Atomic structure

1. The wave motion of electron in a Bohr's orbit of hydrogen is as shown in diagram. The potential
energy of electron in the given orbit of hydrogen atom is :
(A) –3.4 eV (B) + 3.4 eV (C) –3.02 eV (D) –1.51eV

Ans. (C)
n=3
Z2
PE = – 27.2 × eV
n2
12
PE = –27.2 × = – 3.02 ev
32

2. For a hypothetical H like atom which follows Bohr,s model, some spectral lines were observed as
shown. it is known that line 'E' belongs to the visible region, then the lines possible belonging to
ultra violet region will be (n., is not necessarily ground state) [Assume for this atom, no spectral
series shows overlap with other series in the emmission spectrum]
N5

N4
C
N3
D
N2
E
N1
(A) B and D (B) D only (C) C only (D) A only
Ans. (D)
In the given figure if line ‘E’ is in visible region then line belonging to ultraviolet region will have
more energy then ‘E’ i.e. line A

3. The number of photons emitted in 10 hours by a 60 W sodium lamp (l of photon = 6000 Å)

[Take hc = 12400 eVÅ, h = Planck's constant, c = speed of light]
(A) 6.50 × 1024 (B) 6.40 × 1023 (C) 8.40 × 1023 (D) 3.40 × 1023
Ans. (A)
Let n be the number of photons emitted
12400
 × 1.6 × 10–19 × n = 60 × 10 × 60 × 60
6000
 n = 6.5 × 1024

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4. The De-broglie wavelength of a tennis ball of mass 66 g moving with the velocity of 10 metre per
second is approximately :
(A) 1O–35metres (B) 10–33 metres (C) 10–31 metres (D) 10–36 metres
Ans. (B)
De-broglie wavelength
h 6.62 10–34
= = 10–33 M
mv 66 10–3 10
5. The photon emitted due to electronic transition from 5th excited state to 2nd excited state in Li2+, is
used to excite He+ already in first excited state. He+ ion after absorbing the photon reaches in an
orbit having total energy equal to:
(A) -3.4eV. (B) –13.6eV (C) –6.8eV (D) –27.2 eV
Ans. (A)
(A) For Li2+ , n = 6 to n = 3
For H, the similar transition is 2 to 1
For He+ the similar transition is 4 to 2
22
Energy of 4th orbit of He+ = –13.6 × = –3.4 eV
42

6. A proton accelerated from rest through a potential difference of 'V' volts has a wavelength ,
associated with it. An alpha particle in order to have the same wavelength must be accelerated from
rest through a potential difference of
V
(A) V volt (B) 4Vvolt (C) 2Vvolt (D) volt
8
Ans. (D)
h
= ….. (i)
2mp eV
h
 = ….. (ii)
2m  (2e)V
Equation (i) & (ii) we have
2mp eV = 2 × 4 × mp × 2eV
V
 Va =
8

7. The ionization energy of hydrogen atom in terms of Rydberg constant (RH) is given by the
expression
(A) RH hc (B) RHc (C) 2RH h (D) RHNAhc
Ans. (A)
1 1 1
= R H Z2  2 − 2 
  n1 n 2 
For ionization energy
1 hc
n1 = 1 and n2 = ∞  = R H  IE1 =E∞ – E1 = = RHhc.
 

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Atomic structure

8. Number of electrons having  + m value equal to zero in 26Fe may be

(A) 13 (B) 14 (C) 7 (D)12
Ans. (A,B)
26Fe → 1S2, 2S2 SP6 , 3s2 3p6 ,3d6 , 4S2

+ m=0   = 0, m = 0 i.e.. s-subshell

= 1, m = –1 i.e. one orbital of p.

 =2, m = –2 i.e. one of d-orbitals

Hence there are 13 or 14 electron as in d-orbital it may be one or two electron having m= –2

9. The ratio of the "e/m" (specific charge) values of a electron and an a-particle is
(A) 2:1 (B) 1 : 1 (C) 1 : 2 (D) None of these
Ans. (D)
e e e 2e 4e 2e (e / m)e
  =   = = =  = 3680
 m e m e  m  m  4m p 4  1840m e (e.m) 

SECTION - ll : MULTIPLE CORRECT ANSWER TYPE

l0. Which of the following statement is correct for 3dxy orbitals?


X

(A) The orbitals drawn has two nodal planes, xz and yz.
(B) The minimum probability point lie along  = 45°.
(C) +ve and – ve signs represent sign of amplitude of electron wave.
(D) It is a non-axial orbital.
Ans. (A,C,D)
These are the fact.

