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ATOMIC STRUCTURE 2

CHAPTER
FUNDAMENTAL PARTICLES

Atoms are made up essentially of three fundamental particles, proton neutron and electron

Electron Proton Neutron

Symbol e or e p n

Relative mass 1/1836 of mass of proton 1 1

Relative charge 1 +1 0

Mass in kg 9.109534 1031 1.6726485 10-27 1.6749543 10-27

Mass in amu 5.4858026 10-4 1.007276471 1.008665012

Actual charge in C 1.6021892 10-19 1.6021892 10-19 0

Discovered in 1887 1911 1932

Discovered by J.J. Thomson Goldstein Chadwick

e/m in C/g 1.76 108 9.58 104 -

Named by Stoney Rutherford Rutherford

Terms related to Atomic Structure

Atomic number (Z) : The number of protons in the nucleus of an atom. This when subtracted from A,
gives the number of neutrons.

Mass number (A) : Sum of the number of protons and neutrons, i.e, the total number of nucleons.

Nucleons : Sub-atomic particles in the nucleus of an atom i.e. protons and neutrons.

Isotopes : Atoms of an element with the same atomic number but different mass number
(different number of neutrons but same number of protons) e.g. 15P32 and 15P31.

Isobars : Atoms, having the same mass number but different atomic numbers, (different
number of neutrons as well as protons but their sum is same) e.g. 15P32 and 16S32.

Isotones : Atoms having the same number of neutrons but different number of protons and
hence different mass number (different number of protons but same number of
neutrons), e.g 14 16 15
6 C , 8 O, 7 N ,

Isoelectronic species : Atoms, molecules or ions having the same number of electrons, e. g N2, CO, CN.
Chemistry-XI(Advanced) 2

Isodiaphers : Atoms having same neutron excess i.e. same (n p) or (A 2Z) e.g. 6C14 and 8O18

Isosters : Molecules with same number of atoms and valence electrons e.g. N2O and CO2,
O22- and F2
Nuclear isomers : Atoms with the same atomic and mass numbers but different radioactivity, e.g.,
Uranium X (half life1.4 min) & Uranium Z (half-life 6.7 hours).

Atomic mass unit : Exactly equal to 1/12th of the mass of 6C12 atom.
(amu) : 1 amu = 1.66 1024 g 931.5 MeV

Rutherfords -rays scattering experiment on gold foil

Rutherford observed that alpha particles deflect considerably from original path. Hence, to explain his
observations, Rutherford suggested that an atom has a nucleus, or center, in which its positive charge and mass
are concentrated. The quantitative results of scattering experiments such as Rutherfords indicate that the nucleus
of an atom has a radius of about 10-13 cm, which is only about one hundred thousandth size generally ascribed to
atoms. Later when neutrons and protons were discovered, it was noted that the radius of a particular nucleus can
be expressed roughly as r ( in centimeters ) ~ 1 1013 A1/3, where A is the total number of neutrons and protons
in that nucleus.

Some useful results from Rutherford experiment

(i) Z
XA , Mass number (A) = Atomic number (Z) + number of neutrons (n)

1 Z .2e
(ii) m v2 K ; r = distance of closest approach, v = initial velocity of a -particle
2 r
1
(iii)

sin 4
2
Where = no. of deflected particles and = deflected angle.
(iv) Order of size of nucleus = 1015 m (1 fermi)
(v) Order of size of Atom = 1010 m (l)

Plancks quantum theory:


Progress in working out the arrangement of electrons in an atom came first when Bohr in 1914, applied the
ideas of the quantum theory, put forward by Planck in 1900, for interpretation of hydrogen spectrum.
The essential idea of the quantum theory is that the energy of a body can only change by some definite whole-
number multiple of a unit of energy known as the quantum. This means that the energy of a body can
increase or decrease by 1, 2, 3, 4, ....n quanta, but never by 1 1/2 , 2 1/2 , 1.3 etc. quanta
However, the value of the quantum is not fixed, but is related to the frequency of radiation which, by its emission
or absorption, causes the change in energy. This relationship is expressed as
E h or E hc /

Where E is the energy of one quantum or photon, h is the Planck constant (6.626176 10-34) J, is the frequency
(S1 or Hz), is the wavelength and c is velocity of light (ms-1).
When radiation of frequency , or wavelength , is absorbed by a body, there will be an energy increase by
hc
E = Energy of one photon = h = hcv

3 Atomic Structure

Emission of similar radiation would cause an equal decrease in energy.


Total Energy transferred by N photons = N Energy of one photon.
Remember : hc = 2 1025 (In SI unit)
12375
E (eV) =
in

Example: If 10-7 J of light energy is needed by the interior of human eye to see an object. The photons
of green light of wavelength 550 nm needed to see the object are
(a) 26 (b) 28
(c) 27 (d) 30
hc 6.625 1034 3 108
Solution: Required energy = 10-17 J = N =N 9
J 1017 J
550 10
N = 28
(b)
Example: Which have the same number of s electrons as are d electrons in Fe2+
(a) Li (b) Na
(c) N (d) P
Solution: The number of d electrons in Fe2+ is 6. Out of the above species, P has 6 electrons in s
subshell
(d)
Example: Of the following sets which one does not contain isoelectronic species?
(a) PO43 , SO42 , ClO4 (b) CN , N 2 , C22

(c) SO32 , CO32 , NO3 (d) BO33 , CO32 , NO3


Solution (c)
Example: Which one of the following sets of ions represents the collection of isoelectronic species?
(a) K+, Ca2+, Sc3+, Cl (b) Na+, Ca2+, Sc3+, F
(c) K+, Cl, Mg2+, Sc3+ (d) Na+, Mg2+, Al3+, Cl
(Atomic numbers: F = 9, Cl = 17, Na = 11, Mg = 12, Al = 13, K = 19, Ca = 20, Sc=21)
Solution: The species having same number of electrons are called isoelectronic ones.
The ions K+, Ca2+, Sc3+ and Cl have equal number of electrons i.e. 18 electrons
(a)
Chemistry-XI(Advanced) 4

