ATOMIC STRUCTURE

Molecule :
SYNOPSIS
 The smallest particle of an element which has
MATTER: independent existence and chemically inert is called
 Any thing that has mass and occupies molecule.
some space is called matter eg : H 2 , Cl2 , HCl , etc...
Matter Atom :
 The word atom is derived from greek word
Pure substances Mixtures ATOMIO which means indivisible.
 The term atom was proposed by John Dalton.
 Matter is made up of molecules and molecules are
Elements Chemical made up of atoms.
compounds  Atoms are fundamental building blocks of matter.
Dalton’s atomic theory-postulates
Homogeneous Heterogeneous
 The matter is made of small indivisible particles
called atoms, which can take part in chemical re-
Elements: actions.
 The substances which can give same atoms upon  The atoms of the same element are identical in size,
fine division are called elements. mass and in other properties in all respects.
 Elements may contains atoms or molecules  Atoms of different elements differ from each other
eg : He, H 2 , Cl2 , O2 etc..... in their properties and masses.
 Atoms of different elements can combine in simple
Compounds : ratios to form compounds.
 These are formed when two or more different  Atoms can be neither created nor destroyed.
elements combine.
 The properties of compounds are different from
Merits of Dalton’s theory :
 Dalton’s theory is able to explain law of conser-
those of the elements.
vation of mass, law of constant composition and
eg : HCl , NaOH , H 2O . law of multiple proportions.
Mixture: Draw backs of Dalton’s theory :
 A material containing two or more substances in  It failed to explain the internal structure of atoms
any proportions is called mixture.  It could not explain how atoms of different ele-
 The components in the mixture are present with ments differ from one another and combine with
out losing their identity. one another.
 It failed to explain the experiments like when glass
Homogeneous Mixture :
or ebonite rubbed with silk or fur generate elec-
 Mixtures having a constant composition through-
tricity.
out are said to be homogeneous mixture.
eg : air, sea water, alloys. Sub atomic particles:
 Atom consists of smaller particles like electron,
Heterogeneous mixture:
proton , neutron, neutrino, anti neutrino, positron
 Mixtures having different compositions in differ-
antiproton, pions and measons etc...
ent regions are said to be heterogeneous mixture.
 Electron, Proton and Neutron are considered as
eg : sand+water, dust+air.
fundamental particles of atom.
ATOMIC STRUCTURE
Electron-discovery:  Greater the magnitude of the charge on the particle
 Electron was discovered by J.J.Thomson. greater is the deflection when electric and mag-
 The name eletctron was proposed by Stoney. netic field is applied.
 The discharge tube is a sealed tube,made of glass  Lighter the mass of the particle greater will be the
containing two thin metal plates called electrodes. deflection.
 During the discharge tube experiment “Crookes”  The deflection of electrons from its original path
observed that rays were found to pass from increases when voltage increases.
negatively charged plate (cathode) to positively  From the above points J.J.Thomson was able to
charged plate (anode). determine the value of charge to mass ratio.
 The electrical discharge through the gases could e
 1.7588  1011 cKg 1 (or )1.7588  108 cg 1
be observed only at very low pressures(0.01mm m
of Hg) and at very high voltages(10000 V).
 The rays emitted from cathode are called cathode
rays. Cathode Anode +
 Cathode rays are stream of electrons. A
N
Air at very B
low pressure Green glow
Discharge
tube S
C
+
Cathode rays
Cathode Anode
Fluorescent
To vaccum pump Magnet screen

+ High voltage generator

Properties of Cathode Rays :
 The cathode rays move from cathode to anode.
 These rays are invisible but their behaviour can be
observed with the help of fluorescent or
phosphorescent materials, which glow when hit by
them.
 These rays travel in straight lines in the absence of
electric and magnetic field.
 In the presence of electric field they are deflected
towards anode and in magnetic field towards south
pole.
 Cathode rays contain negatively charged particles
called electrons.
 The nature of cathode rays is found to be
independent of nature of the cathode material and
nature of the gas in the tube.
 Hence electrons are considered as constituent par-
ticles of all atoms.
e
Charge to mass ratio of Electron ( ) :
m 
 The charge to mass ratio is known as specific
charge J.J.Thomson measured e/m ratio of the elec-
tron based on following points.
 As the velocity of the electron increases, the
specific charge of the electron decreases due to
the increase of relative mass of the electron.
 The mass of a moving electron may be calculated
by applying the formula
m0
m=
2
v
1  
C 
Where m0 = rest mass of electron
v = velocity of the electron
C = velocity of light
 If v = C, mass of the moving electron becomes
infinity.
 The value of e/m of cathode rays is independent of
the nature of the metal forming the cathode and the
gas used in the discharge tube.
 This shows that electrons are universal
constituents of all matter
Note : e/m value of ions w.r.t. H-atom
magnitude of ch arg e(relative ch arg e)
mass number (relative mass no)
 JEE-MAIN-JR-CHEM-VOL-I
W.E.1: Find the e/m value of   particle
 He  w.r.t. H-atom?
2
2 2 W.E.3: In an oil drop experiment, the charges
Sol: e / m value of He   0.5
4 on oil drops were found as 1.5 10 –15 ,
Charge of Electron :
 The charge of electron is the smallest known
electrical charge. It is taken as unit negative charge.
 Millikan determined the charge of the electron by
an oil drop experiment.
 Charge on the oildrops was always an integral
multiple of 1.60  10 19 C .
e 1.60  1019
me    9.1094  1031 kg
e / me 1.758820  1011 ckg 1
Millikan’s Oil Drop experiment :
 In this , oil droplets which are in the mist form were
allowed to enter through a tiny hole in the upper
plate of electrical condenser.
 The downward motion of these droplets was
viewed through the telescope, equipped with a
micrometer eye piece.
 In chamber, the forces acting on oil drop are
gravitational, electrostatic due to electrical field and
a viscous drag force when the oil drop is moving.
 By measuring the rate of fall of these droplets,
Millikan was able to measure the mass of oil
droplets.
 The air inside the chamber was ionized by passing
a beam of X-rays through it.
 The electrical charge on these oil droplets was
acquired by collisions with gaseous ions.
 The fall of these charged oil droplets can be
retarded, accelerated or made stationary depending
upon the charge on the droplets and the polarity
and strength of the voltage applied to the plate.
 By carefully measuring the effects of electrical field
strength on the motion of oil droplets.
 Millikan concluded that the magnitude of electrical
charge ‘q’ on the droplets is always an integral
multiple of the electrical charge ‘e’ that is q  ne ,
where n = 1,2,3......
W.E.2: An oil drop has 8.0  10–19C charge. How
many electrons does this oil drop has?
Sol: Charge on the oil drop= 8.0  1019 C
Charge on the electron=1.6  1019 C
ATOMIC STRUCTURE
we know that q  ne ,
q 81019
n 
e 1.61019
5
310–15 , 4.510–15 , 6.010–15 .Calculate the
magnitude of the charge on the electron.
Sol: The magnitude of charge should be smallest &
other charges should be integral multiples of that
smallest charge( q  ne ). So in the problem,the
smallest charge 1.510 –15 and is also an
integral multiple of all other charges.
case 1 : 1.5  1015  1 e
case 2 : 3  1015  2  e
case 3 : 4.5  10 15  3  e
case 4 : 6  1015  4  e
so charge on the electrons is same in all cases and
it will be 1.5 10 15
Discovery of Protons :
 Protons are discovered by Gold Stein.
 He used perforated cathode in the discharge tube
and repeated J.J.Thomson experiment and ob-
served the formation of anode rays.
 These rays also termed as positive or Canal rays.
 These are simply the positively charged gaseous
ions.
 The name proton is suggested by Rutherford
Properties of anode rays :
 Anode rays travel in straight line, and these are
material particles.
 Anode rays are positively charged, and get deflected
by external magnetic field and effect the photo-
graphic plate.
e e
 value of these rays is smaller than that of
m m
value of electrons.
e
 value of anode rays depends upon nature of the gas.
m
e
 value of anode rays is maximum when the gas
m
present in the tube is hydrogen.
( 9.58  107 C.kg 1 or 9.58  104 Cg 1 )
 The protons carry unit positive charge with unit Spherical cloud
mass. of positive charge
 Rutherford obtained protons by bombarding nitro- + +
gen atomic nucleus with   particle . + + +
+
14 4
7 N 2 He  11 H 17
8 O + +
+
proton
+ +
Neutron: Electron
Thomson's Plum pudding model
 Neutrons are discovered by James Chadwick.
 When Berilium or Boron nuclides bombarded by Rutherfords Model of Atom :
 -particles, neutrons are formed.  Rutherford proposed atomic model based on
 They have no charge but posses mass almost equal  - ray scattering experiment.
to proton.  A beam of  - particles are passed through a thin
9 4 12 1 gold foil which is enclosed with flouroscent ZnS
4 Be  2 He  6 C  0 n screen capable of producing scintillations.
Beryllium  -particle Carbon Neutron