11. If the wave number of 1st line of Balmer series of H-atom is 'x' then:
108x
(A)Wave number of 1st line of lyman series of the He+ ion will be
5
36x
(B) Wave number of 1st line of lyman series of the He+ ion will be
5

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5
(C) The wave length of 2nd line of lyman series of H-atom is
32x
32x
(D) The wave length of 2nd line of lyman series of H-atom is
5
Ans. (A,C)
 1 1   1 1  5R
v = RZ2  2 − 2   x =R  2 − 2  =
 n1 n 2   2 3  36
 1  36 108x
v1 = R  22 1 − 2  = 3R = x  3 =
 2  5 5
Weve length of 2nd line of lyman series of H-atom
1 1 1  1 8
= R  12  2 – 2  =R
 1 3   9
1 36x 8 5
=    = x.
 5 9 32

12. Electrons revolving around the nucleus in n1th orbit of an atom, have atomic number Z1, and in the
n2th orbit of other atom, have atomic number Z2, then [Where P = Linear momentum, L=Angular
momentum, f =frequency of revolution K.E. = kinetic energy
( K.E.)1  Z1 n2 
2 3 2
L n P Zn f z  n 
(A) 1 = 1 (B) 1 = 1 2 (C) 1 =  2   1  (D) = .
L2 n 2 P2 Z2n1 f2  z1   n2  ( K.E.)2  Z2 n1 
Ans. (A,B,D)

Z1 n12 Z1

L1 mv1r1 n Z1 n1 P mv1 n1 Z1n 2
= = 1 2
=  1 = = =
L 2 mv 2 r2 Z2 n 2 n 2 P2 mv 2 Z2 Z2 n1

n 2 Z2 n2
v1 z1 z1 1 2
 2 3 m1  2   2  2
f1 2r1 n1 n 22  Z1   n 2  K.E1 2 Z1 n2 Z1n 2 
= = =  = =     = 
Z2 Z2  Z2   n1  
.
f2 v2 K.E 2 1 mv 2  Z2   n1   Z2 n1 
 2
2r2 n 2 n 2
2
2
1 KZ1e 2 Z1
.Z1 2
K.E1 2 r1 n12  z1 n 2 
= = = . 
K.E 2 1 kZ2 e 2 Z . Z2  z 2 n1 
2
2 r2 n 22
13. Which of the following statements is/are INCORRECT:
(A) All spectral lines belonging to Balmer series in hydrogen spectrum lie in visible region.
(B) If a light of frequency v falls on a metal surface having work function hv, photoelectric effec't
will take place.
(C) The number of photoelectrons ejected from a metal surface in photoelectric effect depends
upon the intensity of incident radiations.

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Atomic structure
4
(D) The series limit wavelenglh of Balmer series tor H-atom is , where R is Rydberg's constant
R
Ans. (A,B)
A) Only first four spectral lines belonging to Balmer series in hydrogen spectrum lie in visible
region.
(B) If a light of frequency v falls on a metal surface having work functional hv , photoelectric effect
will take place only if v ≥ v0, since v0 is the minimum frequency required for photoelectric effect

14. Select the connect statement(s) :

(A) The value of spin only magnetic moment of Co3+ ion (in BM) = 24
(B) The number of radial nodes in a 3p-orlcital = 1
(C) The number of electrons with (m = 0) in Mn2+ ion = 11
6h
(D) The orbital angular momentum for the unpaired electron in v4+ =
4
Ans. (A,B,C)
(a) Co3+ : 1s2 2S2 2p6 3s2 3p6 3d6 ∴ 4 unpaired electrons ∴  = 4(4 + 2) = 24 = 4.9 BM
(b) Number of radial nodes = n –  —1
Number of radial nodes in 3p orbital = 3 —1—1 = 1
(c) Number of electrons with (m = 0) in Mn2+ (1s2 2s2 2p6 3s2 3p6 3d5) ion = 1s (2) + 2s (2) + 2p (2)
+ 3s (2) + 3p (2) + 3d (1) = 11
(d) Orbital angular momentum for the unpaired electron in V4+ lies in 3d orbital. ∴  = 2

h 6h
∴ Orbital angular momentum = ( + 1) =
2 2

15. Select the correct statement (s) :

(A) Radial function [R(r)] a part of wave is dependent on quantum number n only
(B) Angular function depends only on the direction and is independent to the distance from the
nucleus
(C) 2 (r, , ) is the probability density of finding the electron at a particular point in space
(D) Radial distribution function (4pr2R2) gives the probability of the electron being present at a
distancer from the nucleus

Ans. (B,C,D)

16. In a hydrogen like sample two different types of photons A and B are produced by electronic
transition Photon B has it's wavelength in infrared region if photon A has more energy than B, then
the photon A must belong to the region.
(A) ultraviolet (B) visible (C) infrared (D) None
Ans. (A,B,C)
Since B is in infrared region and A has more energy than B hence it will have lesser wave length i.e
ultra violet, visible or infrared region.

