PHYSICAL CHEMISTRY

TARGET IIT-ENTRANCE 2014

XI

ATOMIC STRUCTURE
PREREQUISITE:
Basic concept of electrostatics force,
electrostatic potential energy, circular motion.
Basic idea of wave, electromagnetic wave,
dual of light and spectrum

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Atomic Structure [2]
Constants Symbol SI Value
Speed of light in vaccum c 2.99 ×108 m/s 2.99 × 1010 cm/s
Proton & electron charge e 1.60 × 10–19 C 4.8 × 10–10 esu
Permittivity of vaccum 0 8.85 × 10–12 C2/N-m2
Avogadro constant NA 6.02 × 1023 mol–1 6.02 × 1023 mol–1
Electron rest mass me 9.10 × 10–31 kg 0.000548 amu
Proton rest mass mP 1.67 × 10–27 kg 1.00757 amu
Neutron rest mass mn 1.67 × 10–27 kg 1.00893 amu
Planck constant h 6.62 × 10–34 J s 6.62 × 10–27 erg s
Bohr magneton (BM) e 9.27 × 10–24 J/T
Gas constant R 8.3145 J/mol-K 0.0821 atm-lit / mol / K
Boltzmann constant k 1.38 × 10–23 J/K 1.30 × 10–16 erg/K
Gravitional constant G 6.67 × 10–11 m3/kg -s2 6.67 × 10–8 cm3/g-s2

Energy Conversion Factors

1 erg = 10–7 J
1 cal = 4.184 J
1 eV = 1.602177 × 10–19 J = 1.602177 × 10–12 erg = 23.0605 kcal/mol

Greek Alphabet
Alpha   Beta  
Gamma   Delta  
Epsilon   Zeta  
Eta   Theta  
Iota   Kappa  
Lambda   Mu  
Nu   Xi  
Omicron   Pi  
Rho   Sigma  
Tau   Upsilon  
Phi   Chi  
Psi   Omega  

Atomic Structure [3]

 KEY CONCEPT
STRUCTURE OF ATOM

1. Rutherford's Model
(a) Electrons, protons & neutrons are the most important fundamental particles of atoms of all elements
(Except hydrogen)

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

(c) Rn = R1 (A)1/3 , R1 = 1.33 ×10–13 cm A = mass number

1 Z . 2e
(d) m  v 2  K ; r = distance of closest approach , v = initial velocity of a -particle
2 r

2. Light
(a) Photon is considered massless bundle of energy.
(b) E = mc2
(c) Ephoton = h = hc/  = hc 

hc 1240 eV . nm
(d) E= 
 
no. of molecules reacting
(e) Quantum efficiency or Quantum Yield =
no. of quanta absorbed

3. Bohr’s Model

Kq1q 2 1
(a) Electrostatic force = where K = 4 = 9 × 109 N-m2 / C2
r2 0

Kq1q 2
(b) Potential energy due to electrostatic force =
r

KQ
(c) Potential due to a charge particle (Q) at a distance r =
r

h
(d) Bohr quantization rule mvr = n· = n .
2
(e) According to newtons second law in a uniform circular motion resultant of all the forces towards

mv 2
centre must be equal to .
r

Kq1q 2 mv 2
(f) 
r2 r

Atomic Structure [4]

 E1 2 2 2 me 4 K 2 2  2 2 me 4 K 2 Z 2
(g) En = Z =– Z ; E1 =
n
2 n 2h 2 h2

2 2
h n
(h) rn = 2 2 
4 e m K Z

2
2e K Z
(i) vn = 
h n
(j) Revolutions per sec = v/2r
(k) Time for one revolution = 2r/v
(l) Ionisation energy = E n  – Eelectron = – Eelectron

4. Spectral lines

1 1 1  2
(a) Rydberg’s Equation    RH 
2
—
2
Z ; RH  109700 cm–1

 n1 n 2 

(b) For First line of a series n2 = n1 + 1

(c) Limiting spectral line (series limit) means n2 = 

(d) H line means n2 = n1+1 ; also known as line of longest , shortest  , least E

(e) Similarly H line means n2 = n1+ 2

n ( n  1)
(f) Number of spectral line observed in the spectrum =
2
when e– de-excites to ground state , n = number of higher orbit

(g)

n=5

n=4
Bracket
series
n=3
Paschen
series
n=2
Balmer
series
n=1
H H H
 

Lyman
series

Atomic Structure [5]

5. Photoelectric effect
(a) Kinetic energy = = h – w = h – h0
where w = work function
0 = Threshhold frequency
1 2
(b) Accelerating potential = eV = KE = mv
2
(c) 1/2 = a(z–b) b = screening constant

6. De-broglie, Heisenberg & Schrodinger equations

(a) Number of waves = n = principal quantum number
(b)  = h/mv = h/p
150
(c) wavelength of electron ()  Å
Vin volts
(d) x.p  h/4
h
(e) Orbital angular momentum = l (l  1)
2
h
(f) Spin angular momentum = S = S(S  1)
2
(g) Magnetic momentum () = n ( n  2 ) B.M. ; n = number of unpaired electron
(h) Radial Nodes = (n – l – 1)
(i) Angular nodes =l
(j) Total nodes = (n–1)

7. Terms associated with elements

(a) Isotopes
(b) Isobars
(c) Isotones (A – Z)
(d) Isoelectronic
(e) Isosters
(f) Isodiaphers (A – 2Z)
(g) paramagnetic
(h) Diamagnetic

