i.

Introduction & Dalton’s Atomic Theory,

ii. Sub atomic particles, Charge & Mass ratio of es- A
iii. Various Atomic Models,
iv. /’
Atomic Number & Mass Number
v. Various iso terms,
vi. Nature of radiations,
vii. Spectrum of Elements & Hydrogen Spectrum
viii. Quantum Mechanical model,
ix. Cathode rays production and properties,
x. Heisenberg’s uncertainty principal, A
xi. Shapes of Atomic orbitals,
xii. Quantum numbers,

Atomic Structure
A
Structure of an Atom

Prof. Abdul Wajid Hyder

BUSTAB EDUCORP
abdulwajidhyder@gmail.com

CELL # 0091 - 971 866 2585/ 80 9650 6592

 Atomic Structure
Sunday, June 30, 2024 5:14:07 PM
1) Dalton’s atomic theory (1808) - John Dalton gave atomic hypothesis to explain the laws of chemical
combinations, he regarded atom as ultimate structure less particle, can’t be subdivided further.
Tomio (Latin) –“divisible”.

I) Atom is hard, dense, smallest particle of matter (Structure less indivisible).

II) Can neither be created nor be destroyed during chemical reactions but in nuclear reactions can
be destroyed or created.
III) Atoms of different elements are different and of same elements are alike in physical & chemical
properties.
IV) Always combine in whole no. to form compounds (form a strong basis for understanding
stoichiometry, the quantitative laws of chemical combination).
V) It explained the laws of chemical combinations such as conservation of mass and multiple
proportions.

Drawbacks-

I) Fails to explain why atoms of different kinds should differ in masses and valence et cetera.
II) Doesn’t explain structure of atom.
III) Fails to explain binding forces between atoms in compounds.
IV) Doesn’t explain Gay Lussac’s law, and law of definite proportion, if different isotopes are used.
V) Doesn’t differentiate between atoms & molecules. The discovery of isobars and isotopes
showed that atoms of same elements may have different atomic masses (isotopes) and atoms of
different kinds may have same atomic masses (isobars).
1) Sub atomic particles- About 72 sub atomic particles but e-, p+, and n0 are fundamental particles due
to their greater stability the tav for n0 is 23 minutes, heaviest and least stable amongst these three
particles in an atom, particles other than these three are not so stable.

Electron --1e0 Proton +1 p1 Neutron 0n1

1) 2) Relative mass (1/1835 X heavier than H) 1 1
3) 4) mass in kg 9.1 Χ 10 -31 kg 1.672 Χ 10 -27 kg 1.674 Χ10 -27 kg
5) 6) mass in amu, 0.0005485 amu 1.00758 amu 1.00893 amu
7) 8) mass relative to the e- 1 1836 1839
9) 10) Relative charge -1 +1 0
11) 12) actual charge 1.602 Χ 10 -19 C 1.602 Χ 10 -19C, 0
13) 14) actual charge 4.8 Χ 10-10 esu 4.8 Χ 10-10 esu 0
15) 16) Discovery J J Thomson (1887) Goldstein (1886) observed James Chadwick (1932)
1st but discovered by
Rutherford
17) 18) Experiment Cathode-ray discharge Anode ray discharge tube 4Be9+2He4→6C12+0n1 ∝
tube experiment experiment - Ray experiment
19) 20) Spin ½ ½ ½

Sub atomic particles Symbol Spin Charge Mass in µ Mass w.r.t. e- Life time Chemical reaction associated Discovery
with Particles

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 Atomic Structure
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0 - -19
Electron- stable -1 e /ẞ 1/2 -1.602X 10 C 0.0005486 1 Stable Thomson

Positron- stable 1 e0 /ẞ+ 1/2 1.602X 10-19 C 0.0005486 1 Highly unstable & Anderson & Dirac
produces ᵞ rays - highly unstable
Proton- stable 1 P1 1/2 1.602X 10-19 C 1.007276 1836 Goldstein
observed 1st but
discovered by
Rutherford
Antiproton- Stable -1 P1 1/2 -1.602X 10-19 C 1.007276 1836 tav= 932 seconds Segre &
Chamberlin
Neutron - used in 0 n1 1/2 0 1.008665 1838.5 t1/2 = 23 minutes Chadwick
chemotherapy
Anti-neutron -1 Anti-
0 1.008665 1838.5 Cork
0n clockwise

ᵞ0
½ anti -
Neutrino -stable 0 ˂0.0002 0 Stable Pauli, no mass &
clockwise
charge - Fermi
½-
Antineutrino ᵞ 0 ˂0.0002 0
clockwise

Photon – stable, 0 0 0
energy elementary
particle
Graviton- stable G 0 0 0
energy particle
Muon –vely μ 1/2 -ve 207
Muon +vely 1/2 +ve 207
Meson –vely/ Kaons, Π- -ve H Yukawa
unstable elementary
particle
Meson +vely/ Kaons Π+ +ve H Yukawa
elementary particle
Meson neutral η Eta 0 0.7680 – 1200 – 1400 Kemmer detected
elementary particle 0.1152 in Cosmic rays
γ Particles, un stable +,- or 0 1.2014 - 2190 – 2200
1.2069
Pions (Mesons) π +/-/0 1/2 +,- or 0 276 times
Hyperons – -ve, +ve mass 2180, Particles obtained from the
or 0, Xi, Sigma, 2330 & 2580 nucleus
lambda, omega times. larger
particles than those of
protons
Bosons – 0, 1, Heaviest
and 2 elementary
particle,
Fermions - Beryons spin
Elementary particles ½
(Leptons)
Baryons – Nucleons,
Hyperons
Leptons – Electron,
neutrino,
muon, tau
JJ Thomson (1897) found that e/m = charge/ mass = specific charge = 1.76 Χ 108 C/g.
Absolute mass of an electron = Millikan’s value of 1.6 Χ 10-19 C/1.76 Χ 108 C/g = 9.1 Χ 10-31 Kg
e/Thomson’s value of e/m
Absolute mass of H atom 1.008 amu = 1.008/6.023 Χ 1023g = 1.67Χ 10-24g
Mass of H atom/ mass of e- 1.67Χ 10-24/ 9.1 Χ 10-28 = 1835,
H = 1839 x electron
3) Atomic models –
Origins of atomic theory- J Dalton, J L Gay Lussac and Avogadro experiments were quantitative

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 Atomic Structure
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measurements based on weight & their postulates mainly concerned weight as a fundamental
atomic property.

i) Thomson’s atomic model- Atom is a hard sphere of positive charge particles uniformly distributed,
with the e- scattered as points throughout the sphere, known as plum pudding model. However
scattering experiments studied by Rutherford and Mardson. Atomic radius-10 -10 m, positive charge =
negative charge.

