Spark MDCAT [CLICK HERE TO ORDER] Atomic structure

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure

Chapter 02:
Atomic Structure
PM&DC Syllabus
2.1 Define photon as a unit of radiation energy.
2.2 Describe the concept of orbitals.
2.3 Distinguish among principle energy levels, energy sub-levels, and atomic orbitals.
2.4 Describe the general shapes of s, p, and d orbitals.
2.5 Use the Aufbau Principle, the Pauli Exclusion Principle, and Hund's Rule to write the electronic
configuration of the atoms.
2.6 Write electronic configuration of atoms.

NUMS syllabus
a. Concept of orbitals b. Electronic configuration
c. Discovery and properties of proton (positive rays) d. Quantum numbers
e. Shapes of orbitals

Chronological Development towards Atomic Structure

 From Democritus, our ideas about structure of atom have gone radial changes over time.
 William Crooks, in 1879, discovered cathode rays which led J.J Thomason to the discovery of electron
in 1897.
 J.J Thomson put forth his Plum-Pudding theory, according to which atoms were solid spheres of
positive charges with tiny negative particles stuck inside.
 In 1886, Eugene Goldstein discovered canal rays which led to the discovery of positive particles in
atom. Rutherford called them proton.
 Rutherford, in 1920, predicted the presence of some neutral particles in atom whose mass must be
equal to the mass of proton because mass of electron and proton alone could not account for the mass
of whole atom.
 James Chadwick discovered neutrons in 1932 by artificial radioactivity.
 It was a nuclear fusion reaction of 24He and 49Be nuclei.
 Anderson discovered positron (anti-electron) in the same year 1932 from cosmic rays.
 In 1911, Ernst Rutherford presented his planetary or nuclear model from his gold foil experiment on
the basis of Maxwell’s Classical theory of electromagnetic radiation.
 Rutherford’s model was the first proper atomic model, but it did not account for the stability of atom
and atomic structure would collapse in 10-8s.
 A Danish chemist Neil Bohr presented his model for mono-electron systems in 1913 on the basis of
Max Plank’s Quantum theory given in 1900.
 In 1915, Sommorfeld suggested the moving electrons must describe, in addition to circular orbits,
elliptic orbits as well, wherein the nucleus lies at one of the foci of the eclipse.

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure

 Finally, in 1926, Quantum Wave mechanical model was proposed by Erwin Schrödinger.

Model / Theory Date Basis Atomic Composition

Democritus’s idea 485 B.C No experimental basis. Atoms are indivisible.
Dalton’s atomic theory 1808 Law of conservation of mass Atoms are indivisible.
and law of definite/constant
proportions.
Thomson’s plum pudding 1904 Uniform distribution of mass. Positive charge with tiny
or water melon theory negative particles stuck inside.
Rutherford’s atomic 1911 Maxwell’s classical theory of Nucleus (proton) and electron.
model electromagnetic radiation.
Neil Bohr’s atomic model 1913 Max Plank’s Quantum theory. Proton and electron.
Sommorfeld atomic model 1915 Three-dimensional motion of Electron, proton and neutron.
electron.
Schrödinger’s wave 1926 Wave mechanics. Electron, proton and neutron.
mechanical model

Discovery of Electron (Cathode Rays - 1879)

 A gas or vapour is filled in a discharge tube connected to a high voltage source.

 The exact voltage required for discharge depends on the length of the tube and pressure inside the tube.
 At ordinary pressure, gases do not conduct electricity due to frequent collisions (hindrance) between
gas molecules.
 Conductivity is inversely related to pressure:
Pressure ∝ Hindrance ∝ Resistance ∝ 1/Conductivity
 At low pressure and voltage between 5,000–10,000 V, electric discharge is observed.
 If the pressure is reduced below 0.01 torr, the discharge disappears.
 Under optimal conditions, rays are emitted from the cathode and travel toward the anode.
 These rays cause fluorescence (glow) when they strike the walls of the tube.
 The colour of the glow depends on the composition of the glass of the discharge tube.
 The electric field between the cathode and anode is the driving force behind the emission of cathode
rays.

Properties of Cathode rays

 J. Perrin (1895) observed that cathode rays were deflected by magnetic fields, proving they are charged
particles.
 J.J. Thomson (1897) showed cathode rays are negatively charged as they deflect towards the positive
plate in an electric field.
 Thomson used simultaneous electric and magnetic fields to measure the charge-to-mass (e/m) ratio of
cathode rays.
 He adjusted both fields to cancel each other’s effects, allowing accurate measurement.
 The e/m value he found was 1.7588 × 10¹¹ C/kg = 1.7588 × 10⁸ C/g = 1.7588 × 10⁵ C/mg.
 Cathode rays travel in straight lines, confirmed by casting sharp shadows.
 A paddle wheel placed in their path moves, proving cathode rays are particles with mass and velocity.
 They produce X-rays when hitting metals of high atomic number, due to energy released as
electromagnetic radiation.
 Cathode rays produce heat when striking matter; e.g., Pt foil glows when focused rays fall on it.
 They ionize gases by knocking out electrons: M + 1e⁻ → M⁺ + 2e⁻.

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
 They have a reducing effect and can bring about chemical changes.
 Cathode rays can penetrate thin aluminium or gold foil, showing penetration power.
 The same e/m ratio in all setups proved cathode rays are identical electrons.
 Thomson showed that all atoms contain electrons.
 Stoney, an American chemist, named these particles electrons.
 The nature of cathode rays is independent of the type of gas, cathode/anode material, voltage, or
discharge tube.
 R.A. Millikan (1909) determined the electron's charge through his oil drop experiment.
 He found the charge to be 1.59 × 10⁻¹⁹ C, close to the modern value of 1.6022 × 10⁻¹⁹ C.
 He proved this is the smallest unit of electric charge.
 These findings confirmed that electrons are basic, negatively charged particles found in all atoms.

Target Constitute Effect of cathode rays

i. Discharge tube Treated glass Greenish fluorescence
ii. Rare earth metals f-block elements Fluorescence / Luminescence
iii. Alumina Al2O3 Glows red
iv. Tin stone SnO2 Glows yellow

Discovery of Proton (Positive Rays - 1886)

 In 1886, German physicist Eugene Goldstein discovered canal rays by taking a discharge
tube having perforated cathode.
 These rays do not originate from anode.
 These rays are produced by oxidation of gas molecules in
the discharge tube.
 Cathode rays strike the residual gas molecules and knock
out their electron as :
M (g) + 1e- → M+ (g) + 2e-
 These positive ions start moving towards cathode (-), canal
or pass through the perforations in cathode and produce a
glow on the wall of discharge tube.
 Positive rays can be produced by :

Chemical species Equation

-
1) Atoms Ne (g) + 1e → Ne+ (g) + 2e-
2) Ions He+ (g) + 1e- → He2+ (g) + 2e-
3) Molecules O2 (g) + 1e- → O2+ (g) + 2e-

 The most feasible spot for the production of positive rays is the middle of discharge tube between
cathode and anode.
 There are no chances of their production from electrodes or at the backside of electrodes.

Properties of Canal Rays / Positive Rays or Channel Rays

1. Deflection by Electric and Magnetic Field :
 They are deflected by the magnetic field perpendicular to the field showing that they are
charged.
 They are deflected towards negative plate in an electric field showing that they are positively
charged.
(Note that charge detector in chemistry is electric field.)
2. Direction of Travel : These rays travel in straight line opposite to the cathode rays.
3. Fluorescence :
 They produce a glow on the wall opposite to anode (backside of cathode).
 They produce flashes on ZnS plate.
4. e/m Value :
 Their mass is greater than that of cathode rays or electrons.
 So, their e/m value is less than e/m value of electrons or cathode rays.
5. Nature of Canal Rays :

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
 The nature of canal rays depends upon the nature of gas present in the discharge tube.
 Lighter is the gas, greater is its e/m value and vice versa.

 Order of e/m value :

e- = e+> p+> He2+ = (D+ or 21H+) > (0n1 = 0)
 For neutron :
I. e/m ratio is zero.
II. m/e ratio is infinity. (∞)
 Mass of proton is 1836 times greater than that of electron.
 Thus, e/m of proton is 1836 times less than e/m of electron.
 The nature of canal rays is independent of the material of glass tube, metal of electrodes,
perforations in cathode and applied voltage.
6. Discovery of Proton :
 Different gases produce canal rays of different nature.
 Canal rays produced by helium has are called as α-particles (He2+).
 The canal rays produced by hydrogen gas are the lightest and hence have highest e/m.
 They were called proton by Rutherford in 1911.

Discovery of Neutron (Artificial Radioactivity - 1932)

 Proton and electron were discovered before 1895 and thought to be the only components of atom
till 1932.
 Rutherford (1920) proposed the existence of neutral particles due to unexplained atomic mass.
 In 1932, James Chadwick discovered the neutron and won the Nobel Prize in 1935.