8. Eleectromegnetic Spectrum
 increases

Cosmic -rays X-rays Vaccum UV Visible Near Far Micro Radio

Rays UV IR IR Waves Waves

–11 –9 –7 –6 –5 –3 –1 0
= 10
–14
10
–13
10 10 10 10 10 10 10 10
–8 –4 –2
10
–10
10 10 10
–12
10
Atomic Structure [6]
 SHAPES OF ATOMIC ORBITALS

The spherical Polar Coordinates S

pX py pz

d z2 d dxy
x 2  y2

Atomic Structure [7]

 dxz dyz f z3

fxyz f f
x ( y2 z2 )
z ( x 2  y2 )

f f f
y( z2  x 2 ) x3 y3

Atomic Structure [8]

 EXERCISE -I

BOHR’S MODEL

Q.1 Calculate the wavelength of radiation emitted, producing a line in Lyman series, when an electron falls
from fourth stationary state in hydrogen atom.
 1 
[Given :   = 912 Å]
 Rn 

Q.2 Calculate energy of electron which is moving in the orbit that has its radius. sixteen times the radius of first
Bohr orbit for H–atom.
[Given : E1,H = 2.176 × 10–18 J/atom]

Q.3 The wavelength of a certain line in the Paschen series in 1094.4 nm of H-atom. What is the value of nhigh
for this line.

Q.4 Wavelength of the Balmer H line is 6565 Å. Calculate the wavelength of H , line of same hydrogen
like atom.

Q.5 Calculate the Rydberg constant R if He+ ions are known to have the wavelength difference between the
first (of the longest wavelength) lines of Balmer and Lyman series equal to 133.7nm.

Q.6 What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition, n=4
to n=2 of He+ spectrum.

Q.7 Calculate the total energy emitted when electrons of 1.0 g atom of hydrogen undergo transition giving the
spectral line of lowest energy in the visible region of its atomic spectrum.
[Given : E1(H) = 2.176 × 10–18 ]

Q.8 A photon having  = 800 Å causes the ionization of a nitrogen atom. Give the I.E. per mole of nitrogen in KJ.
[Given : E = 1240 eV-nm, 1eV = 96.43 kJ/mol]

Q.9 H- atom is exposed to electromagnetic radiation of 1028 Å and gives out induced radiations (radiations
emitted when e– returns to ground state).Calculate  of induced radiations.

 21.7  10 12
Q.10 The electron energy in hydrogen atom is given by E n  ergs. Calculate the energy required
n2

to remove an e completely from n = 2 orbit . What is the largest wavelength in cm of light that can be
used to cause this transition.

Q.11 Calculate the wavelength in angstrom of photon that is emitted when an e in Bohr orbit n=2 returns to
the orbit n=1. The ionization potential of the ground state of hydrogen atom is 2.17×1011 erg/atom.

Q.12 The radius of the an orbit of hydrogen atom is 0.85 nm. Calculate the velocity of electron in this orbit.

Atomic Structure [9]

Q.13 The velocity of e in a certain Bohr orbit of the hydrogen atom bears the ratio 1:275 to the velocity of
light. What is the quantum no. "n" of the orbit and the wave no. of the radiation emitted for the transition
from the quatum state (n+1) to the ground state.

Q.14 A doubly ionised lithium atom is hydrogen like with atomic number z = 3. Find the wavelength of the
radiation required to excite the electron in Li2+ from the first to the third Bohr orbit.
1
[Given : R = 912 Å]
H

Q.15 Estimate the difference in energy between I and II Bohr Orbit for a hydrogen atom. At what minimum
atomic number a transition from n=2 to n=1 energy level would result in the emission of Xrays with
= 3.0 × 108 m? Which hydrogen like species does this atomic number correspond to.

Q.16 Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic hydrogen.
[ Given : RH = 1.097 × 107 m–]

Q.17 1.8 g hydrogen atoms are excited to radiations. The study of spectra indicates that 27% of the atoms are
in 3rd energy level and 15% of atoms in 2nd energy level and the rest in ground state. If I.P. of H is
21.7 × 1012 erg. Calculate 
(i) No. of atoms present in III & II energy level.
(ii) Total energy evolved when all the atoms return to ground state.

Q.18 The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e– in the given orbit .

Q.19 The vapours of Hg absorb some electrons accelerated by a potential diff. of 4.5 volt as a result of which
light is emitted. If the full energy of single incident e is supposed to be converted into light emitted by
single Hg atom, find the wave no. of the light.

Q.20 If the average life time of an excited state of H atom is of order 10–8 sec, estimate how many orbits an e–
makes when it is in the state n = 2 and before it suffers a transition to n =1 state.

Q.21 Calculate the frequency of e– in the first Bohr orbit in a H-atom.

Q.22 A single electron orbits around a stationary nucleus of charge +Ze where Z is atomic number and ‘e’ is
the magnitude of the electric charge. The hydrogen like species required 47.2 eV to excite the electron
from the second Bohr orbit to the third Bohr orbit. Find
(i) the value of Z and give the hydrogen like species formed.
(ii) the kinetic energy and potential energy of the electron in the first Bohr orbit.

Q.23 A stationary He+ ion emitted a photon corresponding to a first line of the Lyman series. The photon
liberated a photoelectron from a stationary H atom in ground state. What is the velocity of photoelectron.

Q.24 In a hydrogen atom, in transition of electron a photon of energy 2.55 eV is emitted, then calculate
change in wavelength of the electron.

Q.25 In a hypothetical H-atom the mass of electron & it charge is double of what we consider then calculate
the total energy of electron in the Ist orbit of such a hypothetical H-atom ?
[Assuming all others concepts and parameter to be same as we considered in Bohr's model.]