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17. Hydrogen atoms in a particular excited state 'n', when all returned to ground state, 6 different
photons are emitted. Which of the following is/are incorrect.
(A) out of 6 different photons only 2 photons have speed equal to that of visible light.
(B) lf highest energy photon emitted from the above sample is incident on the metal plate having
work function 8 eV, KE of liberated photo-electron may be equal to or less than 4.75 eV.
(C) Total number of radial nodes in all the orbitals of nth shell is 14.
(D) Total number of angular nodes in all the orbitals in (n–1)th shell is 13.
Ans. (A,C,D)
Number of photons emitted
n(n − 1)
So, =6;n=4
2
Excited state is 3rd or n = 4
Photon having highest energy will ge 4 → 1
1 1  15
So, its energy will be = 13.6  2 − 2  = 13.6 × = 12.75
1 4  16
When it is incident on plate having work function 8 eV then
KE = 12.75 – 8 = 4.75
KE will be equal to this value or may be less if electron is inner electron. So option (B) is correct.
Option (A) incorrect because all photon have equal velocity which is 3× 108 m/s.
(C), (D) also incorrect because number of nodes in nth & (n–1)th shall are 6 (Radial node) & 3
(Angular node) respectively.

18. ln a H-like sample electrons make transition from 4th excited state to 2nd state then
(A) 10 different spectral lines are observed
(B) 6 different spectral lines are observed
(C) number of lines belonging to the balmer series is 3
(D) Number of lines belonging to paschen series is 2.
Ans. (B,C,D)
5
4
3
2
n=1
Transition is taking place from 5 → 2
 n = 3
3(3 + 1)
Hence maximum number of spectral line observed = = 6.
2
(C)Number of lines belonging to the balmer series = 3
(D) Also we can see that number of lines belonging to paschen series = 2

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Atomic structure
SECTION-III : Assertion and Reason type
19. Statement-1 : e/m ratio in case of anode ray experiment is different for different gases.
Statement-2 : The ion of gases formed after the ejection of electron are different if gas is different.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-l.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-I
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Ans. (A)
Specific charge depends on mass of ion, which is different for different gases.

20. Statement-I : If an electron is located within the range of 0.1 Å then the uncertainty in velocity is
approximately 6 × 106 m/s.
Statement-2: Trajectory (path of motion) of above electron can be defined.
[h = 6.6 × 10–34, me = 9.1 × 10–31 kg]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement 1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-l
(B) Statement-1 is True, Statement-2 is False
(D) Statement-l is False, Statement-2 is True
Ans. (C)
h 6.62 10–34
mV x =  v = 6 106 m/s
4 9.110−31  4  3.14 10−11
as uncertainty in velocity is very high so we cannot define the trajectory of an electron.

SECTION - IV : COMPREHENSION TYPE

Comprehension # 3
DEFINITION VALID FOR SINGLE ELECTRON SYSTEM :
Ground state :
Lowest energy state of any atom or ion is called ground state of the atom. lt is n = 1.
Excited State :
Sates of atom other than the ground state are called excited states.
ionisation energy GE) :
Minimum energy required to move an electron from ground state to
n =  r is called ionisation energy of the atom or ion.
Ionisation Potential (I.P.) :
potential difference through which a free electron must be accelerated from rest, such that its
kinetic energy becomes equal to ionisation energy of the atom is called ionisation potential of the
atom.
Excitation Energy :
Energy required to move an electron from ground state of the atom to any other state of the atom
is called excitation energy of that state.

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 JEE (Main + Advanced) Chemistry
Excitation Potential :
Potential difference through which an electron must be accelerated from rest to so that its kinetic
energy become equal to excitation energy of any state is called excitation potential of that state.
Blinding Energy 'or' Seperatation Energy :
Energy required to move an electron from any state to n = o is called binding energy of that state.

