Atomic Structure
Uploaded by
ashfaqahad08Atomic Structure
Uploaded by
ashfaqahad08Structure of atom
CHAPTER
2 STRUCTURE OF ATOM
LEARNING OBJECTIVES
(i) Know about electron, proton and neutron.
(ii) Describe Thomson, Rutherford and Bohr atomic models;
(iii) Define an atomic orbital in terms of quantum numbers. An atomic orbital is the wave function for an electron in an atom.
The probability of finding an electron at a point within an atom is proportional to the square of the orbital wave function i.e.,
| |2 at that point.
(iv) Understand the important features of the quantum mechanical model of atom. Quantum mechanical model of atom is the
picture of the structure of the atom, which emerges from the application of the Schrödinger equation to atoms. According to the
quantum mechanical model of the atom, the electron distribution of an atom containing a number of electrons is divided into
shells. The shells, in turn, are thought to consist of one or more subshells and subshells are assumed to be composed of one or
more orbitals, which the electrons occupy.
(v) State aufbau principle, Pauli exclusion principle and Hund’s rule of maximum multiplicity. The lower the value of (n +) for an
orbital, the lower is its energy. If two orbitals have the same (n + ) value, the orbital with lower value of n has the lower energy.
In an atom many such orbitals are possible and electrons are filled in those orbitals in order of increasing energy in accordance
with Pauli exclusion principle (no two electrons in an atom can have the same set of four quantum numbers) and Hund’s rule of
maximum multiplicity (pairing of electrons in the orbitals belonging to the same subshell does not take place until each orbital
belonging to that subshell has got one electron each, i.e., is singly occupied).
(vi) Write the electronic configurations of atoms.
(vii) State the de Broglie relation and Heisenberg uncertainty principle;
(viii) Understand nature of electromagnetic radiation and Planck’s quantum theory;
(ix) Explain the photoelectric effect
INTRODUCTION
We know that an atom is electrically neutral, if it contains negatively charged electrons it must also contain some positively
charged particles. This was confirmed by Goldstein in his discharge tube experiment with perforated cathode. On passing high
voltage between the electrodes of a discharge tube it was found that some rays were coming from the side of the anode which
passed through the holes in the cathode. These anode rays (canal rays) consisted of positively charged particles formed by
ionization of gas molecules by the cathode rays. The charge to mass ratio (e/m value) of positively charged particles was found
to be maximum when the discharge tube was filled with hydrogen gas as hydrogen is the lightest element. These positively
charged particles are called protons.
e/m varies with the nature of gas taken in the discharge tube. The positive particles are positive residues of the gas left when the
gas is ionized. The electrically neutral charge particle, neutron was discovered by James Chadwick by bombarding boron or
beryllium with -particles.
9
4 Be 24 He
12
6 C 0n
1
Characteristics of the three fundamental particles are:
Electron Proton Neutron
Symbol e or e
–1 P n
Approximate relative mass 1/1836 1 1
Approximate relative charge –1 +1 No charge
Mass in kg 9.109 10 –31
1.673 10 –27
1.675 10 –27
Mass in amu 5.485 10 –4 1.007 1.008
Actual charge (coulomb) 1.602 10 –19 1.602 10 –19 0
Actual charge (e.s.u.) 4.8 10 –10 4.8 10 –10 0
IIT-JEE Chemistry 1
Structure of atom
The atomic mass unit (amu) is 1/12 of the mass of an individual atom of 6 C12 , i.e., 1.660 × 10–27 kg.
The neutron and proton have approximately equal masses of 1 amu and the electron is about 1836 times lighter, its mass can
sometimes be neglected as an approximation.
The electron and proton have equal, but opposite, electric charge while the neutron is not charged.
Non-fundamental particles :
1. Positron ( 1e0 or e+) :
(i) Also called as positive electron.
(ii) Discovered by Anderson in 1932.
(iii) Positive counterpart of electron.
(iv) Mass of positron is same as that of electron m = 9.1 × 10–28 g
(v) Charge of positron is same but with opposite sign as that of electron, e = + 1.6 × 10–19 C.
(vi)Positrons are very unstable and combines with electron producing -rays.
2. Neutrino and Antineutrino :
(i) These are particles of approximately zero mass and charge.
(ii) Discovered by Pauling (1933) and Fermi (1934).
3. Antiproton :
(i) Discovered by segre.
(ii) Mass of antiproton is equal to 1.673 × 10–24 g.
(iii) Charge of antiproton is equal to – 1.6 × 10–19 C.
4. Meson :
(i) Discovered by Yukawa in 1935.
(ii) It may be positively charged, negatively charged and neutral.
(iii) On the basis of charge, the meson are of 3 types : - meson, - meson and neutral meson (º )
(iv)- mesons are called pions.
(v) Meson indicates the stability of nucleus.
(vi) Mass of meson is 200 times that of electron i.e.. it is heavier than electron but lighter than proton.
MODELS OFATOM :
Thomson atomic model : J.J. Thomson proposed an atomic model which is
called apple pie pudding model of atom. (Plum Pudding Model). According to
this model, an atom is made up of positively charged substance which is
spread very thinly in the form of a sphere. Into this sphere are embedded
negatively charged electrons, much the same way as pieces of apple are
embedded in the apple pie. Furthermore, it was assumed that total positive
charge is equal to total negative charge, therefore, the atom remains electri-
cally neutral. J.J. Thomson's model of atom was not accepted by fellow
physicists, as it was unable to explain how positively charged particles are Fig. : Thomson atomic model
shielded from the negatively charged particles, without getting neutralised.
Rutherford’s Model: -particle emitted by radioactive substance were shown to be
dipositive Helium ions (He++) having a mass of 4 units and 2 units of positive charge.
Rutherford allowed a narrow beam of -particles to fall on a very thin gold foil of
thickness of the order of 4 × 10–4cm and determined the subsequent path of these
particles with the help of a zinc sulphide fluorescent screen.
The zinc sulphide screen gives off a visible flash of light when struck by an -particle,
as ZnS has the remarkable property of converting kinetic energy of particle into visible Fig. : Rutherford’s experiment
light. [For this experiment, Rutherford specifically used -particles because they are
relatively heavy resulting in high momentum].
Observation :
(a) Majority of the -particles pass straight through the gold strip with little or no deflection.
(b) Some -particles are deflected from their path and diverge.
(c) Very few -particles are deflected backwards through angles greater than 90°.
(d) Some were even scattered in the opposite direction at an angle of 180°.
On the basis of the above observation, and having realized that the rebounding -particles had met something even more
massive than themselves inside the gold atom, Rutherford proposed an atomic model as follows.
2 IIT-JEE Chemistry
Structure of atom
(i) All the protons (+ve charge) and the neutrons (neutral charge) i.e. nearly the total mass of an atom is present in a very small
region at the centre of the atom. The atom’s central core is called nucleus.
(ii) The size of the nucleus is very small in comparison to the size of the atom. Diameter of the nucleus is about 10–13 while the
atom has a diameter of the order 10–8 of cm. So, the size of atom is 105 times more than that of nucleus.
(iii)Most of the space outside the nucleus is empty.
(iv) The electrons, equal in number to the net nuclear positive charge, revolve around the nucleus with high speed in various
circular orbits.
Defects in Rutherford’s model of atom :
(i) When electron (Negatively charged particle) revolve continuously around the positively charged nucleus then energy would be
lost and due to the attraction of nucleus electron will merge with the nucleus. Rutherford has no explanation for this problem.
(ii) If electron will continuously radiate energy then its spectra should be continuous but this is not the case. Atoms give line
spectra.
In order to overcome the defects of Rutherford Neil Bohr proposed the atomic model.
BOHR’S MODEL OFTHEATOM :
Bohr proposed the following postulates for revising the Rutherford model.
(i) Electrons moves around the nucleus in stationary circular orbits of fixed energy. They are termed as energy levels or shells.
h
(ii) Electrons move around only in those circular orbit in which its angular momentum is integral multiple of . Where h = Plank’ss
2
constant.
(iii) Energy is neither absorbed nor emitted when electron is moving in an orbit. But energy is absorbed when it jumps from lower orbit
to higher orbit whereas energy is emitted when it jumps from higher orbit to lower orbit.
(iv) Energy is absorbed or emitted in the form of quanta or bundles, so various energy levels of atom are quantised.
The quantized energy levels in the hydrogen atom can be compared with a stairway in your home. Since you cannot stand (with
both feet together) between steps, we can say that each step represents a discrete or quantized amount of energy. On the other
hand, a ramp between the two floors represents a continuous change in energy. In this case, all energy levels are possible
between floors.
Under normal conditions, the single electron in a hydrogen atom will occupy the lowest energy level, which is the orbit closest
to the nucleus. This is called the ground state. When energy is supplied to a hydrogen atom, as when it is heated, the electron
can absorb the appropriate amount of this energy to "jump" from the ground state (i.e., the n = 1 level) to a higher energy level
(i.e., n = 2, 3, 4, etc.). Because of its new position in a higher energy level, the electron now has potential energy just like a weight
suspended above the ground. Energy levels higher than the ground state are called excited states. What is most significant
according to Bohr was what happened when the electron fell back down to lower excited states or all the way to the ground state.
He suggested that the electron gives up this energy in the form of light when it falls back. Since energy levels are quantized, the
difference in energy between any two levels is quantized. Thus, when an electron falls back to a lower energy level, it must emit
a discrete amount of energy. Since this energy is emitted as light, the light would have a discrete energy, a discrete wavelength,
and a discrete color (if the light is in the visible region of the spectrum).
This is qualitative explanation of the discrete spectrum. The real significance of Bohr’s model is that he was able to calculate the
expected wavelength of light in the hydrogen spectrum from the mathematical relationships.
Applications of Bohr's theory :
(i) Line spectrum of one electron system can be explained like H, He+, Li2+, Be+3.
(ii) Calculation of the radius of the Bohr's orbit : If an electron having mass 'm' and charge 'e' revolves around the nucleus of charge
'Ze' (Z is atomic number and e is charge) with a linear velocity of v and let 'r' is the radius of the orbit in which electron
revolves.Then by Coulomb's law, the electrostatic force of attraction (F) between the moving electron and nucleus is
2
KZe 2 1 9 Nm2/C2 and the centripetal force F = mv
F= where, K = constant = = 9 × 10
r2 4 0 r
Electrostatic force will provide necessary centripetal force
KZe 2 mv 2 KZe 2
Hence , = or v2 = .......(1)
r2 r mr
From Bohr's Postulate
nh nh n2h2
mvr = v= v2 = .......(2)
2 2mr 4 2 m 2 r 2
IIT-JEE Chemistry 3
Structure of atom
KZe 2 n2 h2 n2h2
From equation (1) and (2) = . Thus we get r =
mr 4 2 m2 r 2 4 2 mKZe 2
n2 h2
In C.G.S. unit since K = 1 r=
4 2 mze 2
substituting values of e, h and m
n2 v
r = 0.529 × Å and orbital frequency f =
z 2 r
Radius of first orbit of hydrogen atom = 0.529 Å = 0.529 × 10–10 m
(iii) Calculation of Velocity of an electron in Bohr's orbit :
Velocity of an electron revolving in nth orbital is given by–
nh nh
mvr = or v=
2 2mr
on putting the value of r in equation
nh 4 2 mZe 2 2Ze 2 c z
v= or v=
= [c = speed of light]
2mn h 2 2
nh 137 n
on putting the values of , e– and h, v = 2.188 × 108 cm/sec.
If n is constant v Z, If Z is constant v 1/n
(iv) Calculation of energy of an electron :
Total energy of an electron revolving in particular orbit is T.E. = K.E. + P.E.
1 KZe 2
Kinetic energy of an e– = mv2 ; Potential energy of an e– =
2 r
1 KZe 2 mv 2 KZe 2 KZe 2
Hence T.E. = mv2 + . Since = or mv2 =
2 r r r r
2
On putting the value of mv in above equation
KZe 2 KZe 2 KZe 2 KZe 2
T.E. = – = T.E. =
2r r 2r 2r
Ze2
In C.G.S. unit K = 1 T.E. =
2r
On putting the value of r in equation of T.E.
Ze2 4 2 Ze 2 m 2 2 Z 2 e 2 m th orbit is E =
2 2 Z 2 e 4 m
E= × = . Thus, the total energy of electron is n
2r n2h2 n2h2 n n2h2
(v) Relation between P.E., K.E. & T.E. :
Ze2 1 Ze2 1 Ze2
P.E. = , K.E. = and T.E. = –
r 2 r 2 r
1 Ze 2 1 Ze 2
T.E. 2 r 1 1 T.E.
So, = = T.E. = P.E. = 2 r2 1
P.E. Ze 2 2 2 P.E. 1 Ze
r 2 r
P.E.
T.E. = – K.E. or T.E. = – K.E. =
2
Z2 Z2
(a) T.E. = – 13.6 × eV/atom (b) T.E. = – 21.8 × 10–19 J/atom (c) T.E. = – 21.8 × 10–12 × erg/atom
n2 n2
Z2 1
(d) T.E.= – 313.6 × 2 kcal/mole. or T.E. – Z2 and T.E. –
n n2
4 IIT-JEE Chemistry
Structure of atom
(vi) Calculation of Rydberg constant :
Suppose that an electron transits from first energy level to second energy level. Then, the change of energy is given by
E = E2 – E1
h = E2 – E1
2 2 mZ2 e4 2 2 mZ2 e4
or h = 2 2 – 2 2
n 2 h n1 h
2 2 mZ2 e 4 2 2 mZ2 e 4 c
or h = =
n12 h 2 2 2
n2 h
hc 2 2 mZ2 e4 1 1 2 2 me 4
R = Rydberg constant
h2 n1
2
n 22 H ch 3
Where m = 9.1 × 10–28 gram, e = 4.8 × 10–10 e.s.u., c = 3 × 1010 cm/sec, h = 6.625 × 10–27 erg-sec
1 1 1
Then, = = RHZ2 2 2
n1 n 2
by the theoretical value of RH = 109737 / cm , by the practical value of RH = 109677 / cm
Quantization of energy of electron :
(i) In ground state : No energy emission. In ground state minimum energy state of atom for 1st orbit of H-atom, n = 1.
E1 = – 13.6 eV
(ii) In Excited state : Energy levels greater than n1 are excited state.
i.e. for H-atom n2, n3, n4 are excited state.
For H-atom first excitation state = n2
(iii) Excitation potential : Energy required to excite electron from ground state to any excited state.
Ground state excited state
Ist excitation potential for H atom = E2 – E1 = – 3.4 + 13.6 = 10.2 eV
IInd excitation potential = E3 – E1 = – 1.5 + 13.6 = 12.1 eV
(iv) Ionization Potential or Ionization energy :
The amount of energy required to remove an electron from an isolated gaseous atom in its ground state to the infinite excited
state is called ionization potential. The result is ion formation.
Ground state infinite
I.P. = E – E1 = 0 – E1
So I.P. = – E1
I.P. = – (– 13.6)
For H-atom I.P. = + 13.6 eV
(v) Separation energy : Energy required to excite an electron from excited state to infinity.
S.E. = E – Eexcited
ATOMIC SPECTRUM :
When a radiation is passed through a spectroscope for the dispersion of the radiation, the pattern (photograph) obtained on the
screen (photographic plate) is called as spectrum of the given radiation.
(a) Absorption spectrum : If the atom gains energy the electron passes from a lower energy level to a higher energy level, energy is
absorbed that means a specific wave length is absorbed. Consequently, a dark line will appear in the spectrum. This dark line
constitutes the absorption spectrum.
(i) If white light is passed through atomic gas then the obtained spectrum is called as absorption line spectrum.
(ii) If white light is passed through molecular gas then the obtained spectrum is called as absorption band spectrum.
(b) Emission spectra :
(i) Continuous spectra: When white light from any source such as sun or bulb is analysed by passing through a prism, it splits
up into seven different wide bands of colour from violet to red (like rainbow). These colour also continuous that each of them
merges into the next. Hence the spectrum is called as continuous spectrum.
IIT-JEE Chemistry 5
Structure of atom
(ii) Line spectra: When an electric discharge is passed through a gas at low pressure light is emitted. If this light is resolved by
a spectroscope, it is found that some isolated coloured lines are obtained on a photographic plate separated from each other by
dark spaces. This spectrum is called line spectrum. Each line in the spectrum corresponds to a particular wavelength. Each
element gives its own characteristic spectrum.
Spectral evidence for quantization :
(i) The light absorbed or emitted as a result of an electron changing orbits produces characteristic absorption or emission spectra
which can be recorded on the photographic plate as a series of lines, the optical spectrum of hydrogen consists of several series
of lines called Lyman, Balmar, Paschen, Brackett and Pfund series.
(ii) The Lyman series lies in the ultra-violet region (wavelength lesser than violet). Balmer series in the visible region and Paschen,
Brackett and Pfund series lie in the infra-red region. (wavelength more than red)
(iii) The Frequency (nu) of light absorbed or emitted is given by the following Planck and Einstein equation :
E = h (Where h = Planck's constant)
n=7
n=6
n=5
Pfund
series
n=4
Brackett
series
Energy level
n ge
ra
n=3
.
Paschen
I.R
series
n=2
Balmer series n ge
ra
b le
si
Vi
n=1
Lyman series e
ng
. ra
V
U.
(iv) By the time the Bohr theory was known, spectroscopist had already suggested the following simple equation to describe the
position of these emission lines in the spectrum of hydrogen atom.
Where n and m are integer, R' is a constant and H is the frequency of light emitted or absorbed by a hydrogen atom.
1 1
Since H = c = R' 2 2
n m
R' 1 1 1 1
= 2 2 or = R 2 2
c n m n m
where R is a constant called Rydberg Number.
(v) The transition energy E (absorbed or emitted) of any electron jump in the hydrogen atom is the energy difference between an
initial state I and a final state II. That is, EH = EII – EI
2 2 me4 2 2 me4 2 2 me4 1 1
therefore, EH 2 2
2 2
n II 2 h 2 nI h h 2
nI n II
6 IIT-JEE Chemistry
Structure of atom
Since, E = h So, EH = hH
(where H is the frequency of light emitted or absorbed by hydrogen atom.)
2 2 me 4 1 1 2 2 me 4 1 1
Hence, h H = 2 or H = 2
h2 nI n II 2 h3 nI n II 2
(vi) The velocity of light, c, is related to its frequency H and wavelength by the following equation :
c
c = H or H =
The reciprocal of i.e., 1/ is designated as the wave number . Hence H = c
2 2 me 4 1 1
(vii) We have = 2
h3 nI n II 2
2 2 me 4 1 1
or = 2
ch 3 nI n II 2
(viii) By substituting the respective value, the constant R can be theoretically calculated.
2 2 me 4 2(3.1416) 2 (9.1085 1028 )(4.8029 1010 ) 4
R= or = 109, 737 cm–1
ch 3 (29979 1010 ) (6.6252 1027 )3
R =
where, m = 9.1085 × 10–28; e = 4.8029 × 10–10, = 3.1416; h = 6.6252 × 10–27; c = 2.9979 × 1010 cm./sec.
The experimental value of R is 109,677.581 cm–1.
This remarkable agreement between the theoretical and experimental results was great achievement of the Bohr model.
1 1
(ix) The equation can now be written as =R 2 2
nI n II
(x) Further, when the electron jumps from an orbit of higher energy to that of lower energy in a hydrogen atom, it emits energy and
produces spectrum. Different series of lines produced, when we substitute the value of R, nI and nII in equations above are
assigned the following names ;
Lyman from n = 2, 3, 4.....to n = 1 ; Balmer from n = 3, 4, 5.....to n = 2
Paschen from n = 4, 5, 6.....to n = 3 ; Brackett from n = 5, 6, 7.....to n = 4
Pfund from n = 6, 7, 8.....to n = 5 (where n is the quantum number).
(xi) Thus, at least for the hydrogen atom, the Bohr theory accurately describes the observed atomic spectrum.
Failure of Bohr Model :
(i) Bohr theory was very successful in predicting and accounting the energies of line spectra of hydrogen i.e. one e – system. It
could not explain the line spectra of atoms containing more than one e– .
(ii) This theory could not explain the presence of multiple spectral lines.
(iii) This theory could not explain the splitting of spectral lines in magnetic field
(Zeeman effect). The intensity of these lines was also not explained by the Bohr model.
(iv) This theory was unable to explain de -broglie’s concept of dual nature of matter.
(v) This theory could not explain uncertainty principle.
(vi) No conclusion was given for the principle of quantization.
Example 1 :
Calculate the ratio of the radius of Li+2 ion in 3rd energy level to that of He+ ion in 2nd energy level.
2
n2 r1 n1 z 2
r
r2 n 2 z1
Sol. ;
z
n1 = 3, n2 = 2, z1 = 3 (for Li2+), z2 = 2 (for He+)
2
r1 3 2 3
r2 2 3 2
IIT-JEE Chemistry 7
Structure of atom
Example 2 :
Which of the following transitions will emit the photons of highest frequency in hydrogen atom ?
(A) From n = 1 to n = 2 (B) From n = 2 to n = 1 (C) From n = 2 to n = 6 (D) From n = 6 to n = 2
Sol. (B). The emission of photon is due to the transition of electrons from higher to lower energy levels. So the answer may be (B) or
(D). From Planck’s equation v E i.e., The frequency of emitted photon is directly proportional to the difference of energies of
two energy levels
Energy of n = 1 for H-atom : E1 = – 13.6 eV
13.6
Energy of n = 2 for H-atom : E2 = – eV
4
13.6
Energy of n = 6 for H-atom : E6 = – eV
36
13.6 3
So E2 – E1 = 13.6 – = 13.6 ×
4 4
13.6 13.6 1 1 2
E6 – E2 = = 13.6 = 13.6 ×
4 36 4 36 9
(E2 – E1) > (E6 – E2)
Example 3 :
Find the wavelengths of the first line of He+ ion spectral series whose interval between extreme lines is
1 1
– 2.7451 104 cm –1
1 2
Sol. Extreme lines means first and last.
1 1 1 1 1 1 RZ2
– RZ2 2 – 2 – RZ2 2 –
2 n1 n1 (n1 1)
2
(n1 1) 2
109677.76 22
2.7451 104
(n1 1) 2
(n1 + 1) = 4 n1 = 3
1 1 1
Wavelength of first line, 109677.76 2 2 2 – 2 ; 4689 10 –8 cm 4689Å
3 4
Example 4 :
How much energy will be emitted when electrons in a gram atom of hydrogen falls from third Bohr orbit to first orbit.
Sol. E = hc v (per atom) = NAhc v (per g atom)
1 1
v = 1.09 × 107 2 2 = 9.68 × 106 m–1
1 3
E = 6.023 × 10 × 6.626 × 10–34 × 3 × 108 × 9.68 × 106 = 1.160 × 106 J
23
TRY IT YOURSELF
Q.1 In which of the following orbits, the angular momentum of an electron of He+ will be h/ –
(A) First (B) Second (C) Third (D) Fourth
Q.2 Which of the following pairs indicates respective radii of the first and the second orbit of hydrogen atom?
(A) 0.0529 nm, 2.116 Å (B) 0.529 Å, 1.058 Å (C) 0.059 nm, 1.0858 Å (D) None of these
Q.3 If the radii of first orbits of H, He+, Li+2 and Be+3 are r1, r2, r3 and r4 respectively, then their correct decreasing order will be:
(A) r1 > r2 > r3 > r4 (B) r3 < r2 > r4 < r1 (C) r1 < r2 < r3 > r4 (D) Radius of all are equal
Q.4 The ratio of radii of the fifth orbits of He+ and Li+ will be
(A) 2 : 3 (B) 3 : 2 (C) 4 : 1 (D) 5 : 3
Q.5 If the velocities of first, second, third and fourth orbits of hydrogen atom are v1, v2, v3 and v4 respectively, then which of the
following should be their increasing order?