Atomic Structure [10]

 PHOTOELECTRIC EFFECT
Q.26 Calculate the threshold frequency of metal if the binding energy is 198.9 KJ mol1 of electron.
[Given : NA = 6 × 1023]

Q.27 Calculate the binding energy per mole when threshold wavelength of photon is 240 nm.
[Given : hc = 20 × 10–26 , NA = 6 × 1023]

Q.28 A metal was irriadated by light of frequency 3.25 × 1015 S1. The photoelectron produced had its KE,
2 times the KE of the photoelectron which was produced when the same metal was irriadated with a
light of frequency 2.0 ×1015 S1. What is work function.[Given :NA = 6 × 1023]

Q.29 U.V. light of wavelength 800 Å & 700 Å falls on hydrogen atoms in their ground state & liberates
electrons with kinetic energy 1.8 eV and 4 eV respectively. Calculate planck’s constant.

Q.30 A potential difference of 20 KV is applied across an X-ray tube. Find the minimum wavelength of X-ray
generated.

Q.31 The K.E. of an electron emitted from tungstan surface is 3.06 eV. What voltage would be required to
bring the electron to rest.

Q.32 The eyes of certain member of the reptile family pass a single visual signal to the brain when the visual
receptors are struck by photons of wavelength 132.6 nm . If a total energy of 3 10 14 J is required to
trip the signal, what is the minimum number of photons that must strike the receptor.

Q.33 Find the number of photons of radiation of frequency 5 × 1013 s–1 that must be absorbed in order to melt
one gm ice when the latent heat of fusion of ice is 331.5 J/g.

Q.34 Suppose 1017 J of light energy is needed by the interior of the human eye to see an object. How many
photons of green light ( = 550 nm) are needed to generate this minimum amount of energy.

GENERAL
Q.35 What is de-Broglie wavelength of a He-atom in a container at 300 K.(Use Uavg)

Q.36 Through what potential difference must an electron pass to have a wavelength of 500 Å.

Q.37 A proton is accelerated to one- tenth of the velocity of light. If its velocity can be measured with a
precision + 1%. What must be its uncertainity in position.

Q.38 To what effective potential a proton beam be subjected to give its protons a wavelength of 1 ×1010 m.

Q.39 Calculate magnitude of orbital angular momentum of an e– that occupies 1s, 2s , 2p , 3d , 3p.

Q.40 He atom can be excited to 1s1 2p1 by  = 58.44 nm. If lowest excited state for He lies 4857cm–1 below
the above. Calculate the energy for the lower excitation state.

Q.41 A certain dye absorbs 4700 Å and fluoresces at 5080 Å these being wavelengths of maximum absorption
that under given conditions 47% of the absorbed energy is emitted. Calculate the ratio of the no. of
quanta emitted to the number absorbed.
Atomic Structure [11]
Q.42 The reaction between H2 and Br2 to form HBr in presence of light is initiated by the photo decomposition
of Br2 into free Br atoms (free radicals) by absorption of light. The bond dissociation energy of Br2 is
192.86 KJ/mole. What is the longest wavelength of the photon that would initiate the reaction.
[Given : E = 1240 eVnm]

Q.43 The quantum yield for decomposition of HI is 0.2. In an experiment 0.01 moles of HI are decomposed.
Find the number of photons absorbed.

Q.44 Calculate the wavelength of the radiation that would cause photo dissociation of chlorine molecule if the
Cl- Cl bond energy is 241 KJ/mol.

Q.45 The dissociation energy of H2 is 430.53 KJ/mol. If H2 is exposed to radiant energy of wavelength
253.7 nm, what % of radiant energy will be converted into K.E.

Q.46 X-rays emitted from a copper target and a molybdenum target are found to contain a line of wavelength
22.85 nm attributed to the K line of an impurity element. The K lines of copper (Z = 29) and molybdenum
( Z = 42) have wavelength 15.42 nm and 7.12 nm respectively. Using Moseley’s law, 1/2 = a (Z – b)
calculate the atomic number of the impurity element.

Q.47 What is de Broglie wavelength associated with an e– accelerated through potential difference = 100 KV.

Q.48 Calculate the de-broglie wavelength associated with motion of earth (mass 6 × 1024 Kg) orbiting around
the sun at a speed of 3 × 106 m/s.

Q.49 A base ball of mass 200 g is moving with velocity 30 × 102 cm/s. If we can locate the base ball with an
error equal in magnitude to the  of the light used (5000 Å), how will the uncertainty in momentum be
compared with the total momentum of base ball.

Q.50 An electron has a speed of 40 m/s, accurate up to 99.99%. What is the uncertainity in locating its
position.

Atomic Structure [12]