Subatomic Relative
particle Discoveres Mass Mass Charge e/m
-19 11
Electron Thomson 0.000546 amu 1 -1.602×10 C -1 1.76 × 10 C/Kg
-31 -10
9.18 × 10 Kg 1837 -4.8 × 10 esu
-19 7
Proton Gold Stein 1.00728 amu 1 1.602×10 C 1 9.58 × 10 C/Kg
-27 -10
1.673×10 Kg 4.8×10 esu
Neutron Chadwick 1.008665 amu 1 0 0 0
-27
1.675×10 Kg

Atomic Models : Observations - conclussions :

J.J.Thomson atomic model:
 J.J.Thomson proposed that an atom is in spherical
10
shape with radius approximately10 m in which
the positive charge is uniformly distributed .
 The electrons are embeded into it in such a manner
as to give more stable electrostatic arrangment
 According to J.J.Thomson atom is like water
melon.
 The positive charge is distributed like fibrous
 Most of the  - particles passes through the foil
without any deflection which indicates that most of
the atom is empty.
 A small fraction of  - particles were deflected
from its original path which indicates that the posi-
tive charge is at the centre of the atom and due to
repulsive forces deflections takes places.
Observation Interpretation
} The atom is mostly
empty space
Gold

material and electrons are embeded like seeds . Detector foil

}
 An important feature of this model is that the mass
of the atom is assumed to be uniformly distributed Radoactive }
source
over the atom.
 It can not explain electrical neutrality of the atom. Rutherford's Gold Foil Experiment
 This model also called plum pudding, raisin
pudding model of atom.
 A very few  - particles bounced back which Atomic mass number :
indicates that the whole mass is concentrated at the  The sum of protons and neutrons in an atom of an
centre of atom. This heaviest part is named as element is called its mass number(A).
“nucleus” A = no.of neutrons + no.of protons
A=n+z
Number of neutrons = A  Z .
Mass number is always a whole number.
+ Atomic weight :
 One-twelfth the mass of an atom of C612 is called
as atomic mass unit(a.m.u). It is also known as
Dalton(Da)
Rutherford's Alpha-ray Experiment
 The radius of the atom is very small and in the or- W.E.4: What will be the difference in mass number if
the number of neutrons halved and the number of
der of 1010 m , where as for nucleus is 1015 m .
 The electrons revolve around the nucleus like plan- electrons doubled in 12
6 C

ets revolve around the sun hence this model is called Ans: Mass no is the sum of protons and neutrons
planetary model or nuclear model. If 12
6 C  Initial  final
Defects of Rutherford’s Model : protons : 6 - 6
 It is against to law of electrodynamics. Neutrons: 6 - 3
 It was failed to explain stability of atom. mass no : 12 - 9
 According to classical electromagnetic theory, the Hence the decrease in mass no is 25.0%
revolving electron should loss energy continuosly W.E.5: Calculate the no.of protons,neutron and
and travel in a spiral path. Finally it must fall into the 37
electrons in 17 Cl
nucleus. But it does not happen.
Ans: No.of protons = Atomic number(z)=17
 The atomic spectrum should be continuous band
spectrum due to continuous loss of energy but it is mass number(A)=37
a line spectrum. No.of neutrons=A-Z=37-17=20
 It can’t explain the electronic structure of atom and No.of electrons=17
energies of electrons. W.E.6: Calculate the no.of protons, neutron and
Atomic Number : electron in 14 3
7 N ion

 The number of electrons or protons present in an Sol: No.of protons=atomic number(z)=7

atom of an element is called its atomic number(Z).
 Moseley gives the relation between atomic number
(Z) and frequency( v ) of the characteristic X-rays
of the element by the equation
v  a  Z  b
Where ‘a’ and ‘b’ are constants and depends on
nature of the elements.
 A neutral atom contains equal number of electrons
and protons.
For Cation :
Number of protons = z
Number of electrons  z  no.of electrons lost
For Anion :
Number of protons = z
Number of electrons = z + no.of electrons gained
No.of neutrons =(A-z)=14-7=7
No.of electrons in an ion
= z  magnitude of ch arg e =7+3=10
W.E.7: The no.of electrons ,protons and neutron
in a species are equal to 10,11,12 respectively.
Assign proper symbol to the species.
Sol. No.of protons=11, hence atomic no. = 11
so the element is Na.
It has one eletron less than the no.of electrons, hence
it has a unit +ve charge.
No.of neutrons =12
Mass number = no.of protons + no.of
neutrons = 11 + 12 = 13
therefore the symbol of that species= 11 23
Na 
 Isotopes :  The percentage of isotope wit h A.wt
 The nuclides of same element having same atomic 10.01=20%
number but different mass numbers are called The percentage of isotope with A.wt 11.01=80.0%
isotopes. Isobars :
 Isotopes show similar chemical properties but
 The nuclides of different elements having same
different physical and radioactive properties.
mass number but different atomic numbers are
 Fractional atomic masses of elements is due to the
called
presence of Isotopes.
isobars.
Avg.atomic mass
 Isobars show similar physical properties but

 % abundance of isotope  atomic weight different chemical properties.
total ratio eg. 1) : 6 C 14 , 7 N 14
eg. 1) Isotopes of hydrogen : 48 20 40
2) : 18 Ar ,19 K ,20 Ca
Protium  1 H  , Deuterium  1 H  or
1 2
D2 130
1 3) : 54 Xe, 130
56 Ba