The wavelength of the photon emitted upon an electronic transition from n2 to n1 orbit in a H-like
species in given by the formula :
1 1 1
= RZ2  2 − 2 
  n1 n2 
Now answer the following questions :

21. If the binding energy of ll excited State of a H-like species is 13.6 eV then:
(A) The atomic number Z of given H-like species is 2.
(B) A photon of energy 30 eV can ionise an electron from excited state of given H-like species.
(C) Upon de-excitation from n = 4 to n = 2 in given H-like species' the emitted photon has wavenumber
3R
v= ( R = Rydberg's cons tan t )
16
(D) Ionisation potential of given H-like species is 122.4 V.
Ans. (D)
 Z2 
Binding energy of II excited state (n = 3) = 13.6  2  = 13.6 eV ∴ Z = 3
3 
∴ Ionisation potential = 13.6 Z2 = 13.6 × 32 = 122.4 V

22. If the wavelength of photon emitted from an electron jump n = 4 to n = 2 in a H-like species is 1216
Å there the species
(A) H-atom (B) He+ ion (C) Li2+ ion (D) Be3+ ion
Ans. (B)
12400
Energy of photon = = 10.2 eV =(H)2→1 = (He+)4→1
1216
So, species is He+ ion
23. If the excitation potential of a hypothetica H-like atom is 162 V, then the value of II excitation energy
about :
(A) 192 eV (B) 30eV (C) 216 eV (D) 40.5 eV
Ans. (A)
I excitation potential = 10.2 Z2 = 162 V
162
∴ II excitation energy = 12.09 Z2 = 12.09 × = 192 eV
10.2

Comprehension # 1

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Atomic structure
If hydrogen atoms (in the ground state) are passed through homogeneous magnetic field the beam
is become split into two parts. This interaction with magnetic field shows that the atoms must have
Magnetic moment. However, the moment cannot split be due to the orbital angular momentum
since  = 0. Hence one must assume existence of intrinsic angular momentum, which as the
experiment shows , has only two permitted orientations.
h 1
Spin of he electron produces angular momentum equal to s = s(s + 1) where s = + .
2 2
n n
Total spin of an atom = + or –
2 2
Where n is the number of unpaired electron
The substance which contains species with unpaired electrons in their orbitals behave as
paramagnetic substances. The paramagnetism is expressed in terms of magnetic moment.
The magnetic moment of an atom.
e n  n  eh n
s = s(s + 1) =  + 1 s=
2mc 2  1  2mc 2
 s = n(n + 2) B.M.
N – number of unpaired electrons
eh
1. B.M. (Bohr magneton) =
4mc
If magnetic moment is zero the substance is diamagnetic.

10.24 Which of the following ion has highest magnetic moment?

(A) Fe2+ (B) Mn2+ (C) Cr3+ (D) V3+
Ans. (B)

Fe2+ – [Ar]3d6
Mn2+ –[Ar] 3d5
Cr3+ – [Ar] 3d4
V3+ [Ar] 3d1
Clearly Mn2+ has maximum number of unpaired electrons therefore it has highest magnetic
moment.

10.25 If an ion of 25Mn has a magnetic moment of 3.873 B.M. Them Mn is in which state.
(A) +2 (B) +3 (C) +4 (D) + 5
Ans. (C)
Magnetic moment = n(n + 2) = 3.873  number of unpaired electron n = 3

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∴ 25Mn – [Ar] 3d5 4s2 therefore Mn should be in + 4

3d2 4s

3d2 4s

10.26 Which of the following is a paramagnetic substance.

(A) Mg2+ (B) Cu+ (C) Mn+7 (D) Ti+2
Ans. (D)
There is two unpaired electron in Ti2+

10.27 The number of unpaired electrons in Mn4+ (Z = 25) is-

(A) Four (B) Two (C) Five (D) Three
Ans. (D)
Mn4+ – [Ar] 3d3

Comprehension # 2
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 rnaterial 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 decrease 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 Broglies 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 o waves, hence the beam of electron behaves as a wave
, as proposed by de Broglie.