 EXERCISE-II
Q.1 An energy of 68 eV is required to excite a hydrogen like atom from its second Bohr orbit to the third.
The nuclear charge is Ze. Find the value of Z, the kinetic energy of the electron in the first Bohr orbit and
the wavelength of the radiation required to eject the electrons from the first Bohr orbit to infinity.
Q.2 A particle of charge equal to that of an electron and mass 208 times the mass of the electron moves in a
circular orbit around a nucleus of charge +3e. Assuming that the Bohr model of the atom is applicable to this
system, (a) derive an expression for the radius of the nth bohr orbit, (b) find the value of n for which the radius
of the orbit is approximately the same as that of the first Bohr orbit for th ehydrogen atom, and (c) find the
wavelength of the radiation emitted when the revolving particle jumps from the third orbit to the first.
h2
[Given: = 7.72 × 10–13]
4  2 Ke 2
208 m e
Q.3 An alpha particle after passing through a potential difference of 2 × 106 volt falls on a silver foil. The
atomic number of silver is 47. Calculate (i) the K.E. of the alpha-particle at the time of falling on the foil.
(ii) K.E. of the  – particle at a distance of 5 × 10–14m from the nucleus, (iii) the shortest distance from
the nucleus of silver to which the particle reaches.
ke 2
Q.4 Suppose the potential energy between electron and proton at a distance r is given by  . Use
3r 3
Bohr’s theory to obtain energy of such a hypothetical atom.
Q.5 A proton captures a free electron whose K.E. is zero & forms a hydrogen atom of lowest energy-level
(n = 1). If a photon is emitted in this process, what will be the wavelength of radiation? In which region
of electromagnetic spectrum, will this radiation fall? (Ionisation potential of hydrogen = 13.6 volt,
h = 6.6 × 10–34K/s, C = 3.0 × 108 m/s)
Q.6 The ionisation energy of the hydrogen atom is given to be 13.6 eV. A photon falls on a hydrogen atom
which is initially in the ground state and excites it to the (n = 4)state.
(a) show this transition in the energy-level diagram &
(b) calculate the wavelength of the photon.
Q.7 Find the wavelength of the first line of He+ ion spectral series whose interval between extreme line is
1 1 4 1 
   2.7451 10 cm 
 1  2 
Q.8 The ionisation energy of a H-like Bohr atom is 4 Rydbergs
(i) What is the wavelength of radiation emitted when the e– jumps from the first excited state to the ground state.
(ii) What is the radius of first Bohr orbit for this atom. [ 1 Rydberg = 2.18 × 10–18 J]
Q.9 Photon having wavelength 12.4 nm was allowed to strike a metal plate having work function 25 eV.
Calculate the
(a) Maximum kinetic energy of photoelectrons emitted in eV.
(b) Wavelength of electron with maximum kinetic energy in Å.
(c) Calculate the uncertainity in wavelength of emitted electron if the uncertainity in the momentum is
6.62 × 10–28 Kg m/sec.
Q.10 Electron present in single electron specie jumps from energy level 3 to 1. Emitted photons when passed
through a sample containing excited He+ ion causes further excitation to some higher energy level (Given
Z2
En = –13.6 ). Determine
n2
(i) Atomic number of single electron specie.
(ii) principal quantum number of initial excited level & higher energy level of He+.
Atomic Structure [13]
Q.11 The angular momentum of an electron in a Bohr's orbit of H-atom is 3.1652×10–34 kg-m2/sec. Calculate
the wavenumber in terms of Rydberg constant (R) of the spectral line emitted when an electron falls from
this level to the ground state.[Use h = 6.626 × 10–34 Js]
Q.12 A cylindrical source of light which emits radiation radially (from curved surface) only, placed at the
centre of a hollow, metallic cylindrical surface, as shown in diagram.
The power of source is 90 watt and it emits light of wavelength 4000 Å only. The emitted photons strike
the metallic cylindrical surface which results in ejection of photoelectrons. All ejected photoelectrons
reaches to anode (light source). The magnitude of photocurrent is [Given : h = 6.4 × 10–34 J/sec.]

Q.13 Mr. Santa has to decode a number "ABCDEF" where each alphabet is represented by a single digit.
Suppose an orbital whose radial wave function is represented as
(r) = k1 · e  r / k 2
(r2 – 5k3r + 6k 32 )
From the following information given about each alphabet then write down the answers in the form of
"ABCDEF", for above orbital.
Info A = Value of n where "n" is principal quantum number
Info B = No. of angular nodes
Info C = Azimuthal quantum number of subshell to orbital belongs
Info D = No. of subshells having energy between (n + 5)s to (n + 5)p where n is principal quantum
number
Info E = Orbital angular momentum of given orbital.
Info F = Radial distance of the spherical node which is farthest from the nucleus
(Assuming k3= 1)
Q.14 In the Bohr's model, for unielectronic species following symbols are used
rn,z  Radius of nth orbit with atomic number "z"
Un,z  Potential energy of electron in nth orbit with atomic number "z"
Kn,z  Kinetic energy of electron in nth orbit with atomic number "z"
vn,z  Velocity of electron in nth orbit with atomic number "z"
Tn,z  Time period of revolution of electron in nth orbit with atomic number "z"
Calculate z in all in cases.
(i) U1, 2 : K1,z = – 8 : 1 (ii) r1,z : r2, 1 = 1 : 8
(iii) v1, z : v3, 1 = 9 : 1 (iv) T1, 2 : T2, z = 9 : 32
Represent your answer as abcd, where a, b, c and d represent number from 0 to 9. a, b, c and d
represents the value of "z" in parts (i), (ii) ,(iii) & (iv). Suppose your answer is 1, 2, 3 & 4 then the
same must be filled in OMR sheet as1234.00.

Q.15 Calculate the distance of spherical nodes for '3s' orbital from nucleus?
1 
 2r
2
R3s = 9 3a 3 / 2 (6 – 6  +  ) e 2 where  = na
0 0

Atomic Structure [14]

 EXERCISE-III
Fill in the blanks :
Q.1 Radiation of  = 155 nm was irradiated on Li (work function = 5 eV) plate. The stopping potential
(in eV) is __________.

Q.2 Increasing order of magnetic moment among the following species is ________.
Na+, Fe+3, Co2+, Cr+2

Q.3 If in the hydrogen atom P.E. at is chosen to be 13.6 eV then the ratio of T.E. to K.E. for 1st orbit of
H-atom is ________.

Q.4 The light radiations with discrete quantities of energy are called ______.

