum or atomic spectrum..
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propagation.
-rays
Deflecte
d
-
particles
(5) To evaluate wavelength of various H-lines Ritz (3) Properties of the nucleus
introduced the following expression, (i) Nucleus is a small, heavy, positively charged
portion of the atom and located at the centre of the
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1 1 1
R 2 2 atom.
c n1 n 2
(ii) All the positive charge of atom (i.e. protons)
Where R is universal constant known as Rydberg’s are present in nucleus.
constant its value is 109, 678 cm 1 . (iii) Nucleus contains neutrons and protons, and
Plum pudding model of Thomson hence these particles collectively are also referred to as
nucleons.
(1) He suggected that atom is a positively
(iv) The size of nucleus is measured in Fermi (1
charged sphere having electrons embedded uniformly Fermi = 10–13 cm).
giving an overall picture of plum pudding.
Positively (v) The radius of nucleus is of the order of
+ – + charged sphere 1 .5 10 13 cm . to 6 .5 10 13 cm . i.e. 1.5 to 6.5 Fermi.
– –
+ – +
+ Electron
+ – unifromly
– + embedded
Positive charge spreaded throughout the
sphere
Fig. 2.3
Structure of atom 41
Generally the radius of the nucleus ( rn ) is given by the This phenomenon is called photoelectric effect and the
following relation, electrons emitted are called photo-electrons. The
current constituted by photoelectrons is known as
rn ro ( 1 . 4 10 13 cm ) A 1 / 3 photoelectric current.
This exhibited that nucleus is 10 5 times small in (2) The electrons are ejected only if the radiation
size as compared to the total size of atom. striking the surface of the metal has at least a
minimum frequency ( 0 ) called Threshold frequency.
(vi) The Volume of the nucleus is about 10 39 cm 3
The minimum potential at which the plate photoelectric
and that of atom is 10 24 cm 3 , i.e., volume of the nucleus
current becomes zero is called stopping potential.
is 10 15 times that of an atom. (3) The velocity or kinetic energy of the electron
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(vii) The density of the nucleus is of the order of ejected depend upon the frequency of the incident
10 15 g cm 3 or 10 8 tonnes cm 3 or 10 12 kg / cc . If nucleus radiation and is independent of its intensity.
is spherical than, (4) The number of photoelectrons ejected is
proportional to the intensity of incident radiation.
Density
(5) Einstein’s photoelectric effect equation
mass of the nucleus mass number
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= According to Einstein,
volume of the nucleus 4
6 .023 10 23 r 3 Maximum kinetic energy of the ejected electron =
3
absorbed energy – threshold energy
(4) Drawbacks of Rutherford's model
1 1 1
(i) It does not obey the Maxwell theory of 2
mv max h h 0 hc
2 0
electrodynamics, according to it “A small charged
particle moving around an oppositely charged centre
continuously loses its energy”. If an electron does so, it
should also continuously lose its energy and should set
up spiral motion ultimately failing into the nucleus.
ID Where, 0 and 0 are threshold frequency and
threshold wavelength.
Bohr’s atomic model
Bohr retained the essential features of the
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(ii) It could not explain the line spectra of H
Rutherford model of the atom. However, in order to
atom and discontinuous spectrum nature. account for the stability of the atom he introduced the
Planck's quantum theory concept of the stationary orbits. The Bohr postulates
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are,
When black body is heated, it emits thermal
radiation’s of different wavelengths or frequency. To (1) An atom consists of positively charged nucleus
explain these radiations, max planck put forward a responsible for almost the entire mass of the atom
theory known as planck’s quantum theory. (This assumption is retention of Rutherford model).
(i) The radiant energy which is emitted or (2) The electrons revolve around the nucleus in
absorbed by the black body is not continuous but certain permitted circular orbits of definite radii.
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called a 'photon'.
(ii) The energy of each quantum is directly m is the mass and v is the velocity of the electron in a
proportional to the frequency ( ) of the radiation, i.e. permitted orbit of radius r, then
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hc nh
E or E hv L mvr ; n 1 , 2, 3, ……
2
Where, h Planck's constant = 6.62×10–27 erg. Where L is the orbital angular momentum and n
sec. or 6 .62 10 34 Joules sec . is the number of orbit. The integer n is called the
(iii)The total amount of energy emitted or principal quantum number. This equation is known as
absorbed by a body will be some whole number quanta. the Bohr quantization postulate.