(A) v1 > v2 < v3 < v4 (B) v4 < v3 < v2 < v1 (C) v1 > v2 < v3 > v4 (D) Equal for all
8 IIT-JEE Chemistry
Structure of atom
Q.6 What should be the velocity of the electrons present in the first, second and third orbits of H, He +
and Li+2, respectively?
8
(A) 2.188 × 10 cm per second 7
(B) 5.47 × 10 cm per second
(C) 4.376 × 108 cm per second (D) 2.188 × 106 cm per second
Q.7 What should be the ratio of energies of the fifth orbits of Li+2 and He+?
(A) 4 : 9 (B) 9 : 4 (C) 12 : 16 (D) 7 : 2
Q.8 What should be the ratio of energies of the electrons of the first orbits of Na+10 and H ?
(A) 11:1 (B) 121 : 1 (C) 1 : 121 (D) 1 : 11
Q.9 What should be the energy in the first excited state of Be+3?
(A) –54.4 eV (B) –3.4 eV (C) –0.85 eV (D) –13./6 eV
Q.10 Which of the following should be the expression for the last line of Paschen series?
1 1 1 1 1 1 1 1 1 1 1 1
(A) R 9 2 (B) R
4 9 (C) R
9 16 (D) R
16
Q.11 In hydrogen atom which of the following transitions should be associated with highest absorption of energy?
(A) n = 1 to n = 4 (B) n = 2 to n = 3 (C) n = 4 to n = 1 (D) n = 3 to n = 2
ANSWERS
(1) (B) (2) (A) (3) (A) (4) (B)
(5) (B) (6) (A) (7) (B) (8) (B)
(9) (A) (10) (A) (11) (A)
ATOMIC ORBITALS : 4 or N
An atomic orbital is defined as "the region in space around the nucleus 3 or M
in which the probability of finding an electron is maximum is called an
2 or L
atomic orbital".
An electron in any atom does not always remain at a definite distance 1 or K
from the nucleus. It can move anywhere, but most of the time, it will be Nucleus
found within a small region of space around the nucleus this region of
space is called the atomic orbital.
Difference between orbit & orbital
Orbit Orbital
(i) An orbit is a well defined circular path in which An orbital is the region of space around the nucleus where
electrons revolve. These are numbered as 1, 2, 3, 4 the probability of finding the electron is maximum.
........... or labelled as K, L, M, N ..... It may be spherical or dumbbell in shape.
(ii) It represents the movement of electrons around It represents the three-dimensional motion of electrons
the nucleus in one plane. around the nucleus.
(iii) An orbit means that the position as well as momentum An orbital does not represent the position and momentum
of an electron can be known with certainty. of an electron with complete certainty.
(iv) It can accommodate at the maximum 2n2 electrons, An orbital can accommodate at the most two electrons
where n is the number of the orbit. with paired spins.
QUANTUM MECHANICALMODELOFATOM :
The atomic model which is based on the particle and wave nature of the electron is known as wave or quantum mechanical model
of the atom. This was developed by Schrodinger in 1926. This model describes the electron as a three dimensional wave in the
electronic field of positively charged nucleus. Schrodinger derived an equation which describes wave motion of positively
charged nucleus. Schrodinger derived an equation which describes wave motion of an electron. The differential equation is
d2 d2 d2 8 2 m
(E – V) 0
dx 2 dy 2 dz 2 h2
where x, y, z are certain coordinates of the electron, m = mass of the electron, E = total energy of the electron. V = potential energy
of the electron; h = Planck’s constant and (psi)= wave function of the electron.
Significance of : The wave function may be regarded as the amplitude function expressed in terms of coordinates x, y and z.
The wave function may have positive or negative values depending upon the value of coordinates. The main aim of Schrodinger
equation is to give solution for probability approach. When the equation is solved, it is observed that for some regions of space
IIT-JEE Chemistry 9
Structure of atom
the value of is negative. But the probability must be always positive and cannot be negative, it is thus, proper to use 2 in
favour of .
Significance of 2:2 is a probability factor. It describes the probability of finding an electron within a small space. The space
in which there is maximum probability of finding an electron is termed as orbital. The important point of the solution of the wave
equation is that it provides a set of numbers called quantum numbers which describe energies of the electron in atoms, informa-
tion about the shapes and orientations of the most probable distribution of electrons around nucleus.
Quantum numbers : The result of schrodinger wave equation gives three variable parameters and these 3 parameters are called
quantum numbers n, , m. These tell the position and energy of electron.
But 4th quantum number was discovered by spectroscopy. Exact information of an electron can be determined by 4 set of
quantum numbers.
n, , m position & energy (By schrodinger wave equation)
s spin (By spectroscopic study).
These are principal, azimuthal, magnetic and spin quantum numbers. Each orbital in an atom is specified by a set of three quantum
number and each electron is designated by four quantum numbers.
TYPES OF QUANTUM NUMBERS :
(A) Principal Quantum Number :
(a) Discovered by Bohr and designated by 'n', where n = 1, 2, 3......
(b) It determines the size of an atom i.e. the average distance between electron and nucleus.
r n2
(c) It determines the energy of the electron in an orbit where electron is present.
2 2 me 4 1
En = or En –
(4 0 ) 2 n 2 h 2 n2
Where m = mass of electron = 9.1 × 10–31 kg, e = electronic charge = 1.602 × 10–19 C, h = Planck's constant = 6.626 × 10–34 JS
0 = Permittivity factor = 8.854 × 10–12 C2 kg–1 m–3 S2
n = Principal quantum number (n = 1, 2, 3, 4.....)
1313.3
En = KJ mol–1
n2
En = energy of nth electronic level.
(d) It signifies the total number of electron in an orbit ie. 2n2.
nh
(e) Angular momentum of electron = .
2
(f) It gives the information of orbit K, L, M, N........
Azimuthal Quantum Number () :
(a) Discovered by Sommerfeld and denoted by ''.
(b) It determines the number of subshells or sublevels to which the electron belongs and tells about the shape of subshells.
(c) For given , total number of orbitals = (2 + 1)
For given , total number of electron = 2 (2 + 1)
For given , total number of subshells or total values of = n.
for eg. n = 2, will be 2.
(d) Designation of the sub-shells value of also determines the angular momentum of electron.
h
For given angular momentum = ( 1)
2
Value of 0 1 2 3
Name of subshell s p d f
shape of subshell spherical dumbbell double dumbbell complex
(e) The energy of an electron depends on the value of n & .
The electron enters the sub orbit whose (n + ) value or the value of energy is less.
Magnetic Quantum Number :
(a) Discovered by Zeeman and denoted by 'm'.
(b) It specifies the orientation of atomic orbital in magnetic field in different directions.
(c) The value of m varies from – to + through zero.
10 IIT-JEE Chemistry
Structure of atom
(d) It informs about the splitting of spectral lines in the magnetic field i.e. this quantum number proved the Zeeman effect.
(e) For a given value of 'n' the total value of m is equal to n2.
(f) For a given of '' the total value of 'm' is equal to (2 + 1).
(g) Orbitals having same energy are called degenerate orbitals.
For s, number of degenerate orbitals = 0
For p, number of degenerate orbitals = 3
Spin Quantum Number (s) :
(a) Discovered by Goldshmidt and Ullenback and denoted by the symbol 's'.
(b) Value of 's' is +/2 and –/2 which specifies the spin or rotation or direction of electron about its axis during the movement.
Spin could be clockwise and anticlockwise.
h
(c) Spin angular momentum = s (s 1)
.
2
(d) Maximum spin of an atom = 1/2 × number of unpaired electron.
Example 5 :
Write down the values of quantum numbers of all the electrons present in the outermost orbit of argon (At. No. 18)
Sol. The electronic configuration of argon is 1s 2 , 2s 2 2p6 ,3s 2 3p 2x 3p 2y 3p 2z
Values of quantum numbers are:
n m s
3s 2 3 0 0 +1/2, –1/2
3p 2x 3 1 1 +1/2, –1/2
3p 2y 3 1 1 +1/2, –1/2
3p2z 3 1 0 +1/2, –1/2
Example 6 :
Which set of quantum number is not consistent with the quantum mechanical theory?
(a) n = 2, = 1, m = 1, s = ½ (b) n = 4, = 3, m = 2, s = –1/2
(c) n = 3, = 2, m = 3, s = +1/2 (d) n = 4, = 3, m = 3, s = +1/2.
Sol. (c). The e is a well defined co-relation between n, , m and s quantum numbers in an atom. = (n – 1), m will be ± ½, for n = 3 there
cannot be m = 3. Highest value m will be 2.
Example 7 :
(a) An electron is in 5f-orbital. What possible values of quantum numbers n, l, m and s can it have?
(b) What designation is given to an orbital having (i) n = 2, = 1, and (ii) n = 3, = 0?
Sol. (a) For an electron in 5f-orbital, quantum number are: n = 5, = 3; m = –3, –2, –1, 0, +1, +2, +3 and s = either + 1/2 or –1/2
(b) (i) 2p, (ii)3s
SHAPES OFATOMIC ORBITALS ONTHE BASIS OF QUANTUM NUMBER
(i) S-orbital: An electron in considered to be immersed out in the form of a cloud. The y
shape of the cloud is the shape of the orbital. The cloud is not uniform but denser in
the region where the probability of finding the electron in maximum.
The orbital with the lowest energy is the 1s orbital. It is a sphere with its center of the
1s 2s
nucleus of the atom. The s-orbital is said to spherically symmetrical about the nucleus, x
nucleus
so that the electronic charge is not concentrated in any particular direction. 2s orbital
is also spherically symmetrical about the nucleus, but it is larger than (i.e., away from)
radial node
the 1s orbit. Z
(ii) p-orbitals: There are three p-orbitals: px, py and pz They are dumb-bell shaped, the two levels being separated by; a nodal plane,
i.e., a plane where there is no likely hood of finding the electron. The p-orbitals have a marked direction character, depending as
whether px, py and pz orbital is being considered. The p-orbitals consist of two lobes with the atomic nucleus lying between
them. The axis of each p-orbital is perpendicular to the other two. The p x, py and pz orbitals are equivalent except for their
directional property. They have same energy; orbitals having the same energy are said to be degenerated.
IIT-JEE Chemistry 11
Structure of atom
z z
z
y y y
x x x
px py pz
(iii) d-orbitals: There are five d-orbitals. The shapes of four d-orbitals resemble four leaf cloves. The fifth d-orbital loops different. the
shapes of these orbitals are given below.
y z z
x y x
dxy dyz dzx
z
y
d 2 2 dz 2
x y
NODE AND NODAL PLANE :
Node is defined as a region where the probability of finding an electron is zero.
The planes passing through the angular nodal points are called nodal planes.
Nodes : No. of radial or spherical nodes = n – – 1. No. of angular nodes = , Total no. of nodes = n – 1
SHAPE OF ORBITALS ON THE BASIS OF PROBABILITY DISTRIBUTION:
(a) Wave function provides information about the electron's location in space, ie. the shape of orbital.
(b) An electron cloud is dense where the probability of finding electron is maximum Z
(c) The plane and point at which zero electron density exist (ie. 2 goes to
zero) is called as nodal plane or nodal point.
(d) An orbital function , can be written as product of two function radial P
function and angular function.
r
(e) The radial function is a function of distance only where as the angular
function is a function of two angle variables.
= r . (, ) X
Where & are spherical co-ordinates
r is the length of line between origin and point P.
(f) The complete wave function represents an orbital in which radial part (r) depends upon quantum number n and and
suggests the size of the orbitals where as the angular part ( & ), depends upon quantum number n, and m and suggests
the shape of orbitals.
(g) Since three variable r, ( and ) are involved, it is not easy to plot variation of with these variable in a single diagram and
therefore distance variation and angular variations are plotted separately.
12 IIT-JEE Chemistry
Structure of atom
The s-orbitals :
(a) These are spherically symmetrical
(b) Their size increases with increase in the value of n
(c) The relative radii of the spheres correspond to a 90 percent probability of finding electron within each sphere.
(d) There are several ways to visualize the radial variation of ns orbitals with n = 1, 2, 3 ....
One way is to make a three dimensional picture, in which the shading is heaviest where 2 is largest.
Another way is to plot the wave function (1s, 2s, 3s.......) verses r, the distance from the nucleus.
The p-orbitals :
(a) In p-orbital electron density is concentrated on two sides of the nucleus separated by a nodal plane at the nucleus
(b) each p-orbital has two lobes.
(c) There are three equivalent p-orbitals corresponding to three possible values of m for = 1 i.e. 1, 0, – 1.
(d) In case of s-orbitals, the radial nodes in p-orbitals occurs so close to the nucleus that they have little effect on the chemical
bonding of atoms.
(e) Since p-orbitals have angular nodes that pass through the nucleus, the electron density at the nucleus is zero.
(f) Infect in all types of orbitals excepts s-orbital electron is never at the nucleus in wave function with > 0.
The d-orbitals :
(a) d-orbital can not exist for the value of n below 3.
(b) There are five equivalent d-orbitals.
(c) Although d orbital looks different, it has the same energy as the other four d-orbitals.
z2
(d) Their wave function also have n – 3 radial nodes giving once again total nodes angular and radial as n – 1.
SHIELDING OR SCREENING EFFECT :
According to the screening rule, "the electrons in the completely filled inner shells screen the outer electrons against the
attraction by the nucleus", i.e., the outer electrons are not attracted by the nucleus so effectively as they would have been
attracted had the inner shell electrons not have been present. This is known as Shielding or Screening Effect.
Due to this effect, the ns orbitals are filled with electrons earlier than the (n – 1) d-orbitals. In a similar way the 5s, 5p and 6s-
orbitals are occupied by electrons before the 4f-orbitals. In a given shell, the decreasing order of screening effect is :
s > p > d > f.
ELECTRONIC CONFIGURATION OF ELEMENTS :
The distribution of electrons in various shells and sub-shells is called electronic configuration of elements. This arrangement of
electrons in an atom decides the properties of an element. The following rules are used for writing the electronic configuration.
(A) Aufbau principle :
Aufbau is a German word meaning ‘building up’. This gives us a sequence in which various sub-shells are filled up depending
on the relative order of the energy of the subs-hells. The sub-shell with minimum energy is filled up first and when this obtains
maximum quota of electrons, then the next sub-shell of higher energy starts filling.
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d
6s 6p
7s
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p.
IIT-JEE Chemistry 13
Structure of atom
Sub-shell n (n+)
1s 1 0 1
2s 2 0 2
2p 2 1 3 Lowest value of n
3s 3 0 3
3p 3 1 4 Lowest value of n
4s 4 0 4
3d 3 2 5 Lowest value of n
4p 4 1 5
5s 5 0 5
4d 4 2 6 Lowest value of n
5p 5 1 6
6s 6 0 6
4f 4 3 7 Lowest value of n
5d 5 2 7
6p 6 1 7
7s 7 0 7
5f 5 3 8 Lowest value of n
6d 6 2 8
7p 7 1 8
Exceptions to Aufbau Principle: In some cases it is seen that actual electronic arrangement is slightly different from arrangement
given by Aufbau principle. A simple reason behind this is that half-filled and full-filled sub-shell have got extra stability.
Cr(24)
1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 4 , 4s 2 (wrong)
1s 23 , 2s 2 2p6 ,3s 2 3p6 3d5 , 4s1 (right)
Cu(29)
1s 2 , 2s 2 2p6 , 3s 2 3p6 3d9 , 4s 2 (wrong)
1s 2 , 2s 2 2p6 , 3s 2 3p6 3d10 , 4s1 (right)
Similarly the following elements have slightly different configurations than expected.
Nb
[Kr] 4d 4 5s1 ; Mo
[Kr] 4d 4 5s1 ; Ru
[Kr] 4d 7 5s1
Rh
[Kr] 4d8 5s1 ; Pd
[Kr] 4d10 5s0 ; Ag
[Kr] 4d10 5s1
Pt [Xe] 4f 14 5d9 6s1 ; Au [Xe] 4f 14 5d10 6s1
(B) Hund's rule of maximum multiplicity :
(a) According to this rule, "pairing of electrons in sub-shell starts after all the available atomic orbitals of that sub shell are singly
filled (half-filled) with electrons having parallel spins" or pairing of electrons in a sub-shell is impossible in the presence of vacant
atomic orbitals in that sub shell.
(b) In p-sub shell, the fourth electron starts pairing, and the sixth electron starts pairing in d-sub-shell. In f-sub-shell, pairing
starts with eighth electron.
(c) This rule gives the number of unpaired electrons in an atom, ion or molecule.
(d) Exactly half-filled sub-shells have lesser energy and thus assume more stability than any other arrangement. Thus, p3 is more
stable arrangement than p2, p4 or p5.
(e) When the electronic configuration ns2np6 is attained in the outermost shell of an atom, the next incoming electron enters the
(n + ) s-subshell. The nd-and nf-sub-shells will be vacant.
(C) Pauli's exclusion principle :
(a) According to this principle, "No two electrons in an atom can have all the four quantum number n, , m and s identical.
(b) In an atom, any two electrons may have three quantum number identical but fourth quantum number must be different.
(c) Since this principle excludes certain possible combinations of quantum number for any two electrons in an atom, it was given
the name exclusion principle,
14 IIT-JEE Chemistry
Structure of atom
Its results are as follows :
(i) The maximum capacity of a main energy shell is equal to 2n2 electron.
(ii) The maximum capacity of a subshell is equal to 2(2 + 1) electrons.
(iii) Number of sub-shells in a main energy shell is equal to the value of n.
(iv) Number of orbitals in a main energy shell is equal to n2.
(v) One orbital cannot have more than two electrons.
Example 8 :
The orbital angular momentum of an electron in 2s orbital is
(A) 4 (B) 1 (C) zero (D) h/2
h h
Sol. (C). The orbital angular momentum of an electron is calculated as ( 1) , 0(0 1) 0
2 2
Example 9 :
The energy of an electron of 2py orbital is
(A) greater than 2p orbital (B) less than 2pz orbital
(C) equal to 2s orbital (D) same as that of 2px and 2pz orbitals.
Sol. (D). All the 2p orbitals are degenerate
Example 10 :
Number of nodal planes (planes of zero electron density) in the dxy orbital is
(A) 1 (B) 2 (C) 0 (D) 4
Sol. (B). xz and yz are planes with zero electron density for dxy orbital.
TRY IT YOURSELF
Q.1 Magnetic quantum number specifies :
(A) size of orbitals (B) shape of orbitals (C) orientation of orbitals in space (D) nuclear stability
Q.2 In ‘Aufbau principle’, the term aufbau represents :
(A) the name of scientist (B) German term meaning for building up
(C) the energy of electron (D) the angular momentum of electron
Q.3 Non-directional orbital is :
(A) 3 s (B) 4 f (C) 4 d (D) 4 p
Q.4 In a set of degenerate orbitals , the electrons distribute themselves to have like spins as far as possible. This statement is known
as :
(A) Pauli’s exclusion principle(B) Aufbau principle (C) Hund’s rule (D) Slater rules
Q.5 The shape of an orbital is governed by :
(A) Spin quantum number (B) Principal quantum number
(C) Azimuthal quantum number (D) Magnetic quantum number
Q.6 The total number of orbitals in a shell with principal quantum number ‘n’ is :
(A) 2n (B) 2n2 (C) n2 (D) n + 1
Q.7 Which represents the correct set of four quantum number of a 4 d - electron ?
(A) 4 , 3 , 2 , + 1/2 (B) 4 , 2 , 1 , 0 (C) 4 , 3 , –2 , + 1/2 (D) 4 , 2 , 1 , + 1/2
Q.8 The total number of electrons that can be accommodated in all the orbitals having principal quantum number 2 and azimuthal
quantum number 1 is :
(A) 2 (B) 4 (C) 6 (D) 8
Q.9 A neutral atom of an element has 2 K , 8 L , 11 M and 2 N electrons . Total number of electrons with = 2 will be :
(A) zero (B) 3 (C) 6 (D) 10
Q.10 The probability of finding an electron residing in a px orbital is not zero :
(A) In the yz plane (B) In the xy plane (C) In the y direction (D) In the z direction
ANSWERS
(1) (C) (2) (B) (3) (A) (4) (C) (5) (C)
(6) (C) (7) (D) (8) (C) (9) (B) (10) (B)
IIT-JEE Chemistry 15
Structure of atom
DUAL NATURE OF ELECTRON-THEWAVE NATURE OF ELECTRON :
(a) In 1924, the french physicist, Louis de Broglie suggested that if light has both particle and wave like nature, the similar duality
must be true for matter. Thus an electron, behaves both as a material particle and as a wave.
This presented a new wave mechanical theory of matter. According to this theory, the electrons, protons and even atoms when
in motion possess wave properties.
According to de-Broglie, the wavelength associated with a particle of mass m, moving with velocity v is given by the relation
h
= , where h = Planck’s constant
mv
hc
It can be derived as follows according to Planck’s equation E = h =
Einstein proved theoretically that mass and energy are interrelated by the equation
E = mc2
hc h
Equating both, = mc2 or =
mc
This was verified experimentally by Davisson and Germer by observing diffraction effects with an electron beam.
Let the electron is accelerated with a potential of V then the K.E. is
1 h
mv2 = eV ; m2v2 = 2eVm ; mv = 2eVm = p ; =
2 2eVm
If Bohr’s theory is associated with de- broglie’s equation then wavelength of an electron can be determined moving in bohr’s
orbit and relate it with circumference and multiply with a whole number.
2r
2r = or =
n
h
From de - broglie equation, =
mv
h 2r nh
Thus = or mvr =
mv n 2
Example 11 :
13.6 eV is needed for ionization of a hydrogen atom. An electron in a hydrogen atom in its ground state absorbs 1.50 times as
much energy as the minimum required for it to escape from the atom. What is the wavelength of the emitted electron?
( me = 9.109 10–31 kg, e = 1.602 10–19 coulomb, h = 6.63 10–34 J.s)
Sol. 1.5 times of 13.6 eV i.e., 20.4 eV is absorbed by the hydrogen atom out of which 6.8 eV (20.4 –13.6) is converted to kinetic energy.
KE = 6.8 eV = 6.8 (1.602 × 10–19 coulomb) (1 volt) = 1.09 × 10–18 J.
Now, KE
1
mv 2 or, 2 KE 2(1.09 10 –18 J
1.55 106 m / s
2 m (9.109 10 –31
kg)
h (6.63 10 –34 J.s)
4.70 10 –10 metres
mv (9.109 10 –31 kg) (1.55 106 m / s)
Example 12 :
An electron beam can undergo diffraction by crystals. Through what potential should a beam of electron be accelerated. So that
its wave length becomes equal to 1.54 Å .
h h 150
Sol. Å
mv 2meV V
150
1.54 = V = 63.24 volts
V
16 IIT-JEE Chemistry
Structure of atom
HEISENBERG’S UNCERTAINITY PRINCIPLE :
All moving objects that we see around us e.g., a car, a ball thrown in the air etc, move along definite paths. Hence their position
and velocity can be measured accurately at any instant of time. Is it possible for subatomic particle also?
As a consequence of dual nature of matter. Heisenberg, in 1927 gave a principle about the uncertainties in simultaneous
measurement of position and momentum (mass × velocity) of small particles. This principle states.
It is impossible to measure simultaneously the position and momentum of a small microscopic moving particle with absolute
accuracy or certainty i.e., if an attempt is made to measure any one of these two quantities with higher accuracy, the other
becomes less accurate.
The product of the uncertainty in position (x) and the uncertainty in the momentum (p = m v), where m is the mass of the
particle and v is the uncertainty in velocity) is equal to or greater than h/4 where h is the Planck’s constant.