Try Yourself-1
1. Which of the following symbol is acceptable.
35 79
(a) 79 Br (b) 35 Br
35
(c) Br (d) All of these
2. An element with mass number 81 contains 31.7% more neutrons as compared to protons. Assign the
atomic symbol.
81
(a) 35 Br (b) 35 Br
35 82
(c) Br (d) 35 Br
3. An ion with mass number 37 possess one unit of negative charge. If the ion contains 11.1% more
neutrons than the electrons, find the symbol of the ion.
(a) 37
17 Cl 1 (b) 17 Cl 1

(c) 37
Cl 1 (d) 37
17 Cl 2
4. An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons than
electrons. Assign the symbol to this ion.
(a) 56
26 Fe3 (b) 56
Fe3

(c) 56
Fe3 (d) 56
26 Fe2

Notes:
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5 Atomic Structure

The Bohr Atom


Bohr developed a model for hydrogen atom and hydrogen like one electron species. He applied the quantum
theory in considering the energy of an electron bound to the nucleus. He developed an expression for the energy
of the electron in hydrogen atom, and hence derived the value for R (Rydberg constant) from fundamental
constants.

Bohrs model of an atom can be described as follows


1. The electron in an atom has only certain definite stationary states of motion allowed to it; each of these
stationary state has a definite, fixed shell or energy. These stationary states are known as orbits.
2. When an atom is in one of these states it does not radiate; but when changing from a high-energy state
to a state of lower energy, the atom emits a quantum of radiation whose energy h is equal to the
difference of the energies of these two orbits.
3. In any of these states the electron moves in a circular orbit about the nucleus.
4. The states of allowed electronic motion are those in which the angular momentum of the electron
(mvr) is an integral multiple of h/2p . (angular momentum quantization postulate)

Radius & Energy Levels of Hydrogen Atom


The mechanical stability of the electron orbit requires that the coulomb force between the electron and nucleus
be balanced by the centrifugal force due to the circular motion.

Coulombic force = Centrifugal force


KZe 2 mv 2

r2 r
KZe 2
v2
mr
where m and v are the mass and velocity of the electron, Z is the number of units of elementary charge e
and r is the electron - nucleus separation. K is Coulombs fundamental constant (9.0 109 J - m C2). In C. G.
S system, the value of K = .
Bohrs postulate for the angular momentum, mvr, was
h
mvr n , n 1, 2,3....
2
nh n2 h2
v v2
2 mr 4 2 m 2 r 2
Where h is Plancks constant, 6.626 10-27 erg sec. That is, the angular momentum had to be integral multiple
of h/2p. Eliminating v between

KZe 2 n 2 h 2
mr 4 2 m 2 r 2
n2 h2
r , n 1, 2,3...
(2 )2 mZe2 K
Hence only certain orbits whose radii are given by the above equation are allowed to the electron. The total
energy, E of the electron, is the sum of the kinetic energy, mv2 / 2, and potential energy, Ze2/ r :
Chemistry-XI(Advanced) 6

1 Ze 2 K Ze 2 K 1 Ze 2 K
But we can write E
2 r r 2 r
2 2 mZ 2 e 4 k 2
Substituting for r give us E , n 1, 2,3...
n2 h2
The expression shows that the consequence of the postulates is that, only certain energies are allowed to the
electron.
Z2
En 21.8 1012 erg per atom ( 1erg = 6.2419 x 1011 ev )
n2
Z2
= 13.6 eV per atom
n2
Z2
= 313.6 K cal per mole
n2
Z2
= 2.18 1018 J per atom
n2
The energies are negative only because the energy of the electron in the atom is less than the energy of a free
electron, which is taken as zero. The lowest energy level of the atom corresponds to n = 1, and as the quantum
number increases, E becomes less negative. When n = , E = 0, which corresponds to an ionized atom:
According to Bohrs second postulate, the energy of wave number of any photon radiated by the atom should
be equal to the difference in the energy of two levels.
Radius of nth Bohrs orbit for hydrogen like particles is obtained from the expression
52.9(n 2 )
rn pm
Z

ATOMIC SPECTRUM
Spectrum is the impression produced on a photographic film when the radiation(s) of particular wavelength(s) is
(are) analysed through a prism or diffraction grating.
Types of Spectrum
(1) Emission spectrum:
Spectrum of the emitted radiation is known as emission spectrum. This spectrum corresponds to the
radiation emitted (energy evolved) when an excited electron returns back to the ground state.
Types of Emission Spectrum
(i) Continuous Spectrum:
When white light from any source such as sun or bulb is analyzed by passing through a prism, it
splits up into seven different wide bands of colour from violet to red (like rainbow). These colours
are so continuous that each of them merges into the next without any gap or break. Hence the
spectrum is called continuous spectrum.
e.g., Carbon arc in vacuum and electric glow lamp give continuous spectrum.
(ii) Line Spectrum:
When an electric discharge is passed through a gas at low pressure light is emitted. If this light is
resolved by a spectroscope, it is found that some coloured lines are obtained on a photographic
plate separated from each other by dark spaces. This spectrum is called line spectrum. Each line
in the spectrum corresponds to a particular wavelength. Each element gives its own characteristic
spectrum.
7 Atomic Structure

(iii) Band Spectrum:


The spectrum which consists of bright bands each having sharp edge is called band spectrum.
Example: Vapours in the molecular state like that of Ca, Ba or even nitrogen gas in vacuum tube
give band spectrum. All molecules give band spectra.
(2) Absorption spectrum:
Spectrum of the absorbed radiation is called absorption spectrum.