Hence E nh , where n is an integer. (4) When electrons move in permitted discrete
Photoelectric effect orbits they do not radiate or lose energy. Such orbits
are called stationary or non-radiating orbits. In this
(1) When radiations with certain minimum
manner, Bohr overcame Rutherford’s difficulty to
frequency ( 0 ) strike the surface of a metal, the
account for the stability of the atom. Greater the
electrons are ejected from the surface of the metal. distance of energy level from the nucleus, the more is
42 Structure of atom
the energy associated with it. The different energy Z2
21 .8 10 19 J per atom (1 J 10 7 erg)
levels were numbered as 1,2,3,4 .. and called as n2
K, L, M, N, …. etc.
Z2
E 13 .6 eV per atom (1eV 1.6 10 -19 J )
(5) Ordinarily an electron continues to move n2
in a particular stationary state or orbit. Such a state Z2
of atom is called ground state. When energy is given 13 .6 k .cal / mole (1 cal = 4.18J)
n2
to the electron it jumps to any higher energy level
1312 2
and is said to be in the excited state. When the or Z kJmol 1
electron jumps from higher to lower energy state, n2
the energy is radiated. When an electron jumps from an outer orbit
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(higher energy) n2 to an inner orbit (lower
Advantages of Bohr’s theory
energy) n1 , then the energy emitted in form of radiation
(i) Bohr’s theory satisfactorily explains the
spectra of species having one electron, viz. hydrogen is given by
atom, He , Li 2 etc. 2 2 k 2 me 4 Z 2 1 1
E En2 En1
n2 n2
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h2 1 2
(ii) Calculation of radius of Bohr’s orbit :
According to Bohr, radius of n th orbit in which electron 1 1
moves is E 13 . 6 Z 2 2 2 eV / atom
n1 n 2
h2 n2 1 E
rn 2 2 . As we know that E h , c and ,
4 me k Z
9.1 10
Where,
31
n Orbit number,
kg , e Charge on the
Z Atomic number of element, k = Coulombic constant
m Mass number
electron 1.6 10
ID
19
2 2 k 2 me 4 Z 2
ch 3
1
1
1
n2 n2
2
hc
1
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1 1
9 10 9
Nm 2 c 2 This can be represented as
RZ 2 2 2
n1 n 2
After putting the values of m,e,k,h, we get. 2 2 k 2 me 4
Where, R ; R is known as Rydberg
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ch 3
n2
rn 0.529 Å constant. Its value to be used is 109678 cm 1 .
Z
(iii) Calculation of velocity of electron The negative sign in the above equations shows
1/2 that the electron and nucleus form a bound system, i.e.,
2e 2 ZK Ze 2 the electron is attracted towards the nucleus. Thus, if
Vn , Vn ;
nh mr electron is to be taken away from the nucleus, energy
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(iii) This theory could not explain the splitting of
(iii) Although H-atom consists of only one electron
spectral lines in magnetic field (Zeeman effect) and in
yet it's spectra consist of many spectral lines.
electric field (Stark effect). The intensity of these
(iv) Comparative study of important spectral
spectral lines was also not explained by the Bohr
series of Hydrogen is shown in following table.
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atomic model.
(v) If an electron from nth excited state comes to
various energy states, the maximum spectral lines (iv) This theory was unable to explain of dual
nature of matter as explained on the basis of De
n(n 1)
obtained will be = . n= principal quantum broglies concept.
2
(v) This theory could not explain uncertainty
number.
principle. (vi) No conclusion was given for the
=
2
As n=6 than total number of spectral lines
6(6 1) 30
2
15 .
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Table: 2.5
concept of quantisation of energy.