Tritium  1 H 3  or 1T 3 . Protium (99.985%),

Isotones :
Deuterium (0.015%)  The nuclides of the different elements with different
2) Isotopes of chlorine : 17 Cl 35
and 17 Cl 37 atomic number and mass number but having same
235 238
number of neutrons(A-Z) are called isotones.
3) isotopes of uranium : 92 U and 92U  Isotones show different physical and chemical
W.E.8 The mass number of three isotopes of an properties.
element are 10,12,14 units. Their percentage eg. 1) 30 31 32
14 Si , 15 P , 16 S
abundance is 80,15 and 5units respectively. 14 16
What is the atomic weight of the element? 2) 6 C,8 O
Sol: Percentage abundances of Isotopes=80,15,5 3) 23 24
11 Na , 12 Mg
ratio of percentage abundances of Isotopes=16:3:1
The total ratio = 16+3+1=20 Isodiaphers :
 ratio of % abundance  Atomic weight  The nuclides having same isotopic number(A-2Z)
Avg. Awt 
Total ratio are called isodiaphers. They posses same differ-
ence of neutrons and protons (n-p).
10  16  12  3  14  1
  10.5 eg. F919 , Na1123
20
The Avg.Awt=10.5. Isosters :
W.E.9: Naturally occuring boron consists of two  The molecules with same atomicity and same
isotopes whose atomic weights are 10.01 and number of electrons are called isosters.
11.01 the atomic weight of natural boron is eg. CO2, N2O
10.81. Calculate the percentage of each C6H6 & B3N3H6
Isotope in natural boron? (Atomicity = total no.of atoms in molecule)
Ans: Let the percentage of isotope with atomic weight
10.01 = x Iso-electronic species :
Let the percentage of isotope with atomic weight  The molecules or ions with same number of
11.01=(100-x) electrons are called iso electronic species
m1 x1  m2 x2 eg 1: N 3 , O 2 , F  , Ne, Na  , Mg 2  , Al 3
Avg. Awt 
x1  x2 eg2 : P 3 , S 2 , Cl  , Ar , K  , Ca 2 , Sc 3
x  10.01  (100  x)11 Nature of light :
10.81 
100  It can be explained by two theories
x=20% a) wave theory of light b) corpuscular theory of
light
 ATOMIC STRUCTURE
Wave theory : Frequency    :
 It was proposed by Huygens
 The number of waves that pass through a given
 According to Huygens Light and other forms of
point in one second is called frequency.
radiant energy propagate through space in the form
of waves. Units : The SI units are sec 1 , cycles per second
 Maxwell proposed when electrically charged (cps) or Hertz (Hz). 1cps = 1 Hz= sec 1
particle moves under acceleration,alternating Frequency( v ) and wavelength (  ) are related as
electrical and magnetic fields are produced and
transmitted. C
v
 These are transmitted in the form of wave and are 
associated with electric and magnetic fields are Where C = Velocity of light
called electromagnetic radiation(EMR) or = 3 x 108 m/sec or 3 x 1010 cm/sec
electromagnetic waves.
 Both electric and magnetic fields are perpendicular to Wave Number    :
each other and to the direction of the propagation.  The number of wave lengths per unit length
 These electromagnetic waves do not require any (or )
medium and can travel in vaccum.  The reciprocal wave length is called wave number.
Electromagnetic wave Units: cm 1 or m 1
Magnetic Field(B)
1
Electric Wave number v 
Field(E) 
Propagation  The relation between v and v is v  Cv
Direction Amplitude (a):
 The height of the crest or depth of the trough of a
wave is called amplitude.
Characteristic properties of wave : Units: m, cm, pm
Wave Length (  ):  Amplitude is a measure of the intensity or bright-
 The distance between two similar points in a wave ness of a beam of light.
is known as wave length. Velocity (C):
 The units of wave length are m, cm, A0, nm,  The distance travelled by a wave in one second is
 , m or pm. called its velocity.
Units: m/sec or cm/sec.
1A 0  108 cm  1010 m
 All types of electromagnetic radiations have the same
7 9 0
1nm  10 cm 10 m  1m  10 A velocity which is equal to the velocity of light
1 pm 1010 cm  1012 m (3  108 ms 1 )
Property Formula Units
-8 -10
c 1Å = 10 cm = 10 m
l =
u
-10 -12
1pm = 10 cm = 10 m
c
u = or u = cu Hertz
l
-1
1 u m
u = or u =
l c
-1
ms
W.E.10: The vividh bharati station of All india = 4.00  1014 Hz
Radio, delhi,broadcasts on a frequency of The range of visible spectrum is from
1,368 kHz (kilo hertz). Calculate the
4.0  1014 to 7.5  1014 Hz in terms of frequency
wavelength of the electromagnetic radiation
emitted by transmitter. Which part of the W.E.12: Ca l c u l a t e ( a ) Wa ven u m ber a n d
electromagnetic spectrum does it belong to? (b) frequency of yellow radiation having
wavelength 5800A0.
c
Sol:   where c = velocity of E.M.R in Sol: a) Calculation of wavenumber ( )

vaccum   5800 A0  5800  108 cm
= 3  108 m sec 1 = 5800  1010 m
  frequency  1368kHz
1 1
= 1368  103 sec 1  
 5800  1010 m
3.00  108 ms 1  1.724  106 m 1
=
1368  103 s 1  1.724  104 cm 1
= 219.3m
b) Calculation of the frequency ( )
This is a characteristic radiowave wavelength.
W.E11: The wavelength range of the visible c 3 108 ms 1
spectrum extends from violet(400 nm) to    5.172  1014 s 1
 5800  1010 m
red (750 nm). Express these wavelengths
in frequencies (Hz).(1nm=10 –9 m) Electromagnetic spectrum :
Sol: Frequency of violet light  The arrangement of different radiations in the increasing
order ofwavelengths or decreasing order of frequencies
c 3.00 108 ms 1
  with equalvelocities.
 400 109 m  The visible region is a small part of the entire
14
 7.50  10 Hz spectrum. It ranges from 400 nm to 750 nm
frequncy of red light
c 3.00 108 ms 1
 
 750 109 m
The Electromagnetic Spectrum
micrometers
0.4 0.5 0.6 0.7
UV blue green red near-IR

Visible light
Wavelength
(micromet) -6 -5 -4 -3 -2 -1 2 3 4 5 6 7 8 9
10 10 10 10 10 10 1 10 10 10 10 10 10 10 10 10

Cosmic Gamma X UV near & micro radio

rays rays rays middle wave and
IR T.V
visible thermal
IR
 Corpuscular theory :
 According to Newton, light and other form of
radiant energies are propagated in the form of
corpuscules(simple invisible particle) .
 After the wave theory of light, the corpuscular
theory lost significance
Black body radiation :
 The ideal body which emits and absorbs radiations
of all frequencies, is called a black body.
 The radiation of black body is called black body
radiation.
 A hollow sphere coated inside with platinum black,
which has a small hole in its wall can act as a near
black body.
eg :1. The reddish glow from the heating element
in an electric stove
eg :2 white light emitted by the hot filament in light
bulb
 A graph is obtained by plotting the intensity of
radiation against wave length as shown in fig.
special radiancy
T2 > 1.3 * T1
T1
Wavelngth
A Study of the curve reveals that :
 At a given temperature the intensity of radiation
emitted increases, reaches a maximum value and
then decreases.
 As the temperature increases the maximum inten- 
sity shifts towards the shortest wave lengths.
Planck’s Quantum Theory :
 The phenomenon of the black body radiation is  The increase in wave length or decrease in energy
given by Max planck.
 The absorption or emission of radiation is mainly
due to the vibrations of charged particles.
 The radiation is associated with definite amount of
energy.
 The radiant energy is always in discontinuous wave
form. It is absorbed or emitted discontinuosly in
the form small packets of energy called quantum.
 The energy of a quantum of radiation is directly
proportional to the frequency of the radiation.
E  E = hv
hc
E  hc

Where E = Energy of radiation
h = Planck’s constant
= 6.625 1027 erg  sec
= 6.625  10 34 Joule  sec (SI unit)
= 3.99  1013 KJ  sec/ mole
 Energy is emitted or absorbed in simple integral
multiples of quantum, but not fractional values
E  nhv Where n = 1, 2, 3, 4, ........
Einstein’s approach :
 According to Einstein the radiant energy is absorbed
or emitted in the form of small particle is called
photon.The radiation is propagated in the form of
photons.
 The energy of a photon is directly proportional to
frequency of the radiation.
 The energy of a photon is
hc
E = hv (or) E 

12375
E

Where E = energy in eV
  wavelength in A 0
 The energy of 1mole of photons is
E = Nhv
Where N = Avogadro’s number
= 6.023 x 1023
Plank’s quantum theory was extended by Einstein
for all types of electromagnetic radiations.
Compton Effect:
of the X - rays after scattering from an object is
called the compton effect.
W.E.13: calcutate energy of one mole of photons
of radiation whose f requency is 5 1014 Hz
Ans: Energy (E) of one photons
E = hv
h = 6.626 10–34 Js
v = 5  1014s–1 (given)
E = ( 6.626 10–34 Js )  (5  1014s–1)
= 3.313  10–19 J
Energy of one mole of photons
= (3.313  10–19 J) (6.022  1023mol–1)
= 199.51kJmol–1
W.E.14 : A 100watt bulb emits monochromatic light
hc
of wavelength 400nm. Calculate the no.of  
photons emitted per second by the bulb? E
Sol: Power of the bulb =100watt 6.626  1034 Js  3.0  108 ms 1

=100 Js 1 3.84  1019 J
Energy of one photon =517nm this wavelength corresponds to green
colour in visible spectrum.
hc
E  h  W.E.16 : Calculate the energy of photons of
 r adi at i on wh ose wavel en gth i s 5000A 0 ?
6.626  1034 Js  3  108 ms 1 Ans:   5000 A0  5000  1010 m  5  107 m

400  109 m
c  3  108 m / sec; h  6.62  1034 Js
 4.969  1019 J hc 6.62 1034  3 108
 Number of photons emitted E 
 5 107
100 Js 1  3.97 1019 J
  2.012  1020 s 1
4.969  1019 J W.E.17: What is the number of photons of light
W.E.15: When electromagnetic radiation of wave- with a wave length 4000pm that provide 1J
length 300nm falls on the surface of energy?
sodium,electrons are emitted with a kinetic
energy of 1.68  10 5 Jmol –1 . What is the wavelength   4000 pm  4 109 m
Sol:
minimum energy needed to remove an h  6.625 1034 Js, c  3.0  108 ms 1
electron from sodium? What is the maximum
wavelength that will cause a photoelectron hc
Energy of one photon, E 
to be emitted? 
Sol: The energy(E) of a 300nm photon is given by 6.625 1034 Js  3 108 ms 1
 = 4.969  10 17 J
hc 4 109 J
h  Number of photons providing 1 joule of energy