The possible number of lines produced by an electron in nth orbit


n(n 1)
(n 1) or
2
Hydrogenic Ions or Hydrogen like particles
If we remove all the electrons from an atom except one, we get hydrogenic ion. e. g. He+, Li ++, Pb+81, Au+78

Some useful formulae


Spectral lines
1 1 1
(a) Rydbergs Equation RH Z 2 ; RH 109700 cm1
n 2 n2
2
1
(b) For First line of a series n2 = n1 + 1 , for second line n2 = n1 + 2
(c) Limiting spectral line (series limit) means n2 = , it is also called limiting line or marginal line
(d) H line means n2 = n1+1; also known as first line, starting line, Initial line, line of longest shortest ,
least E
(e) Similarly H line means n2 = n1+ 2 is second line
n( n 1)
(f) Number of spectral line observed in the spectrum = when e de-excites to ground state,
2
from higher orbit n.
Chemistry-XI(Advanced) 8

(n2 n1 )(n2 n1 1)
(g) Total number of lines in emission spectrum ( for n2
n1 ) when e de-excites
2
to ground state, from higher energy orbit n2 to n1

T.E. of any H-like species = T.E. of Hydrogen xZ2 (For same orbit)
for H-like species E = E (For Hydrogen) x Z2 (For same transition)
E1
Energy in nth orbit-for H like species = [For same atom]
n2
Ionisation Energy corresponds to transition, n 1
n
Separation energy =

Excitation Energy =

2 e2 K Z 2.18 106 Z C Z
(i) vn = = ms1 =
h n n 137 n
(ii) Revolutions per sec = v/2r
(iii) Time for one revolution = 2r/v
(iv) Ionisation energy = Eelectron

Example: The highest excited state that an unexcited hydrogen atom can reach when they are
bombarded with 12. 2 eV electron is :
(a) n=1 (b) n=2
(c) n=3 (d) n=4
Solution: E1 = -13.6 eV . After absorption of 12. 2 eV, energy of electron = - 13. 6 + 12.2 = 1.4 eV
n=3 (c)
Example: Ionisation potential of hydrogen is 13.6 eV. Hydrogen atom in the ground state are excited by
monochromatic light of energy 121. eV. The spectral lines emitted by hydrogen according to
Bohrs theory
(a) One (b) Two
(c) Three (d) Four
Solution: The electron in H atom is excited to III shell after absorbing 121. eV. The possible transition
3(3 1)
state = 3
2
(c)
9 Atomic Structure

Example: The wavelength of a spectral line for an electronic transition is inversely related to
(a) number of electrons undergoing transition
(b) the nuclear charge of the atom
(c) velocity an electron undergoing transition
(d) the difference in the energy levels involved in the transition.
hc hc
Solution: E
E
(d)
Example: The wave number of the shortest wave length transition in Balmer series of atomic hydrogen
will be
(a) 4215 (b) 1437
(c) 3942 A (d) 3647
1 1 1 1 1
Solution: RZ 2 2 2 109678 12 2 2
shortest n1 n2 2

3.647 105 cm 3647 (d)


Example: A doubly ionised Lithium atom is hydrogen like with atomic number 3. Find the wavelength
of radiation required to excite the electron in Li++ from the first to the third Bohr Orbit.
(a) 114 (b) 918 nm

(c) 918 (d) 114 nm


13.6 Z 2
Solution: En
n2
1 1
Excitation energy = E E3 E1 13.6 32 2 2
3 1
= + 13.6 9 [ 1 1/9 ] = 13. 6 9 8/9 = 108.8 ev .
hc 6.63 1034 3 108
Wavelength
E 13.6 8 1.6 1019
6.63 3 107 10
= = 114. 26 10 m = 114. 3
13.6 8 1.6
Example: Ionization energy of hydrogen atom is 13.6 eV. Calculate the ionization energy for Li2+.
(a) 30.6eV (b) 30.6eV
(c) 30.6eV (d) 30.6eV
Solution: Ionization energy of hydrogen = - E1 (Energy of first Bohr orbit
Z2 12
I .E E1 13.6 2 13.6 2 13.6eV
n 1
Ionization energy of Li2+
Z =3
n = 2 (for 1st excited state)
32
I .E. 13.6 2 30.6eV
2
Chemistry-XI(Advanced) 10

Example: Calculate the energy emitted when electrons of 1.0 gm atom of Hydrogen undergo transition
giving the spectral lines of lowest energy in visible region of its atomic spectra. Given that,
RH = 1.1 107 m-1, c = 3 108 m / sec, h = 6. 625 10-34 J sec.
(a) 182.5kJ (b) 182.5kJ
(c) 182.5kJ (d) 182.5kJ
Solution: Visible region of H- spectrum correspond to Balmer series n1 = 2, n2 = 3 ( for minimum
energy transition )
1 1 1 1 1
l / RH 2 2 RH 2 2
n1 n2 2 3

1 1 1.1 10 4
7
1
1.1 107
4 9 49
6.55 107
hc 6.625 1034 3 108 19
E = 3.03 10 Joule
6.55 10 7

Energy released by 1-gram atom of H (i.e. 1 mol)


19 23 4
= 3. 03 10 6. 023 10 = 18.25 10 J = 182.5 k J
th
Example: How many spectral lines are emitted by atomic hydrogen excited to n energy level
n(n 1)
(a) (b) n(n 1)
2
n(n 1)
(c) (d) 2n(n 1)
2
Solution : Thus the number of lines emitted from nth energy level
= 1 + 2 + 3 + ............................. n -1 = S (n-1)
(n 1)(n 1 1) (n 1)(n)
= (n 1) 2

2
Number of spectral lines that appear in hydrogen spectrum when an electron de
th n( n 1)
excites from n energy level =
2
(c)
Example: If the speed of electron in the Bohr's first orbit of hydrogen atom is x, the speed of the electron
in the third Bohr's orbit is
(a) x/9 (b) x/3
(c) 3x (d) 9x
Solution : According to Bohrs model for hydrogen and hydrogen like atoms the velocity of an electron
2Ze
in an atom is quantised and is given by v .
nh