Thus, the mathematical expression for the Heisenberg’s uncertainty principle is simply written as
h
x.p h / 4 or E t
4
Explanation of Heisenberg’s uncertainty Principle: Suppose we attempt to measure both the position and momentum of an
electron, to pin point the position of the electron we have to use light so that the photon of light strikes the electron and the
reflected photon is seen in the microscope. As a result of the hitting, the position as well as the velocity of the electron is
distributed. The accuracy with which the position of the particle can be measured depends upon the wavelength of the light
used. The uncertainty in position is + . The shorter the wavelength, the greater is the accuracy. But shorter wavelength means
higher frequency and hence higher energy. This high energy photon on striking the electron changes its speed as well as
direction. But this is not true for macroscopic moving particle. Hence Heisenberg’s uncertainty principle is not applicable to
macroscopic particles.
MOSELEY'S LAW :
This law relates the frequency of particular lines of characteristic spectrum
and the atomic number of the target. According to it,
(Z – ) where is screening constant.
For the characteristic lines as Kand K. Lines graph
between and Z will be straight line.
Example 13 :
The uncertainty in position and velocity of a particle are 10–10 m and 5.27 × 10–24 ms–1 respectively. Calculate the mass of the
particle (h = 6.625 × 10–34 J-s)
Sol. According to Heisenberg’s uncertainty principle.
h h 6.625 10 34
x.m v = or m= = = 0.099 kg.
4 4x.v 4 3.143 10 10 5.27 10 24
Example 14 :
(a) Calculate the wavelength of electron moving with K.E. 10 eV.
(b) An electron has a speed of 600 ms–1 with an accuracy of 0.004%. Determine the uncertainty with which its position can be
located. Also comment on the result.
h 6.625 1034
Sol. (a)
2mE 2 9.11 1031 10 1.6 10 19
(b) p = m v = 9.11 × 10–31 × 0.024 = 2.1864 x 10–32 kg ms–1
h 6.625 10 –34
x 2.41 x 10–3 m
4p 4 3.14 2.1864 10 32
The uncertainty in position is many times more than the radius of atom which is of the order of 1010 m. With the uncertainty in
position it can't be said whether electron is within the atom.
IIT-JEE Chemistry 17
Structure of atom
Example 15 :
On the basis of Heisenberg’s uncertainty principle, show that the electron cannot exist within the nucleus.
Sol. Radius of the nucleus is of the order of 10–13 cm and thus uncertainty in position of electron i.e. (x), if it is within the nucleus
will be 10–13 cm.
h
Now, x.u
4m
6.626 10 27
u = = 5.79 × 1012 cm/sec
4 3.14 9.108 10 28 10 13
i.e., order of velocity of electron will be 100 times greater than the velocity of light which is impossible.
Thus possibility of electron to exist is nucleus is zero.
ELECTROMAGNETIC SPECTRUM :
Maxwell, in 1956 proposed that radiant energy (light) has wave characteristics. Light according to him is Electromagnetic Wave
arising due to the disturbance created by electric and magnetic fields oscillating perpendicular to each other in space. Like all
other mechanical waves, it is characterised by velocity c, frequency , wavelength which are related as :
c = . The value of c is constant and equal to 3 × 108 m/s.
Electromagnetic wave or radiation is not a single wavelength radiation, but a mixture of various wavelength or frequencies.
All the frequencies have same speed.
If all the components of Electromagnetic Radiation (EMR) are arranged in order of decreasing or increasing wavelengths or
frequencies, the pattern obtained is known as Electromagnetic Spectrum. The following table shows all the components of light.
S.No. Name Wavelength(Å) Frequency(Hz) Source
1. Radio wave 3 1014 – 3 107 1 105 –1 109 Alternating current of high frequency
2. Microwave 3 107 – 6 106 1 109 – 5 1011 Klystron tube
3. Infrared (IR) 6 106 – 7600 5 1011 – 3.95 1016 Incandescent objects
4. Visible 7600–3800 3.95 1016 – 7.9 1014 Electric bulbs, sun rays
5. Ultraviolet(UV) 3800–150 7.9 1014 – 2 1016 Sun rays, arc lamps with mercury
vapours
6. X-Rays 150–0.1 2 1016 – 3 1019 Cathode rays striking metal plate
7. -Rays 0.1–0.01 3 1019 – 3 10 20 Secondary effect of radioactive decay
8. Cosmic Rays 0.01–zero 3 1020 –Infinity Outer space
PHOTOELECTRIC EFFECT :
When light of particular wavelength of frequency falls on a metal, electrons are emitted form it. This phenomenon of emission of
electrons from a metal surface is called photoelectric effect. The electrons emitted are called photoelectrons.
18 IIT-JEE Chemistry
Structure of atom
Laws of Photoelectric Effect :
(a) The number of photoelectrons emitted from a metal surface in a unit time (the rate of emission of photoelectrons) is proportional
to the intensity of incident light.
(b) The maximum kinetic energy of the emitted photoelectrons increases with increasing frequency or decreases with increasing
wavelength of the incident light. The kinetic energy of the electrons does not depend upon the intensity of the incident light.
(c) The emission of photoelectrons occurs upto a definite minimum frequency (maximum wavelength) of the incident light. This
minimum frequency is called threshold frequency and the maximum wavelength is called threshold wavelength. Threshold
wavelength depends upon the maximum wavelength is called threshold wavelength. Threshold wavelength depends upon the
nature of the substance and it is different for different metals.
(d) Within the limits of accuracy (~ 10–9 second) there is no time lag between the incidence of light at the metal surface and the
emission of electrons from the metal surface, whatever is the intensity of incident light.
Photoelectric current and stopping potential :
(a) The negative potential of the plate relative to the electron emitter,
Photo-electric
i.e., cathode at which photoelectric current becomes zero is called current
stopping potential. It measures the maximum kinetic energy of the I
(High Intensity)
photoelectrons. a
1 b
Emax = mv2max = eV0 (Low Intensity)
2
V0 ( ) 0 (+) V
Potential difference (V)
Y
(b) The stopping potential does not depend upon
Stopping potential
the intensity of incident light.
VO
O X
vo v
Work function : The minimum energy per electron given to the free electrons of the metal which enables them to cross the
potential barrier present at the surface of the metal, is called work function.
W0 = h0
Einstein's photoelectric equation :
1 2 1 1 0
(a) mv max = eV0 = h ( – 0) = hc = hc
2 0 0
(b) Maximum velocity of emitted electrons :
2h(v v0 ) 2hc ( 0 )
vmax = = m 0
m
2eV0
(c) vmax =
m
Example 16 :
What will be the K.E. of photoelectron ejected by a metal upon irradiation with electromagnetic radiation of wavelength equal to
that of the last line in Lyman series of He+ ion? RH = 109677 cm–1 and I.P. of metal = 3.8 eV.
Sol. For Lyman series :
1 1
= RH. Z2 1 2
n
For series limit n =
1
= RH. Z2 = 1096 77 × 22 cm–1
= 2.279 × 10– 6 cm
IIT-JEE Chemistry 19
Structure of atom
c 3 x1010
= = = 1.316 × 1016 Hz
2.279 x106
h0 = 3.8 eV = 3.8 × 1.6 × 10–12 erg
3.8 x1.6 x1012
0 = = 9.17 × 1014 Hz
6.05 x10 –27
K.E. = h ( – 0) = 6.625 × 10–27 (3.316 × 1016 – 0.0917 × 1016) = 8.11 × 10–11 erg = 50.68 eV
Example 17 :
In a photoelectric experiment, the collector plate is at 2.0 V with respect to emitter plate made of copper (work function 4.5 eV). The
emitter is illuminated by a source of mono-chromatic light of wavelength 200 nm. Find the minimum and maximum kinetic energy
of photoelectrons reaching the collector.
Sol. Since plate potentials 2 V, minimum K.E. will be 2 eV. For max. K.E. use the following relation:
Absorbed energy = Threshold energy + K.E.
c
h 4.5 1.6 10 –19 K.E.
6.626 10 –34 3 108
4.5 1.6 10 –19 K.E.
200 10 –9
K.E. = 2.739 × 10–19 J = 1.7 eV
Max K.E. = 2eV + 1.7 eV = 3.7 eV.
Example 20 :
A photon of wavelength 5000 Å strikes a metal surface, the work function of the metal being 2.20 eV. Calculate
(i) the energy of the photon in eV
(ii) the kinetic energy of the emitted photo electron and
(iii) the velocity of the photo electron.
Sol. (i) Energy of the photon
hc (6.6 1034 Js) (3 108 ms 1 )
E = hv = = = 3.96 × 10–19 J ; 1eV = 1.6 × 10–19 J
5 107 m
3.96 1019 J
Therefore E = = 2.475 eV
1.6 1019 J / eV
(ii) Kinetic energy of the emitted photon electron work function = 2.20 eV
Therefore, KE = 2.475 – 2.20 = 0.275 eV = 4.4 × 10–20 J
1
(iii) Velocity of the photon electron KE = mv2 = 4.4 × 10–20 = 0.275 eV = 4.4 × 10–20 J
2
1
(iii) Velocity of the photon electron KE = mv2 = 4.4 × 10–20 J
2
2 x 4.4 x1020
Therefore, velocity (v) = = 3.11 × 105 ms–1
9.1x1031
TRY IT YOURSELF
Q.1 The number of photons of light having wavelength 100 nm which can provide 1.00 J energy is nearly
(A) 107 photons (B) 5 × 1018 photons (C) 5 × 1017 photons (D) 5 × 107 photons
Q.2 The electromagnetic radiation of wavelength 3186 Å is just sufficient to ionise the outermost electron of a gaseous Cs atom.
Calculate the ionization energy of Cs in kJ/mole.
Q.3 Calculate the energy in kilocalories of the photons of an electromagnetic radiation of wavelength 3800 Å.
Q.4 The maximum kinetic energy of the photo-electrons is found to be 6.63 × 10–19 J when the metal is irradiated with a radiation of
frequency 3 × 1015 Hz. The threshold frequency of the metal is
(A) 1 × 1015 Hz (B) 3 × 1015 Hz (C) 2 × 1016 Hz (D) 2 × 1015 Hz
20 IIT-JEE Chemistry
Structure of atom
Q.5 If threshold wavelength (º) for ejection of electron from metal is 330 nm, then work function for the photoelectric emission is
( A
–10 J ) 6 × (B) 1.2 × 10–18 J
1 0 (C) 3 × 10–19 J (D) 6 × 10–19 J
Q.6 The photo electric emission requires a threshold frequency v0. For certain metal 1 = 2200Å and 2 = 1900 Å produce electrons
with a maximum kinetic energy KE1 and KE2. If KE2 = 2KE1, calculate v0 and corresponding 0.
Q.7 A ball of mass 200 g is moving with a velocity of 10 m sec–1. If the error in measurement of velocity is 0.1%, the uncertainty is its
position is:
(A) 3.3 × 10–31m (B) 3.3 × 10–27 m (C) 5.3 × 10–25 m (D) 2.64 × 10–32 m
Q.8 The de Broglie wavelength of a particle with mass 1 g and velocity 100 m/s is:
(A) 6.63 × 10–33 m (B) 6.63 × 10–34 m (C) 6.63 × 10–35 m (D) 6.65 × 10–35 m
ANSWERS
(1) (B) (2) 375 kJ/mol (3) 1.248 × 10–22 K Calorie (4) (D)
(5) (D) (6) 4.52 × 1011 per sec (7) (D) (8) (A)
USEFUL TIPS
1. Magnetic moment : n(n 2) B.M.; n = number of unpaired e–.
2. Radial nodes ; Angular nodes ; Total nodes
(n – – 1) (n – 1)
3. Total no. of e– in an energy level = 2n2
Total no. of e– in sublevel = 2 (2 + 1)
Maximum no. of e– in an orbital = 2
Total no. of orbitals in a sublevel = 2 ( + 1)
No. of subshells in main energy shell = n
No. of orbitals in a main energy shell = n2.
= 0 1 2 3 4
s p d f g
4. Revolution per sec = v/2r
5. Separation energy = E n E n given 2,3,4,......
6. No. of waves = n = principle qauantum no.
I.E. In E
7. ground state of e (K,L,M,N)
mM
8. Reduce mass , where m = mass of e–, M = mass of nucleus.
mM
no. of molecules reacting
9. Quantum yield =
no. of quanta absorbed
10. Nucleus radius R = R0A1/3, R0 = 1.33 × 10–13 cm., A = mass number.
11. The most probable distance for orbitals belonging to a particular principal quantum number follows the order
d-orbital < p-orbital < s-orbital
12. Radial distribution functions for various orbitals in the hydrogen atom
6 2p
16 1s 2s
5.0 5
14
12 4.0 node 4
4 r2R210/1010m–1
10 3.0 3
8
6 2.0 2
4
1.0 1
2
0 0 0
0 1 2 3 4 0 1 2 3 4 5 6 7 8 9 0 1 2 3 3
r/a0 r/a0 r/a0
IIT-JEE Chemistry 21
Structure of atom
MISCELLANEOUS SOLVED EXAMPLES
Example 1 :
(i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
Sol. (i) Mass of an electron = 9.1 × 10–31 kg = 9.1 × 10–28 g
So, 9.1 × 10–28 g 1 electron
1 electron 1g
1g = 1.1 × 1027 electrons
9.1 1028 g
(ii) 1 mol 6.023 × 1023 units.
So, Mass of 1 mole of electrons = Mass of an electron × 6.023 × 1023
= 9.1 × 10–31 kg × 6.023 × 1023 = 5.48 × 10–7 kg
Charge on 1 mol of electrons = Charge on an electron × 6.023 × 1023
= 1.602 × 10–19 C × 6.023 × 1023 = 94688 C
Example 2 :
How far from the nucleus is the electron in a hydrogen atom if it has energy of –0.850 eV.
Z2 Z2
Sol. E n – 21.69 10 –19 ; – 21.69 10 –19 –0.85 1.6 10 –19 ; n = 4 (Z = 1)
n2 n2
n2 16
r 0.529 0.529 8.46Å
Z 1
Example 3 :
In an atom two electrons move around the nucleus in circular orbits of radii R and 4R. Calculate the ratio of the time taken by them
to complete one revolution.
Sol. Time taken for one complete revolution is given by
2rn 2r1xn 2
T= v = ; T n3
n u1 / n
rn 4R r1 n 2
; = 4, n2 = 4 n = 2
r1 R r1
The ratio of time taken = 13 : 23 = 1 : 8
Example 4 :
(i) Calculate the total number of electrons present in 1 mol of methane.
(ii) Find (a) the total number and (b) the total mass, of neutrons in 7 mg of 14C.
(Assume that mass of a neutron = 1.675 × 10–27 kg)
(iii)Find (a) the total number and (b) the total mass, of protons in 34 mg of NH3 at STP. Will the answer change if the temperature
and pressure are changed ?
Sol. (i) No. of electrons in one molecule of methane, (CH4) = 6 + 4 = 10
So, no. of electrons in one mole of methane = 10 × 6.023 × 1023 = 6.023 × 1024
(ii) Mass of 14C = 7 mg = 7 × 10–3 g
Molar mass of 14C = 14g/mol
7 103 g
So, amount of 14C in 7 mg sample = = 5 × 10–4 mol
14g / mol
Each carbon-14 nucleus contains 8 neutrons. So,
(a) No. of neutrons in 7 mg sample of 14C = 8 × 5 × 10–4 mol × 6.023 × 1023 mol–1 = 2.41 × 1021
(b) Total mass of neutrons in 7 mg sample of 14C = 2.41 × 1021 × 1.675 × 10–27 kg = 4.037 × 10–6 kg
(iii) Mass of NH3 = 34 mg = 34 × 10–3 g
Molar mass of NH3 = 17 g/mol
34 103 g
Amount of ammonia = = 2 × 10–3 mol
17 g / mol
So, no. of NH3 molecules in 34 mg sample = 2 × 10–3 mol × 6.023 × 1023 mol–1 = 1.2046 × 1021
22 IIT-JEE Chemistry
Structure of atom
Each molecule of NH3 contains 10 protons (7 protons in N + 3 in three H atoms)
(a) No. of protons in 34 mg of ammonia = 10 × 1.2046 × 1021 = 1.2046 × 1022
(b) Mass of a proton = 1.675 × 10–27 kg
So, total mass of protons in 34 mg of NH3 = 1.2046 × 1022 × 1.675 × 10–27 kg = 2.018 × 10–5 kg
The number of neutrons, protons, molecules and mass does not depend upon temperature and pressure. Therefore, there will be
no change in the answers, if temperature and pressure are changed.
Example 5 :
Wavelength of high energy transition of H–atoms is 91.2nm. Calculate the corresponding wavelength of He atoms.
Sol. The expression of ionisation energy is E = RHZ2hc
For Li2+ ion, Z = 3 Hence
E = (1.0974 x 107 m–1) (9) (6.626 x 10–34 Js (3 x 108 ms–1) = 1.964 x 10–17 J
For one mole of ions, we have
E ' = NA E = (6 .023 × 1023 mol–1) (1. 964 × 10–17 J) = 1.1829 × 107 J mol–1 = 11829 kJ mol–1
Example 6 :
Yellow light emitted from a sodium lamp has a wavelength () of 580mm. Calculate the frequency () and wavenumber ( ) of the
yellow light.
Sol. Wavelength, = 580 nm = 580 × 10–9 m, Velocity of light, c = 3 × 108 ms–1
c 3 108 ms 1
Then, frequency, = = = 5.17 × 1014 s–1 = 5.17 ×1014 Hz
580 109 m
1 1
Wavenumber, = = = 1.72 × 106 m–1
580 109 m
Example 7 :
Find energy of each of the photons which –
(i) Correspond to light of frequency 3 × 1015 Hz (ii) Have wavelength of 0.50 Å.
Sol. Energy of a photon of light of frequency is given by h, and that having wavelength is ch/ .
(i) Energy of photon of light having the frequency of 3 × 1015 Hz
= h= 6.626 × 10–34 J s × 3 × 1015 s–1 = 1.99 × 10–18 J
(ii) Energy of photon of light having wavelength of 0.5 Å
ch 3 108 ms 1 6.626 10 34 Js
= = = 3.98 × 10–15 J
0.5 10 10 m
Example 8 :
The energy levels of hypothetical one electron atom are :
0 eV —n=
– 0.50 eV — n = 5
– 1.45 eV — n = 4
– 3.08 eV — n = 3
– 5.3 eV —n=2
– 15.6 eV — n = 1
(a) Find the ionisation potential of atom ?
(b) Find the short wavelength limit of the series terminating at n = 2?
(c) Find the wave no. of photon emitted for the transition made by the electron from third orbit to its orbit ?
(d) Find the minimum energy that an electron will have after interacting with this atom in the ground sate. If the initial kinetic
energy of the electron is (i) 6 eV ; (ii) 11 eV?
Sol. (a) I.P. of the atoms is I.P. = E. E1 = 0 – (– 15.6) = 15.6 eV
(b) Series limit at n = 2 is E = E – E2 = 0 – (5. 3) = 5.3 eV
hc 1240
= 5.3 eV ; = 5.3 eV ; = 233.9 nm
(c) E for the transition n = 3 n = 1 is E = E3 – E1 = 3.08 – (15.6) = 12.52 eV = 2.005 × 10–18 J
hc = 2.055 × 10–18
= 1.009 ×107 m–1
(d) The difference in energy between n = 1 and n = 2 is 10.3 eV
(i) Since the incoming electron has 6 eV energy, it will not be able to do anything hence it will not interact with the atom.
(ii) In case it has 11 eV energy is carried by this electron. Due to transfer of 10.3 eV of energy it will jump from n = 1 to n = 2 level.
IIT-JEE Chemistry 23
Structure of atom
Example 9 :
Calculate the wavelength, frequency and wavenumber of a light wave whose period is 2.0 × 10–10 s.
Sol. Period of the light wave, T = 2 × 10–10 s
1 1
So, frequency of the light wave, = = = 5 × 109 s–1 = 5 × 109 Hz
T 2 1010 s
c
Wavelength of the light wave, = = c × T = 3 × 108 ms–1 × 2 × 10–10 s = 6 × 10–2 m
1 1
Wavenumber of the light wave, = = = 16.66 m–1
6 102 m
Example 10 :
What is the number of photons of light with a wavelength of 4000 pm that provide 1 Joule of energy ?
Sol. Wavelength of light, = 4000 pm = 4000 × 10–12 m
hc
Energy provided, E = 1 J , Energy per photon =
If N is the number of photons that provide 1 J energy, one can write
hc 1J 1J 4000 1012 m
1J = N × or N = = = 2.0 × 1016
hc 6.626 1034 Js 3 108 ms 1
Example 11 :
A photon of wavelength 4 × 10–7 m strikes on metal surface, the work function of the metal being 2.13 eV. Calculate (i) the energy
of the photon (eV) (ii) the kinetic energy of the emission and (iii) velocity of the photoelectron. (1 eV = 1.6020 × 10–19 J)
Sol. Wavelength of the photon, = 4 × 10–7 m
Work function of the metal, W = 2.13 eV = 2.13 × 1.6020 × 10–19 J = 3.41 × 10–19 J
Then,
ch 3 108 ms 1 6.626 1034 Js –19 J =
4.97 1019 J
(i) Energy of the photon = = = 4.97 × 10 = 3.10 eV
4 107 m 1.6020 1019 J / eV
(ii) Kinetic energy of the emission = Ephoton – W = 4.97 × 10–19 J – 3.41 × 10–19 J = 1.56 × 10–19 J = 3.10 eV – 2.13 eV = 0.97 eV
1
(iii)Kinetic energy of the emitted photoelectron = m × v2
2
2 Kinetic energy 2 1.56 1019 J
So, v = = or v = 5.85 × 105 ms–1
m 9.1 1031 kg
Example 12 :
The power output for a certain laser transition was found to be 2.79 watt per square meter. Given = 520 nm, calculate the number
of quanta emitted per square meter per second.
6.626 x1034 x 3 x108
Sol. Energy corresponding to the photon = = 3.822 × 10–19 J
520 x109
The power output = 2.79 Watt / m2 = 2.79 J/ sec / m2
2.79
Therefore no. of photons emitted per sq. meter sec. = = 7.30 × 1018
3.822 x1019
Example 13 :
Electromagnetic radiation of wavelength 242 nm is just sufficient to ionise the sodium atom. Calculate the ionisation energy of
sodium in kJ mol–1.
Sol. Wavelength of the radiation, = 242 nm = 242 × 10–9 m
N A .hc
Energy (per mole) of the photons =
6.023 1023 mol 1 6.626 10 34 Js 3 108 ms 1
= = 4.95 × 105 J mol–1 = 495 kJ mol–1
242 109 m
This energy is equal to the ionisation energy of sodium.
So, ionisation energy of sodium = 495 kJ mol–1
24 IIT-JEE Chemistry
Structure of atom
Example 14 :
A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57 m. Calculate the rate of emission of quanta per second.
Sol. Power of the bulb = 25 W = 25 J s–1
Wavelength of light, = 0.57 µm = 0.57 × 10–6 m
6.626 1034 Js 3 108 ms 1
Energy of the photon, E = h = = 3.487 × 10–19 J
0.57 106 m
25 J s 1
So, rate of emission = = 7.17 × 1019 s–1.
3.487 10 19 J
Example 15
1.8 g hydrogen atoms are excited to radiation . 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. IP of H is 13.6 eV. Calculate
(i) No. of atoms present in 1st, 2nd and 3rd energy level (ii) Total energy evolved when all the atoms return to ground state.
Sol. 1 gH contains = N atoms
1.8 g contains = N × 1.8 atoms = 6.023 × 1023 × 1.8 = 10.84 x 1023 atoms
10.84 x1023 x27
(a) No. of atoms in III shell = = 292.68 x 1021 atoms
100
10.84 x1023 x15
No. of atoms in II shell = = 162.6 × 1021 atoms
100
10.84 x1023 x 58
And no. of atoms in I shell = = 628.72 × 1021 atoms
100
(b) When all the atoms return to l shell, then
13.6
E' = (E3 – E1) × 292 .68 ×1021 = 13.6 × 1.602 × 10–19 × 292.68 × 1021 = 5.668 × 105 joule
9
13.6
E'' = (E2 – E1) × 162.6 × 1021 = 13.6 × 1.602 × 10–19 ×162.6 × 1021 = 2.657 x 105 joule
4
5 5
E = E' + E'' = 5.688 × 10 + 2.657 ×10 joule = 832.50 KJ
Example 16 :
When light of frequency 3.2 x 1016 Hz is used to irradiate a metal surface, the maximum kinetic energy of the emitted photoelec-
trons in 3/4th of the energy of the irradiating photon. What is the threshold frequency of the metal ?