 In the experiment, alpha particles from polonium were directed at a beryllium target.
 The reaction emitted neutral particles later identified as neutrons. ₂⁴He + ₄⁹Be → ₆¹²C + ₀¹n
 This reaction is a type of nuclear fusion and part of artificial radioactivity.
 The white surface of beryllium turned blackish due to C-12 formation.
 Order of penetration: Neutron > Electron > Proton > Alpha particle.
 Neutrons are unstable compared to protons and electrons.
 A free neutron decays into a proton, electron, and neutrino (Anti-neutrino in physics):
₀¹n → ₁¹p + ₋₁⁰e + ₀⁰n.
 Neutrons cannot ionize gas due to neutral charge.
 They can expel high-speed protons from hydrogen-rich substances like paraffin and water.
 Neutrons are highly penetrating and have mass 1843 times greater than electrons.
Energy Effectiveness for fission Target Ejects Product
Fast Neutron 1.2 MeV Less effective N – 14 α-particle B – 11
Slow Neutron Below 1 eV More effective Cu - 65 γ - rays Cu – 66 *
 Fast neutrons can induce nuclear reactions like: ₇¹⁴N + ₀¹n → ₅¹¹B + ₂⁴He.
 The above is not alpha decay but a nuclear reaction using fast neutrons.
 Slow neutrons hitting copper metal cause emission of gamma radiation: ₂₉⁶⁵Cu + ₀¹n → ₂₉⁶⁶Cu +
₀⁰γ.
 Gamma emission in this context is not gamma decay as atomic numbers remain unchanged.

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
 Radioactive copper undergoes beta decay: ₂₉⁶⁶Cu → ₃₀⁶⁶Zn + ₋₁⁰e.
 Neutrons are used in cancer treatment due to their strong biological effects.

Particle Discoverer Year Experiment performed Process involved

I. Electron J.J Thomson 1897 Discharge tube experiment Thermionic emission
II. Proton Eugene Goldstein 1886 Discharge tube experiment Oxidation
III. Neutron James Chadwick 1932 α-particle bombardment Nuclear fusion

Properties of Sub-atomic Particles

- Proton Neutron Electron Positron α-particle

(1) Charge (C) +1.6022 x 10-19 0 -1.6022 x 10-19 +1.6022 x 10-19 +3.2044 x 10-19
(2) Relative Charge +1 0 -1 +1 +2
(3) Mass (kg) 1.6726 x 10-27 1.6750 x 10-27 9.1095 x 10-31 9.1095 x 10-31 6.644 x 10-27
(4) Mass (amu) 1.0073 1.0087 5.4858 x 10-4 5.4858 x 10-4 4
-
(5) Heavier than e 1836 times 1843 times Equal Equal 7344 times
(6) e/m ratio +1 0 -1 +1 +2
(7) m/e ratio +1 ∞ -1 +1 +1/2
(8) e/m (in SI) 1 x 108 0 1.7588 x 1011 1.7588 x 1011 4.82 x 107
-1
C kg

Planck’s Quantum Theory (1900)

 Max plank proposed quantum theory in 1900 to explain both :
i. Absorption of radiation. ii. Emission of radiation.
 A wave can be described by its 4 parameters :
1. Energy (E) 2. Frequency (𝑣) 3. Wavelength (𝜆) 4. Wave number (𝑣̅ )
 This theory explains the corpuscular or particle nature of light.

Difference between a wave and particle

(1) A wave has zero rest mass. (1) Particle has non-zero rest mass.
(2) Wave is distributed in space. (2) Particle is localized in space
(3) It is justified by its wave function. (3) It is justified by its coordinates.

I. Concept of wave packets :

 Energy is not emitted or absorbed continuously.
 Rather, it is absorbed or released in a discontinuous manner in the form of wave
packets.
 A body can emit or absorb energy only in terms of quanta.
 Each wave packet or quantum has a definite amount of energy associated.
 In case of light, quantum of energy is called photon.
II. Relation between energy and frequency :
 Frequency (𝑣) is the number of vibrations or cycles per second.
 It is the number of waves passing through a point per second.
 It is purely a source parameter.
 Its units are hertz. In SI, 1 Hz = 1 s-1.
 The amount of energy associated with the quantum of radiation is directly proportional to
the frequency of radiation.
E ∝ 𝒗

E = 𝐡𝒗
Where, h is Plank’s Constant 6.626 x 10-34 J s. It is, in fact, ratio of energy and frequency of a wave.
h = 𝐄
𝒗
III. Relation between energy and wavelength :
 Wavelength is the distance between two adjacent or consecutive crests or troughs.
 It represents the distance between two similar points on a wave.

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
.
c = 𝒗𝜆 ⇒ 𝒗 = 𝐜
𝜆
.
E = h𝒗 ⇒ E = 𝐡𝐜
𝜆
 Wavelength is expressed in Å.
i. 1 Å = 10-10 m ii. 1 nm = 10-9 m iii. 1 pm = 10-12 m
 Greater the wavelength associated with the photon, smaller is its energy.
IV. Relation between energy and wave number :
 Wave number (𝑣̅ ) is the number of waves per unit length.
1
 It is the reciprocal of wavelength. (𝑣̅ = )
𝜆
. .
E = 𝒉𝐜 ⇒ E = ̅
𝒉𝐜𝒗 ⇒ E ∝ ̅
𝒗
𝜆
 Greater the wave number, greater the energy associated with the wave and vice versa.
V. Relation between energy and amplitude :
 Energy of a single wave is given by its amplitude.
 Amplitude is the maximum displacement of a wave on the either side of its mean position.
 Greater is the amplitude, greater is the energy.
Summary :
1
Energy (E) ∝ Frequency (𝒗) ∝ ̅)∝ Amplitude (xo)
∝ Amplitude (𝒗
Wavelength (𝛌)

Bohr’s atomic model

 In 1913, Bohr's atomic model was proposed based on Planck's quantum theory.
 Bohr stated that the atom consists of a nucleus with protons, and electrons revolve around it in fixed
orbits.
 Neutrons were not part of this model as they were discovered later in 1932.
 Electrons move in circular orbits, each assigned a principal quantum number and having a fixed
energy.
 These orbits are equivalent potential surfaces, so electrons in them do not radiate energy while
revolving.
 Energy is emitted or absorbed only when an electron jumps between orbits: ΔE = E₂ – E₁ = hv.
 An electron moving from an outer to inner orbit releases energy; from inner to outer, it absorbs energy.
 This angular momentum is quantized, and electrons cannot exist between orbits.
Angular momentum:
 The value of angular momentum (mvr) depends upon principle quantum number of orbit.
 Its units are same as Plank’s constant i.e., 6.626 x 10-34 J s. (1 J s = 1 kg m2 s-1)
mvr = nh
2π
 For sub-shell, angular momentum depends upon azimuthal quantum number (𝑙)

mvr = h
√l (l+1) 2π
Radius: r = 0.529 (n2) Å
r = ∈o n2 h2
π m Ze2
r2 – r1 < r3 – r2 < r4 – r3 < r5 - r4 < ...
 Radius is inversely proportional to the square of velocity.
 Electron moves fast nearer to the nucleus.
 When electron makes a transition to higher orbits, it becomes slow.
Energy:
E = − m Z 2 e4
2
8 ∈o 2 n2 h

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
 Thus, the total energy of an electron in an atom is negative.
 Note that the energy of a free electron w.r.t nucleus is zero.
Putting values in above expression of energy, we get :
1
E = − 2.178 x 10-18 2 J/atom
n
If we multiply it with Avagadro’s number and divide by 1000, we get energy in kJ/mol.
23 −18 1
E = − 6.02 × 10 × 2.178 × 10 x
1000 n2
𝟏
E = − 1313.31 x kJ mol-1
𝐧𝟐
 The differences in the values of energy go on decreasing from lower to higher orbits.
E2 – E1 > E3 – E2 > E4 – E3 > E5 - E4
 Energy difference between first and infinite level gives ionization energy as :
I.E = E.∞ - E1 = 0 – (-1313.31) = +1313.31 kJ mol-1

Spectrum
 Spectrum is the dispersion of white light into different wavelengths when passed through a prism.
 It is a visual display of light showing its wavelength composition.
 Light rays refract when passed through a prism, and their bending depends on wavelength.
 Longer wavelength bends less, and shorter wavelength bends more.
 White light contains all visible wavelengths from 400 to 750 nm.
 The order of colors is VIBGYOR, from violet (high energy) to red (low energy).
 As wavelength increases, energy, frequency, and wave number decrease.
 There are two types of spectra: Continuous and Line (Discrete) spectrum.
1. A Continuous spectrum has
no sharp boundaries; colors
merge smoothly.
 It is produced by sunlight or
incandescent bulbs and
shows matter in bulk.
2. Line/Atomic spectrum shows
distinct lines separated by dark
regions.
 It is the property of individual
atoms, not matter in bulk.
 Sodium line spectrum shows
two yellow lines; hydrogen
has many lines.
 As wavelength decreases,
spectral lines get closer, and
spectrum appears
continuous.
 Atomic spectra appear when
atoms are heated or
subjected to electric
discharge.
 There are two types of atomic spectra: Emission and Absorption.
i. In Atomic Emission Spectrum (AES), excited electrons fall back and emit radiation.
It appears as bright lines on a dark background and gives info about source.
ii. In Atomic Absorption Spectrum (AAS), some wavelengths are absorbed by atoms.
Absorption spectrum has dark lines on a bright background and gives info about
absorbent.