(b)
Example: Of the following transitions in hydrogen atom, the one which gives an absorption line of lowest
frequency is
(a) n =1 to n = 2 (b) n= 3 to n = 8
(c) n = 2 to n = 1 (d) n = 8 to n = 3
Solution: Absorption line in the spectra arise when energy is absorbed i.e., electron shifts from lower to
higher orbit, out of a & b, b will have the lowest frequency as this falls in the Paschen series.
(b)
11 Atomic Structure

Example: The wavelength of the radiation emitted, when in a hydrogen atom electron falls from
infinity to stationary state 1, would be (Rydberg constant = 1.097 107 m1)
(a) 91 nm (b) 192 nm
(c) 406 nm (d) 9.1 108 nm
1 1 1
Solution: Wavenumber = 1.097 107 1.097 107 m-1
1
= 91.15 109 m 91 nm
(a)

Try Yourself-2
1. A series of lines in the spectrum of atomic hydrogen lies at wavelengths 656.46 , 482. 7, 434. 17, 410.
29 nm. What is the wave length of next line in this series?
(a) 397.2 (b) 397.2
(c) 397.2 (d) 397.2
2. Calculate of the radiations when the electron jumps from III to II orbit of hydrogen atom. The
12 12
electronic energy in II and III Bohr orbit of hydrogen atoms are 5.42 10 and 2.41 10 erg
respectively.
(a) 6603 (b) 6603
(c) 6603 (D) 6603
3. Calculate the wavelength for shortest wavelength transition in the Balmer series of atomic hydrogen.
1 1
(a) 27434 cm (b) 2743 cm
1 1
(c) 427 cm (d) 5274 cm

4. Calculate the ratio of the wavelength of first and the ultimate line of Balmer series of Li2+ ?
(a) 9/5 (b) 9/5
(C) 9/5 (d) 9/5

Notes:
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Chemistry-XI(Advanced) 12

Shortcomings of Bohrs theory


The main shortcomings of Bohrs theory are as follows:
1. Bohrs theory failed to explain the spectra of multi- electron atoms.
2. Bohrs atomic model failed to account for the effect of magnetic field and electric field on the spectra of
atoms or ions. It was observed that when the source of a spectrum is placed in a strong magnetic
field, each spectral line is further split into a number of lines. This is called Zeeman effect. Also splitting
of spectral lines occurs in electric field. This is called Stark Effect. These observations could not be
explained on the basis of Bohrs model.
3. In 1923, de Broglie suggested that electron, like light has a dual character. It has particle as well as
wave character. Bohr treated the electron only as a particle.
4. Another objection to Bohrs theory came from Heisenbergs uncertainty principle. According to this
principle, it is impossible to determine simultaneously the exact position and momentum of a small
moving particle like an electron. The postulate of Bohr, that electron revolve in well-defined orbits
around the nucleus with well-defined velocities is, thus, not tenable.

Dual Character of Electrons (Particle and Wave Character)


Einstein had suggested in 1905 that light has a dual character as wave and also as particle. De Broglie
proposed that matter also has a dual character - as wave and as particle.
In Bohrs theory, electron is treated as a particle. But according to de Broglies theory electron has a dual
character, both as a material particle and as a wave. He derived an expression for calculating the wave length,
of a particle.
Derivation of de Broglies equation
The de Broglies equation can be easily derived by using Einsteins mass-energy relationship Viz.
E = mc2
In the above equation, c is the velocity of light. Equating this energy with the energy of a photon, we have
hv = mc2
since v = c/
hc / mc 2
Hence, h / mc
Replacing c by the velocity v of the subatomic particles, and m its mass, we have
= h/mv = h/p
Where p is the momentum of the particle.
Above equation is known as the de Broglies equation.
We know that Kinetic Energy = mv2
m2v2 = 2mKE
Thus de-Broglie Equation also implies that
h

2mKE
where h = Plancks constant
m = mass of particle
v = velocity of particle
KE = Kinetic energy of particle
13 Atomic Structure

Heisenbergs Uncertainty Principle


According to this principle, it is not possible to determine simultaneously the accurate position and the accurate
momentum (or velocity) of a microscopic moving particle. This principle is mathematically expressed as
(x) mV h / 4
(x) mV h / 4
(x) (V ) h / 4 m
h
Remember: 5.27 1035 Js
4
h
And for an electron = 5.8 10-5 m2s-1
4m
Where x is uncertainty with regard to the position and p is uncertainty with regard to the momentum of
the particle. If x is very small, i.e., the position of the particle is determined almost exactly, uncertainty with
regard to momentum (or velocity) will be large.
Similarly, if an attempt is made to measure exactly the velocity (momentum) of the particle, the uncertainty
with regard to position will become large.

Photo Electric Effect


Let us try to analyses the Einsteins experiment. He irradiated sodium metal with visible/ultraviolet light and
observed.
1. Electrons came out as soon as the light was irradiated on the surface.
2. There was no emission of electrons for light having frequency less than a certain frequency,
irrespective of the intensity of light used.
3. Photoelectric current increased with increase in intensity of light of same frequency if emission is
permitted.
On the basis of this Einstein had concluded that light must have streams of energy particles or
quanta of energy.
K .E.max = Energy of incident photon- Energy required to liberate an electron.

mv2max = h h 0

h 0 = work function = Minimum energy of the photon to liberate an electron.

0 = Threshold frequency
= Frequency of incident radiation
For electrons to be emitted the frequency of incident light should be threshold frequency
Threshold frequency work function of the metal
Also , h K .E.