Sol. Energy corresponding to the incident photon
E = 6.626 × 1034 × 3.2 × 1016 = 2.12 × 10–17 J
3 3
K.E. of photoelectron = the energy of photon = × 2.12 × 10–17 = 1.590 × 10–17 J
4 4
h = h0 + KE
2.12 × 10–17 = h0 + 1.590 × 10–17
h0 = 5.297 × 10–18 J
5.297 x1018
0 = = 7.995 × 1015 Hz
6.626 x1034
Example 17 :
Electrons are emitted with zero velocity from a metal surface when it is exposed to radiation of wavelength 6800 Å. Calculate the
threshold frequency (0) and the work function (W0) of the metal.
Sol. Wavelength of the radiation, = 6800 Å = 6800 × 10–10 m
hc 6.626 10 34 Js 3 108 ms 1
Work function of the metal, W0 = h0 = =
6800 10 10 m
W0 2.92 10 19 J
and Threshold frequency, 0 = = = 4.41 ×1014 s–1 or 0 = 4.41 × 1014 Hz
h 6.626 10 34 Js
IIT-JEE Chemistry 25
Structure of atom
Example 18 :
Calculate the kinetic energy of an electron emitted from the surface of a metal by light of wavelength 5.5 x 10–8 cm. Threshold
energy for the metal is 2.62 x 10–9 ergs.
c 3x1010 cm s 1
Sol. = = = 5.45 x 1017 s–1
5.5 x108 cm
1 2
mv = h – h0 = (6.63 × 10–27 ergs – sec) (5.45 × 1017 s–1) – 2.62 × 10–9 ergs
2
K.E = 9.93 x 10–10 ergs
Example 19 :
How much energy is required to ionise a H atom if the electron occupies n = 5 orbit ? Compare your answer with the ionisation
potential of H atom (energy required to remove the electron from n = 1 orbit).
1312
Sol. For hydrogen atom, E = kJ mol–1
n2
1312
Then, E5th orbit = 2
kJ mol–1 = – 52.48 kJ mol–1
5
E5th orbit 52.48 kJ mol 1
E'5th orbit = = = – 8.71 × 1023 kJ = – 8.71 × 10–20 J
NA 6.023 1023 mol 1
E1st orbit 1312kJmol 1
E'1st orbit = =
1 NA 6.023 10 23 mol 1
2
= – 2.178 × 10–21 kJ = – 2.178 × 10–18 J
Example 20 :
(i) The energy associated with the first orbit in hydrogen atom is – 2.18 × 10 –18 J/atom. What is the energy associated with the
fifth orbit ?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
Sol. Energy of the first orbit in a H-atom = – 2.18 × 10–18 J atom–1 So,
2.18 1018 J atom 1
(a) Energy of the 5th orbit in a H atom = = – 8.72 × 10–20 J atom–1
(5) 2
0.53n 2 1010 m
(b) Bohr’s radius for H atom is given by, rn =
Z
0.53 1010 52
For n = 5 : r5 = m = 1.325 × 10–9 m = 1.325 nm.
1
Example 21 :
Calculate the wavenumber for the shortest wavelength transition in the Balmer series of atomic hydrogen.
Sol. The wavenumber of the radiation emitted from a hydrogen atom is given by
1 1 1 1
= R n 2 n 2 = 109678 cm–1 ×
2 2
1 2 n1 n 2
For Balmer series, n1 = 2 and for the shortest wavelength (or highest wavenumber) transition n2 = . Then,
1 1 109678
= 109678 cm–1 × 2 2 = cm–1 = 27419.5 cm–1
2 4
27419.5 27419.5
or = =
1cm 1 1012 m
= 2741950 cm = 2.742 × 106 m–1
–1
26 IIT-JEE Chemistry
Structure of atom
Example 22 :
What is the energy in joules, required to shift the electron of the hydrogen atom from the first Bohr orbit to the fifth Bohr orbit,
and what is the wavelength of the light emitted when the electron returns to the ground state ? The ground state electron energy
is – 2.18 × 10–11 ergs.
2.18 10 11 erg
Sol. Energy of electron in nth orbit of H atom is given by
n2
2.18 1011
–11 –13
Then E1 = – 2.18 × 10 erg = – 218 × 10 erg and E5 = erg = – 8.72 × 10–13 erg
(5) 2
Energy required for the electronic transition,
E = E5 – E1 = – 8.72 × 10–13 erg – (–218 × 10–13 erg) = 2.09 × 10–11 erg
ch 3 1010 cm 6.626 10 27 erg.s
Wavelength of the emitted radiation, = =
E 2.09 1011 erg
or = 9.511 × 10–6 cm = 951.1 × 10–8 cm = 951.1 Å
Example 23 :
The electron energy in hydrogen atom is given by E = (–2.18 × 10 –18)/n2 joules. Calculate the energy required to remove an
electron completely from the n = 2 orbit. What is the longest wavelength (in cm) of light that can be used to cause this transition?
2.18 1018
Sol. We know, En = J
n2
Energy required to remove an electron from n = 2,
1 1 2.18 1018 J
E = E – E2 = – 2.18 × 10–18 J 2 2 = = 5.42 × 10–19 J
2 4
Energy is related to the wavelength through the relationship.
hc hc 6.626 10 34 Js 3 108 ms 1
E = or = =
E 5.42 10 19 J
or = 3.667 × 10–7 m = 3.667 × 10–5 cm.
Thus, the wavelength of the light that can be used to cause this transition is 3.667 × 10–5 cm (or 3667 Å).
Example 24 :
Calculate the wavelength of an electron moving with a velocity of 2.05 × 107 ms–1.
Sol. Velocity of electron, v = 2.05 × 107 ms–1
Wavelength of the electron, = ?
The de Broglie equation gives = ?
h 6.626 1034 Js
The de Broglie equation gives = So, = = 3.552 × 10–11 m.
mv 9.1 1031 kg 2.05 107 ms 1
Example 25 :
The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its wavelength.
1 2
Sol. K.E. of the electron = mv = 3.0 × 10–25 J
2
Mass of the electron, m = 9.1 × 10–31 kg
h
If is the wavelength associated with the electron, =
mv
1
From above, mv2 = 3.0 × 10–25 J
2
2 3.0 1025 J 2 3.0 1025 J 2 3.0 1025 kg.m 2s 2
v2 = = =
m 9.1 1031 kg 9.1 1031 kg
IIT-JEE Chemistry 27
Structure of atom
1
2 3.0 1025 2 1 2
This gives, v = 31
m s = 812 ms–1
9.1 10
h 6.626 1034 Js
So, = = = 8.967 × 10–7 m
mv 9.1 1031 kg 812ms 1
or = 8.967 × 10–7 m × 102 cm/m = 8.967 × 10–5 cm = 8967 Å
Example 26 :
(i) Write the electronic configurations of the following ions : (a) H– (b) Na+ (C) O2– (d) F–
(ii) What are the atomic numbers of the elements whose outermost electrons are represented by
(a) 3s1 (b) 2p3 and (c) 3d6.
(iii)What atoms are indicated by the following configurations :
(a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1
Sol. (i) The electronic configurations of the given species are,
(a) H– 1s2 (b) Na+ 1s2 2s2 2p6 3s1 (c) O2– 1s2 2s2 2p6 (d) F– 1s2 2s2 2p6
(ii) Outer Complete Total Atomic
Species Electronic configuration Electronic configuration no. of electrons number
(a) 3s 1 1s2 2s2 2p6 3s1 11 11
(b) 2p3 1s2 2s2 2p3 7 7
(c) 3d6 1s2 2s2 2p6 3s2 3p6 4s2 3d6 26 26
(iii) Condensed Complete electronic Total no. of Atomic Element
Electronic configuration configuration electrons number
(a) [He] 2s1 1s2 2s1 3 3 Li
(b) [Ne] 3s2 3p3 1s2 2s2 2p6 3s2 3p3 15 15 P
(c) [Ar] 4s2 3d1 1s2 2s2 2p6 3s2 3p6 4s2 3d1 21 21 Sc
Example 27 :
The energy of the electron in the second and third Bohr orbits of the hydrogen atom is – 5.42 × 10 –19 J and – 2.41 × 10–19 J,
respectively. Calculate the wavelength of the emitted radiation when the electron drops from third to second orbit.
Sol. We have
| E3 2 | = – 2.41 × 10–19 J – (– 5.42 × 10–19 J) = 3.01 × 10–19 J
hc (6.626 1034 J s) (3 108 m s 1 )
= E = = 6.604 × 10–7 m.
(3.01 1019 J)
Example 28 :
An atom of an element contains 29 electrons and 35 neutrons. Deduce (i) the number of protons and (ii) the electronic configu-
ration of the element.
Sol. No. of electrons in the atom of an element = 29.
No. of neutrons in the atom of an element = 35
So, (i) No. of protons in the atom of the given element = 29
(ii) Electronic configuration of the given element
1s2 2s2 2p6 3s2 3p6 3d10 4s1.
Example 29 :
Give the number of electrons in the species H2+, H2, O2+
Sol. Species Corresponding Atomic no. No. of electrons in the
molecule of the element atom species
H2 + H2 1 1 1
H2 H2 1 1 2
O2+ O2 8 8 15
28 IIT-JEE Chemistry
Structure of atom
Example 30 :
(i) An atomic orbital has n = 3. What are the possible values of and m ?
(ii) List the quantum numbers (m and ) of electrons for 3d orbital.
(iii)Which of the following orbitals are possible ? 1p, 2s, 2p and 3f.
Sol. (i) n = 3 So, = 0, 1, 2
For = 0, m = 0
= 1, m = – 1, 0, + 1
=2, m = – 2, –1, 0, +1, +2
(ii) For d orbital, = 2
So, m = – 2, –1, 0, +1, +2
(iii)The possible orbitals are 2s, 2p.
Example 31 :
How many electrons in an atom may have the following quantum numbers ?
1
(a) n = 4, ms = – (b) n = 3, = 0
2
1
Sol. (a) In the shell, n = 4, a total of 32 electrons can be accommodated. Therefore half of these i.e., 16 can have ms = –
2
(b) = 0 describes s orbital. A s orbital can accommodate only two electrons at the most. Therefore, 2 electrons can have the
quantum numbers, n = 3 and = 0.
Example 32 :
Show that the circumference of the Bohr orbit for the hydrogen atom is an integral multiple of the de Broglie wavelength
associated with the electron revolving around the orbit.
Sol. According to the Bohr’s principle of quantisation of angular momentum (mvr) of a moving electron, one can write
h
mvr = n . ; where m is mass of the electron, v is velocity of the electron, r is radius of the orbit,
2
h is the Planck’s constant, n is an integral number, (n = 1, 2, 3, .......... )
h
The de Broglie wavelength associated with the electron is given by, =
mv
mvr nh / 2
From the two equations, one can write = or 2r = n
mv h/
Hence, Circumference of the orbit = Integral multiple of the de Broglie wavelength.
Example 33 :
Calculate the energy required for the process
He+(g) He2+(g) + e–
The ionisation potential for the H atom in the ground state is 2.18 × 10–18 J atom–1.
Sol. Ionisation potential (energy) for the ground state H atom = 2.18 × 10–18 J
The nuclear charge of helium is 2. So,
E = Z2 × E H H
He He 2
Energy required for removing one electron from He+ = 22 × (2.18 × 10–18 J) = 4 × 2.18 × 10–18 J = 8.72 × 10–18 J
Example 34 :
Suppose 10–17 J of energy is needed by the interior of human eye to see an object. How many photons of green light (= 550 nm)
are needed to generate this minimum amount of energy ?
Sol. Let the number of photons required = n
hc
n = 10–17
1017 x 1017 x 550 x109
n= = 27. 6 = 28 photons
hc 6.626 x1034 x 3 x108
IIT-JEE Chemistry 29
Structure of atom
Example 35 :
A gas of identical H like atoms has some atoms in the lowest (ground) energy level A and some atoms I a particular upper (excited)
energy level 'B' and there are no atoms in any other energy level. The atoms of the gas make transition to a higher energy level
by absorbing monochromatic light of photon energy 2.7 eV. Subsequently, the atoms emit radiations of only six different photon
energies. Some of the emitted photons have energy of 2.7 eV. Some have more and some less than 2.7 eV.
(i) Find the principal quantum number initially excited level B ?
(ii) Find the transition energy for the gas atoms ?
(iii) Find the maximum and the minimum energies of the emitted photons ?
Sol. The electrons being present in l shell and another shell n1. These are excited to higher level n2 by absorbing 2.7 eV and on
deexcitation emits six and thus excited state n2 comes to be 4.
R H.ch R H.ch R h.ch
Now E1 = ; E n1 ; E4 =
1 2 n12
42
Since deexcitation leads to different having photon energy < 2.7 eV and thus, absorption of 2.7 eV energy causing excitation
to 4th shell and then re-emitting photons of < 2.7 eV is possible only when n1 = 2 (the deexcitation from 4th shell occurs in I, II
and III shell. )
E1 – E2 = 2.7 eV ; E4 – E3 < 2.7 eV ; E4– E1 > 2.7 eV
R h.ch E1
E n1 E 2 2
. Since n1 = 2
2 22
Also E4 – E2 = 2.7 eV
E1 E1
– 2
+ = 2.7 eV E1 = – 14.4 eV
4 22
I.P. = 14.4 eV
E1 E1 14.4
Emax = E4 – E1 = 2 + 2 = + 14.4 = 13.5 eV
4 1 16
E1 E1
Emin = E4 – E3 = 2 + = 0.7 eV
4 32
Example 36 :
If the diameter of a carbon atom is 0.15 mm, calculate the number of carbon atoms which can be placed side by side in a straight
the across length of scale of length 20 cm long.
Sol. Diameter of C atom, d = 0.15 nm = 0.15 × 10–9 m.
20 l 0.2m
Length of the scale, = 20 cm = m = 0.2 m. So, No. of C atoms along the scale = = 1.33 × 109
100 d 0.15 109 m
Example 37 :
2 × 108 atoms of carbon are arranged side by side. Calculate the radius of carbon atom if the length of this arrangement is 2.4 cm.
Sol. No. of C atoms placed side by side, N = 2 × 108
2.4
Length of the arrangement, = 2.4 cm = m = 0.024m
100
1 l 1 0.024m
Radius of C atom = × = × = 6 × 10–11 m = 0.06 m
2 N 2 2 108
Example 38 :
The diameter of zinc atom is 2.6 A. Calculate (a) radius of zinc atom in pm and (b) number of atoms present in a length of 1.6 cm
if the zinc atoms are arranged side by side lengthwise.
Sol. Diameter of zinc atom, d = 2.6 Å = 2.6 × 10–8 cm = 2.6 × 10–10 m
d 2.6 1010 m
Then (a) Radius of zinc atom = = = 1.3 × 10–10 m = 130 × 10–12 m = 130 pm
2 2
l 1.6cm
(b) No. of atom of Zn in a length of 1.6 cm = = = 6.15 × 107
d 2.6 108 cm
30 IIT-JEE Chemistry
Structure of atom
Example 39 :
A certain particle carries 2.5 × 10–16 C of static electric charge. Calculate the number of electrons present in it.
Sol. Charge on particle = 2.5 × 10–16 C
We know, Charge on an electron = 1.6 × 10–19 C
2.5 10 16 C
So, No. of electrons in the particle = = 1563
1.6 1019 C
Example 40 :
What in the minimum error in position of an electron moving with a speed of 500 ms–1 measured to an accuracy of 0.006 %
(mass of the electron = 9.1 × 10–31 kg) ?
0.006
Sol. p = m v = 9.1 × 10–31 × 500 × = 2.73 × 10–31 kgms–1
100
h 6.626 x1034
x = = = 1.932 × 10–3 m
4mv 4 x x 2.73 x1032
Example 41 :
In Millikan’s experiment, static electric charge on the oil drops has been obtained by shining X-rays. If the static electric charge
on the oil drop is –1.282 × 10–18C. Calculate the number of electrons present on it.
Sol. Charge on the oil drop = – 1.282 × 10–18 C
We known, charge on an electron = – 1.6 × 10–19 C
1.282 10 18 C
So, no. of electrons in the drop = = 8.
1.6 1019 C
Example 42 :
An element with mass number 81 contains 31.7% more neutrons as compared to protons. Assign the atomic symbol.
Sol. Mass number of the element = 81
So, no. of nucleons (or neutrons + protons) = 81
Pr otons 100
From the given data, =
Neutrons 131.7
Pr otons 100
or = = 0.431
Pr otons neutrons 100 131.7
One can then write, No. of protons = 0.431 × No. of nucleons = 0.431 × 81 = 35
So, no. of neutrons = 81 – 35 = 46
So, the atomic symbol of the element is 81 .
35 X
Example 43 :
Electrons in H-like atom (z = 3) make transition from the fifth to the fourth orbit and fourth to third orbit. The resulting radiations
are incident on a metal surface and eject photoelectrons. The stopping potential of the photoelectrons ejected by the shorter
wavelength is 3.95V. Calculate the work function of the metal and stopping potential for the photoelectrons ejected by the larger
wavelength. (R = 1.094 x 107 / m).
Sol. Let 1 wavelength for the transition 5 4 and 2 be that of 4 3 transition
1 1 1
= 1.094 × 107 × 32 2 2 1 = 4.502 × 10–7 m = 450.2 mm
4 5
1 1 1
= 1.094 × 10 7 × 32 2
2 32
4
2= 2.089 × 10 m = 208.9 nm
–7
Shorter wavelength is 2, longer wavelength is 1
Stopping potential for the photo electrons ejected by the light of wavelength 2 is 3.95 Volts
1240
Energy corresponding to 2 is E2 = = 5.95 eV
208.9
IIT-JEE Chemistry 31
Structure of atom
Since stopping potential = 3.95 V: K.E. = 3.95 eV
E = + KE1 ; 5.95 = + 3.95 ; = 2.00 eV
1240
Energy corresponding to 1 is E1 = = 2.75 eV
450.2
E1 = + KE2 ; 2.75 = 2 + KE2 ; KE2 = 0.75 eV
Stopping potential = 0.75 V
Example 44 :
An ion with mass number 37 possesses one unit of negative charge. If the ion contains 11.1% more neutrons than the electrons
find the symbol of the ion.
Sol. Mass number of the ion = 37
Charge = 1 unit negative charge
Total number of electrons in the ion, = No. of protons + 1 = p + 1
Total number of the nucleons in the ion, n + p = 37
So, number of neutrons in the ion, n = 37 – p
No. of electrons 100
From the given data, No. of neutrons =
111.1
No. of electrons 100 100
or = = = 0.474
No. of electrons No. of neutrons 100 111.1 211.1
p 1 p 1
Then = 0.474. This given = 0.474
(p 1) (37 p) 38
p = 0.4784 × 38 – 1 = 17. So, n = 37 – 17 = 20 and no. of symbol of the ion is 37
17 X
The element having atomic number 17, is chlorine. So the ion is 37 .
17 Cl
Example 45 :
An electron collides with a hydrogen atom in its ground state and excited it to a state of n = 3. How much energy was given to the
hydrogen atom in this inelastic collision?
E1
Sol. From equation En = , the energy change of a H atom that goes from initial state of quantum number ni to a final state of
n2
quantum number nf is
E1 E1 1 1
E = Ef –Ei = = 2 2 = E1 2 2
n1 n1 nf ni
Hence ni = 1, nf = 3, Ei = 3, E1 = – 13.6 eV
1 1
E = – 13.6 2 2 eV = 12.08 eV..
3 1
Example 46 :
An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons than electrons. Assign the symbol to
this ion.
No. of electrons p3
Sol. =
No. of electrons No. of neutrons (p 3) (56 p)
100 p3
= = 0.434 or = 0.434
230.4 53
This givens p = (0.434 × 53) + 3 = 26
So, no. of neutrons = 56 – 26 = 30. Then, the symbol of the ion is 56 3 .
26 X
The element having atomic number 26 is iron. So, the ion is 56 3 .
26 Fe
32 IIT-JEE Chemistry
Structure of atom
Example 47 :
Hydrogen atom in states of high quantum number have been created in the laboratory and observed in space.
(a) Find the quantum number of the Bohr orbit in a H- atom whose radius is 0.0100 mm ?
(b) What is the energy of H– atom in this state ?
Sol. (a) From equation rn = n2a0
r0 1.00 x105 m
n= a0 = = 435
5.29 x1011 m
E1 13.6 eV
= – 7.18 x 10–5 eV
(b) En =
n2
=
435 2
(Such an atom would obviously be extremely fragile and can be easily ionized).
Example 48 :
Arrange the following type of radiations in increasing order of frequency; (a) radiation from microwave oven, (b) amber light from
traffic signal, (c) radiation from FM radio, (d) cosmic rays from outer space and (e) X-rays.
Sol. The order is c < a < b < e < d
Example 49 :
A particle of charge equal to that of an electron and mass 200 times the mass of an electron moves in a circular orbital around a
nucleus of charge + 3e. Assuming that Bohr model of the atom is applicable to this system.
(a) Derive an expression for 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 the hydrogen
atom ?
(c) Find the wavelength of the radiation emitted when the revolving particle jumps from the third orbit to the first ? Given RH =
1.097 x 10–7 m–1
Sol. The basic expressions in Bohr model of the atom are as follows.
(a) Stability of the circular motion of the electron i.e,
Ze e mv 2
Attractive force = Centrifugal force = ..........(1)
40 r 2
r
h
Quantization of angular momentum mvr = n ........(2)
2
Eliminating v in the above two expressions, we get
Ze e m n h
2
40 r 2
=
r mr 2
h2
2
This gives r = n 2 ...(3)
4 m Ze / 40
2
(b) Now for the given problem, m = (200) me and Z = 3
34 2 10 1 2 2
6.626 x10 Js 1.112 x10 N C m
r = n2 2 = n2 (8.856 × 10–14 m)
Hence,
4 3.14 200x9.1x10 31 kg 3 1.6 x10 19 C
2
Equation Eq. (3) with the first Bohr orbit for the hydrogen atom, we get
h2 h2
n2
e
4 2 200m 3e 2 / 4
0
=
42 e2 / 40
or n2 = 200 × 3 or n = 600 = 24
IIT-JEE Chemistry 33
Structure of atom
(c) The energy of the electron in the Bohr model of atom is
1 Ze 2
E = KE + PE = mv2 –
2 40 r
1 Ze2 Ze 2 1 Ze2
0
0 0
Using Eq. (1), we get E = 2 4 r – 4 r = 2 4 r
Substituting the expression of r from Eq. (3) we get
2
2 4
2 200m e 3e 2 / 40 2 3.14 200 x 9.1x10 kg 9 1.6x10 C
31 19
2
1 1 1
E= 2 = 2 = 2 (3.899 x 10–15 J)
h2
34 2 10 2 1 2 2
n n 6.626x10 Js 1.112 x10 C N m n
Hence, for the transition 3 1, we get
1
E = (3.899 x 10–15 J) 1 2 = 3.465 × 10–15 J
3
hc
6.626 x1034 Js 3 x108 ns 1
= 5.736 x 10–11 m = 57.36 pm
=
E 3.45x1015 J
Example 50 :
Nitrogen laser produces a radiations at a wavelength of 337.1 nm. If the number of photons emitted is 5.6 × 1024, calculate the
power of this laser.