Drawbacks-

I) Photo electric effect and thermo ionic emission could not be explained
II) α - particle scattering experiment by heavy atoms could not be explained.

ii) Rutherford’s nuclear model of atom – Positive charge is spread over a sphere of radius 10 -15 m, the
so-called nucleus and that the outermost electron clouds are about 10 -10 m from the centre of the
nucleus. Thus, less than 10 -12 of the volume of the atom occupied by material particles, means most of
the part of atom is empty, between nucleus and revolving e-s in closed orbits (not fixed). Positive charge
of nucleus (named it protons) and but mass is because of neutron and proton both. Different atoms
have different positive charge and e-s revolve around the nucleus with very high speed and are called
planetary e-s.
Au foil thickness-10 -5 cm. Nucleons (neutrons and protons) present in the nucleus.
When alpha particles 24 He2+ fall on a very thin (4 Χ 10 -4 m order) foil of Au, and determined the
subsequent path of these particles with the help of a ZnS fluorescent screen, it has remarkable property
of converting kinetic energy of particle into visible light.
Why alpha particles - because heavy so high momentum.
Most alpha particles pass straight (99.9 %); some deflected back with angle 90° and 180° (only one in
20,000). So, most of the part of an atom is empty and whole mass is concentrated in nucleus which is
positively charged. (Done in vacuum so no α - particle collision with the particles of air)
Some α particle scattered min. angle, N α 1/Sin4(θ/2). N = no. of alpha particles.
Electrons actually revolve around the nucleus in circular planetary orbits in which the required
centripetal force is derived from the electrostatic force of attraction between nucleus (+Ze) and electron
= mv2/r = K Ze2/r2

Drawbacks of Rutherford’s atomic model-

I) Exact positions of electron from the nucleus are not mentioned.

II) According to law of electro dynamics (Maxwell), electron should continuously emit radiation and lose
energy and will fall ultimately into the nucleus in less than 10-8 seconds but as we know electron
keeps on moving outside the nucleus.
III) According to Rutherford atom possesses continues spectra (because it emits light continuously) but it
shows line spectrum.
4) Atomic number, Mass number & Various Iso terms in Chemistry

Isotopes (Soddy) Isotones Isobars Iso electronic Isosters Isodiaphers

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- + 0 - + -
Same e , p Same n Different e , p , Same e Same Same isotopic
different n0 different e-, p+ n0 atomicity & no. no.= n0- p+
Of e-
Same chemical Different Different Same chemical
properties chemical chemical properties
properties properties
35 37 39 40 40 40
17Cl , 17Cl 19K , 20Ca 20Ca , 18Ar N3-,O2-, Na+, Ne CO2, N2O 39
19K , 9F
19

Isotopomers or Isotopic Iso structural or Isotypic Nuclear Isomorphism

isotopic isomers mass of Cl isomers
are isomers with = ratio of Cl Pair of isomorphous compounds The Size of metal ion
isotopic atom 35 X mass of in which relative sizes of the radioactive is same-transition
having the same Cl 35, + ratio ions to each other are the same elements metal compounds
number of each of Cl 37 X in each pair but their absolute having same exhibit
isotopic atom but mass of Cl sizes are different, have same atomic isomorphism,
different in their 37/sum of chemical composition, e.g., number & same atomic
positions. It can ratio CaCO3, NaNO3 & FeBO3. same mass composition &
be constitutional = 3 X 35 + CH4 & NH4+ are iso electrical and no. but crystalline
or stereo isomer 1X 37/4 = are iso structural as both have different structure.
for example 35.5 tetrahedral structural but C-H & radioactive The central atom
CH3CHDCH3 and (Average N-H bond lengths are different. properties has same
CH3CH2CH2D Atomic Mass AuBr & AuCl, Benzene & are called oxidation no.
Topos - place in of chlorine) Borazine are iso structural. nuclear ZnSO4.7H2O and
periodic table. isomers. FeSO4.7H2O
5) Nature of Radiations – Electromagnetic radiations or Radiations means waves which don’t require
any medium to travel.

i) According to Corpuscular theory of light (Newton) –Light is stream of particles, can explain reflection
and refraction of light but failed to explain interference and diffraction.

ii) Wave theory of Radiations – iii) Quantum or Particle theory of radiation –

(Maxwell) (Max Planck)
Radiations travel in the form of wave and Radiations travel in the form of discrete bundles of
consist of electric & magnetic fields which energy called Photon (quanta). Photon is mass less
oscillate perpendicular to each other and also bundle of energy not a material body. Thus, a body can
perpendicular to the direction in which the lose energy in multiples of quantum h√, 2h√, 3h√…., nh√
radiations propagate & the velocity will be where n is an integer.
3x108m/`s.

Radiations can interfere, are delocalized and Radiations can’t interfere, are localized and have
have continuity. discontinuity.
This could explain interference and diffraction This could explain photoelectric effect and black body
but couldn’t explain photoelectric effect and radiation.
black body radiation.