K.E. h h( 0 ) ( work function)


1 2
mv h( 0 )
2
Observation of photoelectric effect made by Einstein had confirmed electromagnetic radiation as streams of
particles. When we stop the radiations by any physical obstruction we cannot convert radiations into matter.
m0
Therefore, rest mass of photons ought to zero. Besides according to Einsteins formula m a particle
1 v2 / c2
travelling with the speed of light must be massless. Otherwise its effective mass during motion will be infinite.
Chemistry-XI(Advanced) 14

mo 0
Energy of a photon, E = hv = pc

Where v is the frequency of the wave and p is the momentum associated with the particle E=pc is valid for
all the particles which are massless (travelling with the speed of light).
Difference between orbit and orbital
Orbit Orbital
An orbit is a well-defined circular path in which An orbital is the region of space around the nucleus
electrons revolve. These are numbered as 1, 2, 3, where the probability of finding the electron is
4or labelled as K, L, M, N. maximum.
It represents the movement of electrons around the It represents the three-dimensional motion of
nucleus in one plane. electrons around the nucleus.
The position as well as momentum of an electron can The position and momentum of an electron can not be
be known simultaneously with certainty. known simultaneously with complete certainty.
It can accommodate at the maximum 2n2 electrons, An orbital can accommodate at the most two electrons
where n is the number of the shell with opposite spins.

Some useful formulae


Wavelength of matter wave
h

2mKE
For an electron
150
, where V is accelerating potential
V
Frequency of matter waves.
v v.p mv 2 2 KE

h h h
Where all terms have their usual meaning.
Electron microscope is based on the wave nature of electron.
de-Broglie equations is based on mullikans oil drop experiment (which showed particle nature) and diffraction
study (which showed wave nature) suggested the dual nature of electron.
E in Ev = 12375 / wavelength in angstrom

Example: If the total energy of an electron in a hydrogen like atom in excited state is 3.4 eV, then the
de Broglie wavelength of the electron is
(a) 6.6 10-10 (b) 3 10-10
(c) 5 109 (d) 9.3 10-12
E1 13.6
Solution: Total energy ( En ) 3.4eV 2
E2 n
13.6
n2 4 n 2
3.6
V1 2.18 106
The velocity of electron in 2nd orbit = m / sec
2 2
15 Atomic Structure

h 6.625 1034 2
6.6 1012 m
mv 9.1089 1031 2.18 106
= 6.6 10-10 cm
(a)
Example: If E1, E2 and E3 represent respectively the kinetic energies of an electron, alpha particle and
a proton, each having same de Broglies wave length then
(a) E1 > E3 > E2 (b) E2 > E3 > E1
(c) E1 > E2 > E3 (d) E1 = E2 = E3
h
Solution:
2mKE
Thus if wavelength is same, more mass means less kinetic energy.
(a)
Example: What is the de Broglie wavelength in meters for a ball of mass 0.1 kg moving with a
speed of 60 ms-1.
(a) 6.6 10-34 (b) 1.1 1034
(c) 1.1 10-34 (d) 9.3 10-12
h 6.6 1034
Solution :
mv 0.1 60
1.1 1034 m
(a)
Example: When the frequency of light incident on a metallic plate is doubled, the K.E of the emitted
photoelectrons will be
(a) doubled
(b) halved
(c) increase but more than double of the previous K.E
(d) unchanged
Solution: Upon doubling the frequency, energy of photon will be doubled with work function of metal
will remain constant. So K.E of photoelectron will be more than the double of what it
possessed previously.
(a)
Example: Calculate the kinetic energy of an electron emitted from the surface of a metal by light
of wavelength 5. 5 x 10-8 cm. Threshold energy for the metal is 2.62 10-9 ergs.
(a) 1010 (b) 109 ey
(c) 1010 ey (d) 109J
(b)
C 3 1010 cm s 1
Solution: 5.45 1017 s 1
5.5 108 cm
1
/2 mv2 = hv -hv0
= (6.63 1027 ergs second) (5.45 1017 s1) 2.62 109 ergs
K. E = 9.93 10-10 ergs
Chemistry-XI(Advanced) 16

Try Yourself-3
1. Two particles A and B are in motion. If the wavelength associated with particle A is 5 10-8 m,
Calculate the wavelength associated with particle B if its momentum is half of A.
(a) 100 nm (b) 1010 m
(c) 108 cm (d) All of these
2. Calculate the de Broglie wavelength of an electron that has been accelerated from rest through
a potential difference of 1 kV.
11 12
(a) 3.87 10 m (b) 3.87 10 m
13 10
(c) 3.87 10 m (d) 3.87 10 m
3. Calculate the uncertainty in position of a particle when uncertainty in the momentum is
2 1
1 10 gm cm sec
28 20
(a) 5.27 10 m (b) 5.27 10 m
26 38
(c) 5.27 10 m (d) 5.27 10 m
4 Find the threshold wavelengths for photoelectric effect from a copper surface, a sodium surface and a
caesium surface. The work function of these metals are 4. 5 eV, 2.3 eV and 1.9 eV respectively.
(a) 276 nm, 540 nm, 654 nm (b) 700 nm, 540 nm, 654 nm
(c) 278 nm, 550 nm, 65 nm (d) 372 nm, 540 nm, 644 nm
5 Energy required to stop the ejection of electrons from Cu plate is 0.24 eV. Calculate the work function
when radiation of wavelength 253.7 nm strikes the plate?
(a) 4.65 eV (b) 5.65 eV
(c) 46.5 eV (d) 3.65 eV
6. Which of the following phenomena can be explained by wave like nature of electron?
(a) Electron diffraction (b) Photoelectric effect
(c) Black body radiation (d) All above
7. Which of the following phenomena can be explained by particle like nature of electromagnetic radiation?
(a) Interference of light (b) Photoelectric effect
(c) Black body radiation (d) Both (a) and (b)