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S.No Spectral Lies in Transition n12n22 n12 max n2
max min 2 2 2
. series the n2 n1 (n22 n12 )R R min n 2 n1
region
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n 2 3,4,5.... 36 4 9
max m in
5R R 5
16
series region n 2 4,5,6.... 144 9
max m in 7
7R R
(4) Brackett Infra red n1 4 n1 4 and n2 5 n1 4 and n 2
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series region 25
n 2 5,6,7.... 16 25 16
max m in 9
9R R
Bohr–Sommerfeild’s model
44 Structure of atom
It is an extension of Bohr’s model. The electrons (7) The de-Broglie equation is applicable to all
in an atom revolve around the nuclei in elliptical orbit. material objects but it has significance only in case of
The circular path is a special case of ellipse. microscopic particles. Since, we come across
Association of elliptical orbits with circular orbit macroscopic objects in our everyday life, de-broglie
explains the fine line spectrum of atoms. relationship has no significance in everyday life.
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h
and as a wave. Mathematically it is represented as , x . p
4
(2) This presented a new wave mechanical theory
Where x uncertainty is position of the particle,
of matter. According to this theory, small particles like
p uncertainty in the momentum of the particle
electrons when in motion possess wave properties.
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Now since p m v
(3) According to de-broglie, the wavelength
associated with a particle of mass m, moving with h
So equation becomes, x . m v or
velocity v is given by the relation 4
h
h
, where h = Planck’s constant. x v
mv 4 m
Planck’s equation, E h
h.c
c
ID In terms of uncertainty in energy, E and
uncertainty in time t, this principle is written as,
E . t
h
4
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energy of photon (on the basis of Einstein’s mass
Schrödinger wave equation
energy relationship), E mc 2
(1) Schrodinger wave equation is given by Erwin
hc h
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Equating both mc 2
or which is same Schrödinger in 1926 and based on dual nature of
mc
electron.
as de-Broglie relation. mc p
(2) In it electron is described as a three dimensional
(5) This was experimentally verified by Davisson wave in the electric field of a positively charged nucleus.
and Germer by observing diffraction effects with an
(3) The probability of finding an electron at any
electron beam. Let the electron is accelerated with a
potential of V than the Kinetic energy is point around the nucleus can be determined by the help
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x 2 y 2 z 2 h2
h
mv 2eVm P ;
2eVm Where x, y and z are the 3 space co-ordinates, m
= mass of electron, h = Planck’s constant, E = Total
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60
e is maximum around nucleus and the place where (ii) It determines the number of sub shells or
sublevels to which the electron belongs.
probability of finding e is maximum is called electron
density, electron cloud or an atomic orbital. It is (iii) It tells about the shape of subshells.
different from the Bohr’s orbit.
(iv) It also expresses the energies of subshells
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(iv) The solution of this equation provides a set of s p d f (increasing energy).
number called quantum numbers which describe
(v) The value of l (n 1) always. Where ‘n’ is the
specific or definite energy state of the electron in atom
number of principle shell.
and information about the shapes and orientations of
the most probable distribution of electrons around the (vi) Value = 0 1 2 3…..(n-
of l 1)
nucleus.
Radial probability distribution curves : Radial
probability is R 4r 2 dr 2 . The plats of R
from nucleus as follows
ID
distance
Name of
subshell
Shape of
subshell
=
=
s
Spher
ical
p
Dumbb
ell
d
Double
dumbbe
f
Comple
x
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ll
14
12 (vii) It represent the orbital angular momentum.
10 5 5
4r2 dr 2
4r2 dr 2
4r2 dr 2
h
8 4 4 l(l 1)
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Which is equal to
6 3 3 2
4 2 2
2 1 1 (viii) The maximum number of electrons in
0
2 4 6 8
0
2 4 6 8
0
2 4 6 8 subshell 2(2l 1)
0.53Å r(Å) 0.53Å 2.7Å r(Å) 2.1Å r(Å)
1s 2s 2s s subshell 2 electrons d subshell 10 electrons
Fig. 2.5
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(4) Spin quantum numbers (s) (v) Maximum spin of an atom 1 / 2 number of
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unpaired electron.
(i) It was proposed by Goldshmidt & Ulen Back
and denoted by the symbol of ‘s’. (vi) This quantum number is not the result of
solution of schrodinger equation as solved for H-atom.