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Davison and Germer’s experiment confirm the Scintillation method and photo electric effect confirms
wave nature of electron. the particle nature of electron.
James Clark Maxwell stated that light, X -rays, √-rays and heat etc.
emit energy continuously in the form of radiations or waves and the
energy is called radiant energy. These waves are associated with
electric & magnetic fields and are known as electromagnetic waves.
Intensity of light – is number of photons falling per unit area/second
and depends upon the no. of photons.
Amplitude (a) – It is height of the crest or depth of the trough of a
wave. It determines the intensity or brightness of the beam of light.
The first use of quantum theory to explain the structure of atom was made by Bohr.
Quantum theory of radiation was used by Einstein to explain photo electric effect.

Interference - Interaction of two waves Diffraction – Formation of light and dark bands.
Photo electric effect- Hertz
When a beam of light of sufficiently high frequency (U-V light) is allowed to strike a metal surface in
vacuum, electrons are ejected from the metal surface. This phenomenon is known as photo electric
effect.
Incident energy = KE + Wo(Einstein’s photoelectric equation) Wo= work function)
h√ = h√o+ KE, KE = h√ - h√o= h (√ -√o) = hC (1/λ -1/λo)
λ -wavelength of incident light & λo- threshold wave length
KE α Frequency of incident light but independent of the intensity of light,
Rate of emission α No. of photoelectrons ejected α intensity of light
Energy required to stop the ejection of electrons is given be eV0
where e is the electric charge & V0 is stopping potential/cut off
potential (The negative potential at which the photoelectric current
becomes zero).
Numerical – If P = Momentum of the fastest e- ejected from a metal
surface after the irradiation of light having wavelength λ then for 1.5
P momentum of the photoelectron, the λ of light should be –
(Assume KE >> E°).

Solution –
1/2mv2 =E - E° (because K >> E°), KE = E, 1/2mv2 =hc/ λ , [1/2mv2 = 1/2m2v2 /m= hc/ λ , P2/2m = hc/ λ ]
P2α 1/ λ , (P1 / P2 )2 = λ2/λ1, (P / 1.5 P )2 = λ2/λ1 = (2/3)2 = 4/9, λ2 = 4/9λ1

# Black body radiation (Max Planck) – An ideal body (perfect absorber & perfect emitter- C
black/blackened metallic surface) which emits and absorbs radiations of all the frequencies uniformly is
black body & such radiations are called black body radiations.
Body always first emits IR radiations which can be experienced as warmth with the hand.

Iron ∆→Dull red ∆→ Bright red to Orange ∆→Yellow ∆→ White ∆→ Blue ( ↑ing √ ↓ing Higher
λ Lower λ

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The only factor on which the intensity & frequency of the emitted radiation depends is temperature. At
a given temperature, the intensity of radiation emitted increases with decrease of λ, reaches maximum
value at a given λ and then starts decreasing with further decrease of λ.

Rayleigh – Jeans law - dE = ρdλ, ρ = 8πkT/ λ4, Intensity α KT/λ4

ρ = density of states (J/m-4), dE = energy density (J/m-3), k= Boltzmann’s constant (1.381X10-23J/K)

#Compton Effect – The scattering of electromagnetic radiation (like X rays, √ rays etc.) by an electron or
atom (when energy or frequency of scattered ray is lesser than the incident ray) is known as Compton
Effect.

iv) de -Broglie’s dual nature of Radiations – Based on Mullikan’s oil droplet experiment (particle
nature) and diffraction study (wave nature). Radiation travels in the form of waves as well as in
the form of particles.
Einstein proposed the dual nature of Radiation and de Broglie proposed the dual nature of
matter.
Einstein proved the presence of photons in photoelectric effect on the basis of quantum theory
of radiation.
E= mc² (Einstein’s mass defect equation) E = h⋎ = hC/ʎ (Planck’s Equation)
Energy of radiation α frequency and intensity of radiation.
mc²=hC/ʎ, mc = h/⋋ , P=mC (momentum) = h/⋋ ,ʎ=h/P =h/mC
ϒ=ν/h/ mν = mν2/h =2KE/ʎ. This equation is only applicable to microscopic objects.

Significance of de Broglie’s concept-

(i) Angular Momentum in closed orbits are quantized (mvr = nh/2π)

(ii) The wave length associated with a moving object is inversely proportional to its mass.
The mass of car is more than an electron, the ⋋ of car is very low we can’t measure it, so de
Broglie relationship has no significance in our daily life.

William Crooks Cathode rays J J Thomson Electron

Goldstein Anode rays Rutherford Proton and Nucleus
Mosley’s experiment Atomic number Bohr’s model Orbit and H spectra
Chadwick Neutrons
6) Bohr’s atomic model -
He used quantum or particle theory in considering the energy of an electron bound to the nucleus.
Electron particles revolve around the nucleus in certain orbits. These orbits are having certain fixed

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energy and electron occupies the position according to its energy and will remain be there in the
same orbit, if there is no change in energy stationary orbits.
As distance of these energy level increases from the nucleus, energy also increases and at infinity,
energy will be maximum that is zero.
The force of attraction between the nucleus and an electron is equal to the centrifugal force of the
moving electron then no change in the position of e-.