Spectral series Lower orbit (n1) Higher orbit (n2) Region Spectrum observed
i. Lyman 1 ≥2 Ultraviolet Emission and absorption

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
ii. Balmer 2 ≥3 Visible Emission only
iii. Paschen 3 ≥4 Infrared Emission only
iv. Brackett 4 ≥5 Infrared Emission only
v. Pfund 5 ≥6 Infrared Emission only

 Balmer series is the only spectral series that can be observed by naked eye except Hα-line of Balmer
series.
 The bluish light emitted in hydrogen spectrum falls in Balmer series.
 The first four series were discovered before Bohr (1913).
 When we move from Lyman to Pfund series, energy, frequency and wave number of spectral line
decreases while wavelength increases.
 The energy of the largest line (limiting line) of the series next is even smaller than the energy of the
smallest line of the spectral series before it, and vice versa for wavelength.
 For example : the energy of the largest line of Balmer series (limiting line) is even less than the
energy of the smallest line of Lyman series.
Similarly, the energy of the largest line of Paschen series is even less than the energy of the smallest
line of the Balmer series.
 The spectral lines of Lyman series are produced when the electron jumps from higher orbit n2 = 2 , 3 ,
4 , 5 … to first orbit n1 = 1.
 Lyman did not know the reason of their production.
 Similarly, spectral lines of Balmer series discovered in 1887 originate when electron jumps from
any higher orbit n2 = 3 , 4 , 5 , 6 … to second orbit n1 = 2.
 In the same way, Paschen, Brackett and Pfund series of lines are produced as a result of electronic
transition from higher orbits to 3rd, 4th and 5th respectively.
 Only the lines of Balmer series have been given specific names :
1. Hα Line : When electron jumps from n2 = 3 to n1 = 2.
2. Hβ Line : When electron jumps from n2 = 4 to n1 = 2.
3. H.𝜸 Line : When electron jumps from n2 = 5 to n1 = 2.
When electron jumps from n2 = 6 to n1 = 2.
4. Hδ Line :
 Order of energy : Hα<Hβ<H.𝜸 <Hδ< …
 Limiting line of Lyman series is obtained when electron jumps from infinite orbit to n = 1.
 Similarly, limiting lines of Balmer, Paschen, Brackett and Pfund are developed when electron jumps
from n2 = ∞ to n1 = 2 , 3 , 4 and 5 respectively.
 Limiting line is the line of the highest energy in respective series.
Important information:
 Balmer series lies in visible region partly.
 The limiting line (Hlimit.) of Balmer series lies in UV region, other lines fall in visible region.
 Only limiting line of Balmer series cannot be observed with naked eye.

Calculations of Frequency of Photon of Spectral Series

m Z2 e4 1 1
𝑣 = [ − ]
8 ∈o 2 h3 n21 n22
 The above equation gives the frequency of the photon emitted when an electron jumps from higher
orbit n2 to any lower orbit n1
 The frequency values go on decreasing between the adjacent levels.
𝑣2 − 𝑣1 > 𝑣3 − 𝑣2 > 𝑣4 − 𝑣3 > ⋯

Calculation of Wave number (𝒗̅ ) and Rydberg Constant (1.09678 x 107 m-1)
m Z2 e4 1 1
𝑣̅ = [ − ]
8 ∈o 2 h3 c n21 n22
m Z2 e4
 The factor is called Rydberg constant.
8 ∈o 2 h 3 c
m e4
 Since Z = 1 for hydrogen, Rydberg constant for hydrogen RH =
8 ∈o 2 h 3 c
 Rydberg constant for hydrogen RH has a value of 1.09678 x 10 m-1. 7

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 Rydberg constant for element with atomic number Z (RZ) is Z2 times RH.

The expression of wave number for hydrogen atom thus becomes :

1 1 1 1
𝑣̅ = R H [ − ] = 1.09678 x 107 m-1 [ − ]
n21 n22 n21 n22

Defects of Bohr’s Atomic Model

1. Spectrum of Poly-Electron System :

 Bohr’s theory can successfully explain the origin of the spectrum of mono-electron systems like H-
atom and ions like 2He+, 3Li2+, 4Be3+, etc.
 This theory is not able to explain the origin of the spectrum of multi-electron or poly-electron system
like He, Li, Be, etc.
Remedy :Schrödinger’s wave mechanical model (1926).

2. Fine Structure or Multiple Structure :

 When the spectrum of hydrogen gas is observed by means of a high resolving power spectrometer,
the individual spectral lines are replaced by several very fine lines.
 The original line is seen divided into other lines.
 The Hα line in the Balmer series is found to consist of five component lines.
 This is called Fine Structure or Multiple Structure.
 The appearance of several lines in a single line suggests that only one quantum number is not
sufficient to explain the origin of various spectral lines.
Remedy :Azimuthal quantum number.

3. Three – dimensional motion of Electron :

 Bohr suggested circular orbits of electrons around the nucleus of hydrogen atom.
 Researchers have shown that the motion of electron is not in a single plane.
 It takes place in three-dimensional space due to which atomic model is not flat.
Remedy :Sommorfeld atomic model (1915).

4. Zeeman and Stark Effect :

I. Zeeman Effect :When the excited atoms of hydrogen are placed in magnetic field, its spectral
lines are further split up into closely spaced lines. This is called Zeeman Effect.
For Example :If the source which is producing Na-spectrum is placed in a weak magnetic field, it
causes the splitting of two lines of Na into component lines.
II. Stark Effect : When the excite hydrogen atoms are placed in electric field , then similar splitting
of spectral lines takes place which is called Stark Effect.
Important points :
 Bohr’s theory does not explain either Zeeman or Stark Effect.
 Note that Zeeman and Stark effect both can be observed by emission spectrum of hydrogen.
Remedy : Magnetic Quantum number.
Mnemonic: Stark look like Sparks means electric, Zeeman has ‘m’ so magnetic

Wave Particle Nature of Matter – 1924 (Dual Nature of Matter)

 Light shows a dual character.
 It behaves both as a material particle and as a wave.
 According to de-Broglie, all matter particles in motion have a dual character.
 It means that electrons, protons, neutrons, atoms and molecules possess the characteristics of both
the material particle and a wave.
 This is called wave-particle duality in matter.

h h hv
𝜆 = = =
mv p 2 K.E

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
According to this equation, the wavelength associated with an electron is inversely proportional to its
momentum (p).

𝜆 ∝ p
1 1 1
𝜆 ∝ 𝜆 ∝ v
m
(for different particles moving (for particles of same mass
with same speed) moving with different speeds)
 If we imagine a proton moving in a straight line with the same velocity as mentioned for electron, its
wavelength will be 1836 times smaller than that of electron.
 Similarly, an α-particle moving with the same velocity should have a wavelength 7344 times smaller
as compared to that of electron.
 Heavy material particles also have waves associated with them, but they cannot be captured and we
say that the macroscopic bodies don’t have the waves.
1
Order of 𝝀 for some common particles moving with same speed :(𝜆 ∝ 𝑚 )
Electron = positron > proton > neutron > α-particle

Experimental Verification of Dual Nature of Matter (1927)

 In 1927, two American scientists, Davisson and Germer did an experiment to verify the wave nature
of moving electron.
 Electrons (e) were produced from heated tungsten filament.
 They were accelerated by applying the potential difference (V) through charged plates.
 Davisson and Germer proved that the accelerated electrons undergo diffraction, like waves, when
they fall on a nickel crystal.
 In this way, the wave nature of electron got verified.
 Davisson and Germer got the nobel prize for inventing an apparatus to prove the matter waves.
 De-Broglie got the separate nobel prize for giving the equation of matter wave.

Heisenberg’s Uncertainty Principle (1927)

 Itstates that it's impossible to measure both the position and momentum of an electron exactly at the
same time.
 Introduced by Heisenberg in 1927, it challenged the older Bohr Model of the atom.
 Bohr’s Model assumes electrons have definite paths and both position and momentum can be
measured accurately.
 Discovery of the wave nature of electron proved that simultaneous accurate measurement of position
and momentum is not possible.
 The mathematical form of the principle is:
x · Δp ≥ h / 4π
where Δx = uncertainty in position, Δp = uncertainty in momentum, h = Planck’s constant.
 It implies inverse relationship: higher accuracy in measuring one variable causes greater uncertainty
in the other.
 This principle is only significant for microscopic particles like electrons, protons, and neutrons.
 It does not apply to macroscopic objects (e.g., cars, balls) where uncertainties are negligible.
 Compton Effect explains uncertainty using X-rays, shorter wavelength photons disturb electron
momentum more.
 If we use longer wavelength photons to avoid disturbing momentum, we cannot locate the electron
precisely.
Concept of Orbital (electron cloud)
 Following this principle, the Bohr’s picture of an atom does not appear to be satisfactory.
 In Bohr’s atom, the electrons are moving with specific velocities in orbits of specified radii.
 According to uncertainty principle, both these quantities cannot be measured experimentally.
 A theory involving quantities, which cannot be measured, does not follow the tradition of scientific work.
 In order to solve this difficulty following worked out wave theories of the atom :
(i) Schrödinger (ii) Heisenberg (iii) Dirac
 The best known treatment is that of Schrödinger.
 He set up a wave equation for hydrogen atom.

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 According to Schrödinger, although the position of an electron cannot be found exactly, the probability
of finding an electron at a certain position at any time can be found.
 The solution of the wave equation gives probability of finding an electron present in a given small
region of space.
 When the probability of finding the electron at a distance r from the nucleus is calculated for the
hydrogen atom in the ground state, the maximum probability of finding the electron is at a distance of
0.053 nm = 0.53 Å = 53 pm.
 It is the same radius as calculated for the Bohr’s first orbit.
 There is a possibility that the electron is either closer to the nucleus or outside the radius of 0.053 nm,
where probability of finding electron decreases sharply.