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Designation of Number of Orbitals in the
n l m
orbitals subshell
1 0 0 1s 1
2 0 0 2s 1
3
3
1
0
1
–1, 0, +1
0
–1, 0, +1
ID 2p
3s
3p
3
1
3
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3 2 –2, –1, 0, +1, +2 3d 5
4 0 0 4s 1
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4 1 –1, 0, +1 4p 3
Px PY Pz
Fig. 2.7
(3) Shape of ‘d’ orbital
(i) For the ‘d’ orbital l =2 then the values of ‘m’
1S 2S are –2, –1, 0, +1, +2. It shows that the ‘d’ orbitals has
Fig. 2.6 five orbitals as d xy , d yz , d zx , d x 2 y 2 , d z 2 .
(2) Shape of ‘p’ orbitals
Structure of atom 47
(ii) Each ‘d’ orbital identical in shape, size and (3) Pauli’s exclusion principle
energy. According to this principle “no two electrons in an
(iii) The shape of d orbital is double dumb bell . atom will have same value of all the four quantum
(iv) It has directional properties. numbers”.
Z Z
Y Y If one electron in an atom has the quantum
numbers n 1 , l 0 , m 0 and s 1 / 2 , no other
X X electron can have the same four quantum numbers. In
other words, we cannot place two electrons with the
same value of s in a 1s orbital.
dZX dXY
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Z Z
Y Y The orbital diagram does not represent a
Z possible arrangement of 1s
electrons
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an orbital can hold not more than two electrons.
d
z2
X ID “Electron pairing in p, d and f orbitals cannot
occur until each orbitals of a given subshell contains
one electron each or is singly occupied”.
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This is due to the fact that electrons being
Fig. 2.8
identical in charge, repel each other when present in
(4) Shape of ‘f’ orbital the same orbital. This repulsion can however be
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(i) For the ‘f’ orbital l=3 then the values of ‘m’ minimised if two electrons move as far apart as
are –3, –2, –1,0,+1,+2,+3. It shows that the ‘f’ orbitals possible by occupying different degenerate orbitals. All
have seven orientation as the unpaired electrons in a degenerate set of orbitals
fx (x 2 y 2 ) , fy(x 2 y 2 ) , fz(x 2 y 2 ), fxyz , fz 3 , fyz 2 and fxz 2 . will have same spin.
(ii) The ‘f’ orbital is complicated in shape. As we now know the Hund’s rule, let us see how
Rules for filling of electrons in various orbitals the three electrons are arranged in p orbitals.
D
The atom is built up by filling electrons in various The important point ot be remembered is that all
orbitals according to the following rules, the singly occupied orbitals should have electrons with
parallel spins i.e in the same direction either-clockwise
(1) Aufbau’s principle
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or anticlockwise.
This principle states that the electrons are added
one by one to the various orbitals in order of their 2px 2py 2pz 2px 2py 2pz
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the configuration is 1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s1 3d 10 as this
configuration is more stable. Similarly Cr has the magnetron) of n unpaired e
configuration of 1s 2 2 s 2 sp 6 3 s 2 3 p 6 4 s 1 3d 5 instead of Ion with unpaired electron in d or f orbital will be
coloured.
1s 2 2 s 2 2 p 6 3 s 2 3 p 6 4 s 2 3 d 4 .
Exception of E.C. are Cr (24 ) , Cu (29 ) , Mo (42 ) ,
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Factors responsible for the extra stability of half-
Ag (47 ) , W (74 ) , Au (79 ) .
filled and completely filled subshells,
2r h
(i) Symmetrical distribution : It is well known fact No. of waves n (where )
mv
that symmetry leads to stability. Thus the electronic
v
configuration in which all the orbitals of the same No. of revolutions of e per second is .
2r
subshell are either completely filled or are exactly half
filled are more stable because of symmetrical
distribution of electrons.
(ii) Exchange energy : The electrons with parallel
spins present in the degenerate orbitals tend to
ID The solution of schrodinger wave equation gives
principal, azimuthal and magnetic quantum numbers
but not the spin quantum number.
In the Rydberg formula, when n 2 the line
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exchange their position. The energy released during produced is called the limiting line of that series.
this exchange is called exchange energy. The number of
exchanges that can take place is maximum when the Among various forms of visible light, violet
colour has shortest wavelength, highest frequency
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Discovery and Properties of anode, cathode rays
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neutron and Nuclear structure
[CPMT 1976]
(a) Increase of nuclear charge
(b) Gain of protons
(c) Loss of electrons
(d) Loss of protons
5. The electron is
[DPMT 1982; MADT Bihar 1980]