Angular momentum = mvr = nh/2ᴨ (integral multiple) ∆E = E2 – E1 = h√

Electrons can move only in some particular orbits of definite radii & not all radii as suggested by Rutherford.
K.E. of e- = ½ Zke2/rn Ek =13.6z2/n2 eV −PE
KE = -ve sign indicates work done
2
against force of attraction
P.E. of e- = - Zke2/rn Ep=27.2 z2/n2 En=K.E.+P.E.
KE of α particle = PE of system 1/2mv 2= 1/4 πϵ 0 Χ Ze.2e/rmin rmin = distance of closest approach Ze =
atomic number & charge of p+, e =charge of e
Centrifugal force = force of attraction 1 ϵ 0 =8.854Χ10-12C2Kg-1M3sec2 or
(Coulombs law), mv2/r = 1/ 4 πϵ 0(e) (e) /r2 K= = constant (In CGS unit, k
4 ⋏ ϵo Nm2C-2= Absolute permittivity of the
= 1) medium ( viz. the vacuum in this case)

1 1 En=1/2 mv + 1/4 πϵ Χ e /r =
2 0 2 2
−2 π m z e k
2 4 2
En= (IE) H z² [ 12 - 22 ] 2 En= =
n n Zk e 2 2
n h
2rn
(IE)H = -E₁ (H) =13.6 eV/atom= 2.17 x 10 -18 J/ atom =-1312KJ/mole and if at. No. =Z, (IE)z
E₁= -2.17 x 10 -18 J/atom=-1.312 x 106 J/mol =-13.6 eV/atom 1eV =1.602 x 10 -19J or C x volt
∆E = 2π2mZ2e4k2/h2[1/n12 - 1/n22]
Ionization energy Separation Energy
The energy required to remove an e- from the gaseous E = 0 If an e- is already present in the excited state
state to form cation i.e., to take the e- to infinity then the energy required to remove that e-
Ionization energy = E∞ - E ground E Separation = E∞ – Eexcited
I.P. for n1 → α =E n1/ Electronic charge Excitation potential for n1 → n2 = En2 - En1/Electronic charge
= (IE)H Z2/n2 , E1 is energy of the e- of H atom in its ground state n= α, Eα = 0, EH = -ve means e- in H is bound to the nucleus
=(IE)Z[1/n12 - 1/n22], = (IE)H Z2 [1/n12 - 1/n22]

Radius of e- = 42.8 x 10 – 13 cm Radius of atom= Radius of nucleus Χ105 Effective radius of atom =10 -10 m order
-
Effective radius of e = 10 -15
m order, n²a₀ 0 h² a₀ = 0.529A⁰= Bohr’s radius of H atom in
rn = A, a₀ = its 1st orbit (ground state)
z 4 π ² me ² k
For H like species rn=r1× n2 R nucleus =R0 A 1/3 cm, Ro=1.33×10 -13, R=radius of nucleus, A=mass no
n α size of the atom α 1/Z, R 2 = 4 x R1 radius of orbit α 1/(no. of orbit)2
Merits-

1. Experimental value of radii and energy in H are in good agreement with that calculated on the basis
of Bohr’s theory.
2. It explains the emission and absorption spectra of H like atoms.
3. The experimental values of spectral lines of H spectrum are in close agreement with the calculated
by the Bohr’s theory.
Energy of e- in H atom-

Orbit /Energy level K Cal/mol eV/atom KJ/mol J/atom

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st 2
1 -313.6/1 =-313.6 -13.6 -1312 -21.79X10-19
2nd -313.6/22=-78.4 -3.4 -328 -5.42X10-19
3rd -313.6/32=--34.8 -1.51 -145.77 -2.41X10-19
4th -313.6/42=-19.6 -0.85 -82 -1.36X10-19
𝛂 0 0 0 0

Limitations of Bohr’s atomic model -

1. Does not explain wave properties of electrons and is a flat model.

2. Unable to explain presence of many lines in spectrum of hydrogen atom (fine spectra - fine structure
of spectral lines).
3. Could not explain the group of spectral lines closely packed in a given region of the H Spectrum.
4. Does not explain the spectra of multi-electron atoms
5. Does not explain the splitting of spectral lines under the influence of magnetic field (Zeeman effect)
and electric field (Stark’s effect).
6. Contradictory to Heisenberg’s uncertainty principle, because there was uncertainty of the position &
velocity of the e-.
7. Contradictory to de Broglie’s dual nature of radiation.
8. Unable to explain the distribution & arrangement of electrons in orbits as well as shape of the
molecules formed by the combination of atoms.

Reasons for the failure of Bohr’s atomic model -

i) de Broglie Dual nature of radiation ii) Heisenberg’s uncertainty principle

Wave nature of Radiation Particle nature of radiation

2
E = mC E = hʋ
Interference Photoelectric Effect
Diffraction Blackbody radiation
Heisenberg’s Uncertainty Principle Bohr’s Atomic Model
Dual Nature of Radiation -
Electromagnetic spectrum – Arrangement of all electromagnetic radiations in the
increasing/decreasing order of frequencies or order of wave length is called electromagnetic spectrum.
Spectrometer or spectrograph is developed to record solar spectrum by Bunsen & Kirchhoff.
Spectrum of the atom

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-
When e jumps from a higher energy level to lower radiations are emitted and appear in the form of lines called
spectrum.
Atomic spectra are discrete, i.e., certain specific frequencies are emitted by each atom and other
frequencies are never emitted when excited by heating, passing current or electric discharges.
Dispersion – Splitting of beam of light into radiations of different frequencies after passing through a
prism is called dispersion.
Absorption spectra- Emission Spectrum-
By passing white light through solution/vapour of By passing radiations from the atoms through prism,
substance, few dark lines otherwise Continuous spectrum. bright lines will be obtained.
But if light from a continuous source (a hot body such as a The line emission spectra are produced when
star) passes through an atmosphere of H (such as the star's electrons which had previously been excited to
outer atmosphere), those wavelengths that correspond to values of n greater than 1 fall back to the n=1
the allowed transitions are absorbed, and appear as dark ground state, either directly, or by way of
lines superimposed on the continuous spectrum. intermediate-n states.
Emission Spectrum is of two types –
Continuous/Band spectra (molecular) Discontinuous/line spectra (atomic)
Light from any source (sun/bulb) passed through prism Isolated colour lines separated by dark spaces.
wide bands of 7 colors, merges into each other
Incandescent solids give continuous spectra.
Emission Spectrum of the H atom
The H spectrum was the first to be observed by Johann Balmer related the wavelengths of the various
lines that are observable in the visible and near-U-V parts of the spectrum. This set of lines is now
known as the Balmer Series.
It is obtained by passing light being emitted from discharge tube containing H 2 at low pressure through
spectrograph, series of sharp lines in UV, visible & IR regions are found. (Line, emission spectrum)