Single correct :
Q.5 The ratio of the energy of a photon of 2000 Å wavelength radiation to that of 4000 Å radiation is
(A) 1 / 4 (B) 4 (C) 1 / 2 (D) 2

Q.6 The energy of electron is maximum at

(A) Nucleus (B) Ground state
(C) First excited state (D) Infinite distance from the nucleus

Q.7 Which electronic level would allow the hydrogen atom to absorb a photon but not to emit a photon
(A) 3s (B) 2p (C) 2s (D) 1s

Q.8 The third line in Balmer series corresponds to an electronic transition between which Bohr’s orbits in
hydrogen
(A) 5  3 (B) 5  2 (C) 4  3 (D) 4  2

Q.9 The orbital angular momentum of an electron in 2s orbital is:

1   
(A)  . (B) Zero (C) (D) 2 .
2 2 2 2

Q.10 Which quantum number is not related with Schrodinger equation

(A) Principal (B) Azimuthal (C) Magnetic (D) Spin

Q.11 The shortest wavelength of He atom in Balmer series is x, then longest wavelength in the Paschene series
of Li+2 is
36 x 16 x 9x 5x
(A) (B) (C) (D)
5 7 5 9

Q.12 An electron in a hydrogen atom in its ground state absorbs energy equal to the ionisation energy of Li+2.
The wavelength of the emitted electron is:
(A) 3.32 Å (B) 1.17 Å (C) 2.32 nm (D) 3.33 pm

Q.13 An electron, a proton and an alpha particle have kinetic energies of 16E, 4E and E respectively. What is
the qualitative order of their de Broglie wavelengths?
(A) e > p =  (B) p =  > e (C) p > e >  (D)  < e » p

Atomic Structure [15]

Q.14 Given H for the process Li(g)  Li+3(g) + 3e– is 19800 kJ/mole & IE1 for Li is 520 then IE2 & IE3
of Li+ are respectively (approx, value)
(A) 7505, 11775 (B) 520, 19280 (C) 11775, 19280 (D) Data insufficient

Q.15 The ratio of difference in wavelengths of 1st and 2nd lines of Lyman series in H–like atom to difference in
wavelength for 2nd and 3rd lines of same series is:
(A) 2.5 : 1 (B) 3.5 : 1 (C) 4.5 : 1 (D) 5.5 : 1

Q.16 If radius of second stationary orbit (in Bohr's atom) is R. Then radius of third orbit will be
(A) R/3 (B) 9R (C) R/9 (D) 2.25R

Q.17 The ratio of wave length of photon corresponding to the -line of Lyman series in H-atom and -line of
Balmer series in He+ is
(A) 1 : 1 (B) 1 : 2 (C) 1 : 4 (D) 3 : 16

Q.18 Three energy levels P, Q, R of a certain atom are such that EP < EQ < ER. If 1, 2 and 3 are the wave
length of radiation corresponding to transition R  Q ; Q  P and R P respectively. The correct
relationship between 1, 2 and 3 is
1 1 1 2 1 1
(A) 1 + 2 = 3 (B)      (C) 3 = 1 2 (D)     
3 1 2 3 1 2

Q.19 The value of (n2 + n1) and n 22  n12 for He+ ion in atomic spectrum are 4 and 8 respectively. The
 
wavelength of emitted photon when electron jump from n2 to n1 is
32 9 9 32
(A) R (B) R (C) 32 R (D) 9 R
9 H 32 H H H

Q.20 Number of possible spectral lines which may be emitted in bracket series in H atom, if electrons present
in 9th excited level returns to ground level, are
(A) 21 (B) 6 (C) 45 (D) 5

Q.21 The first use of quantum theory to explain the structure of atom was made by :
(A) Heisenburg (B) Bohr (C) Planck (D) Einstein

Q.22 The wavelength associated with a golf weighing 200g and moving at a speed of 5m/h is of the order
(A) 10–10m (B) 10–20m (C) 10–30m (D) 10–40m

Q.23 The longest wavelength of He+ in Paschen series is "m", then shortest wavelength of Be+3 in Paschen
series is (in terms of m):
5 64 53 7
(A) m (B) m (C) m (D) m
36 7 8 64

Q.24 What is uncertainity in location of a photon of wavelength 5000Å if wavelength is known to an accuracy
of 1 pm?
(A) 7.96 × 10–14 m (B) 0.02 m (C) 3.9 ×10–8 m (D) none

Atomic Structure [16]

Q.25 Consider the following nuclear reactions involving X & Y.
X  Y + 42 He
Y  8O18 + 1H1
If both neutrons as well as protons in both the sides are conserved in nuclear reaction then moles
of neutrons in 4.6 gm of X
(A) 2.4 NA (B) 2.4 (C) 4.6 (D) 0.2 NA

Q.26 Electromagnetic radiations having  = 310 Å are subjected to a metal sheet having work
function = 12.8 eV. What will be the velocity of photoelectrons with maximum Kinetic Energy..
(A) 0, no emission will occur (B) 2.18 × 106 m/s
(C) 2.18 2 × 106 m/s (D) 8.72 × 106 m/s

Q.27 Assuming Heisenberg Uncertainity Principle to be true what could be the minimum uncertainty in de-broglie
wavelength of a moving electron accelerated by Potential Difference of 6 V whose uncertainty in position
7
is n.m.
22
(A) 6.25 Å (B) 6 Å (C) 0.625 Å (D) 0.3125 Å

More than one may be correct :

Q.28 Choose the correct statement among the following
(A) Radial distribution function (  2 ·4r 2dr ) give probability at a particular distance along
one chosen direction
(B)  2 ( r ) give probability density at a particular distance over a spherical surface
(C) For 's' orbitals  ( r )  ()  ()   ( x , y, z ) is independent of  and 
(D) '2p' orbital with quantum numbers. n = 2,  = 1, m = 0, also shows angular dependence