Notes:
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17 Atomic Structure

QUANTUM NUMBERS
The term quantum number is used to label the various energy levels or orbits;
a) Principle quantum number (n):
This represents a group or shell of orbits, and the total number of electrons that can occupy any shell is
given by 2n2, where n is the principle quantum number concerned, i. e.
Shell K L M N
principle quantum number (n) 1 2 3 4
maximum number of electrons 2 8 18 32
b) Subsidiary or angular or Azimuthal quantum number ( ):
This represents the various subsidiary orbits within a shell. they may be visualized as elliptical orbits.
Thus, in any one shell there are various subsidiary orbits denoted as the 1, 2, 3, 4,.. or the s, p, d, f ....
h
orbits. The orbital angular momentum of the electron is given as = ( 1)
2
= ( 1)

c) The Magnetic Quantum Number (ml):


An electron with angular momentum can be thought of as an electric current circulating in a loop,
and consequently a magnetic field due to this current is expected and observed. The observed magnetism
is determined by the value of ml.
Since this magnetism has its eventual source in the angular momentum of the electron, it is reasonable
that the values allowed to m depend on the value of, the angular momentum quantum number. Theory
and experiment both show that ml can assume all integral values between - and + including zero.
Thus, ml can be -1, 0 + 1 for = 1.
d) The Spin Quantum Number (ms):
Besides the magnetic effect produced by its angular motion, the electron itself has an intrinsic magnetic
property. A charged particle spinning about its own axis also behaves like a small magnet; hence we say
that the electron has a spin. The quantum number associated with this spin has only two possible values
+1/2 and -1/2.

Some useful formulae


h
Orbital angular momentum = ( 1)
( 1) h
2
Magnetic Quantum number (me) [by linde]
Indicates orientation of orbitals i.e. direction of e density.
2 +1 different value of ml = .........0.........+
ml for p subshell =

ml for d subshell =
Chemistry-XI(Advanced) 18

Spin Quantum no. (ms) [ by Uhlenback & Goudsmit]


Values of s =
1
Total value of spin in an atom S = number of unpaired e
2
Maximum no of electrons in an orbital = 2 (with opposite spin)
h
Spin Angular momentum = S ( S 1)
2

Example: What is maximum number of electrons in an atom can have n+l = 5


(a) 4 (b) 9
(c) 8 (d) 18

Solution: n + = 5, the ordered pairs of n and l are n = 5, = 0, 5s orbital , n = 4, = 1, 4p orbitals,


n=3, = 2, 3d orbitals Thus total orbitals are 1 + 3 + 5 = 9.
Thus maximum electrons are 18
(d)
Example: Which set of quantum number is not consistent with the quantum mechanical theory
(a) n = 2, = 1, m = 1, s = 1/2 (b) n = 4, = 3, m = 2, s = -1/2
(c) n = 3, = 2, m = 3, s = +1/2 (d) n = 4, = 3, m = 3, s = +1/2
Solution: There is a well-defined co-relation between n, m and s quantum numbers in an atom. If n
= n then = (n - 1), m will be and s will always be . For n = 3 there cannot be m = 3.
Highest value m will be 2.
(c)
Example: What is degeneracy of second excited state of hydrogen atom? (dont consider electronic spin)
(a) 4 (b) 9
(c) 8 (d) 10
Solution: There are nine orbitals in the third shell.
(d)

Try Yourself- 4
1. What is maximum number of orbitals in an atom can have n + l = 5
(a) 4 (b) 9
(c) 8 (d) 18
2. What is maximum number of electrons in an atom can have n + l = 4
(a) 4 (b) 9
(c) 8 (d) 18
3. Which of the following sets of quantum numbers is correct for an electron in 4 f orbital?
(a) n = 4, l = 3, m = +4, s = + (b) n = 4, l = 4, m = -4, s = -
(c) n = 4, l = 3, m = +1, s = + (d) n = 3, l = 2, m = -2, s = +
4. How many spectral lines are observed when in electron in hydrogen atom jump from
(i) third excited state to ground state
(ii) Fifth energy level to second Energy level.
(a) 6, 6 (b) 3, 6
(c) 10, 6 (d) 6, 10
19 Atomic Structure

5. How many spectral lines in visible region are observed when e jump from n = 5 to ground state.
(a) 3 (b) 4
(c) 5 (d) 6
6. How many lines in UV region are observed when H electron is de-excited from 6th shell
(a) 5 (b) 10
(c) 6 (d) 15
7. What is degeneracy of second excited state of H- (hydride) ion. (dont consider electronic spin)
(a) 3 (b) 9
(c) 8 (d) 18

Notes:
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Chemistry-XI(Advanced) 20

Some useful formulae


Shapes and Sizes of Orbitals
Values of orbital denoted as [Shape] Derived from word
0 [s] [Spherical] Sharp
1 [p] [Dumb bell] Principle
2 [d] [Double dumb bell] Diffused
3 [f] [Complex] Fundamental
* Radial Nodes = (n l 1)
* Angular nodes =l
* Total nodes = (n 1)

Example: Consider the ground state of Cr atom (Z = 24). The numbers of electrons with the azimuthal
quantum numbers, l = 1 and 2 are, respectively:
(a) 12 and 4 (b) 12 and 5
(c) 16 and 4 (d) 16 and 5
Solution Electronic configuration of chromium in ground state is 1s22s22p63s23p64s13d5.
Azimuthal quantum number, l = 1 stands for p-subshell while l = 2 refers to d-subshell.
Therefore, the number of electrons with l = 1 is 6 + 6 i.e. 12.
The number of electrons with l = 2 is 5
(b)
Example: Of the following outer electronic configurations of atoms, the highest oxidation state is
achieved by which one of them?
(a) (n-1)d8ns2 (b) (n-1)d5ns1
(c) (n-1)d3ns2 (d) (n-1)d5ns2
Solution: The electronic configuration (n-1)d5ns2 can achieve the maximum oxidation state of +7.
(d)
Example: Which of the following statements in relation to the hydrogen atom is correct?
(a) 3s orbital is lower in energy than 3p orbital
(b) 3p orbital is lower in energy than 3d orbital
(c) 3s and 3p orbitals are of lower energy than 3d orbital
(d) 3s, 3p and 3d orbitals all have the same energy
Solution For hydrogen the energy order of orbital is
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
(d)
21 Atomic Structure