6.626  1034 Js  3.0  108 ms 1 1
  17
 2.01 1016
300  109 m 4.969  10
The energy of one mole of photons W.E.18: Calculate the energy of one mole of
quanta of radiation whose frequency is
 6.626  1019 J  6.022 10 23 mol 1 5  10 10 sec –1
 3.99  105 Jmol 1 Sol: Energy of 1 mol quantum  Nh
The minimum energy needed to remove one mole
 6.023  1023  6.626  1034  5  1010
of electrons from sodium.
J
 (3.99  1.68)105 Jmol 1  19.95
mol
 2.31 105 Jmol 1
W.E.19 : Compare the energies of two radiations
The minimum energy for one electron one with  = 600nm and other with 300nm.
2.31 105 Jmol 1 E1 2 300 1
 Sol: E    600  2
6.022  10 23 electrons mol 1 2 1

 3.84  1019 J The relation between two energies is E2  2 E1

This corresponds to the wavelength

Photo electric effect :
 The phenomenon of ejection of electrons from the
surface of metal when light of suitable frequency 
strikes is called as photo electric effect.
 The electrons ejected are called photo electrons.
 The minimum frequency required to eject the
electrons is called threshold frequency
 The photo electric effect is readily exhibited by
alkali metals like K , Rb and Cs.
 A part of the energy of photon is used to escape
the electron from the attractive forces and the
remaining energy is used in increasing the kinetic
energy of electron.
E  W  KE
Where W = Work function or Threshold energy
W = hv0
h  hv 0  KE
hc hc
K.E  h  h 0  
 0
Where v0 = Threshold frequency
 In photo electric effect the number of photo elec-
trons emitted is proportional to intensity of inci- Sol: According to Einstein’s equation
dent light.
Intensity:
 It is the power transfered per unit area. Its S.I. units
are (W / m2 ) . It is used mostly for waves.
 The kinetic energy of photo electrons depends only
on the frequency of incident light and not on the
intensity of light.
 The minimum energy required for emission of W.E.21: The minimum energy required to overcome
photo electrons is called threshold energy or
work function.
 For each metal, there is a characteristic minimum
frequency v0 (also known as threshold frequency)
below which photoelectric effect is not observed.
 At a frequency v > v0 then photoelectric effect is Sol : Energy of the photons absorbed
observed.
Values of work Function (W0) for Few
Metals:
Metal Li Na K Mg Cu Ag
W0/eV 2.42 2.3 2.25 3.7 4.8 4.3
Note : Stoping potential : It is the minimum potential
at which the photo electric current becomes zero.
ATOMIC STRUCTURE
If V0 is the stopping potential eV0  h(   0 )
If   0 no e  is ejected
= Threshold frequency
K.E
If    0 ; K .E  0
K.E
Intensity
W.E-20 : The threshold frequency v0 for a metal is
7.0  1014s–1. Calculate the kinetic energy of
an electron emitted when radiation of
frequency v = 1.0  1015s–1 hits the metal.
1 2
Kinetic energy  me v  h(v  v0 )
2
 (6.626  1034 Js)(1.0  1015 s 1  7.0  1014 s 1 )
 (6.626  1034 Js)(10.0  1014 s 1  7.0  1014 s 1 )
 (6.626  1034 Js)  (3.0  1014 s 1 )
 1.988  1019 J
the attractive forces between an electron and
the surface of Ag metal is 5.52  10–19J. What
will be the maximum kinetic energy of
electron ejected out from Ag which is being
exposed to UV-light of   360 A0 ?
hc 6.626  1027  3  1010
 
 360 108
 5.52  1011 erg
 5.52  1018 J
E(photon)= Work function+K.E
K .E  5.52 1018  7.52  1019
 47.68 1019 J
W.E.22 : When light of 470nm falls on the surface or  2  0  2 1  2 0
of potassium metal, electrons are emitted with
or  0  2 1  2
a velocity of 6.4  10 4 ms –1 . What is the
minimum energy required to remove one mole  2(2.0  1016 )  (3.2  1016 )  8.0  1015 Hz
electrons from potassium metal?
W.E-24: Threshold wavelength of a metal is
1 2 230nm. What will be the kinetic energy of
Sol: kinetic energy of photo electrons  mv
2 photoelectrons ejected when the metal is
1 irradiated with wavelength 180nm?
  9.1 1031  (6.4  104 ) 2
2 (h  6.626 1034 J sec)
 1.864  1021 J Ans: Absorbed energy from light = Threshold
we know that, energy+kinetic energy of photoelectrons
Absorbed energy from light = Threshold
hc hc 1 1
energy + kinetic energy of photoelectrons   K .E  K .E  hc[  ]
 0  0
hc 1
 W0  mv 2
 2 1 1
 6.626  10 34  3  108 [ 9
 ]
180  10 230  10  9
6.626  1034  3 108

470 10 9 1 1
 6.626  10 34  3  108 109 [  ]
 W0  1.864  1021 J 180 230
 W0  419.206  1021 J  1.9878  10 16 [5.55  10 3  4.347  103 ]
 2.4  10 19 J
Energy required to eject one mole electrons
 419.211021  6.023 10 23 SPECTRA AND ATOMIC MODELS:
 252.4 103 Jmol 1  252.4kJmol 1  The image recorded when radiant energy is passed
through a prism or grating is called a spectrum.
W.E.23: When a certain metal was irradiated with
light of frequency 3.2  10 16 Hz,the  The splitting of white light into seven colours is
photoelectrons emitted had twice the kinetic known as dispersion.
energy as did photoelectrons emitted when the  The device used to record spectrum is called spec-
same metal was irradiated with light of trograph or spectrometer.
frequency 2.0  1016Hz. Calculate v0 for the Continuous spectrum :
metal?
 The spectrum of sun light where one colour merges
Ans : Applyilng photoelectric equation,
into another without any gap is known as continu-
K .E ous spectrum.
K.E  h  h 0 or (   0 ) 
h eg: light emitted from incadescent solid
Given K .E2  2 K .E1 Discontinuous spectrum :
K .E2  The spectrum having distinct and well defined
 2  0      1
h lines wit h gap ( dark areas) is called
K .E1 discontinuous spectrum
And  1  0  2
h Spectra is broadly divided into two types
Dividing equation(1) with (2), a) Absorption spectrum b) Emission spectrum
 2  0 K .E2 2 K .E1
  2
 1  0 K .E1 K .E1
 Absorption Emission  This light when passed through prism ,an emerged
Spectrum Spectrum beam of light is collected over photo graphic film.
1. It is spectrum 1. It is spectrum This is called H-atomic spectrum.
produced by produced by  It is a line spectrum and simplest of all atomic
transmitted lighter emission of spectrum
after absorption of radiation. (de  It contains a series of group of lines.
r a d i a t i o n excitation of  They can be classified into various series.
(excitation of electron in a a) Lyman series b) Balmer series
electrons in a substance c) Paschen series d) Bracket series
substance) e) Pfund series
2. It contains dark 2. It contains bright  The only series visible to the naked eye is termed
lines on the bright lines on the dark as the visible region of hydrogen spectrum.
back ground. back ground  It was discovered by Balmer, so it is called Balmer
3. Eg: sodium vapour 3. Eg: Sodium vapour series.
gives two dark gives two bright Different series of spectral lines in
lines at 5890Å and lines at 5890Å and
5896Å in yellow hydrogen emission spectrum.
5896Å in yellow
region. Name of the n1 n2 Spectral Equation for
region. Series region wave number
4. The spectrum is 4. The spectrummay 1 1
discontinuous be discontinuous. Lyman series 1 2,3,4,5,6,7.... Ultraviolet v  R   2  2 
 1 n2 

Emission Spectrum can be further classified into line  1 1

Balmer series 2 3,4,5,6,7.... Visible v  R   2  2 
and band spectrum (atomic and molecular 2 n2 
spectrum). Near 1 1
Paschen series 3 4,5,6,7.... v  R   2  2 
infrared  3 n2 
 1 1
Brackett series 4 5,6,7.... Infrared v  R   2  2 
 4 n2 