Q.29 Correct statement(s) regarding 3Py orbital is/are

(A) Angular part of wave function is independent of angles ( and )
(B) No. of maxima when a curve is plotted between 4r2R2(r) vs r are '2'
(C) 'xz' plane acts as nodal plane
(D) Magnetic quantum number must be '–1'
Q.30 Select the correct statement(s):
(A) All electromagnetic radiation travel with speed of light in vaccum.
(B) Energy of photon of UV light is lower than that of yellow light.
(C) He+ and H have similar spectrum.
(D) The total energy of an electron in unielectronic specie is greater than zero
Q.31 Choose the incorrect statement(s):
(A) Increasing order of wavelength is
Micro waves > Radio waves > IR waves > visible waves > UV waves
(B) The order of Bohr radius is (rn : where n is orbit number for a given atom)
r1 < r2 < r3 < r4
(C) The order of total energy is (En : where n is orbit number for a given atom)
E1 > E2 > E3 > E4
(D) The order of velocity of electron in H, He+, Li+, Be3+ species in second Bohr orbit is
Be3+ > Li+2 > He+ > H
Atomic Structure [17]
Q.32 Select the correct curve(s):
If v = velocity of electron in Bohr's orbit
r = Radius of electron in Bohr's orbit
P.E. = Potential energy of electron in Bohr's orbit
K.E. = Kinetic energy of electron in Bohr's orbit.

(A) (B) (C) (D)

Q.33 Which is / are correct statement.

(A) The difference in angular momentum associated with the electron present in consecutive orbits of
h
H-atom is (n–1)
2
(B) Energy difference between energy levels will be changed if, P.E. at infinity assigned value other than
zero.
(C) Frequency of spectral line in a H-atom is in the order of (2  1) < (3  1) < (4  1)
(D) On moving away from the nucleus, kinetic energy of electron decreases.

Assertion and Reason :

Q.34 It is a data sufficiency problem in which it is to be decided on the basis of given statements
whether the given question can be answered or not. No matter whether the answer is yes or no.
Question : Is the orbital of hydrogen atom 3px?
1 r
Statement-1: The radial function of the orbital is R(r) = 3/ 2
(4  ) e  / 2 , =
9 6 a0 2
Statement-2: The orbital has 1 radial node & 0 angular node.
(A) Statement (1) alone is sufficient. (B) Statement (2) alone is sufficient
(C) Both together is sufficient. (D) Neither is sufficient

Q.35 Statement-1: Energy emitted when an electron jump from 5  2 (energy level) is less than
when an electron jump from 2  1 in all 'H' like atom.

Statement-2: The |total energy difference| between 1st & 2nd energy level is greater than that of
any two energy level provided level '1' is not part of those two energy levels.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Q.36 Statement-1 : Emitted radiations will fall in visible range when an electron jump from
higher level to n = 2 in Li+2 ion.
Statement-2 : Balmer series radiations belong to visible range in H-atoms.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Atomic Structure [18]
Match the column :
Q.37 Column I & column II contain data on Schrondinger Wave–Mechanical model, where symbols have
their usual meanings.Match the columns.
Column I Column II (Type of orbital)

(A) (P) 4s

(B) (Q) 5px

(C) (,) = K (independent of &) (R) 3s

(D) atleast one angular node is present (S) 6d xy

Q.38 Column-I Column-I

(A) Electron moving in 2nd orbit in He+ ion (P) Radius of orbit in which
electron is moving is 0.529 Å

(B) Electron moving in 3rd orbit in H-atom (Q) Total energy of electron is
(–)13.6 × 9eV

(C) Electron moving in 1st orbit in Li+2 ion (R) Velocity of electron is
2.188  106
m/sec
3
(D) Electron moving in 2nd orbit is Be+3 ion (S) De-broglie wavelength of
150
electron is Å
13.6

Atomic Structure [19]

Comprehension
Question No. 39 to 41 (3 questions)
The French physicist Louis de Broglie in 1924 postulated that matter, like radiation, should exhibit a dual
behaviour. He proposed the following relationship between the wavelength  of a material particle, its
linear momentum p and planck constant h.
h h
= =
p mv
The de Broglie relation implies that the wavelength of a particle should decreases as its velocity increases.
It also implies that for a given velocity heavier particles should have shorter wavelength than lighter
particles. The waves associated with particles in motion are called matter waves or de Broglie waves.
These waves differ from the electromagnetic waves as they
(i) have lower velocities
(ii) have no electrical and magnetic fields and
(iii) are not emitted by the particle under consideration.
The experimental confirmation of the de Broglie relation was obtained when Davisson and Germer, in
1927, observed that a beam of electrons is diffracted by a nickel crystal. As diffraction is a characteristic
property of waves, hence the beam of electron behaves as a wave, as proposed by de Broglie.
Werner Heisenberg considered the limits of how precisely we can measure properties of an electron or
other microscopic particle like electron. He determined that there is a fundamental limit of how closely
we can measure both position and momentum. The more accurately we measure the momentum of a
particle, the less accurately we can determine its position. The converse is also true. This is summed up
in what we now call the "Heisenberg uncertainty principle: It is impossible to determine simultaneously
and precisely both the momentum and position of a particle. The product of uncertainty in the position,
h
x and the uncertainty in the momentum (mv) must be greater than or equal to . i.e.
4
h
x (mv) 
4

Q.39 The correct order of wavelength of Hydrogen (1H1), Deuterium (1H2) and Tritium (1H3) moving with
same kinetic energy is
(A) H > D > T (B) H = D = T (C) H < D < T (D) H < D > T

Q.40 The transition, so that the de-Broglie wavelength of electron becomes 3 times of its initial value in He+ ion
will be
(A) 2  5 (B) 3  2 (C) 2  6 (D) 1  2