Try Yourself- 5
1. Number of nodal planes (planes of zero electron density) in the dxy orbital is
(a) 1 (b) 2
(c) 0 (d) 4
2. Non directional orbital is
(a) 3s (b) 4f
(c) 4d (d) 4p
3. The shape of an orbital is governed by:
(a) Spin quantum number (b) principle quantum number
(c) Azimuthal quantum number (d) Magnetic quantum number
3
4. How many radial nodes are present in 4dxy 5p 6s orbitals respectively
(a) 1,3,5 (b) 1,2,3
(c) 2,3,4 (d) 3,4,5
5. An orbital has 3 redial nodes & 2 angular nodes. Identify the orbital
(a) 6s (b) 6dxy
(c) 6p (d) 6f
6. The probability of finding an electron residing in px orbital is zero in:
(a) In the yz plane (b) in the xy plane
(c) in the zx plane (d) none of the above
Notes:
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Chemistry-XI(Advanced) 22

Filling of orbitals in Atoms:


The distribution of electrons in various orbitals is known as electronic configuration. The atom is built up by
filling electrons in various orbitals one at a time and by placing each new electron in the lowest available
energy orbital. An atom is its lowest energy state is said to be in the normal state or the ground state. This state
is the most stable for the atom. The filling of orbitals in the ground state in multielectron systems takes place
according to the following rules
Rules for filling for orbitals in the ground state of multi electron system
1. Aufbau principle :
The electrons are filled up in increasing order of the energy in subshells.
1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s25f146d10
2. (n + ) rule :
The subshell with lowest (n + ) value is filled up first, but when two or more subshells have same (n
+ ) value then the subshell with lowest value of n is filled up first.
3. Pauli exclusion principle :
Pauli stated that no two electrons in an atom can have same values of all four quantum numbers.
4. Hunds rule of maximum multiplicity :
Electrons are distributed among the orbitals of subshell in such a way as to give maximum number of
unpaired electrons with parallel spin.
In representing positions of electrons in various shells and subshells, the following rules are observed:
1. The major energy shell, 1, 2, 3, 4 etc., is written first.
2. The subshell s, p, d and f is written next.
3. The number of electrons in the particular subshell is shown by a superscript placed to the right of the
symbol for that subshell.
For example, ls2 indicates the location of 2 electrons in the s- subshell of the first energy shell. Similarly, 3d6
denotes the location of 6 electrons in the d-sublevel of the third major energy level.

Electronic Configurations of Elements


Based on the rules, we can easily determine the electronic configurations of most elements. We just need to
know the atomic number of an element, the order in which orbitals are to be filled and the maximum number
of electrons in a shell, sub-shell or orbital. The configuration so obtained can be represented in two ways. As
an illustration, let us consider fluorine (Z= 9):
F( Z = 9 ) 1s2 2s2 2px2 2py2 2p1z

2 2 2 2 1
or 1s 2s 2px 2py 2pz

Importance of knowing the exact electronic configuration of an element lie in the fact that the chemical
properties of an element are dependent on the behavior and relative arrangement of its electrons.
Electronic configurations of heavier elements (beyond Z = 56 ) deviate a little from the order mentioned
previously. These are brief listed below .
a) Lanthanoides La(Z = 57 ) : [Xe] 6s25d1 ( not 4f1)
Ce(Z = 58 ) : [Xe] 6s2 5d1 4f1
Pr(Z = 59 ) : [Xe] 6s2 5d1 4f2
b) Actinoides Ac(Z = 89) : [Rn] 7s2 6d1( not 5f1)
Th (Z = 90 ) : [Rn] 7s2 6d1 5f1
Pa( Z = 91 ) : [Rn] 7s2 6d15f2
23 Atomic Structure

c) Beyond Z = 103 Z = 104 : [Rn] 5f146d27s2


Z = 105 : [Rn] 5f146d37s2
Z = 106 : [Rn] 5f146d47s2
Z = 112 : [Rn] 5f146d107s2

Example: Predict the total spin in Ni2+ ion


(a) 5 / 2 (b) 3 / 2
(c) 1/ 2 (d) 1
Solution: No of unpaired electron = 2
(d)
Example: With increasing principal quantum number, the energy difference between adjacent energy
levels in atoms.
(a) decreases
(b) increases
(c) Remains constant
(d) decreases for low z and increases for high z
1
Solution: E
n2
(a)
Example: The number of electrons in ground state of sodium atom having n + = 3?
(a) 2 (b) 4
(c) 6 (d) 7
Solution: The electronic configuration of Sulphur atoms 1s 2s22p63s1, the orbitals with ( n + ) = 3 are
2

2p and 3s, therefore 7 electrons in sodium atom have (n+ ) = 3


(d)
Example: Which atom contains an electron with quantum number n = 3 , 2, m = 1 s=
(a) Ne (b) Co
(c) Cl (d) K
Solution: Quantum number n = 3, = 2, m = -1 s = - represent 3d electron which is present in
Co.
(b)
Example: A compound of vanadium has a magnetic moment of 1.73 BM. How many 3d electrons are
present in vanadium ion.
(a) 4 (b) 3
(c) 2 (d) 1
Solution: Magnetic moment = n(n 2) where n = number of unpaired electrons.

n(n 2) 1.73 n2 2n (1.73)2


n=1
therefore, vanadium atom must have one unaired electron and thus its electronic
configuration.
(d)
Chemistry-XI(Advanced) 24