10.28 If proton , electron, electron and  - particle are moving with same kinetic energy then he order of
their de0Broglie’s wavelength.
(A) p > e >  (B)  > P > e (C)  < P < e (D) e = P < e
Ans. (C)

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Atomic structure
h 1
= if KE same   m↑ ↓
2mKe m

10.29 Using Bohr’s theory, the transition, so that the electrons de-Broglie wavelength becomes 3 times
of its original value in He+ ion will be
(A) 2 → 6 (B) 2 → 4 (C) 1 → 4 (D) 1 → 6
Ans. (A)
h 1 z
=   3 times V  times V  so, transition will be 2 → 6
mv 3 n

10.30 De-Broglie of an electron travelling with equal o 1% of he speed o light

(A) 400 pm (B) 120 pm (C) 242 pm (D) 375 pm
Ans. (C)
h 6.6 10–34
= =  242 Pm.
mv 9.110–31  3 106

Comprehension # 3
Paragraph for Question Nos. 1027 to 10.29
Instead of principal quantum number (n), Azimuthal quantum number () and magnetic quantum
number (m), a set of new quantum numbers S, t and u was introduced with similar logic but
different values as defined below :
S = 1,2,3 ……….. ∞ (all + ve integral values).
t = (S2 – 12), (S2–22) , (S2 – 32) ……. No negative values.
t +1 t +1
u= − to (Including zero, if t has odd value ) in integral steps.
2 2
Each orbital can have maximum four electrons. (S + t) rule is defined similar to (n + ) rule.
Now answer the following questions :
10.31 The number of subshells present in third shell is equal to
(A) 1 (B) 3 (C) 5 (D) 7
Ans. (B)

10.32 Number of electrons that can be accommodated in S=2 and S=3 shell respectively are:
(A) 14, 38 (B) 28,76 (C) 8, 28 (D) Nome of these
Ans. (B)

10.33. Number of electrons belongs to S = 2, t = 3 for an element with atomic number Z= 24 is:
(A) 8 (B) 4 (C) 0 (D) Nome of these
Ans. (C)

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 JEE (Main + Advanced) Chemistry
Solution 10.31 to 10.33
S=1
T=0
1 1
u= − ,
2 2
No. of subshell = 1, No. of orbital = 2.
No of electrons = 8
S=2
t = 0, 3.
1 1
u = − , (for t =0),
2 2
u = –3,–2,– 1, 0, 1, 2, 3 (for t = 5),

9 7 5 3 1 1 3 5 7 9
u = – ,– ,– ,– ,– , , , , , (for t = 18)
2 2 2 2 2 2 2 2 2 2

No. of subshell = 3, No. of orbit = 19.

No. of electrons = 76.
(1,0), (2,0), (3, o), (4,0), (2,3). ……………………………. Energy order of (S, t).
For atomic No. 24 (S + t) rule.
There is no electron in S = 2, t = 3.
s

SECTION- V : MATRIX – MATCH TYPE

10.34. Match the following
B.E –Binding energy
I.E. – Ionization energy
Column I Column
(A) B.E. of He atom in an excited stage
+ (p) Infrared region
(B) 7→ 3 transition in H-atom (q) 3.4 ev
(C) 5 → 1 transition in H-atom (r) 13.6 ev
(D) series limit of Balmer series in H-atom (s) 10 Spectral lines observed
(t) Ultra violet region
Ans. ()
(A–q, r); (B-P,s) ; (G-P,s,t) ; (D-q)

13.6  22
(A)B.E. of He+ atom = n = 1, 2, 3…………….
n2
Hence it can be 13.6 ev, 3.4ev both
(B) In 17 → 3 transition  n= 7 – 3 = 4

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Atomic structure
4(4 + 1)
 Maximum number of spectral line observeo = = 10
2

Its line of paschen series hence infrared region

(C) 5 → 1 = 10 lines, out of these traniitions 5 → 4, 5 → 3, 4 → 3 transition will be in infrared

Region and 2 → 1 will be in U.V. region.

(D) series limit of Balmer series is the last line having 3.4 ev energy'

10.35 Column-I Column-II

Species Characteristics
(A) Co3+ (Z = 27) (p) Total number of fully filled orbitals is nine.
(B) Sc3+ (Z = 21) (q) The value of magnetic moment (spin only is greater than or
equal to 3.7 BM
(C) Cr3+ (Z = 24) (r) Number of electrons with (n +  = 3) is eight.
(D) Ni2+ (Z = 28) (s) Number of electrons with (m = 0) may be either 11 or 12.
(t) No unpaired electron.
Ans. ()
[A–q, r, s] [B–p, r, t] ; [C-p,q, r,s] ; [D-r's].

(A) Co3+ :1s2 2s2 2p6 3s2 3p6 3d6

so no. of fully filled orbitals is 10.

no. of unpaired electrons = 4.
So, magnetic moment is greater than 3'87.
no. of electrons with n + l = 3.
i.e. 3s, 2p are eight.
no. of electrons with m = 0 may be 11or 12.

(B) Sc3+ :1s2 2s2 2p6 3s2 3p6

no. of fully filled orbitals is nine.

no. of unpaired electrons = zaro.
no. of electrons with n + l= 3.
i.e. 3s & 2P are eight.
no. of electrons with m = 0 are ten.