Q.41 If the uncertainty in velocity & position is same, then the uncertainty in momentum will be
hm h h 1 h
(A) (B) m (C) (D)
4 4 4m m 4

Atomic Structure [20]

 Question No. 42 to 45 (4 questions)
The only electron in the hydrogen atom resides under ordinary conditions on the first orbit. When energy
is supplied, the electron moves to higher energy orbit depending on the amount of energy absorbed.
When this electron returns to any of the lower orbits, it emits energy. Lyman series is formed when the
electron returns to the lowest orbit while Balmer series is formed when the electron returns to second
orbit. Similarly, Paschen, Brackett and Pfund series are formed when electron returns to the third, fourth
and fifth orbits from higher energy orbits respectively.
Maximum number of lines produced when an electron jumps from nth level to ground level is equal
n ( n  1)
to . For example, in the case of n = 4 , number of lines produced is 6. (4  3, 4  2, 4  1,
2
3  2 , 3  1, 2  1). When an electron returns from n2 to n1 state, the number of lines in the spectrum
will be equal to
(n 2  n1 )(n 2  n1  1)
2
If the electron comes back from energy level having energy E2 to energy level having energy E1, then the
difference may be expressed in terms of energy of photon as:
hc
E2 – E1 = E ,  =
E
Since h and c are constants, E corresponds to definite energy; thus each transition from one energy
level to another will produce a light of definite wavelength. This is actually observed as a line in the
spectrum of hydrogen atom.
 1 1 
Wave number of line is given by the formula   R  2  2  .
n 
 1 n2 
where R is a Rydberg's constant ( R = 1.1 × 107 m–1)

Q.42 The energy photon emitted corresponding to transition n = 3 to n = 1 is [ Given : h = 6 ×10–34 J-sec.]
(A) 1.76 ×10–18 J (B) 1.98 ×10–18 J (C) 1.76 ×10–17 J (D) None of these

Q.43 In a collection of H-atom, electrons make transition from 5th excited state to 2nd excited state then
maximum number of different types of photons observed are
(A) 3 (B) 4 (C) 6 (D) 15

Q.44 The difference in the wavelength of the 1st line of Lyman series and 2nd line of Balmer series in a hydrogen
atom is
9 4 88
(A) (B) (C) (D) None
2R R 15R

Q.45 The wave number of electromagnetic radiation emitted during the transition of electron in between two
levels of Li2+ ion whose principal quantum numbers sum is 4 and difference is 2 is
8
(A) 3.5 R (B) 4 R (C) 8 R (D) R
9

Atomic Structure [21]

 EXERCISE-IV

Q.1 With what velocity should an particle travel towards the nucleus of a Cu atom so as to arrive at a
distance 1013 m . [JEE 1997]

Q.2 A compound of Vanadium has magnetic moment of 1.73 BM work out electronic configuration of
Vanadium Ion in the compound. [JEE 1997]

Q.3 The energy of an electron in the first Bohr orbit of H atom is  13.6 eV . The possible energy value(s) of
the excited state(s) for electrons in Bohr orbits of hydrogen is/are :
(A)  3.4 eV (B)  4.2 eV (C)  6.8 eV (D) + 6.8 eV [JEE 1998]

Q.4 The number of nodal planes in a px orbital is:

(A) one (B) two (C) three (D) zero [JEE 2000]

Q.5 Calculate the energy required to excite one litre of hydrogen gas at 1 atmp and 298K to the first excited
state of atomic hydrogen. The energy for the dissociation of H – H is 436 KJ mol–1.
Q.6 The quantum numbers +1/2 and –1/2 for the electron spin represent:
(A) rotation of the electron in clockwise and anticlockwise direction respectively.
(B) rotation of the electron in anticlockwise and clockwise direction respectively.
(C) magnetic moment of the electron pointing up and down respectively.
(D) two quantum mechanical spin states which have no classical analogue. [JEE 2001]

Q.7 Rutherfords experiment , which established the nuclear model of atom, used a beam of :–
(A)  - particles, which impinged on a metal foil and get absorbed.
(B)  - rays, which impinged on a metal foil and ejected electron.
(C) Helium atoms, which impinged on a metal foil and got scattered.
(D) Helium nuclie, which impinged on a metal foil and got scattered. [JEE 2002]

Q.8 The magnetic moment of cobalt of the compund Hg[Co(SCN)4] is [Given : Co+2]
(A) 3 (B) 8 (C) 15 (D) 24 [JEE 2004]

Q.9 The radius of which of the following orbit is same as that of the first Bohr’s orbit of hydrogen atom?
(A) He+ (n = 2) (B) Li2+ (n = 2) (C) Li2+ (n = 3) (D) Be3+ (n = 2)
[JEE 2004]

Q.10 Given in hydrogenic atom rn, Vn, E, Kn stand for radius, potential energy, total energy and kinetic energy
in nth orbit. Find the value of U,v,x,y. [JEE 2006]
Vn
(A) U= K (P) 1
n

1
(B) x
rn  E (Q) –2

(C) rn  Zy (R) –1
(Z = Atomic number)
(D) v = (Orbital angular momentum of electron (S) 0
in its lowest energy )

Atomic Structure [22]

Q.11 Match the entries in Column I with the correctly related quantum number(s) in Column II. Indicate
your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.
[JEE 2008]