Sol. Wavelength of radiation, = 337.1 nm = 337.1 × 10–9 m
No. of photons emitted = 5.6 × 1024
hc 6.626 1034 Js (3 108 ms 1 )
Energy of photon = hv = = = 5.9 × 10–19 J
337.1 109 m
Total energy produced = 5.6 × 1024 s–1 × (5.9 × 10–19 J) = 3.3 × 106 J s–1
So, power of the laser = 3.3 × 106 J s–1 3.3 × 106 W = 3.3 × 103 kW
Example 51 :
With what velocity should an particle travel towards the nucleus of a copper atom so as to arrive at a distance 10–13 metre from
the nucleus of the copper atom.
Sol. At the distance of closest approach of an alpha particle (r)
P.E. = K.E.
1 2KZe2 2 4KZe2 4 (9 109 ) (1.602 1019 ) 2 29 6.023 10 23
mv2 = ,v = = or v = 6.35 × 106 m/ sec
2 r mr 4 103 1013
Example 52 :
Neon gas is generally used in the sign boards. If it emits strongly at 616 nm. Calculate (a) the frequency of emission, (b) distance
travelled by this radiation in 30 s, (c) energy of quantum and (d) number of quanta present if it produces 2J of energy.
Sol. Wavelength of light, = 316 nm = 316 × 10–9 m
Then
c 3 108 ms 1
(a) Frequency, v = = = 9.5 × 1014 s–1 = 9.5 × 1014 Hz
316 109 m
(b) Distance travelled in 30 s = Velocity × Time = 3 × 108 ms–1 × 30s = 9 × 109 m = 9 × 106 km
hc 6.626 10 34 Js (3 108 m / s)
(c) Energy of quantum = hv = = = 6.29 × 10–19 J
316 10 9 m
2J
(d) No. of quanta = = 3.18 × 1018
6.29 1019 J
34 IIT-JEE Chemistry
Structure of atom
Example 53 :
In astronomical observations, signals observed from the distant stars are generally weak. If the photon detector receives a total
of 3.15 × 10–18 J from the radiation of 600 nm, calculate the number of photons received by the detector.
Sol. Total energy = 3.15 × 10–18 J
Wavelength, = 600 nm = 600 × 10–9 m
No. of photons received by the detector = ?
hc 6.626 1034 Js (3 108 ms 1 )
Energy per photon = = = 3.313 × 10–19 J
600 109 m
3.15 10 18 J
So, no. of photons received by the detector = = 9.5 = 9.
3.313 10 19 J
Example 54 :
Photoelectrons are emitted when 400 nm radiation is incident on a surface of work function 1.9 eV. These photoelectrons pass
through a region containing - particle to form a He+ ion, emitting a single photon in this process. H+ ion thus formed are in their
fourth excited state. Find the energies in eV of the photons, lying in the 2 to 4 eV range that are likely to be emitted during and after
the combination (h = 4.14 x 10–15 eVs).
Sol. The energy of the incident photon is
15 8
hc 4.14 x10 x 3 x10
E1 = = = 3.1 eV
400 x109
The maximum kinetic energy of the emitted electrons is
Emax = E1 – W = 3.1 – 1.9 eV = 1.2 eV
It is given that emitted electrons of maximum energy + 2He2+ He+ + Photon in 4th excited state
The 4th excited state implies that the electron enters in the electron enters in then = 5 electronic state. In this state the energy is
13.6Z2 13.6 x 22
E5 = – =– = – 2.18 eV
n2 52
The energy of the emitted photon in the above combination reaction is
E = Emax + (– E5) = 1.2 + 2.1 = 3.3 eV
After recombination reaction, the electron may undergo transitions from a higher level to a lower level thereby emitting photons.
The energies in the lower electronic level of He+ are
13.6.22 13.6.22 13.6.22
E4 = = – 3.4 eV , E3 = = – 6.04 eV , E2 = = – 13.6 eV
42 32 22
The possible transitions are
n = 5 n = 4 E = E4 – E5 = – 3.4 – (2.1) = – 1.3 eV
n = 5 n = 3 E = E3 – E5 = – 6.04 – (2.1) = – 1.3 eV
n = 4 n = 3 E = E3 – E4 = – 6.04 – (3.4) = – 2.64 eV
Hence the photons that are likely to be emitted in the range of 2eV to 4 eV are 3.3 eV., 3.94 eV and 2.64 eV.
Example 55 :
Lifetimes of the molecules in the excited states are often measured by using pulsed radiation source of duration nearly in the
nanosecond range. If the radiation source has the duration of 2 ns and the number of photons emitted during the pulse source
is 2.5 × 1015, calculate the energy of the source.
Sol. No. of the photons emitted = 2.5 × 1015
Duration of radiation source, = 2 ns = 2 × 10–9 s
Thus, time period of the wave, T = 2 ns = 2 × 10–9 s
1
So, frequency = = 5 × 108 s–1
2 109 s
Then, energy of the source = no. of photons emitted × h
= 2.5 × 1015 × 6.626 × 10–34 J s × 5 × 108 s–1 = 8.28 × 10–10 J
IIT-JEE Chemistry 35
Structure of atom
Example 56 :
Wavelength of the K characteristic X -rays of iron and potassium are 1.931 x 10–8 and 3.737 x 10–8 cm respectively. What is the
atomic number and name of the element for which characteristic K wavelength is 2.289 x 10–8cm?
At. No of K = 19, and Fe = 26
Velocity of light = 3 × 1010 cm/ sec
According to Mosely's law, the frequency of emitted X–ray Z2
c c
Sol. Frequency v = Z2 = K (Z)2
2 2
2 Z1 3 Z2
= .......(1) ; = ........(2)
1 Z2 2 Z3
1 (Fe) = 1.931 x 10–6, Z1 = 26 ; 3 (K) = 3.737 x 10–8, Z3 = 19 ; 2 (u) = 2.289 x 10–8, Z2 = ?
2.289 x108
2
26
From eqn (1) = . On solving we get Z2 = 23.88 = 24
1.931x108 Z2
3.737 x108 Z2
2
From equation (2) 8 = . On solving we get Z2 = 24.27 = 24
2.289 x10 19
Thus, the atomic number of that element is 24 and it is chromium.
Example 57 :
The longest wavelength doublet absorption transition is observed at 589 and 589.6 nm. Calculate the frequency of each transi-
tion and energy difference between two excited states.
3 108 ms 1
Sol. Frequency due to first absorption, v1 = = 5.093 × 1014 s–1 = 5.093 × 1014 Hz
589 109 m
3 108 ms 1
Frequency due to second absorption, v2 = = 5.0881 × 1014 s–1 = 5.0881 × 1014 Hz
589.6 10 9 m
hc 6.626 1034 Js (3 108 ms 1 )
Then, energy corresponding to absorption 1 = = = 3.3749 × 10–19 J
589 1019 m
hc 6.626 1034 Js (3 108 ms 1 )
Energy corresponding to absorption 2 = = = 3.3714 × 10–19 J
589.6 109 m
Energy difference = E1 – E2 = (3.3749 × 10–19 J – 3.3714 × 10–19 J) = 0.0035 × 10–19 J = 3.5 × 10–22 J
Example 58 :
Estimate the difference in energy between the 1st and 2nd Bohr orbit for a hydrogen atom. At what minimum atomic number,
would a transition from n = 2 to n = 1 energy level result in the emission of X-rays with = 3.0 × 10–8 m ? Which hydrogen atom-
like species does this atomic number correspond to ?
Sol. For a hydrogen atom, the expression of energy difference between two electromic levels is
1 1
E = Rhc 2 2
n1 n 2
1 1
Hence, E1 2 = (1.09677 × 107 m–1) (6.626 × 10–34 J s) × (3 × 108 m s–1) 2 = 1.635 × 10–8 J
1 2
For hydrogne-like species, the expression is
1 1 1 1 1
E = Z2 Rhc 2 2 or = Z2 R 2 2
n1 n 2 n1 n 2
36 IIT-JEE Chemistry
Structure of atom
1 3
Thus 8 = Z2 (1.09677 × 107 m–1)
3 10 m 4
1
or Z2 = 4.0 or Z=2
(3 10 m) (1.09677 107 m 1 ) (3 / 4)
8
The species is He+.
Example 59 :
The ejection of the photoelectron from the silver metal in the photoelectric effect experiment can be stopped by applying the
voltage of 0.35 V when the radiation 256.7 nm is used. Calculated the work function for silver metal.
hc 6.626 1034 Js (3 108 ms 1 )
Sol. Energy of photon = = = 7.74 × 10–19 J
256.7 109 m
The ejection of photoelectron is stopped when its kinetic energy is zero. So,
K.E. of the photoelectron = 0.35 eV But, 1eV = 1.6021 × 10–19 J
K.E. of photoelectron = 0.35 × 1.6021 × 10–19 J = 0.56 × 10–19 J
So, work function of silver = 7.74 × 10–19 J – 0.56 × 10–19 J = 7.18 × 10–19 J
7.18 10 19 J
or work function of silver = eV = 4.48 eV..
1.6021 10 19 J
Example 60 :
If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is ejected out with a velocity of
1.5 × 107 ms–1, calculate the energy with which it is bound to the nucleus.
Sol. Wavelength, = 150 pm = 150 × 10–12 m
Velocity of the ejected electron, v = 1.5 × 107 ms–1
Mass of electron, me = 9.1 × 10–31 kg
1
We know, W0 = h0 = h – m v2
2 e
hc 1 6.626 1034 Js (3 108 ms 1 ) 9.1 1031 kg (1.5 107 ms 1 )2
W0 = – mev2 = –
2 150 1012 m 2
= 1.3252 × 10 J – 1.024 × 10 J = 1.3252 × 10 J – 0.1024 × 10 J = 1.22 × 10–15 J
–15 –16 –15 –15
Example 61 :
Show that de Broglie’s hypothesis applied to an electron moving in a circular orbit leads to Bohr’s postulate of quantized angular
momentum.
Sol. An electron in a circular orbit must have it’s path length equal to an integral number of wavelengths for reinforcement to occur.
Thus, 2r = n
2r h
= =
n mv
nh
mvr =
2
Example 62 :
The angular momentum of an electron in a particular orbit of Li2+ ion is 5.2728 × 10–34 kg m2/sec. Calculate the frequency of the
spectral line when electron falls from this level to the level where angular momentum of electron will be 3.1638 × 10–34 kg –m2/sec.
Sol. Angular momentum of the electron = 5.2728 × 1034 kgm2/ sec
n1h
= 5.272 × 10–34 ; n1 = 4.99 5
2
Angular momentum of electron after transition = 3.1636 × 10–34 kgm2/sec
n1h
= 3.1636 × 10–34 ; n2 = 2.999 3
2
IIT-JEE Chemistry 37
Structure of atom
The electron makes transition form 5 3
1 1
= c = c × Rh × Z2 2 2
n1 n 2
1 1
= 3 × 1010 × 109678 × 32 × 2 2 = 2.1058 × 1015 Hz
3 5
Example 63 :
A hydrogen like species requires 16.52 eV to excite the electron from the second Bohr orbit to third Bohr orbit. Find.
(a) The atomic no. of element ?
(b) The energy required for transition of electron from first to third orbit ?
(c) Wavelength required removing electron from first Bohr orbit to infinity?
(d) The kinetic energy of electron is first Bohr orbit?
Sol. (a) 1eV = 1.602 × 10–12 erg
hc 1 1
Also E = = E3 – E2 = RH.c.h.Z2 2 2
2 3
1 1
or 16.52 × 1.602 × 10–12 = 109678 × Zt × 2 2 × 3 × 1010 × 6.626 × 10–27
2 3
Z = 8.74 Z = 3
2
1 1 8
(b) E = E4 – E3 = RH.c.Z2 2 2 = 109678 × 3 × 1010 × 6.626 × 10–27 × = 1.744 × 10–10 erg = 108.87 eV
1 3 9
1
(c) = 109678 × 9 ; = 1.01 ×10–6 cm
2
1 1 2Ze2 22 z 2 e 4 m
(d) K.E. = mu2 = m =
2 2 nh n2h2
2 (3.14) 2 (4.803 10 10 ) 4 9.108 10 28
= = 1.962 × 10–10 erg = 122.4 eV
12 (6.625 1027 ) 2
Example 64 :
Applying de Broglie’s equation, calculate the wavelength associated with the motion of the earth, a stone and an electron, the
masses and velocities of which are given below.
Mass of earth = 6 × 1027 g = 6 × 1024 kg
Mass of stone = 100g = 0.1 kg
Mass of electron = 10–27g = 10–30 kg
Velocity of orbital motion of the earth = 3 × 106 cm sec–1 = 3 × 104 ms–1
Velocity of stone = 100cm sec–1 = 1.0 ms–1
Velocity of electron = 6 × 107 cm sec–1 = 6 × 105 ms–1
h = 6.6 × 10–27 erg-sec = 6.6 × 10–34 Js.
In case of which of these three objects, will the wavelength be measurable ?
Sol. Substituting the value of h, m and v of the three cases in the de Broglie relationship.
h 6.6 1034
(a) In case of earth, = ; = = 3.67 × 10–63 m
mv (6 1024 ) (3 104 )
6.6 1034
(b) In case of stone, = = 6.6 × 10–33 m
(0.1) (1.0)
6.6 1034
(c) In case of the electron, = = 1.1 × 10–9 m
(1030 ) (6 105 )
The wavelength is measurable in case of electron.
38 IIT-JEE Chemistry
Structure of atom
Example 65 :
Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and can be represented as
= 3.29 × 1015 (Hz) [1/32 – 1/n2]. Calculate the value of n if the transition is observed at 1285 nm. Find the region of the spectrum.
Sol. The frequency of the emission transition in Paschen series is given by
1 1
= 3.29 × 1015 s–1 2 2
3 n
Wavelength of radiation used, = 1285 nm = 1285 × 10–9 m
c 3 108 ms 1
Frequency of radiation used, = = = 2.3346 × 1014 s–1
1285 109 m
1 1
Then, 2.3346 × 1014 s–1 = 3.29 × 1015 s–1 2
9 n
1 1 2.3346 1014 s 1
9 2 = = 0.07
n 3.29 1015 s 1
1 1 1
=
– 0.07 = 0.11 – 0.07 = 0.04 or
2 n2 = = 25 or n = 5
n 9 0.04
This transition will be observed in the infrared region.
Example 66 :
The ratio of time periods in first and second orbits of hydrogen atom is-
(A) 1 : 4 (B) 1 : 8 (C) 1 : 2 (D) 2 : 1
2r1 2r2
Sol. ( B ) . Time period in first orbit (T1) = ; Time period in second orbit (T2) =
v1 v2
T1 2r1 v r1 v
= × 2 = × 2
T2 v1 2r2 r2 v1
2.188 108
Velocity of electron in first orbit = cm s–1
1
2.188 108
Velocity of electron in second orbit = cm s–1
2
Radius of first orbit = 0.528 × 10–8 cm
Radius of second orbit = 0.528 × 10–8 × 4 cm.
T1 0.528 108 2.188 10 8 1
= 8 × 8 = 8
T2 0.528 10 4 2 2.188 10
Altenatively use T n3.
Example 67 :
Calculate the wavelength for the emission transition, if it starts from the orbit having radius 1.3225 nm and ends at 211.6 pm. Name
the series to which this transition belongs and region of the spectrum.
Sol. The radii of the stationary state of electrons (orbit) are given by
Where a0 is the Bohr’s radius (= 52.9 pm)
1/2
rn
1/2
1.3225 109 m
Then, n = = 12
= 5
a0 52.9 10 m
1/2 1/2
rn 211.6 pm
n' = = =2
a0 52.9 pm
The transition starts from n = 5 and ends at n = 2. So this transition belongs to the Balmer series.
This transition lies in the visible region.
1 1
For this transition, = 109,677 2 2 cm–1 = 23032.17 cm–1
2 5
So, = 1/23032.17 cm = 4.34 × 10 cm = 4.34 × 10–7 m.
–1 –5
IIT-JEE Chemistry 39
Structure of atom
Example 68 :
Dual behaviour of matter proposed by de Broglie led to the discovery of electron microscope often used for the highly magnified
images of biological molecules and other type of material. If the velocity of the electron in this microscope is 1.6 ×10 6 ms–1,
calculate de Broglie wavelength associated with this electron.
Sol. Velocity of the electron, v = 1.6 × 106 ms–1
de Broglie wavelength, = ?
Mass of the electron, m = 9.1 × 10–31 kg
h 6.626 1034 Js
We know = = = 4.55 × 10–10 m
m.v 9.1 1031 kg 1.6 106 ms 1
Example 69 :
Similar to electron diffraction, neutron diffraction microscope is also used for the determination of the structure of molecules. If
the wavelength used here is 800 pm, calculate the characteristic velocity associated with the neutron.
Sol. Wavelength, = 800 pm = 800 × 10–12 m, Velocity, v = ?
Mass of neutron, mn = 1.675 × 10–27 kg
h 6.626 1034 Js
From de Broglie equation, v = = = 494.5 m/s
m 1.675 1027 kg 800 1012 m
Example 70 :
If the velocity of the electron in Bohr’s first orbit is 2.19 × 10 8 ms–1. Calculate the de Broglie wavelength associated with it.
Sol. Velocity of electron, v = 2.19 × 108 ms–1
Mass of electron, me = 9.1 × 10–31 kg
The de Brolie wavelength associated with the electron is given by
h 6.626 1034 Js
= = = 3.32 × 10–12 m
m e v 9.1 1031 kg 2.19 108 ms 1
Example 71 :
The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 × 105 ms–1. If the hockey ball of mass 0.1
kg is moving with this velocity, calculate the wavelength associated with this velocity.
Sol. Mass of the ball, m = 0.1 kg
Velocity of the ball, v = 4.37 × 105 ms–1
Using de Broglie equation, one can write
h 6.626 1034 Js
= = = 1.516 × 10–38 m
mv 0.1kg 4.37 105 ms 1
Example 72 :
If the position of the electron is measured within an accuracy of ± 0.002 nm. Calculate the uncertainty in the momentum of the
h
electron. Suppose the momentum of the electron is 4 × 0.05 nm. Is there any problem in defining this value.
m
Sol. Uncertainty in position, x = ± 0.002 nm., Uncertainty in the momentum = ?
h
From the uncertainty principle, x. p
4
h 6.626 10 34 Js
So, p = 2.64 × 10–23 kg ms–1
4.x 4 0.002 10 9 m
So, the uncertainty in the momentum of the electron is ± 2.64 × 10–23 kg ms–1
h 6.626 1034 Js
Momentum of the electron = = = 1.05 × 10–24 kg ms–1
4 0.05 109 m 4 0.05 109 m
The value of momentum of the electron is less than the uncertainty in its value.
40 IIT-JEE Chemistry
Structure of atom
Example 73 :
The quantum numbers of six electrons are given below. Arrange them in order of increasing energy. If any of these combinations(s)
has/have the same energy list.
1. n = 4 =2 m = –2 ms = –1/2
2. n = 3 = 2 m = 1 ms = + 1/2
3. n = 4 = 1 m= 0 ms = + 1/2
4. n = 3 = 2 m= –2 ms = – 1/2
5. n = 3 = 1 m= –1 ms = + 1/2
6. n = 4 = 1 m= 0 ms = + 1/2
Sol. The (n + ) values of the six electrons are,
Electron : 1 2 3 4 5 6
(n + ) 4+2 3+2 4+1 3+2 3+1 4+1
6 5 5 5 4 5
The arrangement in the increasing order of energy is
5<4=2<3=6<1
Thus, the electrons number 2 and 4 and 3 and 6 are the pairs having the same energy.
Example 74 :
(a) Neglecting reduced mass effects, what possible transition in the He+ spectrum would have the same wavelength as the first
Lyman transition of hydrogen (n = 2 to n = 1) ?
(b) What is the radius of the first Bohr orbit of He+ ?
Sol. (a) He+ has only one electron, hence it can be classified as a hydrogen like species with Z = 2, and the Bohr equation may thus
be applied.
1 1
= RZ2 2 2
n1 n 2
The first Lyman transition for hydrogen (Z = 1) would be given by
1 1
=R 2 2
1 2
Since the reduced mass defect is neglected, the R for He+ is same as for 1H, the Z2 term can be compensate by increasing n1 to
1 1 1 1
2n2 and 4, i.e. = RZ2 2 2 = R(22) 2 2
1
n n 2 2 4
The transition in question is thus the transition from n = 4 to n = 2.
(b) The radii of the Bohr’s orbit of He+ may be determined by the following relation
n2 12 0.529
r= r0 Thus r = = 0.264 Å ( r0 = 0.529 Å)
Z 2
Example 75 :
A neutral atom has 2K, 8L, 5M electrons. Find out the following from the data : (a) Atomic number, (b) total number of s electrons,
(c) total number of p electrons, (d) number of protons in the nucleus, and (e) valency of element.
Sol. (a) Atomic number = No. of protons = No. of electrons
Total number of electrons =2 + 8 + 5 = 15
Hence atomic number = 15
(b) Total number of s electrons. To find out it, we have to write electronic configuration of At. No. = 15
1s2, 2s2, 2p6, 3s2, 3p3 Total s electron = 6
(c) Total number of p electrons = 9
(d) No. of protons in the nucleus = No. of electrons in extra-nuclear part
Number of protons = 15
(e) Valency. The arrangement of electrons in orbits is 2, 8, 5. As the atom tends to gain three electrons, therefore it is trivalent
electronegative (–3).
IIT-JEE Chemistry 41
Structure of atom
Example 76 :
Find the number of quanta of radiations of frequency 4.67 × 1013 s–1 that must be absorbed in order to melt 5g of ice. The energy
required to melt 1g of ice is 333 J.
Sol. Energy required to melt 5g of ice = 5 × 333 = 1665 J
Energy associated with one quantum = h = (6.62 × 10–34) × (4.67 × 1013) = 30.91 × 10–21 J
1665
Number of quanta required to melt 5g of ice = = 53.8 × 1021 = 5.38 × 1022
30.91 1021
Example 77 :
The unpaired electrons in Al and Si are present in 3p orbitals. Which electrons will experience more effective nuclear charge from
the nucleus ?
Sol. The electronic configuration of Al and Si are
1s 2s 2p 3s 3p
Al
3s 3p
Si
The outer electrons in Si will experience more effective nuclear charge due to higher nuclear charge of Si.
Example 78 :
Calculate total spin, magnetic for the atoms having at no. 7, 24, 34 and 36.
Sol. The electronic configuration are
7N : 1s2, 2s2 2p3 Unpaired electron = 3
Cr : 1s2, 2s2 2p6, 3s2 3p5 3d5, 4s1 Unpaired electron = 6
24
Se : 1s2, 2s2 2p6, 3s23p63d10, 4s24p4 Unpaired electron = 2
34
36Kr : 1s2, 2s2 2p6, 3s2 3p63d10, 4s24p6 Unpaired electron = 0
Total spin for an atom = ± 1/2 × no. of unpaired electron
For 7N, it is = ± 3/2 ; For 24Cr, it is = ± 3
For 34Se, it is = ± 1; For 36Kr, it is = 0
Also magnetic moment = [n (n 2)] Bohr magneton
For 7N, it is = (15) ; For 24Cr, it is = (48)
For 34Se, it is = (8)
Example 79 :
Infra red lamps are used in restaurant and cafeterias to keep food warm. The infrared radiation is strongly absorbed by water
raising its temperature and that of the food in which it is incorporated. How many photons per second of I.R. are produced by an
IR lamp that consumes energy at the rete of 100 watt and is 12% efficient in converting this energy to infrared radiation. Assume
that the radiation has a wavelength of 1500 nm.
34 8
Nhc N x6.626 x10 x 3 x10
Sol. E = Nh = =
1500 x109
12
Since I.R lamp is 12% efficient hence energy of the radiation = 100 x watt
100
100 x12 N x 6.626 x1034 x 3 x108
=
100 1500 x109
N = 9.05 x 1019 photons/ sec
Example 80 :
Compute the frequency of a gamma ray produced by position – electron annihilation which results in the production of two
photons of identical energy.