(C) Cr3+ :1s2 2s2 2p6 3s2 3d3

no. of fully filled orbitals is nine.

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 JEE (Main + Advanced) Chemistry
no. of unpaired electrons = 3.
no. of electrons in 3s & 2p are eight.
no. of electrons with m = 0 may be 11.

(D) NI2+ :1s2 2s2 2p6 3s2 3p6 3d8

no, of fully filled orbitals is twelve.

no. of unpaired electrons = 2.
no. of electrons in 3s & 2P is eight.
no. of electrons with m = 0 may be 11 or 12.

10.36 n → orbit no., Z→ Atomic no  rn,z → Radius Vn,z → Velocity

Tn,z → Time period of Revolution  kn,z → kinetic energy of the electron
Column–I Column–II
(for single electron species) (Ratio)
(A) r2,1 : V1,2 (P) 9 : 1
(B) V1,3 : V3,1 (Q) 8 : 1
(C) T1,2 : T2,1 (R) 16 : 1
(D) K1,2 : K2,1 (S) 1 : 32
Ans. ()
(A) → Q (B) → P (C) → S (D) → R

n2 z2
(i)r = 0.521  A (ii) V = 2.18  106 z / n (iii) T  n3 / z2 (iv) K.E. 
z n2

10.37 Match the following :

List-I List-II
(A) n = 6 → n = 3 (in H-atom) (p) 10 lines in the spectrum
(B) n = 7 → n = 3 (in H-atom) (q) Spectral lines in visible region
(C) n = 5 → n = 3 (in H-atom) (r) 6 lines in the spectrum
(D) n = 5 → n = 1 (in H-atom) (s) Spectral lines in infrared region
(t) Spectral lines in U.V. region
Ans. ()

(A → r,s) (B → p,s); (C → q,r,s); (D → p,q,r,s, t)

(A)6 → 3 n = 3

3(3 + 1)
no. of lines = =6
2

All lines are in infrared region

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Atomic structure
(B)7 → 3 n=4

4(4 + 1)
no. of lines = = 10
2

All lines are in infrared region

(C)5 → 2  n =3

Lines are in visible region and also in infrared region

(D)5 →1  n =3

5 4
no. of lines = = 10
2

Lines are in visible region, in infrared region and also in U.V. region.

SECTION – VI : INTEGER TYPE

10.38 if n1, and n2, are the boundary value principal quantum numbers of a portion of spectrum of
emission spectrum of H atom, determine the wavelength (in metre) corresponding to last line
(longest ). Given : n1+n2 = 7, n2 – n1 = 3, and RH = 1.097 × 107 m–1 . (Give your answer in multiple
of 10–6)

Ans. (4)
Here n2 =5 &n1 = 2

So longlest wavelength means least energy difference transition i.e. n2 = 5 to n1 = 4

1  1 1 
= R H (1)2  2 – 2 
  (4) (5) 

So  = 4  10–6 m

10.39 In the assembly as shown below the potential difference across the plates is 4 volts. A positive
particle of charge +4e is projected from the negative plate with an initial kinetic energy of 4eV
and the negative particle of charge (-2e) is projected from the positive plate. Both the particles
reach point 'A with zero kinetic energy. Find the initial kinetic energy of the negative particle in
eV.
4V 0V

(–2e) A (+4e)

+ –

Ans. ()

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 JEE (Main + Advanced) Chemistry
For the positive particle, applying energy conservation initially and at a point A.

K.E.i + P.E.i = K.E.f + P.E.f

 4eV+ (+4e) (OV) = O + (+4e) (x volt) {x = potential at point A}

 x=1volt
Now applying energy conservation for the negative particle at point 'A’ and initially

 K.E.i + (–2e)(4V) = 0 + (–2e)(1volt)

K.E.i –8eV=–2eV

10.40 Electrons in a sample of H--atoms make transitions from state n = x to some lower excited state.
The emmission spectrum from the sample is found to contain only the lines belonging to a
particular series. If one of the photons had an energy of 0.6375 eV. Then find the value of x. [Take
3
0.6375 eV = × 0.85eV]
4
Ans. ()
x=8
We have

3
E =  0.85eV
4

as energy = 0.6375 the photon will belong to brackett series (as for brackett 0.31 < E < 0.85)

 1  4 1 
0.85   1–  = 13.6  2 – 2 
 4 4 n 

 1   4 2  4 1
0.85  1–  = 13.6 1–     =  n=8
 4   n   n 2

Hence x = 8.