1. The line spectrum 1. T h e b a n d Far 1 1

v  R   2  2 
Pfund series 5 6,7....
has sharp, distinct s p e c t r u m h a s Infrared  5 n2 
well defined lines. many closed lines
2. I t i s t h e 2. It is characteristic 0 kJ
characteristic of o f g a s e o u s n=7
n=6
gaseous atom and molecules and is
n=5
is also called a l s o c a l l e d Pfund
atomic spectrum. m o l e c u l a r n=4 -82 kJ
Brackett
spectrum.
n=3 -146 kJ
3. I t i s d u e t o 3. I t i s d u e t o Paschen
t r a n s i t i o n o f vibration and n=2 -328 kJ
electrons between rotational changes Balmer
energy level in an of atoms in a
atom. molecule. n=1 -1312 kJ
Lyman
4. It is given by inert 4. It is given by hot
gases, metal m e t a l s a n d
vapours and atoms. molecules Explanation of line spectrum of Hydrogen:
 The energy gap between the two orbits is given
Hydrogen emission spectrum :
by equation E  E2  E1 -----------(1)
 By applying high potential difference in a discharge
tube containing hydrogen gas a bright light is  The energy of its stationary state is given by the
obtained.
  1   If n2 is taken as infinity the wavelength of the
expression En   RH  2  ----------(2) limiting line(last line) in the series is obtained.
n 
 Introducing the eq (2) in equation (1)
1 1 1  R
 R   RH     RH  2  2   H2
E    H2  2    n1   n1
 n2   n1 
 The wavelength or wave numbers of all the
(where n1 and n2 stand for initial orbit and final
lines in all the series can be calculated by using
orbits. n1 and n2 may be refered as ni and n f ) Rydberg’s equation.

 1 1   1 1  1 1 1
E  RH  2  2  18
  2.18  10 J  2  2     RH  Z 2[ 2  2 ]
 n1 n2   n1 n2   n1 n2
 The frequency (v) associated with the where RH = Rydberg’s constant for H-atom
absorption and emission of the photon can = 1,09,677 cm 1
be evaluated by using equation
n1 = Lower energy level ( ni )
E RH  1 1 
v    
h h  n12 n22  n2 = Higher energy level ( nf )
 Maximum number of spectral lines produced
On substituting RH and h values
when an electron jumps from n2 to n1 state
 1 1 for a simple atom
 3.29  1015  2  2  Hz
 n1 n2  n  n  1
  or   n 2  n1
2
 In terms of wavenumbers v 
 Number of spectral line in a series  n2  n1
v R  1 1 W.E.25: What are the frequency and wavelength
v  H  2  2
C hC  n1 n2  of a photon emitted during a transition from
n=5 state to the n=2state in the hydrogen
On substituting RH , h and C values atom?
 1 1  Ans: Since ni  5 and n f  2 , this transition gives rise
  1.09677  10 7  2  2  m 1
 n1 n2  to a special line in the visible region of the Balmer
 Rydberg constant value is not same for all the series.
elements.
1 1
For hydrogen like species He+, Li2+, Be3+, E  2.18  1018 J [  ]
R = 1,09,677 x Z2 cm-1 52 22
= RH x Z2  4.58  1019 J
1 The frequency of the photon (taking energy in terms
 Note: R =912 A0 of magnitude) is given by
H

 The first line in Balmer series is called H  line and E 4.58  10 19 J
 
its wavelength is 6563 A0. h 6.626 1034 Js
 The second line is called H  line and its wavelength  6.91 1014 Hz
is 4861 A0. c 3.0 108 ms 1
 The spectral lines get closer when the n2 value is    434nm
 6.91 1014 Hz
increased.
W.E.26: Calculate the shortest and longest
wavelength in hydrogen spectrum of Lyman
3  6 will have same wavelength as that of
series. second line of Balmer series in He  spectrum.
Ans: For Lyman series n1  1 W.E.28: Calculate the possible number of lines in
the spectrum of hydrogen,when electrons
For shortest wavelength in lyman series(i.e,series
return from 7th shell to 2nd shell.
limit), the energy difference in two states showing
transition should be maximum,i.e,
Ans:
 (n2  n1 )   7  2   5
n2    5  4  3  2  1  15
W.E.29 : Calculate the wave number and wave
1 1 1
 RH [ 2  ]  RH length of H line in Bracket series of H-
 1 ( ) 2
emission spectrum
1 6
  9.117  10 cm Ans : For H line in Bracket series
3 109678
 911.7 A0 n1 = 4 , n 2 = 5
1 1
For longest wavelength in lyman series(i,e. first line) ν = R[ - ]
the energy difference in two states showing transition n1 n 2
should be minimum,i.e., n2  2 1 1
= 109677[ - ]
42 52
1 1 1 3
 RH [ 2  2 ]  RH = 2467.7325cm -1
 1 (2) 4
1
   4.0 10 4 cm
4 1 4 
 
3 RH 3  109678 Bohr’s atomic model :
 To explain the origin of lines in hydrogen spectrum
 1215.7  108 cm  1215.7 A0 and to overcome the defects in Rutherfords model,
W.E.27 : What transition of Li 2 spectrum will have Neils Bohr proposed his model of atom.
same wavelength as that of second line of Postulates :
 The electron in the hydrogen atom revolves around
Balmer series in He  spectrum?
the nucleus with definite velocity in fixed,closed,
Ans : circular paths, called‘orbits’ or ’shells’.
1 1  These are designed as 1,2,3,4... or K, L, M, N

 He   Li  ..... from the side of the nucleus. [derived from
1 1 1 1 Kepler’s law]
RZ 2 [  ]  RZ 2 [ 2  2 ]  The electron revolves in the orbit whose angular
n12 n 22 n1 n 2
nh
momentum ( I   ) is equal to .
1 1 1 1 2
22 [ 2
 2 ]  32 [ 2  2 ] It is given by the expression
2 4 n1 n2
1 1 1 1 nh
4[  ]  9[ 2  2 ] mvr 
4 16 n1 n2 2
where m = mass of electron
4 3 1 1 v = velocity of electron
 [ 2  2]
9 16 n1 n2 r = radius of orbit
h = plank’s constant
1 1 1 n =1,2,3...
 2
 2   Each orbit is associated with definite amount of
n1 n2 12 energy.So these are also called energy levels or
n1  3, n2  6 energy states.
 JEE-MAIN-JR-CHEM-VOL-I
 The energy of electron does not change as long Expression for energy :
as the electron revolves in the orbit. Hence,
these orbits are called ‘stationary orbits’ or  1 2 Ze 2
Kinetic energy of electron  m V 
‘stationary states’. 2 2r
 The energy of electron changes only when the
Ze 2
electron moves from one orbit to another.  Potential energy of electron 
 If energy is absorbed the electron jumps from lower r
energy state to higher energy state, and if it lose the  Total energy of electron
energy the electron jumps from higher energy state Ze 2 Ze 2  Ze 2
to lower energy state. E  KE  PE   
2r r 2r
 The change in energy is given by the formula
 Expression for the energy of Bohr’s orbit m
E  E2  E1  h (By substituting radius of orbit in the above
 The centripetal force on the electron is balanced expression)
by centrifugal force.
22 m Z2 e 4
Expression for radius: E
n 2 h2
Centrifugal force  As we go to higher orbits, kinetic energy decreases,
potential energy increases and the total energy
increases.
 Energy of orbits in hydrogen atom ( Z = 1 )
2.179 1011
E ergs /atom
n2
Centripetal force
2.179 1018
 The centripetal force of attraction between the  Joules /atom
nucleus n2