Sol. As per question :
+1e + –1e 2 photons of equal energy
0 0
The energy released in the above annihilation process is
42 IIT-JEE Chemistry
Structure of atom
E = 2 mc2 = 2 (9.11 × 10–31) (2.998 × 108)2 = 1.64 × 10–3 J
1.62x10 –13
Energy per photon = = 0.82 × 10–13 J
2
The frequency of -radiation is an given below :
E 0.82x1023
= = = 1.24 × 1020 s–1
h 6.625 x1034
Example 81 :
The first ionization potential of hydrogen is 13.6 eV. It is exposed to electromagnetic radiation of 1028 Å and gives out induced
radiations. Calculate the wavelength of these induced radiations (h = 6.625 × 10–34 Js)
Sol. We know that
E1
En =
n2
6.625 10 34 3 108
En = = 1.933 × 10–18 J = 12.07 eV (1.6 × 10–19 J = 1 eV)
1028 1010
Energy of H-atom after excitation = – 13.6 + 12.07 = – 1.53 eV
E1
13.6
From (1), – 1.53 = = n=3
n2 n2
First induced wavelength,
hc 6.625 1034 3 108
1 = = = 1025 × 10–10m = 1025 Å
E3 E1 (1.53 13.6) 1.602 10 19
Second induced wavelength
hc 6.625 1034 3 108
2 = = = 1216 × 10–1 metre = 1316 Å
E 2 E1 (3.4 13.6) 1.602 1019
Third induced wavelength,
hc 6.625 1034 3 108
3 = = = 6564 × 10–10 m = 6564 Å.
E3 E 2 (1.53 3.4) 1.602 1019
Example 82 :
(a) Calculate the energy required to remove an electron completely from n = 3. What is the longest wavelength in Å of light that
21.7 1012
can cause this transition ? E n ergs
n2
(b) Given the mass of the electron as 9.1 × 10–28 gms and its velocity in a stationary state as 1.1 × 108 cm sec–1, calculate the
uncertainty in its position if the momentum of the electron were to be determined with an accuracy of 1%.
21.7 1012
Sol. (a) E = ergs
n2
1 1 21.7 1012
E = – 21.7 × 10–12 2 2 = = – 2.41 × 10–12 ergs.
3 9
hc hc 6.627 10 27 3 1010
E = or = = = 8.25 × 10–5 cm.
| E | 2.41 10 12
(b) If x is the uncertainty in position and p is the uncertainty in the momentum.
h h
x p = ; x.mv =
4 4
IIT-JEE Chemistry 43
Structure of atom
1.1 108 1
v = = 1.1 × 106 cm sec–1
100
6.624 1027
x × 9.1 × 10–28 × 1.1 × 106 =
4 3.143
6.624 1027
x = = 0.053 × 10–5 cm.
4 3.143 9.1 1028 1.1 106
Example 83 :
(a) Calculate the angles which the three angular momentum vectors make with the z axis. for an electron in the p orbital.
(b) Deduce the life time (approximate) of an energy state that gives rise to a spectral line of width 0.1 cm–1.
Sol. (a) For the 'P' orbital , = 1. The magnitude of the orbital angular momentum is 1x2 = 2 . The space quantization of the
angular momentum vector is obtained thus.:
There are three z values (for = 1), namely + 1, 0 –1.
1
z = 1 (i.e,) 1 (i.e the z- component ) corresponds to the angle, = cos–1 = 450 ; z = 0 corresponds to = 900
2
1
and z = – 1 corresponds to the angle = cos –1 = 1350.
2
Z axis
These are the angles made by the angular +1
momentum vector with the positive direction of the z- axis. 2
(b) The natural width of a spectral line is a manifestation of
h
the uncertainty principle. E. t = 2
4
+1
E is the uncertainty in energy and t, the uncertainty in time
which may be taken as the life time of the energy state.
E = h. v = h. c. . By the principle of uncertainty
h h 1
t = = = s
4.E 4.h.c. 4 3 1010 0.1
1
= 109 = 0.0265 × 10–9 S = 26 .5 × 10–12s i.e, 26.5 ps.
4 3.143 3
Example 84 :
The energy of an electron in hydrogen atom is given by En = (– 21.7 × 10–19 J)/n2. Calculate the energy required to remove an
electron completely from the n= 2 orbit. What is the longest wavelength of radiation that can be used to cause this transition ?
Sol. The energy of n = 2 orbit is
21.7 1019 J
E=– = – 5.425 × 10–19 J
4
To remove electron completely, we will require
E = 5.425 × 10–19 J
34 1
hc (6.626 10 J s) (3 10 m s )
8
Hence, = = = 3.664 × 10–7 m.
E (5.425 1019 J)
44 IIT-JEE Chemistry
Structure of atom
QUESTION BANK
EXERCISE - 1
ONLY ONE OPTION IS CORRECT Q.13 The spectrum of He-atom may be considered similar to the
Q.1 When beryllium is bombarded with -particles, extremely spectrum of-
penetrating radiations are produced which can not be de- (A) H (B) Li+
flected by electrical or magnetic field. These are- (C) Na (D) He+
(A) Protons (B) -rays Q.14 Supposing the energy of fourth shell for hydrogen atom is
(C) Neutrons (D) X-rays – 50 a.u. (Arbitrary unit). What would be its ionization
Q.2 Which transition of electron in the hydrogen atom emits potential-
maximum energy : (A) 50 (B) 800
(A) 2 1 (B) 1 4 (C) 15.4 (D) 20.8
(C) 4 3 (D) 3 2 Q.15 K.E. of the electron is 4.55 × 10–25 J. Its de Broglie wave
Q.3 The total number of neutrons in dipositive zinc ions with length is-
mass number 70 is – (A) 4700 Å (B) 8300 Å
(A) 34 (B) 40 (C) 7285 Å (D) 7400 Å
(C) 36 (D) 38 Q.16 A atom forms an ion by the loss of three electrons. The ion
Q.4 Rutherford’s scattering experiment is related to- has an electronic configuration [Ar]3d6. The symbol of
(A) Nucleus (B) Atom the ion is
(C) Electron (D) Neutron (A) Fe3+ (B) Ni3+
Q.5 Which has highest e/m ratio : (C) Co3+ (D) Mn+3
(A) He2+ (B) H+ Q.17 Mass of neutron is .............. times the mass of electron-
(C) He 1+ (D) H (A) 1840 (B) 1480
Q.6 The number of electrons in one molecule of CO2 are – (C) 2000 (D) None
(A) 22 (B) 44 Q.18 Which type of radiation is not emitted by the electronic
(C) 66 (D) 88 structure of atoms :
Q.7 If the Planck’s constant h = 6.6 × 10–34 Js, the de-Broglie (A) Ultraviolet light (B) X-rays
wavelength of a particle having momentum of 3.3 × 10–24 (C) Visible light ( D -rays
)
kg m s–1 will be- Q.19 When the atoms of gold sheet are bombarded with a beam
(A) 0.002 Å (B) 0.02 Å of -particles, only a few -particles get deflected whereas
(C) 0.2 Å (D) 2Å most of them go straight undeflected. This is because
Q.8 Arrange the following particles in increasing order of val- (A) The force of attraction on the -particles by the oppo-
ues of e/m ratio : Electron (e), proton (p), neutron (n) and sitely charged electron is not sufficient
-particle () (B) The nucleus occupies much smaller volume as com-
(A) n, p, e, (B) n, , p, e pared to the volume of atom
(C) n, p, , e (D) e, p, n, (C) The force of repulsion on fast moving -particles is
Q.9 The maximum number of atomic orbitals associated with a very small.
principal quantum number 5 is (D) The neutrons in the nucleus do not have any effect on
(A) 9 (B) 12 -particles.
(C) 16 (D) 25 Q.20 The energy of the emitted photon when an electron in
Q.10 If frequency of the X-rays produced using an element as Be3+ ion returns from n = 2 level to ground state is-
anti-cathode is found to be 2500 sec–1, the atomic number (A) 2.616 × 10–17 J (B) 26.16 × 10–17 J
of used element is (a, b = 1) (C) 216.6 × 10–17 J (D) 2616 × 10–17 J
(A) 51 (B) 49 Q.21 Calculate the wave-number of lines having the frequency
(C) 56 (D) 72 of 5 × 1016 cycles per sec.
Q.11 To give designation to an orbital, we need (A) 1.666 × 108 m–1 (B) 0.666 × 108 m–1
(A) Principal and azimuthal quantum number (C) 4.126 × 106 m–1 (D) 3.133 × 104 m–1
(B) Principal and magnetic quantum number Q.22 The wavelengths of two photons are 2000 Å and 4000 Å
(C) Azimuthal and magnetic quantum number respectively. What is the ratio of their energies ?
(D) Principal, azimuthal and magnetic quantum numbers. (A) 1/4 (B) 4
Q.12 For a given value of n (principal quantum number), the (C) 1/2 (D) 2
energy of different subshells can be arranged in the order Q.23 Correct set of four quantum numbers for the outermost
of : electron of rubidium (Z = 37) is :
(A) f > d > p > s (B) s > p < d > f (A) 5, 0, 0, 1/2 (B) 5, 1, 0, 1/2
(C) f > p > d > s (D) s > f > p > d (C) 5, 1, 1, 1/2 (D) 6, 0, 0, 1/2
IIT-JEE Chemistry 45
Structure of atom
Q.24 The order of increasing energies of the orbitals follows : Q.36 The energy of electron in first Bohr’s orbit of H-atom is
(A) 3s, 3p, 4s, 3d, 4p (B) 3s, 3p, 3d, 4s, 4p –13.6 eV. What will be its potential energy in n = 4.
(C) 3s, 3p, 4s, 4p, 3d (D) 3s, 3p, 3d, 4p, 4s (A) – 13.6 eV (B) – 3.4 eV
Q.25 The total spin resulting from a d7 configuration is- (C) – 0.85 eV (D) – 1.70 eV
(A) 3/2 (B) 1/2 Q.37 Consider an electron which is brought close to the nucleus
(C) 2 (D) 1 of the atom from an infinite distance, the energy of the
Q.26 The accelerating potential to be imparted to a beam of elec- electron-nucleus system :
trons to give an effective wavelength of 2.42 nm is (A) Increases (B) Decreases
(A) 2.56 V (B) 3.42 V (C) Remains same (D) None of these
(C) 0.256 V (D) 0.342 V Q.38 If the size of the first orbit of hydrogen atom is 5.29 nm, the
Q.27 The increasing order of energy of electromagnetic radia- size of the second orbit of He+ is
tion can be represented as (A) 2.65 nm (B) 21.16 nm
(A) microwave < infrared < visible < X-ray (C) 10.58 nm (D) 5.29 nm
(B) X-ray < visible < infrared < microwave Q.39 The ion that is isoelectronic with CO is-
(C) microwave < infrared < visible < radiowaves (A) CN– (B) O2+
(D) X-ray < infrared < visible < microwave (C) O2 – (D) N2+
Q.28 The most probable radius (in pm) for finding the electron Q.40 Using arbitrary energy units we can calculate that 864 arbi-
in He+ is – trary units (a.u.) are required to transfer an electron in hy-
(A) 0 (B) 52.9 drogen atom from the most stable Bohr’s orbit to the larg-
(C) 26.5 (D) 105.8 est distance from the nucleus
Q.29 Which one of the following statement is not ture about the n= E=0
quantum numbers n, , m and s n = 1 ; E = – 864 Arbitrary units
(A) m gives the information on the energy of the electron The energy required to transfer the electron from third
in a given orbital. Bohr’s orbit to the orbit n = will be-
(B) l gives an idea of the shape of the orbital. (A) 96 Arbitrary units (B) 192 Arbitrary units
(C) n gives information on the size of the orbital (C) 288 Arbitrary units (D) 384 Arbitrary units
(D) s gives the direction of spin of the electron in the or- Q.41 The frequency of line spectrum of sodium is 5.09 × 1014
bital. sec–1. Its wave length (in nm) will be – [c = 3 × 108 m/sec]
Q.30 A photon of wavelength 300 nm causes the emission of (A) 510 nm (B) 420 nm
two photons. If the wavelength of one of them is 700 nm. (C) 589 nm (D) 622 nm
What is the wavelength of the other photon? Q.42 An element with atomic mass Z consists of two isotopes
(A) 525 mm (B) 600 nm of mass number Z – 1 and Z + 2. The percentage abun-
(C) 450 nm (D) 300 nm dance of the heavier isotope is-
Q.31 If uncertainty in position and momentum are equal, the (A) 0.25 (B) 33.3
uncertainty in velocity is : (C) 66.6 (D) 75
1 Q.43 Frequency ratio between violet (400 nm) and red (750 nm)
2m h /
(A) h / 2 (B) radiations in the visible spectrum, is-
(C) h / (D) None (A) 8/15 (B) 4/15
(C) 15/8 (D) None of these
Q.32 Rutherford’s experiment on scattering of particles showed Q.44 The presence of one electron each in the three 3p sub-
for the first time that the atom has – shell of nitrogen is explained by
(A) Electrons (B) Protons (A) Uncertainty principle (B) Hund’s rule
(C) Nucleus (D) Neutrons (C) Pauli’s principle (D) Bohr’s theory
Q.33 There are three energy levels in an atom. How many spec- Q.45 The brackett series of spectral lines arise when an electron
tral lines are possible in its emission spectra ? in an excited hydrogen atom jumps from an energy level
(A) One (B) Two (A) n = 5 to n = 1 (B) n = 5 to n = 3
(C) Three (D) Four (C) n = 5 to n = 4 (D) n = 5 to n = 2
Q.34 Rutherford’s scattering experiment is related to the size of Q.46 Beryllium’s fourth electron will have the four quantum num-
the – bers :
(A) Nucleus (B) Atom n m s
(C) Electron (D) Neutron (A) 1 0 0 1/2
Q.35 For particles having same kinetic energy, the de Broglie (B) 1 1 1 1/2
wavelength is- (C) 2 0 0 –1/2
(A) Directly proportional to its velocity (D) 2 1 0 +1/2
(B) Inversely proportional to its velocity
(C) Independent of velocity and mass
(D) Unpredictable
46 IIT-JEE Chemistry
Structure of atom
Q.47 Which one of the following is not the characteristic of (C) m = 3, = 0 (D) 3 = 4, = 2
Planck’s quantum theory of radiation – Q.56 The sub-shell that comes after f-sub-sell is called g-sub-
(A) The energy is not absorbed or emitted in whole num- shell. The number of g-sub orbitals in g-sub-shell and the
ber or multiples of quantum total number of orbitals in the principal orbital respectively
(B) Radiation is associated with energy are-
(C) Radiation energy is not emitted or absorbed continu- (A) 10 and 25 (B) 9 and 25
ously but in the form of small packets called quanta (C) 11 and 23 (D) 15 and 45
(D) Magnitude of energy associated with a quantum is Q.57 Azimuthal quantum number defines –
proportional to the frequency (A) e/m ratio of electron (B) Spin of electron
Q.48 In Rutherford’s alpha scattering experiment using gold foil, (C) Angular momentum of electron
the kinetic energy of the alpha particle was (D) Magnetic momentum of electron
1.2 × 10–12 J. For a head on collision, using the formula Q.58 Which of the following has maximum energy –
3s 3p 3d
1 2Ze 2
K.E. = 4 × , what may be the magnitude of r0
0 r0 (A)
1
[The nuclear radius of gold, Z = 79; 4 = 9 × 109 new- 3s 3p 3d
0
ton/metre2 coulomb–2, e = 1.6 × 10–19 coulomb] (B)
(A) 3 × 10–14 m (B) 1.3 × 10–14 m
–14
(C) 2.1 × 10 m (D) 4.3 × 10–14 m 3s 3p 3d
Q.49 Which of the following sets of quantum numbers repre- (C)
sent an impossible arrangement –
3s 3p 3d
n m s
(A) 3 2 –2 (+)1/2 (D)
(B) 4 0 0 (–)1/2
(C) 3 2 –3 (+)1/2 Q.59 Using radiation of wavelength 3500 Å, it is observed that
(D) 5 3 0 (–)1/2 the maximum kinetic energy of the emitted photoelectrons
Q.50 The number of electrons in the valence shell of calcium is is 1.6 eV for potassium. Calculate the work function of the
(A) 6 (B) 8 metal. [h = 6.626 × 10–34 Js, 1 eV = 1.6 × 10–19 J]
(C) 2 (D) 4 (A) 3 eV (B) 2.5 eV
Q.51 Elements upto atomic number 103 have been synthesized (C) 3.5 eV (D) 2 eV
and studied. If a newly discovered element is found to Q.60 Velocity of helium atom at 300 K is 2.40 × 102 meter per sec.
have an atomic number 106, its electronic configuration What is its wave length ? (mass number of helium is 4) -
will be – (A) 0.416 nm (B) 0.83 nm
(A) [Rn] 5f14, 6d4, 7s2 (B) [Rn] 5f14, 6d1, 7s2 7p3 (C) 803 Å (D) 8000 Å
14
(C) [Rn] 5f , 6d, 7s 0 (D) [Rn] 5f14, 6d5, 7s1 Q.61 For principle quantum number n = 4 the total number of
Q.52 A 3p orbital has – orbitals having = 3 –
(A) Two spherical nodes (A) 3 (B) 7
(B) Two non-spherical nodes (C) 5 (D) 9
(C) One spherical and one non-spherical nodes Q.62 The configuration 1s2 2s2 2p5 3s1 shows –
(D) One spherical and two non-spherical nodes (A) Ground state of fluorine atom
Q.53 The rest mass of a proton is 1.673 × 10–27 kg and that of (B) Excited state of fluorine atom
the electron is 9.109 × 10–31 kg. What must be the speed of (C) Excited state of neon atom
the proton which has the same de Broglie wavelength as (D) Excited state of ion O2–
an electron moving with a speed of 9 × 106 m/s ? Q.63 Number of unpaired electrons in 1s2 2s2 2p3 is –
(A) 3600 m/s (B) 4900 m/s (A) 2 (B) 0
(C) 4300 m/s (D) 5600 m/s (C) 3 (D) 1
Q.54 The position and momentum of a 1 keV electron are simul- Q.64 How many unpaired electrons are present in Ni2+ cation
taneously determined. If its position is located to within (atomic number = 28)
1 Å, what is the percentage uncertainty in its momentum ? (A) 0 (B) 2
[me = 9.109 × 10–31 kg] (C) 4 (D) 6
(A) 7.81 (B) 8.76 Q.65 Which of the following has the maximum number of un-
(C) 6.178 (D) 7.62 paired electrons –
Q.55 Which of the following set of quantum number is not valid (A) Mg2+ (B) Ti3+
(A) n = 1, = 2 (B) 3 = 2, m = 1 (C) V3+ (D) Fe2+
IIT-JEE Chemistry 47
Structure of atom
Q.66 For a d-electron, the orbital angular momentum is : tion through 32 volts changes the wavelength to 3. What
6h 2h 3 2
(A) (B) is ?
2 2 1
(A) 20/41 (B) 10/63
h 2.h
(C) (D) (C) 20/63 (D) 10/41
2 2 Q.74 Bohr’s atomic model can explain
Q.67 When accelerated electrons are direct against an anticath- (A) the spectrum of hydrogen atom only
ode in an X-ray tube, the radiation obtained has a continu- (B) the spectrum of an atom or ion containing one electron
ous spectrum with a wavelength minimum, only
124 106 (C) the spectrum of hydrogen molecule
min = m, where V is the voltage used for (D) the solar spectrum
V Q.75 What is the ratio of the time period of revolution of elec-
accelerating the electrons. Calculate min for V = 5 × 104 tron He+ ion sample in the orbit where the path length is
volts. three time the de-broglies wavelength to the time period of
(A) 1.25 Å (B) 0.75 Å revolution in the ground state –
(C) 0.25 Å (D) 1.00 Å (A) 27 : 1 (B) 1 : 27
Q.68 For the energy levels in an atom, which one of the follow- (C) 9 : 8 (D) 8 : 9
ing statements is correct – Q.76 Which of the following postulates does not belong to
(A) There are seven principal electron energy levels Bohr’s model of the atom?
(B) The second principal energy level can have four ‘sub (A) Angular momentum is an integral multiple of h/2
energy levels and contains a maximum of eight electrons (B) The electron stationed in the orbit is stable
(C) The M energy level can have maximum of 32 electrons (C) The path of an electron is circular
(D) The 4s sub-energy level is at a higher energy than the (D) The change in the energy levels of electron is continuous
3d sub-energy level Q.77 Which of the following statements is not true with respect
Q.69 The ratio of the wave lengths of last lines of Balmer and to photoelectric effect –
Lyman series is- (A) The plot of kinetic energy of the photoelectrons against
(A) 4 : 1 (B) 27 : 5 frequency of absorbed radiation gives a straight line paral-
(C) 3 : 1 (D) 9 : 4 lel to x-axis
Q.70 Two isotopes of Boron are found in the nature with atomic (B) The plot of K.E. of the photoelectrons against frequency
weights 10.01(I) and 11.01(II). The atomic weight of natural of absorbed radiation gives a straight line with slope equal
Boron is 10.81. The percentage of (I) and (II) isotopes in it to h and intercept r0.
are respectively- (C) The plot of kinetic energy of the photoelectrons ver-
(A) 20 and 80 (B) 10 and 90 sus the intensity of incident radiation with constant fre-
(C) 15 and 75 (D) 30 and 70 quency gives a straight line parallel to x-axis
Q.71 If uncertainty in the position of an electron is zero the (D) When intensity of light is increased the number of
uncertainty in its momentum will be photons ejected increases but the energies of these
h h electrons are the same.
(A) (B ) Q.78 The masses of photons corresponding to the first lines of
4 4
the Lymann and the Balmer series of the atomic spectrum
(C) zero (D) infinite
of hydrogen are in the ratio of
h (A) 5 : 27 (B) 1 : 4
Q.72 The Compton wavelength for an electron is m C , (C) 27 : 5 (D) 4 : 1
0
Q.79 The quantum numbers of most energetic electron in Ne
h atom when it is in first excited state is
calculate = m C (1 – cos ) for a scattering angle (A) 2, 1, 0, ± 1/2 (B) 3, 1, 1, ± 1/2
0 (C) 3, 0, 0, ± 1/2 (D) 3, 1, 0, ± 1/2
Q.80 Of the following transitions in hydrogen atom, the one
= . What is the maximum value for ? which gives an absorption line of lowest frequency is
3 (A) n = 1 to n = 2 (B) n = 3 to n = 8
(A) 0.024 Å, 0.048 Å (B) 0.012 Å, 0.048 Å (C) n = 2 to n = 1 (D) n = 8 to n = 3
(C) 0.012 Å, 0.024 Å (D) 0.006 Å, 0.012 Å Q.81 The minimum value of spin multiplicity possible, when
Q.73 An electron, practically at rest, is initially accelerated = 3, are
through a potential difference of 100 volts. It then has a de (A) 2 (B) 1
Broglie wavelength = 1 Å. It then get retarded through 19 (C) 0 (D) 3
volts and then it has wavelength 2 Å. A further retarda-
48 IIT-JEE Chemistry
Structure of atom
Q.82 According to Moseley, a straight line graph is obtained on (Ionization energy of the ground state hydrogen atom =
plotting- 13.62 eV.) Express the result in kJ mol–1
(A) The frequencies of characteristic X-rays of elements (A) 550 kJ mol–1 (B) 657 kJ mol–1
against their atomic numbers. (C) 851 kJ mol –1 (D) 720 kJ mol–1
(B) The square of the frequencies of characteristic X-rays Q.90 Calculate the de Broglie wavelength of an -particle emit-
of elements against their atomic numbers ted from radium having an energy of 4.8 MeV.