10.41 An element undergoes a reaction as shown :

X + e– → X – Energy released = 30.876 eV
The energy released, is used to dissociate 8 g of H2, molecules equally into H+ and H+, where H+ is
in an excited state, in which the electron travels a path length equal to four times its debroglie
wavelength.
(a) Determine the least amount (moles) of X' that would be required.
Given: I.E. of H = 13.6 eV/atom
Bond energy of H2 = 4.526 eV/molecule.
(b) Why is the amount of X calculated in the above question 'least'?
Ans. (4)

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Atomic structure
4

(a ) x + e− → x–
energy released = E.A, = 30.87 eV/atom
Let no. of moles of X be a

∴ a × NA × 30.87 = 4 × NA × 4.526 + 4 × NA × 13.6 + 4 × NA × 12.75  a = 4 moles

10.42 A hydrogen like atom (atomic number Z) is in a higher excited state of quantum number n. This
excited atom can make a transition to the first excited state by successively emitting two photons
of energies 10.20 eV and 17.00. eV respectively. Alternatively, the atom from the same excited
state can make a transition to the second excited state by successively emitting two photons of
energy 4.25 eV and 5.95 eV respectively. Determine the values of n and Z (ionisation energy of
hydrogen atom = 13.6 eV) Give your answer as (Z + n)
Ans. (9)
n n

10.2eV 4.25eV
n1=2 n1=3
17eV 5.95e
V

1 1  1 1 
10.2 + 17 = 13.6 Z2  2 − 2  and 4.25 + 5.95 = 13.6 Z2  2 − 2 
2 n  3 n 
solving the above two equation we get, Z = 3, n = 6

10.43 In sample of hydrogen atom in ground state electrons make transition from ground state to a
particular Excited state where path length is five times de-broglie wavelength, electrons make
back transition to the Ground state producing all possible photons. If photon having 2nd highest
energy of this sample used to excite the electron in a particular excited state of U+2 ion then find
the final excited state of Li2+ ion.

Ans. (12)
Since electron goes the state where the path length is 5 times de-broglie wavelength.
 2r = 5
2r
also = n=5
n
Hence electron goes to the 5th state.

5
4
3
2
n=1
2nd highest energy line will be 4 → 1
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 JEE (Main + Advanced) Chemistry
If this photon is used for Li+2 then
 1 1 1
13.6  1 − 2  = 13.6  Z2  2 − 2 
 4   n1 n2 
n1 n2
 3 → 12
Hence final excited state = 12.

10.44 A Chemist has one mole of X-atoms. He finds that on absorption of 410 kJ, half of X-atoms transfer
one electron to the other half. If all the resulting X– ions are subsequently converted to X+ ions' an
addition of 735 kJ is required. Find the electron affinity X.
Ans. (325)
X X+ 1
⎯⎯
→ +e I.E. ………………. (i)
2 2 2
X X+ 1
e+ ⎯⎯→ E. A .( − ve) …………. (ii)
2 2 2
(i)+(ii)
1 1 1
→ X+ + X−
X ⎯⎯ (I.E. − E.A.) = 410kJ
2 2 2
I.E. – E.A. = 820 kJ
1 – 1
Now → X + + 2e− …………….. (iii) H = 735
X ⎯⎯
2 2
Now equation (iii) can be achieved by (i) reverse (ii) and we will get
1 1
I.E. + E.A. = 735
2 2
I.E. + E.A. = 1470 …………. (iv)
I.E.A. = 650
E.A. = 325 kJ/mol.

10.45 The famous alien Jadu on his visit to our planet earth brought a sample containing 100 identical
H-like atoms (hypothetical atoms, z can be fractional) from his planet. He gave these atoms to
Rohit (Hritik Roshan) asking him to analyze them. He further gave Rohit the following
informations:
1. Out of the given atoms, some are in ground state and some others are in a higher energy level )n =
x) and the potential energy of electron in the ground state of given atom is – 192 eV.
2. When the samples is exposed to radiations of wavelength 155nm, the electrons jump to another
higher energy level (n = x + 3). Upon back- transition upto ground state, a total of 10 different
spectral lines are produced.
(b)
Then, Jadu asked Rohit two questions in terms of :
(a)