Column I Column I I
(A) Orbital angular momentum of the (P) Principal quantum number
electron in a hydrogen-like atomic orbital
(B) A hydrogen-like one-electron wave (Q) Azimuthal quantum number
function obeying Pauli principle
(C) Shape, size and orientation of hydrogen (R) Magnetic quantum number
like atomic orbitals
(D) Probability density of electron at the nucleus (S) Electron spin quantum number
in hydrogen-like atom
Paragraph for Questions 12 to 14
The hydrogen-like species Li2+ is in a spherically symmetric state S1 with one radial node. Upon absorbing
light the ion undergoes transition to a state S2. The state S2 has one radial node and its energy is equal to
the ground state energy of the hydrogen atom. [JEE 2010]
Q.12 The state S1 is
(A) 1s (B) 2s (C) 2p (D) 3s
Q.13 Energy of the state S1 in units of the hydrogen atom ground state energy is
(A) 0.75 (B) 1.50 (C) 2.25 (D) 4.50
Q.14 The orbital angular momentum quantum number of the state S2 is
(A) 0 (B) 1 (C) 2 (D) 3
Q.15 The work function () of some metals is listed below. The number of metals which will show
photoelectric effect when light of 300 nm wavelength falls on the metal is [JEE 2011]
Metal Li Na K Mg Cu Ag Fe Pt W
(eV ) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75

Q.16 The maximum number of electrons that can have principal quantum number, n = 3, and spin quantum
1
number, ms =  , is [JEE 2011]
2

ANSWER KEY
EXERCISE-I

Q.1 972.8 Å Q.2 – 1.36 × 10–19 Joules Q.3 0006

Q.4 4863 Å Q.5 1.096 × 107 m–1 Q.6 n1 =1, n2=2
Q.7 1.82 × 105 J/mol Q.8 1494.66 KJ/mol Q.9 6563 Å ; 1216 Å ; 1028 Å
Q.10 5.425×10–12 ergs, 3.7×10–5 cm Q.11 1220 Å
Q.12 5.44 × 105 m/s Q.13 2 ; 9.75 × 104 cm–1 Q.14 114 Å
Q.15 10.2 eV , z = 2 Q.16 27425 cm–1
Q.17 292.68×1021 atoms, 162.60×1021 atoms, 832.50 KJ Q.18 h/
Q.19 3.63 ×106 m–1 Q.20 8×106 Q.21 6530×1012Hz
Q.22 340 ev , – 680 eV Q.23 3.09 × 108 cm/sec Q.24 6.64 Å
Q.25 – 13.6 × 32 eV Q.26 5 ×1014 s–1 Q.27 500 KJ/mol
Atomic Structure [23]
Q.28 298.35 KJ/mol Q.29 6.57 ×10–34 Js Q.30 0.62 Å
Q.31 3.06 V Q.32 2000 Q.33 10 22
Q.34 28 photons Q.35 0.79 Å Q.36 6.03×10–4 volt
Q.37 1.05×10–13 m Q.38 0.0826 volts
h h h
Q.39 0;0; 2 ; 6 ; 2 Q.40 3.3 × 10–18 J
2 2 2
Q.41 0.5080 Q.42 6200 Å Q.43 3 × 1022
Q.44 4.96 × 10–7m Q.45 8.68 % Q.46 24
Q.47 3.88 pm Q.48 3.68 × 10–65 m Q.49 1.75 × 10–29
Q.50 0.0144 m
EXERCISE-II
n2 h2
Q.1 6 ; 489.6 eV , 25.28 Å Q.2 rn = n = 25 ; 55.2 pm
4K 2  3e 2  208 m e
n6 h6
Q.3 6.4×10–13 J, 2.1×10–13J, 3.4×10–14m Q.4 E=
384 m3 K 2 e 4 6
Q.5 910 Å ;U.V. Q.6 973.5 Å Q.7 4689 Å
Q.8 303.89 Å , 2.645 × 10 cm –9 Q.9 (a) 75 eV ; (b) 1.414 Å ; (c) 2 × 10–14 m
Q.10 Energy of emitted photons can not be greater than 13.6 eV (otherwise He+ will ionise) therefore single
electron specie must be hydrogen energy emitted = E3 – E1 = –1.51 + 13.6 = 12.09
For He+ ion this energy corresponds to excitation from 2 to 6.
8
Q.11 R  Q.12 10 amp Q.13 300303
9

93 3 93 3
Q.14 1233.00 Q.15 a0, a0
2 2
EXERCISE-III
Q.1 3 eV Q.2 Na+, Co2+,Cr2+, Fe3+ Q.3 zero Q.4 photons
Q.5 D Q.6 D Q.7 D Q.8 B
Q.9 B Q.10 D Q.11 B Q.12 B
Q.13 A Q.14 A Q.15 B Q.16 D
Q.17 A Q.18 B Q.19 C Q.20 B
Q.21 B Q.22 C Q.23 D Q.24 B
Q.25 B Q.26 C Q.27 C Q.28 C,D
Q.29 B,C Q.30 A,C Q.31 A,C Q.32 B,C,D
Q.33 C,D Q.34 B Q.35 A Q.36 D
Q.37 (A) P, (B) P,Q,S, (C) P, R (D) Q, S Q.38 (A) S, (B) R, (C) Q, (D) P
Q.39 A Q.40 C Q.41 A Q.42 A
Q.43 C Q.44 B Q.45 C
EXERCISE-IV

Q.1 6.3 × 106 m/s Q.2 [Ar] 3d1 Q.3 A

Q.4 A Q.5 97.819 KJ Q.6 D
Q.7 D Q.8 C Q.9 D
Q.10 (A) Q, (B) P, (C) R, (D) S Q.11 (A) Q,R (B) P, Q, R,S (C) P, Q, R (D) P, Q
Q.12 B Q.13 C Q.14 B
Q.15 4 Q.16 9
Atomic Structure [24]