Shell or Orbit Sub-shell Orbital

1. These are the paths where an 1. Sub-shell is the path in which 1. Orbital is the volume of space
electron revolves around the an electron moves within a shell. in which there is 95% chance of
nucleus. finding an electron.
2. A shell consists of sub-shells 2. A subshell has different 2. An orbital contains electrons
equal to the n value of shell. orientations called orbitals equal and is mathematical function that
to its (2𝑙 + 1) value. describes wave-like behaviour of
electrons.
3. They are circular or elliptical in 3. They have various shapes i.e., 3. They also may be spherical,
shape. spherical, dumb-bell or dumb-bell or complicated
complicated shapes etc. shapes.
4. It represents the flat or two- 4. It represents the three- 4. It also represents three-
dimensional motion of electron. dimensional motion of electron. dimensional motion of electron.
5. They are represented by 5. They are represented by 5. They are represented by
principle quantum number. azimuthal quantum number. magnetic quantum number.
6. Different shells have different 6. Different sub-shells of same or 6. Orbitals of same sub-shell in
energies. different shells have different the absence of external magnetic
K < L < M <N < … energy. field have same energy. px = py
s <p<d<f = pz
7. Number of electrons in a shell 7. Number of electrons in a sub- 7. An orbital contains 2 electrons
is equal to 2n2. shell is 2 (2𝑙 + 1). with opposite spins.
8. The lines of spectral series is 8. Fine or multiple line structure is 8. The splitting of lines in
due to electronic transitions due to the presence of subshells. magnetic and electric field is due
between shells. to the presence of orbitals
9. They are non-directional. 9. They are directional except s- 9. s – orbital is non-directional
sub-shells (1s, 2s, 3s, etc.) while p, d and f are directional.
10. Position of electrons in shells 10. Position of electron is 10. Position of electron is
is certain. uncertain. uncertain.
Important information :
 The term orbit was used by Bohr which was later called shell by Sommorfeld.
 “Orbital” can be regarded as a spread of charge surrounding the nucleus.
 This is often called the “electron cloud” which is another name for orbital.
Terminologies related to shell :
 Outermost shell or valence / last shell is called ultimate shell.
 The second last shell or the shell just before the valence shell is called penultimate shell.
 The shells between the nucleus and valence shell are called intervening shells.

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 And the electrons in intervening shells are called intervening electrons.
 Penultimate shell is also an intervening shell.
 The core of an atom is the atom minus its valence shell.

Quantum Numbers
 The set of numbers through which the position of an electron can be traced in an atom are called
quantum numbers.
 These are the numerical values that are used to describe the electron completely in an atom.
 Schrödinger’s Wave Equation (SWE) which is based on wave mechanics and not on quantum
mechanics has different possible solutions.
 When it was solved for hydrogen atom, the best known solutions were in the form of quantum
numbers.
 They may be integral, half integral, zero, positive or negative numbers.
(i) Principle Quantum Number (n) (ii) Azimuthal / Angular Quantum Number (𝑙)
(iii) Magnetic / Orientation Quantum Number (m) (iv) Spin Quantum Number (s)
 First three quantum numbers i.e., n, l and m are the constants of Schrödinger Wave equation.
 While spin quantum number is not related to Schrödinger Wave Equation (SWE)
 Quantum numbers fully explain all the lines of hydrogen spectrum.

Principle Quantum number (n)

 The different energy levels in Bohr’s model are represented by ‘n’ value.
 This is called Principle Quantum Number by Schrödinger.
 The value of n represents the shell or energy level.
 It explains the lines of spectral series i.e., Lyman, Balmer, Paschen, Brackett and Pfund.
 Its values are non-zero whole numbers i.e., positive integers up to infinity.
n=1,2,3,4,…,∞
 Letter notation K, L, M, N etc. can also be used to represent shells.
i. When n = 1, it is called K – shell. ii. When n = 2, it is called L- shell.
iii. When n = 3, it is called M – shell. iv. When n = 3, it is called N - shell and so on.

Importance of Principle Quantum Number :

 It determines the location of electron in an atom.
 It gives the distance of electron from the nucleus.
 Greater the value of n, greater will be the distance of electron from the nucleus.
∈o n2 h2
r =
π m Ze2
r ∝ n2
 It is the quantitative measurement of :
i. Electronic shell / orbit. ii. Sub-shell. iii. Orbital (electronic cloud).
 The size of all i.e., shell, sub-shell and orbitals increase with the increase in the value of ‘n’.
 ‘n’ also provides us the energy of electron in a shell
m Z 2 e4
E = − 2
8 ∈o 2 n2 h

− 1313.31
E = kJ mol-1
n2

Formulae :
2
i. Number of electrons in shell = 2n
ii. Number of orbitals in shell = n2
iii. Number of sub-shell in shell = n

n - value Shell Contains Sub-shell Contains Orbitals Electrons

n=1 K – shell 1 s only 1 s only 2

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n=2 L – shell 2 s and p 4 s, px, py, pz 8
n=3 M – shell 3 s, p and d 9 s, px, py, pz, dxy, dyz, dzx,dx2-y2, dz2 16
n=4 N – shell 4 s, p, d and f 16 One s, three p, five d, seven f 32

Azimuthal / Angular / Subsidiary Quantum Number (𝑙)

 Azimuthal Quantum Number tells us about sub-shells and shapes of sub-shells.
 It is represented by ‘𝑙’.
 It explains the lines of fine line
or multiple line structure.
 The splitting of Hα-line of Balmer
series into 5 component lines
when seen through higher
resolving power spectrometer is
explained by azimuthal
quantum number.
 This is explained by saying that
a shell is divided into sub-shells.
 The value of ‘𝑙’ is a whole
number (zero and positive
integers) up to one less than the
value of ‘n’.
𝑙 = 0 , 1 ,2 , 3 ,4 , … , (n -1)
 Its value depends upon n.
 These values represent different sub-shells, which are designated by small letters, s, p, d, f.
 They stand for sharp, principal, diffused and fundamental, respectively.
 These are the spectral terms used to describe the series of lines observed in the atomic spectrum.
 The values of azimuthal quantum number always start from zero.
 A sub-shell may have different shapes depending upon the value of (𝑙).
 It may be spherical, dumb-bell, sausage or some other complicated shapes.
 The value of (𝑙) is related to the shape of the sub-shell as follows:

𝑙 =0 Sharp s - subshell Spherical shape

𝑙 =1 Principle p - subshell Dumb-bell shape
𝑙 =2 Diffused d - subshell Sausage or double dumb-bell
𝑙 =3 Fundamental f - subshell Complicated shape

The relationship between principle and azimuthal quantum number is as follows :

n=1 K – shell 𝑙 =0 s - subshell should be called as 1s

n=2 L – shell 𝑙 =0 s - subshell 2s
𝑙 =1 p - subshell 2p
n=3 M – shell 𝑙 =0 s - subshell 3s
𝑙 =1 p - subshell 3p
𝑙 =2 d - subshell 3d
n=4 N – shell 𝑙 =0 s - subshell 4s
𝑙 =1 p - subshell 4p
𝑙 =2 d - subshell 4d
𝑙 =3 f - subshell 4f

 In 1s, 2s, 2p, …, etc. the digits represent the value of principle quantum number.

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 Number of orbitals in a sub-shell is equal to (2𝑙 + 1) value of the sub-shell.

(2𝑙 + 1) s-subshell 2 (0) + 1 = 1 1 orbital

p-subshell 2 (1) + 1 = 3 3 orbitals
d-subshell 2 (2) + 1 = 5 5 orbitals
f-subshell 2 (3) + 1 = 7 7 orbitals

 The probability of finding electron is zero between two orbitals. This place is called nodal plane or
nodal surface.
 Number of angular nodes in a sub-shell is equal to 𝑙 value.
 For example, s has 𝑙 = 0 and has 0 nodes, p has 𝑙 = 1 and has 1 nodal plane.
 Similarly, d and f have 2 and 3 nodal planes respectively.
 Therefore, azimuthal quantum number is also called angular quantum number because it tells us
about angular nodes.
 𝑙 value also enables us to calculate the total number of electrons in a given sub-shell.
 The formula for calculating electrons is 2 (2 𝑙 + 1)

When 𝑙 =0 s-subshell Total electrons = 2 [2 (0) + 1] = 2 electron

𝑙 =1 p-subshell Total electrons = 2 [2 (1) + 1] = 6 electron
𝑙 =2 d-subshell Total electrons = 2 [2 (2) + 1] = 10 electron
𝑙 =3 f-subshell Total electrons = 2 [2 (3) + 1] = 14 electron

Magnetic / Orientation Quantum number (m)

 It is denoted by ‘m’
 It represents orbitals in a sub-shell.
 It tells us about the orientation of orbitals in space among different axes.
 It has been proposed to explain Stark and Zeeman effect.
 Its value depends upon and is derived from the value of 𝑙.
 Its values include zero, positive and negative non-fractional integers up to the value of 𝑙.
m = 0, ± 1, ± 2, ± 3, … … … , ± 𝑙
 It gives us the information about degeneracy of orbitals in space.
 The orbitals having same energy in the absence of magnetic field are called degenerate orbitals.
 The orbital of a same sub-shell are degenerate.

When 𝑙=0 s-subshell m = 0 (s-subshell has one orbital)

𝑙=1 p-subshell m = -1, 0, +1 (p-subshell has three degenerate orbitals)
𝑙=2 d-subshell m = -2, -1, 0, +1, +2 (d-subshell has five degenerate orbitals)
𝑙=3 f-subshell m = -3, -2, -1, 0, +1, +2, +3 (f-subshell has seven degenerate orbitals)
 For a given value of ‘𝑙’ the total values of m are (2𝑙+1).
 It tells us the number of different ways in which a given s, p, d or f-subshell can be arranged along x,
y and z-axes in the presence of a magnetic field. (Orbital orientation Quantum Number)
 Thus, different values of m for a given value of ‘𝑙’, represent the total number of different space
orientations for a subshell.
 There are 4 types of orbitals depending upon the values of azimuthal quantum number :
(1) s – Subshell :
(i) Possible Orientations :
 In case of s – subshell, 𝒍= 0, so m = 0.
 It implies that s-subshell of any energy level has only one space orientation and can be arranged in
space only in one way along x, y and z-axes.
 So, s-subshell is not sub-divided into any other orbital.
(ii) Shape of s-orbital :
 The shape of ‘s’ orbital is such that the probability of finding the electron in all the directions from the
nucleus is the same.
 It is a spherical and symmetrical orbital.