The four lines in the visible spectrum (designated by α through δ) were the first observed by Balmer (1st
line (3→2) is also known as Lα line, 2nd line (4→2) is Lβ & the line from infinity energy shell is limiting line).
The limiting line for any series of line in H spectrum is when n2 in the Rydberg’s equation is infinity.
Beyond a certain limit in the spectrum of an atom there is continuum. Once the electron has left the
atom, it is in an unbound state and its energy is no longer quantized. When such electrons return to the
atom, they possess random amounts of kinetic energies over and above the binding energy. This reveals
itself as the radiation at the short-wavelength end of the spectrum known as the continuum radiation.
How the Bohr model explains the H line spectrum- Each spectral line represents an energy
difference between two possible states of the atom. Each of these states corresponds to the e - in the H
atom being in an "orbit" whose radius increases with the quantum number n. The lowest allowed value
of n is 1; because the e- is as close to the nucleus as it can get, the energy of the system has its minimum
(most negative) value. This is the "normal" (most stable) state of the H atom, and is called the ground
state.

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Name Wave length (in A°) Frequency Source

1 Radio wave 3 1014-3 107 1X105-1x109 Alternating Current of high frequency
2 Microwave 3 107-6 106 1X109-5x1011 Klystron tube
3 IR 6 106-7600 5X1011-3.95x1016 Incandescent objects
4 Visible 7600-3800 3.95x1016 - 7.9x1014 Electric bulbs, sun rays
5 UV 3800-150 7.9x1014 - 2x1016 Sun rays, arc lamps with Hg vapours
6 X rays 150-0.1 2x1016 - 3x1019 Cathode rays striking metal plate
7 γ rays 0.1-0.01 3x1019 - 3x1020 Secondary effect of radioactive decay
8 Cosmic rays 0.01-zero 3x1020 - Infinity Outer space
Many spectral lines in the spectrum of H atom -If H atom absorbs radiation whose energy corresponds
to the difference between that of n=1 and some higher value of n, the atom is said to be in an excited
state. Excited states are unstable and quickly decay to the ground state, but not always in a single step.
For example, if the electron is initially promoted to the n=3 state, it can decay either to the ground state
or to the n=2 state, which then decays to n=1. Thus, this single n=1→3 excitation can result in the three
emission lines, n=3→1, n=3→2, and n=2→1.
If, instead, enough energy is supplied to the atom to completely remove the electron, we end up with a
H ion and an e- . When these two particles recombine (H+ + e– → H), the e- can initially find itself in a
state corresponding to any value of n, leading to the emission of many lines.
n(n−1)
Maximum no. of Spectral lines in H when e- excite to nth level = , n = higher energy level and e-comes to
2
ground state (n-1) lower energy level.
When an e- returns from n2 to n1, no. of spectral lines
produced= (n2 - n1)(n2 - n1+1)/2
The intensities of spectral line decreases with increase in the
value of n.
The intensity of Ist Lyman line (2→1) is greater than 2nd (3→1).
The lines in each series crowd together as they converge
toward the series limit which corresponds to ionization
of the atom and is observed as the beginning of the
continuous emission.
Ionization energy of H (from its ground state) is 1312 kJ mol–1.
Rydberg’s Formula –introduced by Ritz = 1/λ =R 1/n12 -1/n22]Z2, R= Rydberg’s constant =109677 cm-1
Series of H Spectrum–

Spectral Series Spectral region n1 n2¿ n1 =1/ λ = RH[1 /n2-1/n22]

Lyman U-V region 1 2,3….∞ RH[1 /12-1/n22]
Ballmer visible region 2 3,4….∞ RH[1 /22-1/n22]
Paschen I-R region 3 4,5….∞ RH[1 /32-1/n22]
Bracket I-R region 4 5,6….∞ RH[1 /42-1/n22]
Pfund I-R region 5 6,7….∞ RH[1 /52-1/n22]
Humphrey Far infra-red region 6 7,8….∞ RH[1 /62-1/n22]

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All lines in the visible region are of Ballmer series but all Ballmer lines will not fall in visible region.
First line of a series – called line of longest wave length or line of shortest Energy.
For first line n2 = n1 + 1 similarly for 2nd line n2 = n1 +2, 3rd line n2 = n1 +3,
For4th line n2 = n1+ 4 respectively,⊽ first =1/ʎ first = R [1/n12 – 1/(n1+1)2] z2.⊽ =1/ʎ = R [1/n12 – 1/(n1+X)2] z2
Last line of a series or Series limit –Line of shortest wave length or line of highest energy.
For last line n2=∞ , ⊽Max = 1/ʎ last =R[1 /n12-1/α2] z2 = Rz2 /n12
Lyman limit= Rz2/12, Ballmer limit=Rz2 /22, Paschen limit= Rz2/32,
Bracket limit= Rz2/42, Pfund limit=Rz2/52, Humphrey limit=Rz2/62

6563A°-Hα /4862A°-Hβ/4341A°-H√/4102A°-Hᵟ - Balmer series contains 4 important lines

The solar Fraunhofer spectrum contains thousands of lines that show the presence of 67 elements in the cooler
layers of the solar atmosphere.
Sources of different kinds of radiations –
1. UV Radiations Absorbed by the ozone layer of the
1 H1/1D2 discharge /Hg vapour lamp Quartz filter
atmosphere
2. Visible Radiations Incandescent W filament lamp
3. IR Radiations Nernst glower; mixture of rare gases heated to To treat muscular strain
1500-2000 ͦC
4. Globar SiC rod heated to1300-1700 ͦC
5. Radio waves For broad casting
6. X rays To detect fracture of bones
7) Somerfield’s Concept (Extension of Bohr’s theory) –
a) Electrons revolve in elliptical orbits in addition to circular orbits and the nucleus is situated at one of
the foci.
b) During motion of electron in a circle only the angle of revolution changes not the distance from the
nucleus but in elliptical motion both the distance from the nucleus as well as angle of revolution
changes.
c) The distance from the nucleus is termed as radius vector and the angle of revolution is termed as
Azimuthal angle.
d) The tangential velocity of the electron at a particular instant can be resolved into two components,
one along the radius vector called radial velocity and the other perpendicular to the radius vector
called transverse of angular velocity.
e) These two velocities give rise to radial momentum and the angular or Azimuthal momentum.