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Atomic structure
(a) “What is the final state in which the electrons move after absorbing photons of wavelength
155 nm?’
(b) What is the maximum number of atoms which had their electron in ground state initially?’
Surprisingly, Rothi answered the questions correctly.
Instead or Rohit, If you were asked the same questions by Jadu, what would have been your
answers for the two questions ? Take hc = 12400 eV A.
Ans. (16)
(PE)n=1 = –192 eV  –27.2 Z2 = –192
or 27.2 Z2 = 192 / 13.6 Z2 = 192/2 = 96 eV
12400
 = 1550 Å E = = 8 eV
1550
Electrons from ground state cannot gain this energy as the 1st excitation energy (10.2 Z2 = 72eV)
is given than supplied energy.
 Elecirons from (n = x) state jump to (n=x+3) state absorbing 8eV energy.
1 1 
 13.6 Z2  2 − 2
=8
 n (n + 3) 
1 1 
 96  2 − 2
=8
 n (n + 3) 
n=3
so, electron jumps from 3 → 6
Upon back transitlon, max 10 lines are produced
 To produce max 10 lines, minimum 4 atoms should be present in (n=x+3) state, which were
present in (n=x) state.
I II III IV 6
5
4
3
2
1

So, maximum number of atoms which had their electron in ground state initially = 100 – 4 = 96

SECTION – VII : (3 COLUMN) MATCHIN TYPE

Answer 10. 46, 10. 47 and 10.48 by appropriately matching the information given in the three columns of
the following table
If the electron comes back form energy level having energy E2 to energy level having E1 then the
difference may be expressed
hc
E2 – E1 = E =
E
Each transition form one energy level to another will produce a light of definite wavelength

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 JEE (Main + Advanced) Chemistry
1 1
Wave number v = RZ2  2 − 2 
 n1 n 2 
Where R is a Rydberg constant
Column-1 Column-2 Column-3
(i) First line of Balmer (i) Wave number v = 9R (P) Change in angular
series for H 3h
Momentum is
2
(ii) Third line of paschen (ii) 9 (Q) Difference of energy
Wavelength =
series of He+lon 32R corresponding
transition is 48.4 ev
(iii) Lyman series limit for (iii) Difference of potential (R) 36
Wave light  =
li+2 lon energy of 5R
corresponding
transition is 3.78 ev
(iv) 2nd line of Lyman (iv) Difference of energy (S) Difference of energy
series for He+ lon corresponding corresponding
transition is 4.54 ev transition is 122.4 ev

10.46 The only correct combination is

(A) (I) (ii) (P) (B) (IV) (iii) (Q) (C) (II) (iv) (R) (D) (III) (i) (S)
Ans. (D)

10.47 Only correct combination is

(A) (I) (iii) (R) (B) (II) (i) (S) (C) (III) (ii) (P) (D) (IV) (iv) (Q)
Ans. (A)

10.48 Only correct combination is

(A) (II) (iv) (P) (B) (I) (ii) (Q) (C) (III) (ii) (R) (D) (IV) (iii) (S)
Ans. (A)
Solution 10.46 to 10.48
(I) First line of Balmer series
n1 = 2 n2 = 3
1 1
P.E = 27.2  (Z)2  2 − 2 
 n1 n 2 
1 1
= 27.2  (1)2  −  = 27.2  3.78ev
4 9
1 1
E = 13.6 × (1)2  −  =1.88 eV
4 9

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Atomic structure
 1 1  5R
v = R  (1)2  −  = =1.88 eV
 4 9  36
36
l= =
5R
3h 2h h
Angular momentum = − =
2 2 2
(II) Third line of paschen series of He+ Ion
n1 = 3 n2 = 6
1 1 
P.E = 27.2  (2)2  −  = 9.06 ev
 9 36 
1 1 
E = 13.6  (2)2  −  = 4.54ev
 9 36 
1 1  R
v = R  (2)2  −  =
 9 36  3
3
=
R
6h 3h 3h
Angular momentum = − =
2 2 2
(III) Lyman series limit for Li+2 lon
n1 = 1 n2 = 
1 1 
P.E = 27.2  (3)2  2 − 2  = 27.2 × 9 = 244.8 ev
1  
1 1 
E = 13.6  9  2 − 2  = 122.4ev
1  
1 1 
v = R  (3)2  2 − 2  = 9R
1  
(IV) 2nd line of Lyman series for He+ lon
n1 = 1 n2 = 3
1 1 
P.E = 27.2  (2)2  −  = 96.71 ev
1 9 
1 1 
E = 13.6  (2)2  −  = 48.4ev
1 9 
 1 1  32R 9
v = R  (2)2  −  = ;=
1 9  9 32R
3h h 2h h
Angular momentum = − = =
2 2 2 

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