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(iii) Electronic Probabilities :

 The probability of finding electron on each of the axes (x, y and z) individually is 33.33%.
 While the probability on either positive or negative axis e.g., only +y – axis is 16.67%.
 Therefore, it is non-directional because the probability of finding electron in every direction is same.

(2) p – Subshell :
(i) Possible Orientations :
 For p - subshell, 𝑙= 1 and m = 0, ±1.
I. px (m = -1) II. pz (m= 0) III. py (m= +1)
 These values of ‘m’ imply that p-subshell of any energy level has three space orientations and can
be arranged in space along x, y, and z axes.
 These three orbitals are perpendicular to each other and named as px, py, and pz.
(ii) Shape of p – orbital :
 They have egg-shaped lobes or dumb-bell which touch each other at the origin.
 They are disposed symmetrically along one of the three axes x, y or z called orbital axis.
 So, p-orbital has directional character which determines the geometry of molecules.

(iii) Electronic Probabilities :

 For px, 50% probability of finding electron is on +x – axis and 50% on –x –axis.
 Similarly, py has 50% probability on +y – axis and 50% probability of finding electron on –y – axis.
 Likewise, pz has 50% probability of finding electrons on +z and 50% on –z-axis.
 For all p-orbitals probability of finding electron between axes is zero (nodal planes)
 In the absence of the magnetic field, all the three p-orbitals have the same energy and are degenerate
orbitals.
 Since, they are three in number, so these orbitals are said to be three-fold degenerate or triply
degenerate.
 Each p-orbital has 1 nodal plane.

(3) d – Subshell :
(i) Possible Orientations :
 For d-subshell 𝑙= 2, m = 0, ±1, ±2.
 It implies that it has five space orientations and aredesignated as dxy, dyz, dzx, dx2-y2 and dz2.
I. dxy (m = -2) II. dyz (m = -1) III. dzx = +1
IV. dx2- y2 (m = +2) V. dz2 (m = 0
(ii) Shapes of d – orbitals :
 All these five d-orbitals are not identical in shape.
 First four dxy, dyz, dzx, and dx2-y2 have 4 lobes (tetra-lobed or sausage shaped).
 dx2-y2is clover-leaf shaped.
 While d22, there are two lobes (bi-lobed or dumb-bell) with a collar region around it.

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(iii) Electronic probabilities :

 The collar of dz2 is radial region and has 95% probability of finding electron.
 dxy, dyz and dzx have maximum probability of electron between axes and minimum on the axes.
 While dx2-y2 has maximum probability of finding electron on x and y-axis whereas dz2 has probability on
z-axis.
 dx2-y2 and dz2 have minimum probability of finding electron between the axes.
 dxy, dyz, dzx, and dx2-y2 have 2 nodal regions / planes while dz2 has only 1 nodal region / plane.
 In the absence of a magnetic field, all five d-orbitals have the same energy.
 They are said to be five-fold degenerate orbitals.

(4) f – Subshell :
(i) Possible Orientations :
 For f-subshell, 𝑙= 3 and m = 0, ±1, ±2, ±3.
 It implies that it has seven space orientations.
(ii) Shapes of f-orbitals :
 They have complicated shapes.
 They are also not identical in shapes and their shapes differ very greatly.
 In the absence of a magnetic field, all seven f-orbitals have the same energy.
 They are said to be seven-fold degenerate orbitals.
(iii) Electronic probabilities :
 The probability of finding electrons is different in different directions.
 p, d and f-orbitals have directional nature. S-orbital is non-directional.

s - subshell p - subshell d - subshell f - subshell

1. Spectral terms Sharp Princi0ple Diffused Fundamental
2. Minimum n - 1 2 3 4
value
3. Starting shell K L M N
4. 𝑙 values 0 1 2 3
5. Number of e- 2 6 10 14
6. Shapes Spherically Dumb - bell or bi- Sausage or double Complicated.
symmetrical. lobed. dumb – bell.
7. Electronic Same in every At axes. Between and at axes. Different in every
probabilities direction. direction.
8. Angular nodes 0 1 2 3
9. m values 0 -1, 0, +1 -2, -1, 0, +1, +2 0, ±1, ±2, ±3
10. Possible 1 3 5 7
orientations
11. Orbitals s px, py, pz dxy, dyz, dxz, dx2-y2, dz2 Seven
12. Degeneracy Single orbital. 3 - fold degenerate. 5 - fold degenerate. 7 - fold degenerate
13. Directional No Yes Yes Yes

Spin Quantum Number – 1925 (s)

 It explains doublet line structure.
 It is represented by “s”.
 It value is positive half s = +½ or negative half s = -½.
 The digit ½ represents that 50% probability of electronic spin is clockwise while 50% probability of
electronic spin is anti-clockwise.

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 Alkali metals have one electron in their outermost shell.
 We can record their emission spectra, when the outermost electron jumps from an excited state to a
ground state.
 When the spectra are observed by means of high resolving power spectrometer, each line in the
spectrum is found to consist of a pair of lines, this is called doublet line structure.
 We should keep it in mind that doublet line structure is different from the fine or multiple spectrum of
hydrogen.

Doublet Line Structure Fine or Multiple structure

i. When the spectra are observed by means of high i. When the spectrum of hydrogen gas is observed
resolving power spectrometer, each line in the by means of a high resolving power spectrometer,
spectrum is found to consist of a pair of lines, this is the individual spectral lines are replaced by several
called doublet line structure. very fine lines called fine / multiple structure.
ii. Number of component lines is fixed i.e., 2. ii. Number of component lines is not fixed.
iii. Lines of doublet line structure are widely iii. Lines of fine or multiple structure are closely
separated from each other. spaced together.
iv. Their origin is the spin motion of electron. iv. Their origin is the presence of sub-shells.
v. It is explained by spin quantum number. v. It is explained by azimuthal quantum number.
Example :The emission spectra of alkali metals Example :Hα line of Balmer series is seen divided
give doublet line structure. into 5 component lines.

 In 1925, Goudsmit and Uhlenbech suggested that an electron has 2 types of motion :
1. Motion in an orbital around the nucleus.
2. Rotation or spin about its own axis.

 The rotation occurs either in a clockwise or anti-clockwise direction.

i. Clockwise rotation is represented by -½.
ii. Anti-clockwise rotation is represented by +½.
 This is also called self-rotation.
 This spinning electron is associated with a magnetic field and hence a magnetic moment.
 Hence, opposite magnetic fields are generated by the clockwise and anti-clockwise spins of electrons.
 This spin motion is responsible for doublet line structure in the spectrum.

Path of electron Proof of existence Explained by Represented by

1. Shells Lyman, Balmer, Paschen, Principle quantum number n
Brackett and Pfund series
2. Sub-shells Fine or multiple line structure Azimuthal quantum number 𝑙
3. Orbitals Zeeman and stark effect Magnetic quantum number m
4. Spin Doublet line structure Spin quantum number s

Quantum numbers Characteristics Possible values Importance

1. Principle quantum Non-zero, non-fractional whole n = 1,2,3, ... , ∞ Tells size and energy
number numbers, positive integers of shell.
2. Azimuthal Non-fractional whole numbers, 𝑙 = 0, 1,2, ..., (n -1) Tells shape of sub-
quantum number positive integers shell.
3. Magnetic quantum Non-fractional, positive and m = 0, ±1, ±2, ... , 𝑙 Tells orientation of
number negative integers orbitals.
4. Spin quantum Rational fraction, non-zero, Two possible values Distinguishes two
number positive or negative +1/2 and -1/2 electrons in an orbital.

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Electronic Distribution or Electronic Configuration

 The distribution of electrons in various shells and sub-shells around the nucleus in an order of
their increasing energy is called as electronic configuration.
 Electronic configuration is nothing but a combination of different quantum numbers.
 In order to understand the distribution of electrons in an atom, we should know the following facts :
(1) An orbital like px, py, pz and dxy etc. can have at the most 2 electrons.
(2) The maximum number of electrons that can be accommodated in a shell is given by 2n2.
Where, n = principle quantum number ≠0.
 Moreover, following rules have been adopted to distribute the electrons in sub-shells and orbitals.
 These rules are applicable to atomic as well as molecular orbits (BMOs and ABMOs)
Rules Applied on Explains
I. (n + 𝑙) rule Sub-shells Order of filling.
II. Aufbau Principle. Sub-shells Energy of sub-shells.
III. Pauli’s Exclusion Principle. Orbital. Different sets of quantum numbers
IV. Hund’s Rule Degenerate orbitals. Valency.

I. (n + 𝒍) rule :
 Sub-shells are arranged in the increasing order of (n + 𝑙) values.
 If two sub-shells have same (n + 𝑙) value, the sub-shell with the smaller n value is placed first,
 The arrangement of subshells in ascending order of their energy may be as follows ;
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s and so on.

II. Aufbau Principle(Greek : Auf = build, Bau = on)

 The electrons should be filled in energy sub-shells in order of their increasing energy values.
 The electrons are first placed in 1s, 2s, 2p and so on.
 Note that Aufbau principle is violated in writing the electronic configuration of Cr, Pd, Cu, Ag and Au.