f) Somerfield proposed that both the momentum must be integral multiples,

Radial momentum = nr h/2π, Azimuthal momentum = nφ h/2π

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The brief explanations of Somerfield’s model are as follows –

i) Somerfield model gives introduction of elliptical orbitals.
iii) Bohr’s circular orbit has been considered to be a special case of an elliptical orbit, in which the
length of major and minor axis is same.
iv) Only one coordinate angle of revolution φ is variable in circular orbit but in elliptical, vector
radius r is also variable.
v) Introduction of Azimuthal quantum number in addition to principal quantum number.
vi) Angular momentum of an electron moving around elliptical orbit is the sum of two vectors
termed as follows – P = Pr + Pφ
vii) Introduction of subshells and sub energy levels within principal energy levels. These were
considered to have different energies.
viii) Subshells are termed as s, p, d, f (sharp, principal, diffused, fundamental).
ix) These subshells were considered to have capacity of 2, 6, 10, 14 electrons respectively.
x) Energies of these subshells follow the order s < p < d < f
xi) The relation between principal and Azimuthal Q NO is – n/l = length of major axis/ length of
minor axis.
xii) The subshell (s, p, d, f) in principal energy level have very slight difference in their energies. The
spectral lines corresponding to the transition of electron in their subshells have fine structure.
8) QUANTUM OR WAVE MECHANICAL MODEL OF ATOM–Schrodinger (1976)
Based on the de Broglie’s dual nature of radiation and Heisenberg’s uncertainty principle (wave nature).
Bohr’s Atomic model developed on the basis of Planck’s quantum (particle nature) theory of radiation.
Movement of e¯ around the nucleus is like that of a bee around the hive. Sometimes it may come close
to the nucleus and sometimes it may move away from it. It doesn’t move in one plane (by Bohr) but
moves in all directions and in all planes around the nucleus.
Postulates of Schrodinger quantum or wave mechanical model of atom- Energy of electrons - be
quantized.

i) ∆X and ∆P can’t be determined simultaneously with certainty (HUP).

ii) An atomic orbital is the wave function (Orbit - 1d) (psi) for an e- in an atom, means e-occupies
that orbital and many such wave functions (orbitals-different energy) are possible for an e -.
iii) Probability of finding an electron at a point with in an atom is proportional to the [ᴪ] 2 (Square of
the wave function). [ᴪ] 2 (Orbital – 3d) = Probability density and is always positive.
iv) Existence of quantized electronic energy levels is the direct result of the wave like properties of
electrons and is allowed solutions of Schrodinger wave equation.

( wave Function)(1d) ψ2 (Probability Density) (3d)

may have both +ve & -ve sign, which refers to sign Always +ve sign.
An atomic orbital may be defined as the 3 d
of wave function in various lobes and not to nuclear
spaces around the nucleus within which the

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possibility of finding an e- is 90-95% (node – 90-
or electronic charges.
90% (max.)
The +ve sign represents one phase & -ve sign The probability of finding the e- does not become
represents the second phase of the wave function zero even at very large distance from the nucleus.
𝛹 gives the amplitude of the In other words, 𝛹² determines the probability of
In the physical sense
finding the moving e¯ in a given regions.
wave associated with the electron.
𝛹 has no physical significance. Physical significance of 𝛹2 - In case of light
waves, the square of amplitude of the wave at a
point is intensity of electron at any point.

Louis de Broglie (1924), Heisenberg (1927) and Schrodinger (1930) gave a formula to calculate the
energy state of the electron. According to them e¯ does not revolve in any orbit but there is a probability
of finding the e¯ in a certain region of space. To calculate the probabilities of finding the es¯ in an atom,
Schrodinger derived a wave equation
∂²Ψ ∂²Ψ ∂²Ψ 8π ²m
In three dimensions, the Schrodinger wave equation is: + + + (E-V) = 0 , where
∂ϰ² ∂⋋² ∂z ² h²
ϰ , y, z are three Cartesian (space) coordinates, Laplacian operators specifying direction & distance, m is
the mass of the e¯, h is plank’s constant, E is the total Energy , V (- Ze2/r) is the potential energy of the
e¯ and 𝛹 is the amplitude of wave Hamiltonian operators and is called wave function(contains 3 terms
∂²Ψ
n, l, m). refers to the second derivative of 𝛹 with respect to ϰ and so on.
∂ϰ²

The Solution of Schrodinger wave equations are known as wave functions (Ψ ). When the Schrodinger
wave equation is solved for an e¯ in a hydrogen atom, several solutions are obtained, out of which only
certain solutions are permissible, and are called Eigen’s function (atomic orbitals). Each permitted
solution corresponds to definite energy state and is called orbital.

Each orbital is considered as quantum mechanical analog of e¯ orbits as proposed by Bohr. In an atom or
molecule, only specific or definite energy states are permitted, it implies that an e¯ in an atom or
molecule can have only certain specific values of energy. In other words, the energy of e¯ in an atom is
quantized.

Schrodinger or Dirac equation in relativity - ∂² ∂² ∂²

+ + = -h2/8𝜋2m. V2+V =
∂ϰ² ∂ y² ∂ z²
,

Schrodinger wave equation

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Quantum chemistry- It’s a branch of theoretical chemistry which applies quantum mechanics and
quantum field theory to address problems in chemistry. One application of quantum chemistry is the
electronic behaviour of atoms and molecules relative to their chemical reactivity.