 Ze2 1312
and the electron  2  KJ / mole
r n2
 The centrifugal force of the electron due to revolv- 13.6
 eV / atom
mV 2 n2
ing around the nucleus 
r 313.6
 K.cal / mole
 Expression for the radius of Bohr’s orbit n2
n2h 2 1eV  1.602 1019 J
r
42 m Ze2
 By substituting all constants, radius of orbit is  The energy of the electron in a hydrogen atom has
a negative sign for all possible orbits, because the
0.529  n 2 0
r A energy of the electron in the atom is lower than the
Z energy of a free electron at rest.
For H-atom, Z = 1, hence  Energy of orbits for H - like species
2 0
r  0.529  n A 2.179 1011
E  Z2 ergs
r  0.529  n 2  108 cm n 2

r  52.9  n 2 pm E1
En 
n2
where En = Energy of nth orbit in hydrogen atom.
 ATOMIC STRUCTURE
E1 = Energy of first orbit in hydrogen atom V1 = Velocity of electron in first orbit
n = 1, 2, 3, 4 ......... n = 1, 2, 3, 4 ........
 Similarly For Hydrogen like species V1
 For H atom like species Vn  Z
E1 n
En  2
 Z2
n  Magnitude of velocity of electron increasesw i t h
increase of positive charge on the
where En = Energy of nth orbit in other H - like
nucleus and decreases with increases of
species. principle Quantum Number.
Z = Atomic number
Number of revolutions :
E1 = Energy of first orbit in hydrogen atom
 Number of revolutions per second (or)
 The ratio of PE, KE and T.E = -2 : 1 : -1 orbital frequency by an electron in a shell
Rydberg’s constant :
Velocity v z2
   6.66  1015  3
2 2m Z 2 e4 Circumference 2 r n
R  = 1, 09, 677 x Z2 cm-1
h3 C
Time period of revolution :
 Difference of energy between two Bohr orbits of  Time period of revolution of electron in nth orbirt
hydrogen atom
2 r n3
 1 1  Tn   1.5  1016  2 sec
 E  Rhc  2  2  vn z
 n1 n 2 
Ionisation potential:
Where n1 = lower orbit, n 2 = higher orbit
E1
 As the value of n 2 increases, the difference  For hydrogen atom, ionization potential  .
n2
of energy becomes smaller.  For H - like species,
 The frequency of radiation absorbed (or) emitted
when transitions occurs between two stationary E1  Z2
Ionisation potential  .
states that differ in energy by E , is given by n2
 E  2  E1  Ionisation potential of an atom or
v 
h h  Z2 
ion  13.6  n 2  eV
This expression is commonly known as  
Bohr’s frequency rule.
W.E.30 : Calculate the radius of Bohr’s 3rd orbit
2  1 1  in Li+2 ion.
 E  Z RhC  2  2 
 n1 n 2  Ans : we know that,
where Z = atomic number. n2
Velocity of the electron : rn   0.529 A0
Z
 Velocity of electron in hydrogen atom when n=3 and Z = 3,
2 Ze 2 2.188 108 32
V  cm / sec r3   0.529 A0
nh n 3
V1  3  0.529A0
For hydrogen atom, Vn 
n
 1.587 A0
where Vn = Velocity of electron in n orbit
th
 JEE-MAIN-JR-CHEM-VOL-I
W.E.31: Calculate the velocity (in cm/sec) of Sol: Ionisation energy = -(energy of the 1st orbit)
an electron placed in the third orbit of Energy of the 1st orbit of hydrogen = -13.6eV
the hydrogen atom. Also calculate the Energy of the 1st orbit of He   13.6  Z 2
number of revolutions per second that
this electron makes around the nucleus. (Z for He   2)
Sol: Radius of 3rd orbit = 32  0.529  108  13.6  eV
 4.76110 8 cm  54.4eV
so, Ionisation energy of
h nh
mvr  n or   He   (54.4)  54.4eV
2 2 mr
Energy of 1st orbit of Li 2  13.6  9
27
3  6.624  10
  122.4eV
2  3.14  (9.108 1028 )(4.76110 8 )
8
Ionisation energy of Li 2  (122.4)
 0.729  10 cm / sec
 122.4eV
2 r Limitations of Bohr’s Model :
Time taken for one revolution 
  It failed to explain the line spectra of atoms or ions
Number of revolutions per second having more than one electron.
 It fails to account the fine spectra details (doublet,
1  that is two closely spaced lines) of the hydrogen
 
2 r 2 r atom.
  It failed to explain Zeeman effect and Stark effect.
0.729 108  The splitting of spectral lines of an atom into a group
 of fine lines under the influence of magnetic field is
2  3.14  4.76110 8
called Zeeman effect.
 2.4  1014 revolution / sec  The splitting of spectral lines of an atom into group
W.E.32: Calculate the energy associated with the of fine lines under the influence of an electric field is
called Stark effect.
first orbit of H e  . What is the radius of this
 Bohr model of the hydrogen atom, not only ignores
orbit? dual behaviour of matter but also contradicts
Sol: Heisenberg uncertainity principle.
(2.18  1018 J )Z 2 de-Broglie’s wave theory :
En   atom 1
n2  The wave nature of electron was first proposed by
for He  , n  1, Z  2 de-Broglie.
 According to de-Broglie theory all moving particles
(2.18  1018 J )22
E1   have wave properties.
12  Wave properties are important only for particles
 8.72  1018 J of small mass and high velocity.
The radius of the orbit is given by equation From Planck’s quantum theory
(0.0529nm)n2 hc
rn  E=h = ........(1)
Z 
since n=1,Z=2 Einstein’s mass energy relationship is
(0.0529nm)12 E  mC 2 ...(2)
rn   0.02645nm from equation (1) & (2),
2
W.E.33: The ionisation energy of hydrogen atom hc h h
 mc 2 or  mc or  
is 13.6eV. What will be the ionisation energy   mc
of He+ and Li+2 ions? where ‘c’ is the velocity of light.
 ATOMIC STRUCTURE
 If the velocity of micro particle is ‘v’ then. Velocity of electron
an orbit 
h h circumference
de-Broglie’s equation is λ    Relation between kinetic energy and wave length
mν p
of a moving particle
where λ = wave length h
h = Planck’s constant 
2 KE  m
 6.625  1034 J .sec  Let a charged particle like electron be accelerated
ν = Velocity of the particle with a potential of V, then
mν = p = Momentum of the particle
KE  eV
de-Broglie’s concept and Bohr’s
h
theory :  
 Two types of waves are possible for an electron 2eVm
moving around the nucleus in the circular path 12.27 0
a)A standing or stationary or non-energy  For an electron   A
V
radiating wave:
 The de Broglie wavelength for an electron in a given
orbit = 3.33  n A0
W.E.34: What will be the wavelength of a ball of
mass 0.1 kg moving with a velocity of 10ms–1
Sol: According to de-Broglie equation
h 6.626  1034 Js
i.e., 2 r  n  
mv (0.1kg )(10ms 1 )
2 r  6.626  1034 m( J  kgm 2 s 2 )
 ( n= integer or whole number)
n W.E.35: The mass of an electron is 9.1  10–25J, If
h its K.E. is 3.0  10 –25 J, calculate its
we know that,   wavelength.
mv
2 r h 1 2
  Sol : since K.E  mv
n mv 2
2 K .E
nh v( )
 mvr  m
2
Hence de-Broglie’s theory and Bohr’s theory are 2  3.0  1025 kgm2 s 2 12
( )
in agreement with each other. 9.1 1031
b) Non stationary or energy radiating wave.  812ms 1
h 6.626  10 34 Js
 
mv (9.1  10 31 kg )(812 ms 1 )
 8967  10 10 m  896.7 nm
W.E.36: Calculate the mass of a photon with
wavelength 3.6 A0
Ans:   3.6 A0  3.6  1010 m
In this 2 r  n hence, such an orbit cannot exist. Velocity of photon= velocity of light
de-Broglie’s applications : h 6.626  1034 Js
 Number of waves in an orbit = n m  
 (3.6 10 10 m)(3  108 ms 1 )
 Number of revolutions of an electron per second in
 6.135  1033 kg
 ATOMIC STRUCTURE
W.E.37: Calculate the de- Broglie wavelength of we know,
an electron travelling at 1% of the speed of
light. h