III. Pauli’s Exclusion Principle :

 It is impossible for two electrons residing in the same orbital of a poly-electron atom to have the same
values of four quantum numbers.
 Two electrons in the same orbitals should have opposite spins (↑↓).
 The first element to which Pauli’s exclusion principle is applied is helium (2He).
1. (↑↓ ) True notation. 2. (↓↑) True notation
3. (↑↑) False presentation. 4. (↓↓) False presentation.

IV. Hund’s Rule :

 If degenerate orbitals are available and more than one electrons are to be filled in them, they should
be placed in separate orbitals with the same spin rather than putting them in the same orbital with
opposite spins.
 The first element to which Hund’s rule is applied is carbon (6C).
↑↓ ↑↓ ↑ ↑ 0
6C = .1s , .2s , .2px , .2p , ..
y 2pz
 Hund’s rule describes that way how electron are filled in orbitals of a sub-shell to minimize the
repulsion between them.
 It explains the valency of an element which is equal to the number of unpaired electrons.
 The valency of carbon according to Hund’s rule is 2.

↑↑ ↑ ↑ ↑↓ ↑
(False according to Pauli, true A.C.T Hund’s rule. (True according to Pauli, false A.C.T Hund’s rule)

Electronic Configuration of Elements

↑↓ ↑ ↑ ↑↓ ↓ ↓ ↑↓ ↑↑
(True) (True) (False)

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 Note that half-filled and full-filled orbitals are stable due to :
1. Symmetry of electrons.
2. High electron exchange energy.
 Moreover, full filled atomic orbitals are more stable than half-filled.
Full filled > Half – filled > Partially filled

Element Symbol Atomic Number Electronic Configuration

Hydrogen 1H 1 ↑
.1s
Helium 2He 2 ↑↓
.1s
Lithium 3Li 3 ↑↓ ↑
.1s , .2s
Beryllium 4Be 4 ↑↓ ↑↓
.1s , .2s
Boron 5B 5 ↑↓ ↑↓ ↑ .0 .0
.1s , .2s , .2p x
, . 2p , .
y 2pz
Carbon 0
6C 6 ↑↓ ↑↓ ↑
.1s , .2s , .2p , . ↑ , ..
x 2py 2pz
↑↓ ↑↓ ↑
Nitrogen 7N 7 .1s , .2s , .2p , . ↑ , .↑
x 2py 2pz
↑↓ ↑↓ ↑↓ ↑
Oxygen 8O 8 .1s , .2s , .2px , .2p , .↑
y 2pz
↑↓ ↑↓ ↑↓ ↑↓
Fluorine 9F 9 .1s , .2s , .2px , .2p , .↑
y 2pz
↑↓ ↑↓ ↑↓ ↑↓
Neon 10Ne 10 .1s , .2s , .2px , .2p , .↑↓
y 2pz
Sodium 11Na 11 ↑
[Ne] .3s
Magnesium 12Mg 12 [Ne].↑↓
3s
Aluminium 13Al 13 .0 .0
[Ne].↑↓ ↑
3s , .3px , .3py , .3pz
Silicon 14Si 14 .0
[Ne].↑↓ ↑ ↑
3s , .3px , .3py , .3pz
Phosphorus 15P 15 [Ne].↑↓ ↑ ↑ ↑
3s , .3px , .3py , .3pz
Sulphur 16S 16 [Ne].↑↓ ↑↓ ↑ ↑
3s , .3px , .3py , .3pz
Chlorine 17Cl 17 [Ne].↑↓ ↑↓ ↑↓ ↑
3s , .3px , .3py , .3pz
Argon 18Ar 18 [Ne].↑↓ ↑↓ ↑↓ ↑↓
3s , .3px , .3py , .3pz
Potassium 19K 19 ↑
[Ar] .4s
Calcium 20Ca 20 [Ar].↑↓
4s
Scandium 21Sc 21 ↑ ..0 .0 .0 .0
[Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
Titanium 22Ti 22 ↑ ↑ .0 .0 .0
[Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
Vanadium 23V 23 ↑ ↑ ↑ .0 .0
[Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
↑
Chromium 24Cr 24 ↑
[Ar].4s , .3𝑑 ,.↑ ,.↑ ,.↑ ,.↑
𝑥𝑦 3𝑑𝑦𝑧 3𝑑𝑧𝑥 3𝑑𝑥2 −𝑦2 3𝑑𝑧2
↑ ↑ ↑ ↑ ↑
Manganese 25Mn 25 [Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
↑↓ ↑ ↑ ↑ ↑
Iron 26Fe 26 [Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
↑↓ ↑↓ ↑ ↑ ↑
Cobalt 27Co 27 [Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
↑↓ ↑↓ ↑↓ ↑ ↑
Nickel 28Ni 28 [Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑𝑥2 −𝑦2 , .3𝑑𝑧2
Copper 29Cu 29 ↑
[Ar].4s , .↑↓ ↑↓ ↑↓ ↑↓
3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑 , .↑↓
3𝑑
𝑥2 −𝑦2 𝑧2
↑↓ ↑↓ ↑↓ ↑↓
Zinc 30Zn 30 [Ar].↑↓
4s , .3𝑑𝑥𝑦 , .3𝑑𝑦𝑧 , .3𝑑𝑧𝑥 , .3𝑑 , .↑↓
3𝑑
𝑥2 −𝑦2 𝑧2

P a g e | 20 MATERIAL OF PTB, STB, BTB, KPK, FTB & A-LEVELS

Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
Gallium 31Ga 31 ↑ .0 .0
[Ar] 4s2, 3d10, .4p x
, . 4p , .
y 4pz
Germanium 0
32Ge 32 ↑
[Ar] 4s2, 3d10, .4p , . ↑ , ..
x 4py 4pz
↑
Arsenic 33As 33 [Ar] 4s2, 3d10, .4p , .↑ , .↑
x 4py 4pz
↑↓
Selenium 34Se 34 [Ar] 4s2, 3d10,.4p , .↑ , .↑
x 4py 4pz
↑↓
Bromine 35Br 35 [Ar] 4s2, 3d10,.4p , . ↑↓ , . ↑
x 4py 4pz
↑↓
Krypton 36Kr 36 [Ar] 4s2, 3d10, .4p , . ↑↓ , . ↑↓
x 4py 4pz

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure

P a g e | 22 MATERIAL OF PTB, STB, BTB, KPK, FTB & A-LEVELS

Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
Past MDCAT paper + Most repeated MCQs
Discovery of fundamental particles, Properties of fundamental particles and
Planck’s theory and Bohr’s Model
1. From discharge tube experiments, it is concluded that
A. Mass of proton is in fraction C. Matter contains electrons
B. +ve rays are always lighter than cathode rays D. Nucleus contains positive charge
2. Consider the following reaction 4Be + 2He → 6C + 1n. This reaction is
A. An exothermic reaction C. An example of artificial radioactivity
B. A nuclear reaction D. All of these
3. The nature of cathode rays in discharge tube
A. Depends upon the nature of the gas used in discharge tube
B. Depends upon the nature of the cathode used in discharge tube
C. Is independent of the nature of the gas used in discharge tube
D. Depends upon the nature of anode in the discharge tube
4. Which of the following species has more electrons than neutrons?
A. Na+ B. F-1 C. O-1 D. Mg+2
5. A fast-moving neutron can eject from nitrogen
A. γ-rays B. α-rays C. β-rays D. Electrons
6. e/m ratio of cathode rays is .......... than that of canal rays
A. Condition dependent B. Greater C. Smaller D. Equal
7. Which of the following relationship is incorrect?
A. E ∝ β B. E ∝ α C. ṽ = λ D. E ∝ 1/λ
8. Which of the following is not the unit of wave number?
A. m−1 B. cm-1 C. mm−1 D. cm
9. An electron makes a transition from energy state E2 to E1 will emit a photon of frequency
A. u = E1 – E3/h B. u = (E3 − E1)/h C. u = (E2 − E1)/h D. None of these
10. All of the following were theorized by Bohr in the description of atom except
A. Angular momentum of electron is multiple of h/2π
B. Electrons circulate in discrete circular orbit
C. Electron continuously radiate energy in the form of radiation in a given orbit
D. Distance between successive orbits is increasing

Quantum numbers and shapes of orbitals

11. Which of the following quantum numbers is not derived from Schrodinger wave equation?
A. Principal quantum number from Schrodinger
B. Azimuthal quantum number from Schrodinger
C. Magnetic quantum number from Schrodinger
D. Spin quantum number from Schrodinger
12. The number of orbitals in the 2nd principal quantum number of an atom is
A. 4 B. 9 C. 16 D. 1
13. Which of the following sets of quantum numbers is not allowed?
A. n = 3, l = 2, m = 0, s = -1/2 C. n = 3, l = 0, m = 0, s = -1/2
B. n = 3, l = 1, m = -1, s = -1/2 D. All are allowed
14. Quantum number values for 5p orbital is
A. n = 5, l = 0 B. n = 5, l = 1 C. n = 5, l = 2 D. n = 5, l = 3
15. A sub shell having n = 6, and l = 3 is designated as
A. 6s B. 6p C. 6f D. 6d
16. The number of degenerate orbitals in p-subshell is
A. 2 B. 3 C. 5 D. 7
17. n + l value for 4f will be ______ and 5p will be ______
A. 7, 5 B. 7, 7 C. 6, 6 D. 9, 6
18. The total number of orbitals containing electrons, if atomic number of the element is 19
A. 4 B. 6 C. 10 D. 16
19. When azimuthal quantum number l = 2, then ‘m’ can have ______ value
A. 3 B. 5 C. 7 D. 9
20. How many numbers of clockwise electrons are present in helium?
A. 0 B. 1 C. 2 D. 4