Quantum chemistry lies on the border between physics and chemistry. Quantum chemistry
mathematically describes the fundamental behaviour of matter at the molecular scale.

In quantum mechanics the Hamiltonian or the physical state of a particle can be expressed as the sum of
two operators one corresponding to kinetic energy and the other to potential energy. The Hamiltonian in
the Schrodinger wave equation used in quantum chemistry does not contain terms for the spin of the
electrons. An exact solution for the Schrodinger equation can only be obtained for H atom. Since all other
atomic or molecular systems, involve the motions of three or more particles, their Schrodinger equation
can’t be solved exactly and so approximate solution must be sought.

9) Heisenberg’s uncertainty principle → W. Heisenberg (1972) States that it is impossible to determine

momentum and position of a sub atomic particle precisely and simultaneously.
For microscopic particles, in accordance with wave theory of radiation.
Exact position or direction of motion and speed of motion of a ball rolling down the ramp can be
calculated exactly. We can’t do the same for an e- that exhibits wave properties, it can be made
indefinitely small, but there is an actual limit to the accuracy of measurements. Uncertainty in position
and momentum both decrease in case of large objects so Heisenberg’s uncertainty principle loses its
significance in case of large objects.
Mass ∝certainty in P, C, X (momentum, velocity, position), More the mass less will be the uncertainty in
its position and momentum.
A beam of photons strikes on a ball it doesn’t alter its position or momentum to any practical extent but
can alter the electron’s.
ΔX. ΔP ≥ h/4π, ΔX m ΔC ≥ h/4π, (ΔP = m ΔC),
ΔX = Uncertainty in position, m = Mass, ΔP = Uncertainty in momentum,
ΔX. Δ C ≈ 0.077 X 10-4 J sec/kg,
ΔX∝ 1/m, ΔC∝ 1/m

9) Shapes of orbitals –
(a) S orbital-spherical, non-directional.

(b) P orbital – dumbbell shaped, directional (3 degenerate orbitals)

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(c) d orbital -double dumbbell shaped, directional,(5 degenerate orbitals).

dxy (+/-2),dyz(+/-1), dxz (+/-1),dx2-y2 (+/-2),dz2(0).
In dz22 lobes along z axis only and ring of –ve charge surrounding nucleus in xy plane.

(d) f orbitals – 8 lobes with 3 nodal planes, complex shape (7 degenerate orbitals).

fx(x2-y2), fy(x2-y2), fz(x2-y2), fxyz, fz3, fyz2 ,fxz2

11) The Quantum Numbers- Bohr model introduced a simple Q. N. `n’ to describe an orbit. The
quantum mechanical model uses 3 Quantum numbers n, l, and m to describe an orbital. There are the
results of Schrodinger wave equation and each e- in an orbital is identified by its spin Q.no the e- in Bohr-
Somerfield model were later on characterized by the 4 Q. nos.
The Quantum numbers are the code numbers for an e- which tells us about the energy of the e-,
orientation and spin of the e-, distance of the e- from the nucleus, volume of the orbital, radius of orbit,
Shape of the sub shell in which e- is present, specify orbital angular momentum, size of energy level can
also be determined by all these Q nos.

1. Principal Q. No. –

Denoted by `n’ and given by Bohr, it tells us about the energy level of e-, distance of the e- from nucleus,
no. of shell in which e- is present, volume of orbital and radius of the orbit, size of energy level etc. (n= 1
to ∝)

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1 n²h²
rn For H atom is = or rn ∝n², 4πϵ o is permittivity factor ¿₀= 8.854 x 10-12 C² kg-1 m-3 s²
4 πϵo 4 me ² π ²

¯ 2 π ² me ⁴ 1 −21.77 x 10 ¯ ²² 13.7 1.312 x 10³

En = 2 2 or En∝ , En = KJ/atom En= - eV/atom = - KJ/
( 4 πϵo ) n h ² n ² n ² n ² n²
mol.

13.7
E₁ for H = -13.7 eV/atom, E₂ for H = - = -3.425 eV/atom
4

As the distance of the e- from the nucleus increases energy of e- also increases, at infinity it becomes 0.

2. Azimuthal/Subsidiary/Angular momentum Q. no.-

Denoted by l and given by Somerfield, it accounts for the appearance of groups of closely packed
spectral lines in electric field and the shape of subshell and orbital angular momentum of the electron

l = n -1 where n≤4, l= 0.1, 2, 3,

l = 0 for S¿ )- Sharp, l =1 for P (π) – Principal, l =2 for d (δ ) -diffused, l = 3 for f¿φ) – fundamental.

Energy level s¿ p<¿ d ˂ f.

h
Orbital angular momentum =
2π
√l ( l+ 1 )
Angular momentum =mvr = nh/2 π =moment of inertia x Angular Velocity, l =n-l, n ≤ 4

3. Magnetic Q. no. – denoted by `m’ given by Lande. It tells us about the orientation / location of an e -,
m = 2 l + 1. In the absence of magnetic field 3 orbitals of p subshell as equivalent in energy and are
called threefold degenerate orbitals. m = 2 l+1. The values of m lie from ±l to±l through 0. Zeeman
proposed the concept of sub subshells in a subshell but of same energy level. He noticed that each
fine spectral line splits up into more than one component of nearly same wave length.
This splitting of spectral lines in magnetic field is called Zeeman spin magnetic moment respectively.
The Stark’s and Zeeman’s effects are explained by MQN.
4. Spin Q. No. - denoted by `s’ given by Hollenbeck and Gold Schmidt, it tells us about the spin of e -.
1 1
The spin may be clock wise↑ (+ )or anti-clock wise↓ (- ) S= +1/2 or – 1/2)
2 2
Spin Ang. Momentum(mvr or s =h/2π√ s((S+1),

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-
PQN determine the approximate energy of an e in case of multi electron atoms but gives exact
energy of e- of H-atom.
Maximum number of e- in an orbit = 2n², n = PQN, Maximum no. of orbital in an orbit = n²
10) Rules For writing Electronic Configuration
i) Aufbau principal –“Moeller”, German word building up Moeller gave the order of energy levels.