Sol : de-Broglie wavelength can be calculated as, 2 KE.m
h 6.626  1034
 .......(1) 
m 2 1.6  1017  9.1 1031
where, h  6.626  10 34
Js  1.228  1010 m
31
m  9.1 10 kg W.E.40: The kinetic energy of an electron is
1 4.5510–25J. Calculate the wavelength.
  3  108  3  106 m / sec
100 [h  6.6 1034 Js;
substituting these values in eq(1), we get
mass of electron  9.11031 kg ]
6.626  10 34
 1 2
9.1  1031  3  106 Sol: K .E  mv  4.55  1025
2
 242.7  1012 m
1
 242.7 pm or  9.1 1031  v 2
2
W.E.38 :Two particles A and B are in motion. If
the wavelength associated with particle A is  4.55  10 25
510–8m, calculate the wavelength associated 2  4.55  1025
or v 2 
with particle B if its momentum is half of A. 9.1 1031
Sol: we know ,
v  103 ms 1
h Applying de Broglie equation

p
h 6.6 1034
A p  
 B      1 mv 9.110 31 103
B pA
 A  5  10  8 m ,  0.72 106 m
1 Heisenberg’s Uncertainity Principle:
p B  p A , i.e , p A  2 p B
2  It is impossible to determine simultaneously, the
exact position and exact momentum (or velocity)
 from eqn(i ) of an electron” It is called Heisenberg’s uncertainity
principle.
5 108 p (or)
 B
B 2 pB  It is impossible to determine both the position and
B  107 m momentum of the electron simultaneously and
accurately.
W.E.39: An electron beam emerges from an  It is given by the expression
accelerator with kinetic energy 100eV. what
h
is its de- Broglie wavelength?  x . p 
4π
[m  9.11031 kg , h  6.6  1034 Js,
h
1eV  1.6 1019 J ]   x .m  v 
4π
Sol : Kinetic energy of electron =100eV
h
 100  1.6  10 19 J  x.v 
4 m
 1.6  1017 J where  x =uncertainity in position
 ATOMIC STRUCTURE
 p = uncertainity in momentum W.E.42: A golf ball has a mass of 40g, and a speed
 v = uncertainity in velocity of 45 m/s. If the speed can be measured within
m = mass of the particle accuracy of 2%, calculate the uncertainty in
h = Planck’s constant the position.
Sol :The uncertainty in the speed is 2%, i,e
 It states that if one is determined with high accuracy
,then the other becomes uncertain. 2
45   0.9ms 1
i.e. If position of the electron is determined 100
( x  0 ), then v   using the equation
similarly If velocity of the electron is determined h
x 
( v  0 ) , then x   4 mv
 The product of the uncertainities is inversely
proportional to mass of the particle. 6.626  10 34 Js

4  3.14  40  10 3 g  0.9 ms 1
1
x.v   1.46  10 33 m
m
 The uncertainty principle is mainly applicable for This is nearly 1018 times smaller than the diameter
microscopic particles. of a typical atomic nucleus. As mentioned earlier
If A and B are two particles then for large particles, the uncertainty principle sets no
 x.v  A meaningful limit to the precision of measurments.
mB
 W.E.43. An electron has a speed of 40ms–1 accurate
 x.v  B mA
upto 99.99%. What is the uncertainty in its
Significance of uncertainity principle : location?
 It rules out the existence of definite paths and leads 0.01
to probability which can be given by quantum Sol : Given, v   40  0.004ms 1
100
mechanical model.
eg. If uncertainty in position is of only 10 8 m , then h
we know, x.v 
the uncertainty velocity would be 4 m

104 m 2 s 1 h
 10 4
ms 1
(a large value) x 
108 m 4 mv
W.E.41: A microscope using suitable photons is 6.625  1034
employed to locate an electron in an atom x 
4  3.14  9.1 1031  0.004
within a distance of 0.1A 0 . What is the
uncertainty involved in the measurement of x  1.45  102 m
its velocity? Quantum Mechanical Model of Atom
h h & Its Important Features :
Sol : xp  (or ) xmv   The fundamental equation of quantum mechanics
4 4
was developed by Schrodinger.
h  It explains three dimensional concept of moving
v 
4xm electron.
 This equation is based on de-Broglie’s wave
6.626 1034 Js equation and Heisenberg’s uncertainty principle.
v 
4  3.14  0.11010 m  9.1110 31 kg  Schrodinger’s wave equation is written as

 0.579  107 ms 1 (1J  1kgm 2 s 2 )  2   2   2  8π 2 m

   E  V   0
 5.79  106 ms 1 x 2 y 2 z 2 h2
where ψ = Wave function(amplitude of the wave)
 JEE-MAIN-JR-CHEM-VOL-I
m = Mass of electron higher maximum at 2.6A0 radial distance.
h = Planck’s constant
E = Total energy of the electron
Shapes of Atomic Orbitals :
 The space around the nucleus, where the prob-
V = Potential energy of electron
x, y, z are co - ordinates. ability of finding electron ( ψ2 ) is maximum is called
an orbital.
8 2m
2
  ( E   )  0  The maximum probability of finding an electron in
h2 an orbital is 95 %
2 is the Laplician operator s-orbital :
 Ĥ   E where Ĥ is a mathematical operator  The variation of  2 as function of r for 1s and 2s
called Hamiltonian operator. orbitals is given as follows

h2  2 2 2 
is V    1s 2s
where Ĥ  
8 2 m  x 2 y 2 z 2  (a) 160 50
40
120 30
 The Schrodinger wave equation gives principal, 80 20
azimuthal and magnetic quantum number but not 10
40 0
the spin quantum number -10
0
Important features of the Quantum 0 0.4 0.8 0 0.4 0.8
r(nm) r(nm)
Mechanical Model of Atom:
 It states that the energy of electron in an atom is
quantized. 1s 2s
(b) 5000 300
 It explains the probability of finding the electron 4000 240
2 3000 2 180
around the nucleus in three dimensionally. 2000 120
 An atomic orbital is the wave function  for an 1000 60
electron in an atom. 0 0
0 0.4 0.8 0 0.4 0.8
 Significance of ψ : It is a wave function.It r(nm) r(nm)

corresponds to energy state which contains all  It may be noted that (from b-graph) for 1s orbital
information about electron. the probablity density is maximum at the nucleus
and it decreases sharply as move away from it.
 Significance of ψ 2 : It is a probability function. It
 For 2s orbital the probability density first decreases
indicates maximum probability of finding an electron sharply to zero (node) and again starts increasing.
at a certain point in an atom.
The region where probability density   is zero
2
 The probability of finding an electron at a 
certain distance from the nucleus is called radial called nodes (or) nodal surface.
probability.  For ns-orbital, (n  l ) nodes are present.
 The curves obtained by plotting probability function
eg: for 2s: 2-1 = 1, 3s : 3-1 = 2
D  4π r 2 d r 2 and radial distance (r) are called for 4s : 4-1 = 3, ns : n-1
radial probability distribution curves.  The shape of s orbital ( l = 0,m = 0 ) is spherical.It
 Number of peaks obtained in a curve = n - l is a non directional orbital.
where n = principal quantum number  Size of s- orbital increases with increase in ‘ n’,
l = Azimuthal quantum number that is 4s  3s  2s  1s .
 The nodal surface of 2s orbital exists at a distance  The shapes of s-orbitals are
of 2a 0 from the nucleus. Where a 0 is the Bohr z z Node 3s
z Node
1s 2s
y y
radius  0.529 A 0  x
y
x x
 The curve for 2s orbital has two peaks the curve
passes through lower maximum at 0.53 A0 and
 ATOMIC STRUCTURE
p-orbital : Nodal planes :
 In a p - sub shell, the three orbitals are represented
 The plane where the probability of finding the
as p x , p y , and p z . These are degenerate orbitals.
 The shape of a p - orbital ( l = 1 ) is dumbell. electrons is zero  ψ 2  0  is called a nodal plane.
 p - orbitals are oriented along the axes. So they  Number of nodal planes (or) angular nodes for an
are directional orbitals.
Orbital: px py pz orbital = l.
m : 1 1 0 Orbital Nodal Plane
 With the increase of principle quantum number size, S Nil
and energy of ‘p’ orbitals increases 4 p  3 p  2 p .
 The shapes of p-orbitals are Px 0 YZ
z z z
Py 1 ZX