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
Electronic configuration of elements
21. Which of the following orbitals can accommodate 2 electrons?
A. Atomic orbital B. Hybrid orbital C. Molecular orbital D. All of these
22. If the value of n = 4, what is probable value of l?
A. None of the above B. 0, 1, 2 C. 0, 1, 2, 3 D. 0, 1
23. Electronic configuration of an atom is 1s², 2s², 2p⁶, 3s². Number of unpaired electrons are
A. 1 B. 2 C. 3 D. 0
24. The number of orbitals in M shell are
A. 4 B. 8 C. 18 D. 9
25. The electronic configuration of metal ion Ti⁺² is 2, 8, 14 and its atomic mass is 56. The number of
neutrons in its nucleus is
A. 30 B. 32 C. 42 D. 44
26. Which of the following species has more electrons than neutrons?
A. Na B. F⁻ C. O⁻¹ D. Mg⁺²
27. An electron occupies the available orbital before pairing in any one sub-shell according to
A. Aufbau principle B. Pauli exclusion principle C. Hund’s rule D. Mosleys law
28. Total number of valence electrons in phosphonium PH₄⁺ ion is
A. 16 B. 32 C. 8 D. 18
29. Which of the following oxides of nitrogen is isoelectronic with CO₂?
A. N₂O₃ B. NO C. N₂O D. NO₂⁻
30. The atomic number of an element having maximum number of unpaired electrons in p-subshell
A. 7 B. 10 C. 12 D. 16
31. From anode like cathode rays, produced from cathode
A. By burning of gas C. By ionizing the gas
B. By cooling of the gas D. Positive rays are produced
32. Pressure in gas discharge tube was kept ______ to produce cathode rays
A. 10 torr B. 1 torr C. 0.1 torr D. 0.01 torr
33. Number of electrons, protons and neutrons present in ⁶⁰30Zn⁺² respectively
A. 28, 30, 36 B. 28, 28, 36 C. 32, 30, 36 D. 28, 36, 30
34. Which of the following are not able to ionize the gas?
A. α-rays B. β-rays C. γ-rays D. Neutrons
35. Which order of mass is correct in ascending order
A. e⁻ > p⁺ > n B. e⁻ < n < p⁺ C. e⁻ < p⁺ < n D. n > p⁺ > e⁻
36. The nucleus of an atom is made up of 8 protons and 8 neutrons, which atoms it is
A. C B. N C. O D. F
37. Which rays are more penetrating in nature?
A. α-rays C. γ-rays D. All have same
B. β-rays nature
38. Positive rays give flash on
A. AgNO₃ plate B. BaCl₂ plate C. ZnO D. ZnS
39. The wave number of the light emitted by a certain source is 2 × 10⁶ m⁻¹. The wavelength of this
light will be
A. 500 nm B. 500 mm C. 500m D. 200nm
40. The e/m ratio for the positive rays is maximum for
A. Hydrogen B. Helium C. Oxygen D. Nitrogen
41. Total number of fundamental particles in one atom ⁴₂He of is
A. 6 B. 14 C. 2 D. 4
42. Electronic configuration of species M²⁺ is 1s² 2s² 2p⁶ 3s² 3p⁶ 4s² 3d⁶ and its atomic weight is 56,
number of neutrons in the nucleus of species M is
A. 20 B. 26 C. 28 D. 30
43. Magnetic quantum number is related to ____ of orbital?
A. Size B. Shape C. Orientation D. Spin of electron
44. Existence of pair of lines in spectrum of sodium is explained by
A. Principal quantum number C. Magnetic quantum number
B. Azimuthal quantum number D. Spin quantum number
45. According to Bohr’s atomic theory, the angular momentum (mvr) of an electron is equal to
A. nh/2π B. nh/π C. 3nh/2π D. 2nh/π
46. Which set of quantum numbers is not possible
A. n=5, l=3, s = +1/2 B. n=3, l=3, s = +1/2 C. n=4, l=2, s = +1/2 D. n=6, l=0, s = +1/2
47. The last electron in the Na and K can be distinguished by

P a g e | 24 MATERIAL OF PTB, STB, BTB, KPK, FTB & A-LEVELS

Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
A. Principal quantum number C. Magnetic quantum number
B. Azimuthal quantum number D. Spin quantum number
48. If the value of n = 4 what is probable value of l
A. 0,1 B. 0,1,2 C. 0,1,2,3 D. 0, 1, 2, 3, 4
49. How many electrons can fit into the sub-shell for which n = 3, l = 1?
A. 8 B. 18 C. 6 D. 32
50. Which set of quantum numbers is not possible
A. n=5, l = 3, s = +½ B. n=3, l = 3, s = +½ C. n=4, l = 2, s = +½ D. n=6, l = 0, s = +½
51. The number of unpaired electrons in p-sub shell of sulphur atom is
A. 4 B. 6 C. 2 D. 3
52. The number of electrons in a shell can be calculated by formula
A. 2l + 1 B. 2(2l + 1) C. 2n² D. n²
53. Which quantum number is used to represent the subshells?
A. Principal Quantum number C. Magnetic quantum number
B. Azimuthal quantum number D. Spin quantum number
54. The maximum probability of finding an electron in a hydrogen atom according to Schrodinger is
A. 0.053nm B. 0.043nm C. 0.073nm D. 0.057nm
55. Which of following statement is correct about azimuthal quantum number, It tells
A. Size of orbital C. Orientation of orbital in space
B. Shape of orbital D. Nuclear stability
56. The shape of p-orbital is
A. Spherical symmetrical B. Spherical C. Dumb-bell shape D. Circular
57. Which subshell is nearest to nucleus?
A. 1s B. 2s C. 2p D. Both A and B
58. Which atomic orbital has highest energy
A. 4d B. 4f C. 5d D. 5p
59. An orbital which is spherically symmetrical is
A. p-orbital B. d-orbital C. s-orbital D. f-orbital
60. Which one of the following sub-shells does not exist?
A. 2p B. 3p C. 2d D. 4d
61. (An) ______ is a region of space in which there is a high probability of finding an electron in an
atom
A. Main energy level B. Atomic orbital C. Shell D. Nucleus
62. According to quantum mechanics, the size of electronic shell is told by the quantum number
A. Spin quantum number C. Azimuthal quantum number
B. Magnetic quantum number D. Principal quantum number
63. Which of the following rule/principle helps us to determine order of filling of sub shells by
electrons?
A. Aufbau principle B. Hund’s rule C. Pauli exclusion principle D. Mosleys law
64. Filling order of 4s, before 3d is explained by
A. Aufbau principle B. (n + l ) rule C. Pauli exclusion principle D. Mosleys law
65. Decreasing energy order of subshell of a particular shell is
A. f > d > s > p B. f > d > p > s C. s > p > d > f D. p > s > f > d
66. Which of the following helps to predict valency of element?
A. Aufbau principle B. Pauli exclusion principle C. Hund’s rule D. Mosleys law
67. Which of the following contains unpaired electrons?
A. Ca⁺² B. Ni⁺² C. K⁺¹ D. Zn⁺²
68. The atomic number of an element is sixteen. It belongs to period and group number of the
periodic table respectively.
A. 3, 7 B. 6, 3 C. 3, 6 D. 7, 3
69. Which electronic configuration is not possible?
A. 1s², 2s², 2p⁶, 2d², 3s¹ C. 1s², 2s², 2pₓ¹, 2pᵧ¹, 2p𝓏¹
B. 1s¹ D. 1s², 2s², 2p⁶, 3s², 3p⁶, 4s²
70. How many electrons can fit into the sub-shell for which n = 3, l = 1?
A. 8 B. 18 C. 6 D. 32
71. How many total unpaired electrons are present in an atom with Z = 24
A. Two B. Five C. Six D. Eight
72. When 4f orbital is complete the entering electron goes into
A. 6s B. 5p C. 5d D. 4d

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Spark MDCAT [CLICK HERE TO ORDER] Atomic structure
73. Without applying Hund’s rule the electronic configuration of one of the following cannot be
justified
A. Fluorine B. Neon C. Sodium D. Phosphorous
74. Which one of the following statements is not correct?
A. Unit of frequency is cycle per second
B. Lyman series of hydrogen spectrum occurs in the ultraviolet region
C. The angular momentum of the electron in the ground state of hydrogen atom is equal to h/2π
D. The radius of first Bohr orbit of hydrogen atom is 2.116 × 10⁻⁸ cm
75. Which species has same number of electrons in valence shell and penultimate (second last)
shell
A. Na⁺ B. O⁻² C. Al⁺³ D. Cl⁻
76. Which of the following does not correctly relate the arrangement of electrons?
A. Arrangement of electrons in sub shell is given by (n+l) rule
B. Arrangement of electrons in degenerate orbitals is given by Hund’s rule
C. Arrangement of electron in an orbital is given by Pauli’s exclusion principle
D. Filling of electrons in shells is given by octet rule
77. The electronic configuration of an element with atomic number 29 is
A. 1s², 2s², 2p⁶, 3s², 3p⁶, 3d⁹, 4s² C. 1s², 2s², 2p⁶, 3s², 3p⁶, 3d⁷, 4s²
B. 1s², 2s², 2p⁶, 3s², 3p⁶, 3d¹⁰, 4s¹ D. 1s², 2s², 2p⁶, 3s², 3p⁶, 3d¹⁰, 4s²
78. Which of the following has minimum number of unpaired d-electrons?
A. Fe³⁺ B. Co³⁺ C. Co²⁺ D. Mn²⁺
79. Number of unpaired electron in p subshell of 'F' is
A. 1 B. 2 C. 3 D. 4
80. Electronic configuration of K is
A. [Ar]4s² B. [Ar]4s¹ C. [Kr]5s¹ D. [He]2s¹