The energy of atomic orbital for H atom is (as the energy depends on value of n):
1s<2s=2p<3s=3p 3d<4s=4p=4d=4f.

ii) HUND’S RULE OF MAXIMUM MULTIPLICITY OF e ¯ –

When 2 electrons are in a particular orbital then they have maximum electrostatic repulsion and
to avoid this electron tends to be alone or tends to be maximally singly filled in orbitals or tends
to be maximally multiple. When all orbitals are completely half filled the es¯ in a subshell must
have parallel spin.

This corresponds to a state of lower energy. This can be explained in terms of magnetic effects of e¯
spins. Two es¯ in a particular orbital feel greater electrostatic repulsions, and hence while filling of
orbitals of equal energy, pairing of es¯ is avoided as it is possible and e¯ tends to have total spin
maximum (i.e. max multiplicity)(This keeps them further apart and lowers the energy through electron
exchange or resonance.

iii) Pauli’s exclusion principle-

Electrons in an orbital must have opposite spin. Maximally 2 es- can be accommodated in an orbital.

No two electrons in the same atom can have the same set of quantum numbers (n, l, m, and s).
One-electron atoms
Single electron exhibits a standing wave pattern governed by the quantum numbers n=1, m=0 and l=0,
with the spin quantum number s undefined because there is no other electron to compare it with. The
most important feature of a single-electron atom is that the energy of the electron depends only on the
principal quantum number n. The quantum numbers l and m have no effect on the energy; Thus the
emission spectrum produced by exciting the electron to the n=2 level consists of a single line, not four
lines. The wavelength of this emission line for the atoms H, He+ and Li2+ will diminish with atomic number
because the greater nuclear charge will lower the energies of the various n levels. For the same reason,
the energies required to remove an electron from these species increases rapidly as the nuclear charge

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increases, because the increasing attraction pulls the electron closer to the nucleus, thus producing an
even greater attractive force.
Electron-electron repulsion is a major factor in both the spectra and chemical behavior of the elements
heavier than hydrogen. In particular, it acts to "break the degeneracy" (split the energies) of orbitals
having the same value of n but different l.

The energies of the 1s orbitals fall rapidly as Z increases. The fall in energies of the 2s orbitals is smaller owing to
electron-electron repulsion. The 2p orbitals have a node at the nucleus and are less affected by Z but are more
affected by electron repulsion, so they remain higher than the 2s orbitals.
It takes 1312 kJ of energy to remove the electron from a mole of hydrogen atoms. Helium contains two electrons,
but its nucleus contains two protons; each electron "sees" both protons, so we might expect that the electrons of
helium would be bound twice as strongly as the electron of hydrogen. The ionization energy of helium should
therefore be twice 1312 kJ/mol, or 2612 kJ/mol. However, if one looks at the spectrum of helium, the continuum is
seen to begin at a wavelength corresponding to ionization energy of 2372 kJ/mol, or about 90% of the predicted
value.
The principle, which is a consequence of the electrostatic repulsion between electrons, is known as
Hund's rule.

Extra stability of half and completely filled orbitals-

a) due to greater exchange energy

b) due to greater symmetry

Cause of stability of orbitals –

Cause of stability of orbitals in terms of lowering of energy due to the exchange

energy for a set of two electrons of parallel spins. The exchange energy results from the required
exchange ability of coordinate systems two electrons with parallel spin remains further apart than two
electrons with opposite spins and consequently the columbic repulsion energy is lower.

Lowering of energy = Total number of possible exchangeable coordinates between sets of two electrons
of parallel spin Χ Average exchange energy.
K % of parallel spins in Cr 4S2, 3d4 - 4+ 3+ 2 +1= 10 K and in 4S1, 3d5 – 5+4 +3+ 2 +1= 15 K
Lowering of energy due to 15 possible sets= 15K, greater so it is more stable as compared to 10 K.

Concept map -

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11) Cathode rays -Discovery – William Crooks (1879)

a) Production- Initially originate from the metal (cathode), also formed due to bombardment of the
molecules of the gas, inside the discharge tube by the high-speed particles (e-) which are emitted
from the Cathode but after some time they start originating from the space between cathode &
anode.
i) Normal pressure, 1 atm, even at high voltage, nothing is observed.
ii) If pressure= 0.001 atm, gas emits light, and colour of light depends upon the nature of the gas.
iii) If P = 10-4 atm, Walls of discharge tube opposite to Cathode starts glowing with a faint greenish
light called fluorescence, it is due to bombardment of the glass walls of the tube by the rays
emitted from the cathode, and are called cathode rays.

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Properties- studied by Sir J J Thomson-

a) Travels in a straight line.

b) Rotates a light paddle wheel (mechanical energy).
c) Made of negatively charged material particles, deflected (in both electric & magnetic field) towards
positive electrode.
d) Causes ionization of gases means are charged.
e) Affects photographic plate known as fogging.
f) Produces heating effect when made to strike on a metal foil.
g) Can easily penetrate thin metal foils e.g., Al.
h) X-rays are produced due to secondary effect of cathode rays, when they strike on surface of hard
metals such as W, Cu, Mo et cetera.
i) When strike against the glass surface or screen coated with zinc sulphide produce fluorescence
(glow).

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Anode/ Canal/Positive rays - When high speed cathode rays strike, molecules of a gas placed in the
discharge tube, they knock out one or more es- from it, and results in formation of positive ions in the
space between anode and cathode. These positive ions pass through the perforated Cathode and appear
as positive rays. When electric discharge is passed through the gas under high pressure, its molecules are
dissociated into atoms and the positive atoms (ions) constitute the positive rays.

Electron Proton
Attracted towards anode Attracted towards cathode
Attracted towards south pole Attracted towards north pole

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