Example: Match the orbital angular momentum of an electron in the orbital in series I with value in II
I: (i) 3p (ii) 3d (iii) 3s
II: (p) 2 h/2 (q) 6 h/2 (r) 0
(a) i-p, ii-q, iii-r (b) i-p, ii-q, iii-r
(c) i-p, ii-q, iii-r (d) i-p, ii-q, iii-r
h
Solution: ( 1) ( 1)
2
i) For 3 p, 1, 1(1 1) 2
h
ii) for 3d , 2, 2(2 1) 6
2
iii) for 3s, 0, 1 0
(a)
Example: How many 7s electrons are there in an atom with Z = 104?
(a) 0 (b) 1
(c) 2 (d) 3
Solution : The electronic configuration of the said element is :
1s2,2s2,2p6,3s2,3p6,3d10, 4s2, 4p6, 4d10,4f14, 5s2, 5p6, 5d10, 5f14, 6s2, 6p6, 6d2, 7s2
Hence there are two 7s electrons.
(c)
Example: Ground state electronic configuration of nitrogen atom can be represented by
(a) (b)

(c) (d)
Solution : which configuration follow Hund's rule.
(a) and (d)
Example: In a multielectron atom, which of the following orbitals described by the three quantum
numbers will have the same energy in the absence of magnetic and electric fields?
(a) n =1, l = 0, m = 0 (b) n =2, l = 0, m = 0
(c) n =2, l = 1, m = 1 (d) n =3, l = 2, m = 1
(E) n =3, l = 2, m = 0
(a) (A) and (B) (b) (B) and (C)
(c) (C) and (d) (d) (D) and (E)
Solution: Orbitals having same (n + l) value in the absence of electric and magnetic field will have same
energy.
(d)
25 Atomic Structure

Try Yourself- 6
1. Match the name the orbitals corresponding to given set of quantum numbers in the two columns
Column A Column B
(i) n = 3, =2,m = 2 p. 3dx2 y2
(ii) n=4, =0,m=0 q. 3dxy
(iii) n = 3, = 1, m = 1 r. 4s
(iv) n = 2, =1,m=1 s. 4px
t. 4py
u. 2px
v. 2py
(a) i-p, ii-r, iii-s, iv-t (b) i- q, ii-r, iii- t, iv- v
(c) i-p, q, ii-r,s, iii-t iv-u,v (d) i-p,q, ii-r, iii-s,t iv-u,v
2. How many s electrons are there in an atom with Z = 100 ?
(a) 1 (b) 4
(c) 10 (d) 14
3. Arrange the electrons represented by the following sets of quantum number in decreasing order of
energy.
(i) n 4, 0, m 0, s 1/ 2 (ii) n 3, 2, m 0, s 1/ 2
(iii) n 3, 1, m 1, s 1/ 2 (iv) n 3, 0, m 1, s 1/ 2
(a) (ii) > (iii) > (i) > (iv) (b) (i) > (iii) > (ii) > (iv)
(c) (ii) > (i) > (iii) > (iv) (d) (ii) > (i) > (iv) > (iii)

Notes:
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Chemistry-XI(Advanced) 26

SCHRODINGER WAVE EQUATION AND QUANTUM MECHANICS


8 2 m
2 ( E U ) 0
h2
This equation implies in essence that a body of mass m, velocity V, potential energy U and total energy E has
a wave associated with it of an amplitude given by wave function. The Schrodinger equation has an infinite
many solutions.
For any physical situation must be finite, single valued and continuous. The particular values of which yield
satisfactory solution of above equation are called wave functions wave function for an electron is called an
atomic orbital.
The nature of electron in atom can be discussed in terms of the solution of Schrodinger wave equation
2 2 2 8 2 m
2 ( E v) 0
x2 y 2 z 2 h
The wave function of an electron ( ) in the field of nucleus of atom is called atomic orbital.
It is three-dimensional amplitude of electron wave.
2 is the probability of finding the electron in a volume element surrounding the nucleus of an atom?

Significance of Wave function and | |2:


The orbital wave function has no physical significance. It is the square of the absolute value of wave function
| |2, which has a physical significance. It measures the electron probability density at a point in an atom.

FUNCTION VARIATION OF RADIAL FUNCTION

R is known as radial wave function


R2 is known as radial probability density
4 2 r 2 drR 2 is known as radial probability.

Plot of Radial Wave Function (R) vs r:


In all orbitals R approaches zero as r approaches infinity.
At node is sign of R charges.
There is a node (the probability of finding electron is zero ) in 2s orbital. At the node the value of radial
function changes from positive to negative for 2s orbital. In general ns orbitals have (n 1) radial nodes.
The plots of the radials wave function R Vs. distance r

Radial Probability Density (R2) vs: r:


The square wave function R2 for an orbital gives the radial density. The radial density gives the probability
density of finding the electron at a point along a particular line. The plots of the radials wave function R2 Vs.
distance r.
27 Atomic Structure

Radial Probability Functions ( 4 2 r 2 drR 2 ) vs r:


Radial probability function gives the probability of finding the electron at a distance r from the nucleus regardless
of direction.
The plots of the radial function 4 r 2 R 2 Vs. distance;

Try Yourself-7

1. P is the probability of finding the 1s electron of hydrogen atom in a spherical shell of infinitesimal
thickness, dr, at a distance r from the nucleus. The volume of this shell is 4 r 2 dr . The qualitative sketch
of the dependence of P on r is

(a) (b)

(c) (d)

2. The Schrodinger wave equation for hydrogen atom is


3/2
11 r0 r0 / a0
2s 2 e
4 2 a0 a0
Where a0 is Bohrs radius. If the radial node in 2s be at r0, then the ratio of a0 and r0 will be
(a) 2 (b) 1/2
(c) 4 (d) 3/2

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