Answers and Explanations

Q No. Ans Explanation

Q.1 C In discharge cathode rays is produced from sample gas and cathode are basically
electron
Q.2 D This reaction is nuclear exothermic and artificial radioactivity
Q.3 C Nature of cathode rays is independent of nature of gas
Q.4 C Na⁺: Neutron = 12, Electron = 10 F⁻¹: Neutron = 10, Electron = 10
O⁻¹: Neutron = 8, Electron = 9 Mg⁺²: Neutron = 12, Electron = 10
Q.5 B ¹₄N + ¹₀n → ¹₁B + ⁴₂He (α – particle)
Q.6 B The e/m value for the positive rays is always smaller than that of electrons and depends
upon the nature of the gas used in the discharge tube.
Q.7 C v̅ = λ is incorrect  E ∝ ν (frequency)  E = hν  ν = c/λ ⇒ wave number
So, E = hcν
Q.8 A As wave number ∝ 1/ wave length, its unit is inverse of length
Q.9 C An electron makes a transition from energy state E3 to E1 will emit a photon of frequency:
ν = (E₃ − E₁)/h, Formula used v = ΔE/h
Q.10 C Electrons circulate in discrete orbits with fixed energy, increasing distances, and
quantized angular momentum.
They do not radiate energy in orbit.
Q.11 D Spin quantum number is not derived from Schrodinger wave equation. It was given by
Goudsmit and Uhlenbeck
Q.12 A Number of orbitals = n². If n = 2 → (2)² = 4
Q.13 D All values possible : when n=3, l=2→d present in 3rd shell,
n=3 l =1→p present in 3rd shell
n=3, l = 0→s present in 3rd shell
Q.14 B n = 5 implies that l = 0 → s; l = 1 → p; l = 2 → d, l = 3 → f
Q.15 C n = 6 → number of shell l = 3 → shape of orbital
l = 0 → s; l = 1 → p; l = 2 → d, l = 3 → f
Q.16 B Number of orbitals in subshell = (2l + 1) = 2(1) + 1 = 3
Q.17 C n + l value for: 4f = (4+3) = 7 For 5p = (5+1) = 6
Q.18 C Number of orbitals = total electron / 2 = 19 / 2 = 9.5 ≈ 10 (rounded up)

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Spark MDCAT Atomic structure
Q.19 B m = ±1
m = ± 2 = –2, –1, 0, 1, 2
Q.20 B Helium has 2 electrons; 1 is clockwise and the other is anti-clockwise.
Q.21 D Any orbital of any type can’t accumulate more than two electrons.
Q.22 C If n = 4 then probable values of l = 0, 1, 2, 3. As l = n-1 , l = 0 → s; l = 1 → p; l = 2 → d, l
=3→f
Q.23 B

Q.24 D n = 3, Number of orbitals in shell = n² = 3² = 9

Q.25 A M²+ = 2+ 8 + 14 + 2 = 26 (2 e⁻ are removed to form cation so added again in total)
Number of neutrons = 56 – 26 = 30
Q.26 C Na⁺: 10 e⁻, 12 n⁰ F⁻: 10 e⁻, 10 n⁰
O⁻¹: 9 e⁻, 8 n⁰ Mg⁺²: 10 e⁻, 12 n⁰
Q.27 C Hund’s rule: If degenerate orbital available for more than one e⁻, they will be filled in
different orbitals with same spin rather than same orbital with opposite spin.
Q.28 C

1s², 2s², 2p⁶, 3s², 3p³

Q.29 C (a) N₂O₃ = 38 (b) NO = 15
(c) N₂O = 22, CO₂ = 22 (d) NO₂ = 23
Q.30 A Z₇ = 1s², 2s², 2pₓ¹, 2pᵧ¹, 2p𝓏¹ = 3 Z₁₀ = 1s², 2s², 2pₓ², 2pᵧ², 2p𝓏² = 0
Z₁₂ = 1s², 2s², 2pₓ², 2s² = 0 Z₁₆ = 1s², 2s², 2pₓ², 2pᵧ², 2p𝓏², 3s², 3pₓ¹, 3pᵧ¹
Q.31 C M + e⁻ → M⁺¹ + 2e⁻ (positive ions formed by striking cathode rays)
Q.32 D Pressure should be reduced for movement of cathode rays and to avoid hindrance.
Q.33 A
Q.34 D Neutrons are not able to ionize gas but α, β, and γ-rays can.
Q.35 C Electron is the lightest particle while neutron is the heaviest among the three.
Q.36 C Oxygen: atomic number = 8, atomic mass = 16.
Q.37 C γ-rays are less ionizing and more penetrating.
Q.38 D Positive rays give flash on ZnS plates.
Q.39 A Lesser the mass, greater the e/m value.
When hydrogen gas is used in the discharge tube, the e/m value is found to be the
maximum in comparison to any other gas because the value e/m is the lowest for the
positive particle obtained from the hydrogen gas
Q.40 A e/m of hydrogen is max compared to other gases due to lightest mass.
Q.41 A Protons = 2, Electrons = 2, Neutrons = 2
Q.42 D
Q.43 C Magnetic quantum number is related to orientation of orbital.
Q.44 D Spin quantum number explains double line, while others explain line or multiple
structures.
For valence electron of sodium, spin will be clockwise or anticlockwise.
Q.45 A
Q.46 B n > 1, l > m
Q.47 A The values of Azimuthal, magnetic and spin quantum numbers of sodium and potassium
are same while their value of principal quantum number is changed. For sodium it is
three and for potassium it is four
Q.48 C If n = 4, then l = 0, 1, 2, 3 → s, p, d, f
Q.49 C Number of electrons = 2(2l+1) = 2(2(1)+1) = 6
Q.50 B n = 3 → 3rd shell l = 3 → f-subshell f starts from 4th shell
Q.51 C S₁₆ = [Ne], 3s², 3px², 3py¹, 3pz¹ → 2 unpaired
Q.52 C 2l + 1 = number of orbitals in shell 2(2l + 1) = number of electrons in subshell
2n² = number of electrons in shell n² = number of orbitals in shell
Q.53 B Azimuthal quantum number represents subshell
Q.54 A
Q.55 B Azimuthal quantum number describes orbital shapes:
Q.56 C l = 0 s → spherical l = 1 p→ dumb-bell
l = 2 d→ double dumb-bell l = 3 f→ complicated

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Spark MDCAT Atomic structure
Q.57 A Coefficient = principal quantum number (n); smaller n means closer to nucleus
Q.58 B n + l is highest for 4f (4+3) = 7
Q.59 D s-orbital shape = spherical
Q.60 B d-subshell does not exist in 2nd shell
Q.61 B Atomic orbital: Region of high probability of finding electron
Q.62 D Principal quantum number defines shell size
Q.63 A Aufbau principle helps order of filling subshells
Hund’s rule: electrons occupy separate orbitals
Pauli exclusion: No two e⁻ in same orbital can have same 4 quantum numbers
Mosley: Atomic number arrangement
Q.64 B Filling order can be explained by n + l rule
(a) Electrons fill subshells by increasing (n+l) (b) Lower n preferred if (n+l) is same
Q.65 B Order of subshell energy: f > d > p > s
Q.66 C Valency = number of unpaired e⁻ in half-filled orbitals (Hund’s Rule)
Q.67 B Nickel ions contain unpaired electrons
A. ₂₀Ca⁺² = 1s², 2s², 2p⁶, 3s², 3p⁶
B. ₂₈Ni⁺² = 1s², 2s², 2p⁶, 3s², 3p⁶, 3d²yz, 3d²xz, 3d²xy, 3d¹x²−y², 3d¹z², 4s⁰
C. ₁₉K⁺¹ = 1s², 2s², 2p⁶, 3s², 3p⁶
A. ₃₀Zn⁺² = 1s², 2s², 2p⁶, 3s², 3p⁶, 4s², 3d¹⁰
Q.68 C K = 2, L = 8, M = 6 → Group VI, Period 3
Q.69 A d-subshell starts from 3rd shell
Q.70 C Number of electrons = 2(2l + 1) =2(2(2) + 1)= 6
Q.71 C Cr = [Ar] 4s¹, 3d⁵ → 6 unpaired electrons
Q.72 C Filling order according to n + l rule : 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d
Q.73 D P₁₅ = [Ne] 3s² 3pₓ¹, 3pᵧ¹, 3p𝓏¹
Q.74 D
Q.75 D Na⁺ = K = 2, L = 8 Al⁺³ = K = 2, L = 8
Cl⁻ = K = 2, L = 8, M = 8 O⁻² = K = 2, L = 8
Q.76 D Octet rule is unrelated to electron arrangement by energy.
Q.77 D Atomic weight 29 → Chromium: prefers half/full d-subshells over d⁴/d⁹ because half or
full are relatively more stable
Q.78 C

Q.79 A
Q.80 B K₁₉ = 1s², 2s², 2p⁶, 3s², 3p⁶, 4s¹

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P a g e | 28 MATERIAL OF PTB, STB, BTB, KPK, FTB & A-LEVELS

Spark MDCAT Atomic structure

P a g e | 29 MATERIAL OF PTB, STB, BTB, KPK, FTB & A-LEVELS