x x x Pz 1 XY
y y y dxy 2 YZ, ZX
Px Py Pz
dyz 2 ZX, XY
dxz 2 XY, YZ
z
dx2 - y2 2 YZ, ZX
x
 d z 2 orbital has no nodal plane ,because it has torous
y
 p-sub shell is three fold degenerate. ring.It has two nodal cones above and below the
d-orbital : plane.
 In a d - sub shell, the five orbitals are represented  When the number of nodal planes increases, the
2
as d xy, d yz, d zx, d X 2 Y 2 and d z . energy of the orbital increases. So the energy or-
 These are degenerate orbitals. der of the orbitals is s  p  d  f
 The shape of a d - orbital ( l = 2 ) is double dumb  Number of radial nodes = n - l - 1
bell.
where n = principal quantum number
 d xy, d yz and d zx orbitals are oriented in between the
2
l = Azimuthal quantum number
axes. d X2  Y2 and d z orbitals are oriented along the Quantum Numbers :
axes.  Four quantum numbers are required for the com-
Orbital : d xy d yz d zx d x 2  y2 dz 2 plete explanation of electrons in an atom.
m :  2 1 1 2 0 1. Principal quantum number
 d-sub shell is five fold degenerate. 2. Azimuthal quantum number
 The shapes of d-orbitals are 3. Magnetic quantum number
z z 4. Spin quantum number
x x
Principal Quantum Numbers (n) :
 It was proposed by NeilsBohr
y y
dxy dyz  The values of n =1, 2, 3, 4 ..... or K, L,M, N .......
z
respectively
x  It indicates the size and energy of the orbit.
z y z  With the increase of ‘n’, size and energy of orbital
dz 2
increases
x x
y y  The maximum number of electrons in an orbit  2n 2
dzx dx2- 2
 Total number of orbitals = n2
y
 (where n = no.of the orbit)  The number of orbitals in an energy level  n 2
 Angular momentum of an electron in an
 The number of orbitals in a sub shell  2l  1
h  Maximum number of electrons in a subshell
orbit  n
2
 2  2l  l  where l = Azimuthal quantum number..
Azimuthal Quantum Numbers ( l ) :
 It was proposed by Sommerfeld
 The values of l depends on ‘n’ . Value of l 0 1 2 3 4 5
 The values are = 0, 1, 2, .....( n -1 ). Sub-shell s p d f g h
 The values of l represents various sub shells.
No.of ortbitals (2l+1) 1 3 5 7 9 11
When l = 0, 1, 2, 3 ... the orbitals are
s, p, d, f ....... sub shells respectively. No.of electrons 2(2l+1) 2 6 10 14 18 22
 The energies are in the order of s  p  d  f .
Spin Quantum Number (ms):
 It indicates the shape of an orbital and angular
 It was proposed by Goudsmit and Uhlenbeck.
momentum of electron.
 The values of spin quantum number are indepen-
 Total number of sub shells in an energy level = n
 Angular momentum of the electron in an orbital 1 1
dent. The values of s   and 
h 2 2
 l (l +l)  h l  l  1  For each value of ‘m’, there can be two ‘s’ values.
2π
 It indicates the direction of the spin of the
where h = Planck’s constant
electron.
l = Azimuthal quantum number
 The clock wise    direction spin is represented
Sub-shell
n value
notation 1
1 0 1s by  and anticlock wise    direction spin is
2
0 2s
2 1
1 2p represented by 
2
0 3s  Spin anuglar momentum of the electron
3 1 3p h
= s  s  1 ; where ‘s’ is total spin.
2 3d 2
0 4s  Maximum number of electrons in an
1 4p orbital = 2.
4  The maximum number of electrons present in s, p,
2 4d
d and f shells are 2, 6, 10 and 14 respectively.
3 4f W.E.44: What is the total number of orbitals
Magnetic Quantum number (ml): associated with the principle quantum
 It was proposed by Lande. number n=3?
 The values of m depends on ‘ l ’. Sol: For n=3, the possible values of l are 0,1 and 2.
 The values ranges from = +l ..... 0 ..... -l Thus there is one 3s orbital (n=3, l  1 and
 The total ‘m’ values = 2l + 1 ml  1,0, 1); t here are five 3d orbitals
 The total number of ‘m’ values indicates the total
number of orbitals in the subshell. (n=3, l  2 and ml  2, 1, 0, 1, 2).
 The number of orbitals in s, p,d,f, g and h sub shells The same value can also be obtained by using the
are 1, 3, 5, 7, 9 and 11 respectively.
relation; number of orbitals  n 2 , i, e 32  9
 It indicates the orientation of orbitals in space.
 JEE-MAIN-JR-CHEM-VOL-I ATOMIC STRUCTURE
W.E.45: Using s, p, d, f notations, describe the
orbital with the following quantum numbers l=0 l=1 l=2 l=3
a) n = 2, l = 1 b) n= 4, l = 0,
c) n = 5, l = 3 d) n = 3, l = 2 n=1 1s
Sol: n l orbital
a) 2 1 2p n=2 2s 2p
b) 4 0 4s
c) 5 3 5f
n=3 3s 3p 3d
d) 3 2 3d
Energy of Orbitals : n=4 4s 4p 4d 4f
 The energy of an electron in a hydrogen atom is
determined by the principal quantum number. Thus
the energy of the orbitals increases as follows: n=5 5s 5p 5d 5f
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
 The energy of an electron in a multielectron atom n=6 6s 6p 6d
depends not only on its principal quantum number
(shell), but also on its azimuthal quantum number
(subshell). n=7 7s 7p

 The energy of an electron is given by  n  l  value.

 The lower the value of  n  l  for an orbital, the
lower is its energy. If two orbitals have the same
value of  n  l  , the orbital with lower value of ‘n’
will have the lower energy.
 Energies of the orbitals in the same subshell
decrease with increase in the atomic number (Zeff).
eg. energies of 2s orbital in IA group
E2s  H   E2 s  Li   E2 s  Na   E2 s  K 
Aufbau Principle :
 In the ground state of the atoms,the orbitals
are filled in order of their increasing energies.
 It means , among the available orbitals, the orbitals
of lowest energy are filled first.
 The energy value of an orbital increases as its
(n + l) value increases.
 If two orbitals have the same value for (n + l), the
orbital having lower ‘n’ value is first filled.
 The increasing order of energy’s different orbitals
is as follows.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d 
< 5p < 6s < 4f < 5d < 6p < 7s< .......
Moellar diagram of order of filling of orbitals :
n=8 8s
Pauli’s Exclusion Principle:
 It gives the restrictions in filling of various
orbitals with electrons.
 It states that - No two electrons in an atom can
have the same set of all four quantum numbers .
 The two electrons in a given orbital may have same
values of n, l and m, but different ‘s’ value.
 It says that , an orbital cannot accommodate more
than two electrons.
eg. For 2s orbital,
1
For 1st electron, n = 2, l = 0, m = 0, s = 
2
1
For 2nd electron, n = 2, l = 0, m = 0, s = 
2
 The maximum number of electrons present in s, p,
d and f shells are 2, 6, 10 and 14 respectively.
Hund’s Rule :
It deals with the filling up of degenerate orbitals
with electrons (degenerate = orbitals of equal
energy)
 The orbitals having the same values for n and l are
called degenerate orbitals.
 It states that - Pairing up of electrons in degenerate
 JEE-MAIN-JR-CHEM-VOL-I
orbitals takes place after filling each with one 2.Exchange Energy:
electron of parallel spin.  The stabilizing effect arises whenever two or
 The pairing of electrons in the p,d and f orbitals more electrons with the same spin are present in
start with the entry of 4th, 6th and 8th electrons the degenerate orbitals of a subshell.
respectively.  These electrons tend to exchange their positions
Electronic Configuration of Atoms : and the energy released due to this exchange is
 The distribution of electrons into orbitals of an atom called exchange energy.
is called Electronic Configuration.  The number of exchanges that can take place is
 It is represented as nlx notation or moellar maximum when the subshell is either half filled or
diagram completely filled.
 The electrons in the inner shells are called core  As a result the exchange energy will be maximum
electrons. and so is the stability.
 The electrons that are added to the electronic shell no of exchanges =  N  1
with highest principal quantum number are called
valence electrons. N ( N  1)
Eexchange 
 Half filled and completely filled degenerate orbitals 2
give greater stability to atoms. Here N is the number of electrons having parallel
 Chromium (Z = 24) and copper (Z = 29) have spin.
anomalous electronic configuration due to this
reason.
eg.Electronic configuration of chromium atom is
1
Cr (z=24): 1s2 2s2 2p6 3s23p6 3d5 4s1
but not 1s2 2s2 2p6 3s2 3p6 3d4 4s2.
 Thus p 3 , p 6 , d 5 , d 10 , f 7 , f 14 configurations, 4 exchange by electron 1
which are either half filled or fully filled are more
stable.
Other examples are
Nb  41 5s 0 4d 5 2

Mb  42  5s1 4d 5
3 exchange by electron 2
Pd  46  5s 0 4d 10

Ag  47  5s1 4d 10

Gd  64  6 s 2 5d 1 4 f 7 3

Au  79  6 s1 5d 10 4 f 14
Stability of Completely filled and Half 2 exchange by electron 3
filled subshells:
 The completely filled and half filled sub shells are
stable due to the following reasons. 4
1.Symmetrical distribution of electrons:
 It is well known that symmetry leads to stability.
The completely filled or half filled subshells have 2 exchange by electron 4
symmetrical distribution of electrons in them and
are more stable.