(C) The square root of the frequencies of characteristic X- (Mass of -particle = 6.6 × 10–24 g;
rays of elements against their atomic numbers h = Planck’s constant = 6.626 × 10–27 erg sec)
(D) The reciprocal of the frequencies of characteristic X- (A) 6.18 × 10–13 cm (B) 0.58 × 10–8 cm
rays of elements against their atomic numbers. –13
(C) 6.58 × 10 cm (D) 4.12 × 10–11 cm
Q.83 The quantum numbers of four electrons are given below. Q.91 The first line in the Lyman series in the spectrum of hydro-
n m s gen atom occurs at a wavelength of 1215 Å and the limit for
(1) Electron 1 3 0 0 – 1/2 Balmer series is 3645 Å. Calculate the wavelength corre-
(2) Electron 2 4 0 1 1/2 sponding to series limit of Lyman series.
(3) Electron 3 3 2 0 1/2 (A) 911.2 Å (B) 812.2 Å
(4) Electron 4 3 1 0 –1/2 (C) 712.2 Å (D) 678.4 Å
The correct order of decreasing energy of these electrons Q.92 What is the energy required per mole to excite an electron
is- from the third to fifth Bohr orbit in hydrogen ?
(A) Electron 3 > Electron 1 > Electron 4 > Electron 2 (A) 6.336 × 106 J (B) 7.122× 104 J
(B) Electron 4 > Electron 2 > Electron 3 > Electron 1 (C) 0.343 × 10 J6 (D) 9.343 × 104 J
(C) Electron 3 > Electron 2 > Electron 4 > Electron 1 Q.93 Helium atom can be excited to 1s2, 2p1 configuration by
(D) Electron 2 > Electron 4 > Electron 3 > Electron 1 light of 58.44 nm. The lowest excited state with configura-
Q.84 The electronic energy of helium atom is – 79 eV. The first tion 1s2, 2s1 lies 4857 cm–1 (1/) below the 1s1, 2p1 state.
ionization energy of this atom is about What would be the average He – H bond energy so that
(A) 65.4 eV (B) 51.8 eV HeH2 could form, non-endothermically from the lowest
(C) 24.6 eV (D) 27.2 eV excited singlet state of helium ? Neglect any difference
Q.85 The splitting of spectral lines in a magnetic field, arising between G and H and take Hf as 218 kJ mol–1.
out of orbital motion of electrons only and the further split- (A) 1614 kJ mol–1 (B) 1212 kJ mol–1
ting due to spin motion are respectively called (C) 912 kJ mol –1 (D) 1511 kJ mol–1
(A) Zeeman and Stark effects Q.94 Photochemical dissociation of oxygen results in the pro-
(B) Zeeman and anomalous Zeeman effects duction of two oxygen atoms, one in the ground state and
(C) Stark and Zeeman effects one in the excited state.
(D) Zeeman and Kerr effects O2 hv
O + O*
Q.86 Sodium atoms can be ionised by supplying an energy of
The maximum wavelength () needed for this is 174 nm. If
118 kcal mol–1. Using this data, calculate the lowest pos-
the excitation energy O O* is 3.15 × 10–19 J. How much
sible frequency of light that can ionise a sodium atom.
energy in kJ mole–1 is needed for the dissociation of one
(h = 6.624 × 10–27 erg.sec, c = 3 × 1010 cm sec–1).
mole of oxygen into normal atoms in ground state ?
(A) 1.24 × 1015 sec–1 (B) 0.24 × 1015 sec–1
12 –1 (A) 498.3 kJ mol–1 (B) 418.3 kJ mol–1
(C) 12.4 × 10 sec (D) 2.31 × 1018 sec–1 –1
(C) 524.1 kJ mol (D) 612.8 kJ mol–1
Q.87 With a certain exciting radiation of a particular frequency,
Q.95 The de Broglie wavelength of electron of He+ ion is 3.329Å.
to which hydrogen atoms are exposed, the maximum num-
If the photon emitted upon de-excitation of this He+ ion is
ber of spectral lines obtainable in the emission is 15. The
made to hit H atom in its ground state so as to liberate
uppermost energy level to which the electron is excited is
electron from it, what will be the de Broglie’s wavelength
n=
of photoelectron ?
(A) 4 (B) 5
(A) 0.151Å (B) 6.151Å
(C) 6 (D) 7
(C) 2.351Å (D) 4.121Å
Q.88 A glow worm of mass 5.0 g emits red light (650 nm) with a
Q.96 The wavelength of the photoelectric threshold of a metal
power of 0.1 W. entirely in the backward direction. What
is 230 nm. Determine the K.E. of photoelectron ejected from
velocity would it accelerate to after 10 years, if released in
the surface by UV radiation emitted from the second long-
free space (and assumed to be alive) ?
est wavelength transition (downward) of electron in Lyman
(A) 9.14 ms–1 (B) 28.08 ms–1
–1 series of the atomic spectrum of hydrogen.
(C) 11.05 ms (D) 21.04 ms–1
(R = 1.09677 × 107 m–1)
Q.89 Positronium is an unstable complex of electron and positron,
(A) 0.074 × 10–16 J (B) 1.074 × 10–18 J
both of the same mass, but opposite charge. Apply Bohr's –18
(C) 6.213 × 10 J (D) 7.123 × 10–10 J
theory of hydrogen atom to this system and obtain the
energy required to separate the electron from the positron.
IIT-JEE Chemistry 49
Structure of atom
EXERCISE - 2
ONE OR MORE THAN ONE CHOICE MAY (D) the wave length of 2nd line of lyman series of H-atom is
BE CORRECT 32x
Q.1 For cathode rays the value of e/m
5
(A) Is independent of the nature of the cathode and the
gas filled in the discharge tube Q.6 A hydrogen like atom in ground state ‘n’ photons having
(B) Is constant the same energy and it emits exactly n photons when elec-
(C) Is –1.7588 × 108 coulombs/g tronic transition takes place. Then the energy of the ab-
(D) Is lowest when hydrogen gas is filled in discharge sorbed photon may be –
tube. (A) 91.8 eV (B) 40.8 eV
Q.2 Which of the following statement/s with regard to quan- (C) 48.4 eV (D) 54.4 eV
tum number is/are correct – Q.7 In a hydrogen like sample two different types of photons A
(A) The azimuthal quantum number gives the contribution and B are produced by electronic transition. Photon B has
of energy due to angular momentum towards the total en- it’s wavelength in infrared region if photon A has more
ergy of the electron energy than B, then the photon A may belong to the re-
(B) The azimuthal quantum number gives the relative of gion.
energies of subshells belonging to the same shell (A) ultraviolet (B) visible
(C) The orbital angular momentum is given by azimuthal (C) infrared (D) None of these
Q.8 In a hydrogen like sample electron is in 2nd excited state,
h the binding energy of 4th state of this sample is 13.6eV,
quantum number which is equal ot ( 1)
2 then
(D) The orbital angular momentum depends on the value (A) A 25 eV photon can set free the electron from the sec-
of ‘n’ ond excited state of this sample.
Q.3 Choose the correct statement – (B) 3 different types of photon will be observed if elec-
(A) The nodal surface of 2s-orbital exists at a distance trons make transition up to ground state from the second
1.058 Å from the nucleus. excited state
(B) in the plots of radical probability versus distances from (C) If 23 eV photon is used then K.E. of the ejected electron
the nucleus, the number of peaks equal to n – . is 1eV.
(C) Wave functions of electrons in atoms and molecules (D) 2nd line of Balmer series of this sample has same en-
are called orbitals. ergy value as 1st excitation energy of H– atoms
(D) The azimuthal quantum number determines the shape Q.9 Identify the correct statement(s) –
of an orbital. (A) | | is the probability of finding the electron in an
Q.4 Of the following, which of the statement(s) regarding Bohr orbital
theory is/are correct ? (B) p-orbital is directional in nature
(A) Kinetic energy of an electron is half of the magnitude (C) d has dumb bell shape along x and y-axis
of its potential energy. x 2 y2
(B) Kinetic energy of an electron is negative of total en- (D) d 2 has dumb bell shape along x and y-axis
z
ergy of electron Q.10 Which of the following properties are proportional to the
(C) Energy of electron decreases with increase in the value energy of electromagnetic radiation?
of principal quantum number (A) frequency (B) wave number
(D) The ionization energy of H-atom in the first excited (C) wavelength (D) number of photon
state is the negative of one fourth of the energy of an Q.11 When photons of energy 4.25 eV strike the surface of a
electron in the ground state. metal A, the ejected photoelectrons have maximum kinetic
Q.5 If the wave number of 1st line of Balmer series of H-atom is energy, TA( expressed in eV) and de Broglie wavelength
‘x’ then – A. The maximum kinetic energy of photoelectrons
(A) wave number of 1st line of lyman series of He+ ion will liberated from another metal B by photons of energy 4.20 V
is TB = TA – 1.50 eV . If the de-Broglie wavelength of these
108x
be photoelectrons is B = 2A, then which are correct.
5 (A) The work function of A is 2.25 eV
(B) wave number of 1st line of lyman series of He+ ion will (B) The work function of B is 3.70 eV
36x (C) TA = 2.00 eV (D) TB = 2.75 eV
be Q.12 Which of the following statements are true ?
5
(A) The no. of radial nodes for 4P orbital are 2
(C) the wave length of 2nd line of lyman series of H-atom is
(B) The no. of Angular nodes for 3dxy orbital are 2
5 (C) The total no. of nodes of 3d 2 2 are ‘2’
32x x y
(D) The no. of radial nodes for 3p is ‘1’
50 IIT-JEE Chemistry
Structure of atom
ASSERTION AND REASON QUESTIONS Q.20 Match the column correctly –
(Q.13-Q.18) Column I Column II
Note : Each question contains STATEMENT-1 (Assertion) (A) If P.E. = –13.6 eV, total energy (p) 21
and STATEMENT-2 (Reason). Each question has 5 choices will be
(A), (B), (C), (D) and (E) out of which ONLY ONE is cor- (B) Ionization energy of electron (q) 10
rect. from 2nd shell of Na10+
(A) Statement-1 is True, Statement-2 is True; Statement-2 (C) Number of spectral lines when (r) – 6.8
is a correct explanation for Statement-1. electron jumps from 7th to 3rd shell.
(B) Statement-1 is True, Statement-2 is True; Statement-2 (D) Number of spectral lines when (s) 411.4
is NOT a correct explanation for Statement-1. electron come from 7th shell to 1st shell
(C) Statement -1 is True, Statement-2 is False. Q.21 Match the column correctly –
(D) Statement -1 is False, Statement-2 is True. Column I Column II
(E) Statement -1 is False, Statement-2 is False. h
Q.13 Statement 1 : In Li2+ sample an electron make transition (A) (p) 2 is mathematical
2m(KE)
from higher state to n = 2. Then the photon observed will symbol of an orbital
fall in the visible range.
(q) ( 1) h
Statement 2 : Line falling in n = 2 is balmer series line which h
(B) E t
4 2
belongs to visible range in all type of H-like atom or ion.
Q.14 Statement 1 : Atoms can neither be created nor destroyed. (Where E is energy and t is time)
Statement 2 : Under similar condition of temperature and (C) Schrodinger’s equation (r) de Broglie’s concept
pressure, equal volume of gases does not contain equal (D) orbital angular momentum (s) Simultaneous and
number of atoms. accurate determination of
Q.15 Statement 1 : Absorption spectrum consists of some bright position and momentum of
lines separated by dark spaces. electron at a point is not
Statement 2 : Emission spectrum consists of dark lines. possible.
Q.16 Statement 1: Hypothetically if it is assumed that spin Q.22 Match the column –
quantum, number has values +1/2, –1/2 and 0, the number Column I Column II
of elements present in first period in periodic table will be (A) Binding energy of He+ atom (p) Infrared region
3. in an excited state
Statement 2: No two elements should have same set of (B) 7 3 transition of H-atom (q) 3.4 eV
quantum numbers (C) 5 1 transition of H-atom (r) 13.6 eV
Q.17 Statement 1 : On increasing the intensity of incident (D) Series limit of Balmer series (s) 10 spectral lines
radiation, the number of photoelectrons ejected increases in H-atom observed
and their K.E. increases. PASSAGE BASED QUESTIONS
Statement 2: Greater the intensity means greater the Passage 1- (Q.23-Q.25)
number of photons which in turn means greater total energy If hydrogen gas enclosed in a sealed tube is heated to
of the radiation. high-temperature, it emits radiation, if this radiations is
Q.18 Statement 1 : The threshold frequency is the same for all passed through a prism, components of different
metals. wavelengths are deviated by different amounts and thus
Statement 2 :The number of photoelectrons ejected de- we get the Hydrogen-spectrum. The most striking feature
pends upon the intensity of the incident radiation. in this spectrum is that is only some sharply defined,
discrete wavelengths exist in the emitted radiations. A
MATCH THE COLUMN TYPE QUESTIONS hydrogen sample also emits radiations with wavelengths
(Q.19-Q.22) less than those in visible range and also with wavelength
Each question contains statements given in two columns larger than those in visible range. We get that x lines may
which have to be matched. Statements be grouped in separate series i.e lyman series, Balmer, series,
(A, B, C, D) in column I have to be matched with state- paschen, Brackett, pfund.
Lyman Balmer Paschen Brackett Pfund
ments (p, q, r, s) in column II.
Q.19 Match the column –
Column I Column II
Balmer’s Law. The actual development of the spectroscopy
(A) = 2 (p) m = – 2
started in 1885 when J.J. Balmer found that the wave-length
(B) n = 3 (q) d-orbital
of the hydrogen lines could be represented by the formula:
(C) same energy orbitals (r) degenerate
(d) electron density = 0 (s) node n2
=B 2
2 n2
IIT-JEE Chemistry 51
Structure of atom
where B is a constant, n is an integer with variable values Q.29 Equation(s) related to above statement is/are
3, 4, 5 ,..... etc. h h
Q.23 What is the wavelength of radiation emitted when the (A) x.p (B) x.v
4 4m
e–s in a hydrogen atom jumps from n = to n = 5 h
(A) 6463 nm (B) 2283 nm (C) E.t (D) All of these
4
(C) 3650 nm (D) 8265 nm Q.30 If uncertainties in the measurement of position and
Q.24 The longest wavelength in Lymen’s series in hydrogen momentum of an electron are equal, then uncertainty in the
spectrum is : measurement of its velocity is approximately:
(A) 911.7 Å (B) 1215.7Å (A) 8.0 × 1012 m s–1 (B) 6.0 × 1012 m s–1
(C) 2324.5Å (D) 224.4 Å 12
(C) 4.0 × 10 m s –1 (D) 2.0 × 1012 m s–1
Q.25 The for H line of Balmer series 6500Å. Thus for H Q.31 If a 1.00 g body is travelling along the x-axis at 100 cm s–1
line of Balmer series is within 1 cm s–1, then uncertainty in its position is:
(A) 4814 (B) 4914 (A) 5.28 × 10–30 m (B) 2.64 × 10–32 m
(C) 5014 (D) 4714 –32
(C) 1.32 × 10 m (D) 0.66 × 10–30 m
Passage 2- (Q.26-Q.28) Passage 4- (Q.32-Q.34)
The behaviour of an electron in an atom is described There are set of 4 quantum numbers :
mathematically by a wave function , or orbital . It turns out (a) Principal quantum number is denoted by n. The values
that each wave function contains three variables called of n ranges from 1 to n. It gives information about the size
quantum numbers , which are represented as n , and m. and energy level of major energy shells.
These quantum numbers describe the energy level of an For one electron species, the mathematical expression of
orbital and define the shape and orientation of the region 2 2 me 4 z 2
in space where the electron will be found . energy is E n
Q.26 Which quantum number determines orientation of the n2h2
(b) Azimuthal or angular quantum number is denoted by .
electron ?
Its value ranges from 0 to (n – 1) for s, p, d, f sub-shells
(A) Principal (B) Secondary
respectively. It gives information about shape, energy level
(C) Magnetic (D) Spin
of sub-shell and orbital angular momentum of the electron,
Q.27 Radial nodes are maximum in :
h
(A) 4s (B) 4p ( 1) 2 .
(D) 3d (D) 5f
(c) Magnetic quantum number is denoted by m. The values
Q.28 Total number of electrons in any energy level is :
n 1
of m ranges from – to +. It gives information about
n
(A) 2 (2+ 1) (B) 2 (2 + 1)
possible number of orientations of sub-shells.
(d) Spin quantum number is denoted by s. The values of s
1 1
n 1 n 1 are 1/2 and –1/2. It signifies the direction of spin of electrons
(C) 2 (2+ 1) (D) 2 (2 + 1) in an orbital.
0 0 Q.32 Which of the following sets of quantum number is not
allowed –
Passage 3- (Q.29-Q.31) (A) n 3, 1, m 2 (B) n 3, 1, m 1
Bohr’s theory considers an electron as a material particle.
Its position and momentum can be determined with (C) n 3, 0, m 0 (D) n 3, 2, m 2
accuracy. But, when an electron is considered in the form Q.33 For an electron in f orbital, the orbital angular momentum is
of wave as suggested by de Broglie, it is not possible to (A) 2 (B) 3
ascertain simultaneously the exact position and velocity
of the electron more precisely at a given instant since the (C) 12 (D) 2
wave is extending throughout a region of space. To locate Q.34 The angular momentum of an electron in a Bohr’s orbital
the electron, radiation with extremely short wavelength is is given as –
required. Radiation that has short wavelength is very nh h
energetic in nature. When it strikes the electron, the impact (A) L (B) L ( 1)
2 2
causes a change in the velocity of the electron. Thus, the
h h
attempt to locate the electron changes ultimately the (C) L ( 2) (D) L
momentum of the electron. Photons with longer 2 4
wavelengths are less energetic and cause less effect on
the momentum of the electron. Because of large
wavelength, such photons are not able to locate the
position of an electron precisely.
52 IIT-JEE Chemistry
Structure of atom
EXERCISE - 3
SUBJECTIVE QUESTIONS Q.11 The absorption of energy by an atom of hydrogen in ground
Q.1 The series limit for the paschen series of hydrogen spec- state, results in the ejection of the electron with de Broglie
trum occurs at 8205.8 Å. wavelength = 4.70 × 10–10 m. Given that the ionisation
(a) Ionization energy of hydrogen atom energy is 13.6 eV, calculate the energy of the photon which
(b) Wave length of the photon that would remove the elec- caused the ejection of electron.
tron in the ground state of the hydrogen atom. Q.12 When a metal surface is irradiated by light of wave length
Q.2 Iodine molecule dissociates into atoms after absorbing light 300 m ; the stopping potential is found to be 0.5 V. Com-
of 4500 Å. If one quantum of radiation is absorbed by each pute the work function and threshold wave length. Also
molecule, calculate the kinetic energy of iodine atoms. Bond calculate the stopping potential required for light of wave
e n e r g y o
–1
2 = 240 kJ mol . f I length 200 m .
Q.3 An electron in hydrogen like atom is in an excited state. It Q.13 The minimum energy necessary to overcome the attractive
has total energy of – 3.4 eV. Calculate forces between the electron and the surface of silver metal
(i) Kinetic energy and is 7.52 × 10–19 J. What will be the maximum kinetic energy
(ii) de- Broglie wavelength of the electron. of the electrons ejected from silver metal which is being
Q.4 The wavelength of blue light is 480 nm. Calculate the fre- irradiated with uv light having a wavelength of 360 Å.
quency and wave number of this light. Q.14 The energy of the electron in the second and third Bohr
Q.5 Calculate and compare the energies of two radiations one orbits of the hydrogen atom is – 5.42 × 10–12 ergs and
with a wavelength of 800 nm and other with wavelength of –2.41 × 10–12 ergs respectively. Calculate the wavelength
400 nm. of the emitted radiation when the electron drops from third
Q.6 If we observe any series in H spectrum, we observe gradual to second orbit.
decrease in gap between successive lines and merging of Q.15 Calculate the velocity (cm/sec) of an electron placed in the
the lines at a particular wavelength. What is the wave- third orbit of the hydrogen atom. Also calculate the num-
length at which all the lines appear to merge in Balmer ber of revolutions per second that this electron makes
series of H spectrum ? around the nucleus.
Q.7 A mixture contain atoms of fluorine and chlorine. The re- Q.16 If the energy difference between two electronic states is
moval of an electron from each atom of the sample absorbs 46.12 kcal mol–1. What will be the frequency of the light
272.2 kJ while the addition of an electron to each atom of emitted when the electrons drop from higher to lower states
the mixture releases 68.4 kJ. Determine the percentage com- (Nh = 9.52 × 10 –14 kcal sec mol –1 , where N is the
position of the mixture, given that the ionization energies Avogadro’s number and h is the Planck’s constant).
of F & Cl are 27.91 × 10–22 & 20.77 × 10–22 kJ respectively Q.17 An electron has a speed of 30,000 cm sec–1 accurate upto
and that the electron affinities are 5.53 × 10–22 and 0.001%. What is the uncertainty in locating it’s position.
5.78 × 10–22 kJ respectively. Q.18 Light from a discharge tube containing hydrogen atoms
Q.8 Find the threshold wavelengths for photoelectric from a falls on the surface of a piece of sodium. The kinetic en-
copper surface, a sodium surface and a caesium surface ? ergy of the fastest photo electrons emitted from sodium is
the work function of these metals are 4.5 eV, 2.3 eV and 1.9 0.73 eV. The work function for sodium is 1.82 eV. find
eV respectively. (a) The energy of the photons causing the photo electric
Q.9 The ionisation energy of a H like Bohr atom is Rydberg. emission?
(a) Calculate the wavelength radiated when electron jumps (b) The quantum number of the two levels involved in the
from the first excited state to ground state. emission of these photons ?
(b) What is radius of 1 orbit of this atom ? Q.19 In the photoelectric effect, an absorbed quantum of light
Q.10 The energy of a Bohr electrons is given by the expression. results in the ejection of an electron from the absorber. The
K.E. of the ejected electron is equal to the energy of the
2 2 z 2 Kme 4
En = absorbed photon minus the energy of the longest wave-
n2h2 length photon that causes the effect. Calculate the kinetic
According to this expression, the energy of an electron energy of the photoelectron produced in cesium by 400
depends only upon atomic number z and principal quan- nm light. The critical wavelength for the photoelectric ef-
tum number n. But according to Aufbau principle, the en- fect in cesium is 660 nm.
ergy of orbital is determined by (n + ) rule, where the Q.20 Show that the wavelength of a 150g rubber ball moving
energy depends not only upon n but also upon . Explain. with a velocity of 50m sec–1 is short enough to be ob-
served.
IIT-JEE Chemistry 53
Structure of atom
EXERCISE - 4
PREVIOUS YEAR IIT-JEE QUESTIONS Q.11 With what velocity should an -particle travel towards the
Q.1 Calculate the wavelength of radiations emitted producing nucleus of copper atom so as to arrive at a distance of
a line in Lyman series, when an electron falls from fourth 10–13 metre from the nucleus of copper atom ? [1997]
stationary state in hydrogen atom. (RH = 1.1 × 107 m–1) Q.12 The energy of an electron in the first Bohr orbit of H atom
[1995] is –13.6 eV. The possible energy value(s) of the excited
Q.2 Iodine molecule dissociates into atoms after absorbing light state(s) for the electrons in Bohr orbits of hydrogen is
of 4500Å. If one quantum of radiation is absorbed by each (are) : [1998]
molecule, calculate the kinetic energy of iodine atoms. (A) –3.4 eV (B) –4.2 eV
(Bond energy of I2 = 240 kJ mol–1) [1995] (C) –6.8 eV (D) +6.8 eV
Q.3 A bulb emits light of 4500Å. The bulb is rated as 150 watt Q.13 The energy of the electron in the first orbit of He+ is
and 8% of the energy is emitted as light. How many photons –871.6 × 10–20 J. The energy of the electron in the first
are emitted by the bulb per second ? [1995] orbit of hydrogen would be – [1998]
Q.4 Consider the hydrogen atom to be a proton embedded in a (A) –871.6 ×10–20 j (B) –435 ×10–20 J
cavity of radius a 0 (Bohr’s radius), whose charge is (C) –217.9 ×10–20 J (D) –108.9 ×10–20 J
neutralised by the addition of an electron to the cavity in Q.14 Which of the following statement (s) are correct ? [1998]
vacuum, infinitely slowly – 1.Electronic configuration of Cr is [Ar] 3d5 4s1 (Atomic
(A) Estimate the average of total energy of an electron in no. of Cr = 24)
its ground state in a hydrogen atom as the work done in 2.The magnetic quantum number may have negative value
the above neutralisation process. Also, if the magnitude of 3.In silver atom, 23 electrons have a spin of one type and
the average kinetic energy is half the magnitude of the 24 of the opposite type
average potential energy, find the average potential energy. (Atomic No. of Ag = 47)
(B) Also derive the wavelength of the electron when it is at 4.The oxidation state of nitrogen in HN3 is –3.
distance a0 from the proton. How does this compare with (A) 1, 2, 3 (B) 2, 3, 4
the wavelength of an electron in the ground state Bohr’s (C) 3, 4 (D) 1, 2, 4
orbit ? [1996] Q.15 The electrons identified by quantum number n and
Q.5 The orbital angular momentum of an electron in 2 s orbital (i) n = 4, = 1 (ii) n = 4, = 0 (iii) n = 3, = 2 (iv) n = 3, = 1 can
is – [1996] be placed in order of increasing energy, from the lowest to
highest as – [1999]
1 h
(A) (B) zero (A) (iv) < (ii) < (iii) <(i) (B) (ii) < (iv) < (i) < (iii)
2 2 (C) (i) < (iii) < (ii) < (iv) (D) (iiii) < (i) < (iv) < (ii)
h h Q.16 The wavelength of the radiation emitted when an electron
(C) (D) 2 falls from Bohr’s orbit 4 to 2 in hydrogen atom is [1999]
2 2
(A) 243 nm (B) 972 nm
Q.6 Which of the following has the maximum, number of (C) 486 nm (D) 182 nm
unpaired electrons ? [1996] Q.17 Ground state electronic configuration of nitrogen atom can
(A) Mg2+ (B) Ti3+ be represent by –
(C) V 3+ (D) Fe2+
Q.7 Calculate the wave number for the shortest wavelength 1.
transition in Balmer series of atomic hydrogen. [1996]
2.
Q.8 An electron beam can undergo diffraction by crystals.
Through what potential should a beam of electrons be 3.
accelerated so that its wavelength becomes equal to 1.54Å?
[1997] 4.
Q.9 A compound of vanadium has a magnetic moment of 1.73 (A) 1 only (B) 1,2 only
BM. Work out the electronic configuration of the vanadium (C) 1, 4 only (D) 2, 3 only
ion in the compound. [1997] Q.18 Calculate the energy required to excite one litre of
Q.10 The angular momentum (L) of an electron in a Bohr’s orbit hydrogen gas at 1 atm and 298 K to the first excited state of
is given as – [1997] atomic hydrogen. The energy for the dissociation of H – H
nh h bond is 436 kJ mol–1.Also calculate the minimum frequency
(A) L = (B) L = ( 1) of photon to break this bond. [2000]
2 2
Q.19 The wavelength associated with a golf ball weighing 200 g
mg h and moving with a speed of 5 m/h is of the order of –
(C) L = (D) L = (A) 10–10 m (B) 10–20 m [2000]
2 4 –30
(C) 10 m (D) 10–40 m
54 IIT-JEE Chemistry
Structure of atom
Q.20 The number of nodal planes in px orbital is – [2000] Q.27 A ball of 100g moving with the velocity of 0.1 m/s. Calcu-
(A) one (B) two late the wavelength associated with the ball. [2004]
(C) three (D) zero Q.28 The number of radial nodes of 3s and 2p orbitals are re-
Q.21 The electronic configuration of an element is spectively [2005]
1s22s22p63s23p63d5, 4s1. This represents – [2000] (A) 2,0 (B) 0, 2
(A) excited state (B) ground state (C) 1, 2 (D) 2, 1
(C) cationic state (D) anionic state Q.29 Given in hydrogenic atom rn, Vn, E, Kn stand for radius,
Q.22 The quantum numbers + 1/2 and –1/2 for the electron spin potential energy, total energy and kinetic energy in nth
represents : [2001] orbit. Find the value of U,v,x,y [2006]
(A) rotation of the electron in clockwise and anticlockwise (a) U = Vn/Kn (P) 1
direction respectively (b) 1/rn Ex (Q) 2
(B) rotation of the electron in anticlockwise and clockwise (c) rn Zy (R) 1
direction respectively (Z = Atomic number)
(C) magnetic momentum of electron pointing up and down (d)v = (Angular momentum (S) 0
respectively of electron in its lowest energy level)
(D) two quantum mechanical spin states which have no Q.30 STATEMENT-1 : Band gap in germanium is small
classical analogues because [2007]
Q.23 If the nitrogen atom had electronic configuration 1s7, it STATEMENT-2 : The energy spread of each germanium
would have energy lower than that of the normal ground atomic energy level is infinitesimally small.
state configuration 1s2 2s2 2p3, because the electrons (A) Statement–1 is True, Statement-2 is True, Statement-2
would be closer to the nucleus. Yet 1s7 is not observed is a correct explanation for Statement-1
because it violates – [2002] (B) Statement–1 is True, Statement-2 is True, Statement-2
(A) Heisenberg uncertainty principle is NOT a correct explanation for Statement-1
(B) Hund’s rule (C) Statement-1 is True, Statement-2 is False
(C) Pauli exclusion principle (D) Statement-1 is False, Statement-2 is True
(D) Bohr postulates of stationary orbits Q.31 Match the entries in Column I with the correctly related
Q.24 Rutherford’s experiment, which established the nuclear quantum number(s) in Column II. Indicate your answer by
model of the atom, used a beam of – [2002] darkening the appropriate bubbles of the 4 × 4 matrix given
(A) -particle, which impinged on a metal foil and got in the ORS. [2008]
absorbed Column I Column II
(B) -rays, which impinged on a metal foil and ejected (A) Orbital angular momentum (p) Principal quantum
electrons of the electron in a hydrogen-like number
(C) helium atoms, which impinged on a metal foil and got atomic orbital
scattered (B) A hydrogen-like one-electron (q) Azimuthal quantum
(D) helium nuclei, which impinged on a meal foil and got wave function obeying Pauli number
scattered principle
Q.25 Wavelength of high energy transition of H-atoms is 91.2nm. (C) Shape, size and orientation (r) Magnetic quantum
Calculate the corresponding wavelength of He atoms. of hydrogen-like atomic orbitals number
[2003] (D) Probability density of (s) Electron spin
Q.26 Which of the following will have same radius as hydrogen, electron at the nucleus in quantum number
n=1 [2004] hydrogen-like atom
(A) He+, n = 2 (B) Be3+, n = 2
(C) Li2+, n = 2 (D) Li2+, n = 3
IIT-JEE Chemistry 55
Structure of atom
HINTS & SOLUTIONS
EXERCISE - 1
Q 1 2 3 4 5 6 7 8 9 10 11
A C A B B B A D B D A D
Q 12 13 14 15 16 17 18 19 20 21 22
A A B B C C A D B A A D
Q 23 24 25 26 27 28 29 30 31 32 33
A A A A C A C A A B C C
Q 34 35 36 37 38 39 40 41 42 43 44
A A A D B B A A C B C B
Q 45 46 47 48 49 50 51 52 53 54 55
A C C A A C C D C B C A
Q 56 57 58 59 60 61 62 63 64 65 66
A B C B D A B C C B D A
Q 67 68 69 70 71 72 73 74 75 76 77
A C B A A D D C B A D A
Q 78 79 80 81 82 83 84 85 86 87 88
A C C B B C C C B A C D
Q 89 90 91 92 93 94 95 96
A B C A D B A C B
(1) (C). Neutrons h
hc (15) (C). =
(2) (A). E2 – E1 is maximum for H atom and E2 – E1 = 2mKE
(16) (C). The ion has configuration [Ar] 4s03d6
(3) (B). 30Zn70, Zn2+ has No. of neutrons = 70 – 30 = 40.
Before losing the electrons it would have been
(4) (B). To reveal structure of atom.
[Ar] 4s2 3d7
(5) (B). Mass of H+ is minimum.
The ion is Co3+
(6) (A). One molecule of CO2 have 22 electrons.
(17) (A). Mass of neutron = 1.675 × 10–27 kg,
h Mass of electron = 9.108 × 10–31 kg.
(7) (D). = (18) (D). -rays emission occurs due to radioactive change, a
mv
(8) (B). nuclear phenomenon.
Electron Proton Neutron -particle (19) (B). It was the logical conclusion of his experiment.
e 1 unit 1 unit zero 2 units 1
1 1 hc
m 1/1837 unit 1 unit 1 unit 4 units (20) (A). = RZ2 2 2 , E
e/m 1837 1 zero 1/2 n1 n 2
(9) (D). The number of orbitals in a principle shell is (21) (A). Given c = 3 × 108 m/sec.,= 5 × 1016 cycles/sec, = ?
n2 = 52 = 25.
We know that
(10) (A). Z = + 1 ( = frequency)
5 1016
So, Z = 2500 + 1 = 51 = = = 1.666 × 108 m–1
c 3 108
(11) (D). Quantum numbers are signature of an electron of
particular orbital.
(13) (B). The electronic configuration of He is similar to the c c
(22) (D). E1 = h. ; E2 = h.
electronic configuration of Li+. So its spectrum will be similar 1 2
to the spectrum of Li+.
(14) (B). Ionization potential = – E1 E1 hc 2 4000
= × = 2 = = 2.
E1 E2 1 hc 1 2000
E4 = – 50 × 16 = E1 (23) (A). Its configuration is 5s1
16
Hence ionization potential = – (– 800) = 800 a.u. (24) (A). Follow (n + ) rule.
56 IIT-JEE Chemistry
Structure of atom
1 3 22 me 4 k 2
(25) (A). For d7, three unpaired electrons, spin = 3 × = =– = – 13.6 eV (given)
2 2 h2
h Energy of fourth Bohr’s orbit of H-atom.
(26) (C). =
2meV 22 me 4 k 2 1 1
= 2 × 2 = 13.6 × eV = – 0.85 eV
150 h 4 16
For electron = x 10–8 cm P.E. of electron in nth orbit = 2 × En
V
So P.E. of electron in 4th orbit = 2 × (– 0.85) = – 1.70 eV
150 (37) (B). The energy (P.E.) of the electron is a function of its
2.42 x 10–7 = × 10–8 cm distance from the nucleus and is given by Coulomb’s law
V
e2
150 as P.E. = –
(24.2)2 = V = 0.256 Volt r
V
1 2 e2 1 mv 2 e
(27) (A). Microwaves have the lowest energy with the wave- 2
length of 6 × 106 Å. X-rays have the highest energy with Total energy = K.E. + P.E. = mv – 2r
2 r 2
the wavelength of nearly 0.1 A.
(28) (C). Most probable radius = a0/Z e2
where a0 = 52.9 pm. For helium ion, Z = 2 =–
2r
52.9 as ‘r’ decreases energy will go on decreasing.
rmp 26.45 pm (38) (B). Size of the first orbit of Hydrogen = 5.29 × 10–9 m
2
Size of the second orbit of Helium
(29) (A). Magnetic quantum number ‘m’ describes the orienta-
= 5.29 × 10–9 × 22 = 21.16 nm.
tion or distribution of electron cloud.
(39) (A).
hc hc hc CO 6 + 8 = 14
(30) (A). = + CN– 6 + 7 + 1 = 14
300 700 1
O2+ 8 × 2 – 1 = 15
1 1 1 O2– 8 × 2 + 1 = 17
= – 1 = 525 nm
1 300 700 N2+ 7 × 2 – 1 = 13
(40) (A). The energy of first Bohr’s orbit of H-atom
h h 2 2 me 4
(31) (B). x.m v = or (mv)2 = – = – 864
4 4 h2
The energy of third Bohr’s orbit of H-atom
h h 1 h
mv = or v = = 2 2 me 4 1 1
4 4m 2
2m =– 2 × 2 = – 864 × = – 96 Arbitrary units
h 3 9
(32) (C). Rutherford’s experiment on scattering of particles
showed for the first time that the atom has nucleus Energy required to separate the electron
= E – En = 0 – (–96) = 96 Arbitrary units.
n (n 1) 3(3 1)
(33) (C). Number of spectral lines =
2
=
2
=3 3 108 m.sec 1
(41) (C). =
(34) (A). The central part consisting whole of the positive charge 5.09 1014 m.sec 1
and most of the mass caused by nucleus, it extremely small = 0.5892 × 10–6 m = 589.4 × 10–9 m = 589 nm
in size compared to the size of the atom.
(Z 1)x (Z 2) (100 x)
h 1 (42) (B). Z =
100
(35) (A). = KE = mv2
mv 2
200 100
x , 100 x 33.3
2KE h v 3 3
mv = = ; = h
v
2
KE 2KE c
v (43) (C). =
(36) (D). Energy of nth Bohr’s orbit of H-atom
c
22 me 4 k 2 1 For violet (400 nm) 1 =
=– × 2 400 109
h2 n
Energy of first Bohr’s orbit of H-atom
IIT-JEE Chemistry 57
Structure of atom
c h
For red (750 nm) 2 = 9 (60) (A). =
750 10 mv
1 750 15 4.0 10 3
Mass of helium = kg and h = 6.62 × 10–34
2 = 400 = 8 6.023 10 23
(44) (B). This is based on Hund’s rule of multiplicity. Pairing of
6.023 10 23 1
electrons can be possible only when all the empty orbitals = 6.62 × 10–34 × 3 ×
in 3p level are filled. 4.0 10 2.4 102
(45) (C). This is due to the electronic jump from the level n = 5 = 0.416 × 10–9 meter = 0.416 nm
to the level n = 4. (61) (B). n = 4 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2, 4p6, 4d10,
(46) (C). It is 2s2 4f14. = (n – 1) = 4 – 1 = 3 which is f orbit contain 7 orbital.
(47) (A). Energy is always absorbed or emitted in whole num- (63) (C). In this type of electronic configuration the number of
ber or multiples of quantum unpaired electrons are 3.
(48) (A). 1s 2s 2p
19 2
2 79 1.6 10 =3
1.2 × 10–12 = 9 × 109 ×
r0 (64) (B). Two unpaired electrons are present in
Ni++ (z = 28) cation
9 79 256 2 1038 109
r0 = = 3 × 10–14 m Ni
1.2 1012 28 [Ar]
(49) (C). If = 2, m –3. 3d8 4s0
(50) (C). 2 electron in the valence shell of calcium (65) (D). Fe2+ has 1s2, 2s2 2p6,
3s23p63d6
Ca20 = 2, 8, 8, 2) configuration with 4 unpaired electron.
(51) (D). Unh106 = [Rn] 5f14, 6d5, 7s1 (66) (A). Angular momentum L is given by
(52) (C). A 3p orbital has one spherical and one non-spherical
nodes. h
L= ( 1) .
(53) (B). Since is the same, the momenta are the same. 2
9.109 1031 9 106
For d-orbital, = 2, so
vproton =
1.673 1027 h h
L= 2 (2 1) = 6 2
2
9.109 9
= × 102 m /s = 4900 m/s 1.24 106
1.673
(67) (C). Since V = 5 × 104 V, = m 0.25 Å
5 104
h
(54) (C). Since x . px = 1.0546 × 10–34 Js (68) (B). The second principal shell contains four orbitals viz
2
2s, 2px, 2py and 2pz.
and x = 1 × 10–10 m, p = 1.0546 × 10–24 kgms–1
(69) (A). The wave length of a spectral line may be given by the
2 following expression-
p
Fro 1 ke V electron, = 103 × 1.6 × 10–19 J
2m 1 1 1
p = 17.07 × 10–24 kgms–1 = R 2 2
n1 n 2
1.0546 For Lyman series n1 = 1. For Balmer series n1 = 2
% uncertainty = × 100 = 6.178 For the last line in both the series n2 =
17.07
For Lyman series
(55) (A). n = 1, = 2 is not valid. 1 1
1
(56) (B). For a g-subshell : n = 5 and = 4 =R 1 = R (1 – 0) = R ; L =
L R
Number of orbitals g-subshell = (2 + 1) = 9
Total number of orbitals in atom = n2 = (5)2 = 25 For Balmer series
(57) (C). Generally azimuthal quantum number defines angular
1 1 1 R
momentum. = R =
(59) (D). (Å) = 3500. Converting into h we get nearly B 4 4
5.76 × 10–19 J = 3.6 eV, subtracting 1.6 eV i.e.,
4 B 4 R 4
kinetic energy of the electron, the work function is 2 eV. B= ; = × =
R L R 1 1
58 IIT-JEE Chemistry
Structure of atom
(70) (A). Let x% of I(10.01) is mixed with II(11.01) and the atomic (77) ( A The plot of kinetic energy of the photoelectrons against
) .
weight become 10.81. Then frequency of absorbed radiation gives a straight line paral-
lel to x-axis
(10.01)x (11.01) (100 x)
= 10.81 1 1
100 (78) (C) E = mc2. For Lymann series, m1c2 2 2
1 2
10.01x – 11.01x + 1101 = 10.81 × 100 1 1
or –x = 1081 – 1101 For Balmer series, m2c2 22 32
or –x = –20 x = 20
m1 3 / 4 27
So ratio = 20% and 100 – 20 = 80% m1 : m2 = 27 : 5
(71) (D). x × p h / 4 m 2 5 / 36 5
if x = 0, then p will be infinite. (79) (C). The electronic configuration of Ne atom is 1s22s2 2p6.
h In its first excitation state the electron from 2p will unpair
(72) (B). has the value 0.024 Å. and shift to 3s where its quantum numbers will be
m0 C
3, 0, 0, 0, ± ½.
1 (80) (B). Absorption line in the spectra arise when energy is
= 0.024(1 – cos ) = 0.024 × Å = 0.012 Å absorbed i.e., electron shifts from lower to higher orbit, out
3 2
Maximum value of corresponds to = . of A and B, B will have the lowest frequency as this falls in
the Paschen series
max = 0.024(1 – (– 1)) = (0.024 × 2) Å = 0.048 Å
(81) (B). Spin multiplicity = 2s + 1 for minimum value no. unpaired
12.225 12.225 electrons will be present so s = 0.
(73) (C). 1 Å = =
100 10 Then Spin multiplicity = 1
By retardation through 19 volts the original accelerating (82) (C). The frequencies of X-rays emitted from elements could
voltage is reduced to 81 volts. be correlated by the equation = a (Z – b) where v is the
12.225 12.225 frequency and Z is the atomic number and a and b are
2 Å = = constants which are the same for all the elements.
81 9
(83) (C). The correct order of decreasing energy will be elec-
By further retardation through 32 volts, tron 3 which has higher energy than 2 and in the order
12.225 12.225 given.
3 Å = =
49 7 I II
(84) (C). He He+ + e– ; He+ He2+ + e–
I.E I.E
12.225 12.225
I (I.E) + II(I.E) = 79 eV
3 2 7 9
= II (I.E) = 13.6 eV × Z2 = 13.6 × 4 eV = 54.4 eV
1 12.225
I(I.E) = 79 – 54.4 = 24.6 eV.
10
(85) (B). The splitting of spectral lines when the source is placed
F
1 1I
G J
in an electrical field is known as Stark effect. Kerr effect is
i.e.,
H
7 9 K ( 9 7)
= × 10 =
20
the influence of an electrical field which makes an isotropic
substance (liquid or gas) anisotropic and double refract-
1 63 63 ing. Zeeman and anomalous Zeeman effects deal with the
10 splitting of energy levels when the source is placed in a
(74) (B). In Bohr’s theory while calculating the energy of elec- magnetic field.
tron, the potential energy has been found out by consider- hc 6.624 1027 3 1010 erg sec. cm. sec 1
ing only the attraction between the electron and nucleus. (86) (A). E = =
If there is another electron in the orbit, the potential en-
ergy would change due electron-electron repulsion. There- 6.624 10 27 3 1010 erg.cm
fore the Bohr’s model is meant for all one-electron sys- or =
tems. 118 103 4.184 107 mole1
2 r 6.624 3 10 17 molecule
(75) (A). 2r 3 3 n 3 = × 6.023 × 1023 cm mol
118 4.184 10 10 mol
T1 n13 33 0.2424 10 4
T 3 3 27 = = 2424 Å
2 n2 1 10 8
(76) (D). In Bohr’s model, the energy are discrete and not con-
tinuous. 3 1010
= = 1.24 × 1015 sec–1
2424 10 8
IIT-JEE Chemistry 59
Structure of atom
(87) (C). Uppermost energy level, n = 6 The energy of the positronium is half of this, which is –
Possible/transitions: n = 6 to 5, 4, 3, 2 and 1 : Total 5 6.81 eV. The energy required to remove the electron from
Possible/transitions: n = 5 to to 4, 3, 2 and 1 : Total 4 the positron is
Possible/transitions: n = 4 to 3, 2 and 1 : Total 3 6.81 eV = 6.81 × 1.602 × 10–22 kJ × 6.022 × 1023 mol–1
Possible/transitions: n = 3 to 2 and 1 : Total 2 = 657 kJ mol–1
Possible/transitions: n = 2 to 1 : Total 1d 1
Grand total 15 lines (90) (C). Kinetic energy = mv2
2
(88) (D). Energy of a photon
= 4.8 × 106 × 1.6 × 10–12 erg sec
c 6.626 10 34 2.998 108 (1 electron volt = 1.6 × 10–19 J or 1.6 × 10–12 erg sec)
= h = h. = J
650 10 9 1
Momentum mv = mv 2 2m
2
= 3.056 ×x 10–19 J
Total energy emitted in 10 years = 4.8 106 1.6 1012 2 6.6 1024
= 0.1 × 10 × 365 × 24 × 3600 J = 3.154 x 107 J.
total number of photons emitted in 10 years = 101.4 1030 = 10.07 × 10–15
3.154 x107 h
= = 1.032 × 1026. de Broglie wavelength =
19 mv
3.056 x10
Momentum gained by the glow worm in the forward direc- 6.626 1027 erg sec
= = 6.58 × 10–13 cm
tion, when one photon is released in the backward direc- 10.07 1015
tion
(91) (A). The energy of the lyman series limit = energy of the
Balmer series limit + energy of the first lyman line
h 6.626 1034 corresponding to transition from n = 2 to n = 1
=P= = = 1.019 × 10–27 (S.I. unit) E n = E2– + E1 – 2
650 109
( i . e . , )
Total momentum gained by the glow worm hc hc hc hc
E = = +
(Starting from rest) 3645 1215
= 1.032 × 1026 × 1.019 × 10–27 (S.I. unit) = 1.052 × 10–1. 1 1 1
= +
3645 1215
velocity gained (in 10 years)
1
1.052 10 1 = = 911.2 Å
= = 21.04 ms–1 1.09739 103
5 10 3
(92) (D). We know that
(89) (B). The original Bohr's theory of the hydrogen atom treats
it as a system, in which the electron revolves around the hc 1 1 1
nucleus in orbits. In an advancement of the theory, the E = and = RH 2 2
n1 n 2
electron – nucleus system is assumed to revolve as a whole
about a common axis passing through the centre of mass. where RH = Rydberg constant = 1.09677 × 107 m–1
However, the earlier theory does not suffer from serious h = 6.626 × 10–34 J sec and c = 3 × 108 m sec–1
error, since the reduced mass of electron and nucleus is
1 1
very close to the mass of the electron. The case of positron E = RH. h.c. 2 2
is different, since the electron and positron have compa- n1 n 2
rable masses, in fact the same mass, so that the reduced
mass is half of the mass of the electron. Correspondingly 1 1
= 1.09677 × 107 × 6.626 × 10–34 × 3 × 108 ×
the expression for the energy of the Positronium 9 25
= 1.55 × 10–19 J or 0.97 eV
22 e 4 Z 2 me
=– 2 . 2 (C.G.S system) with = Energy per mole = 0.97 × 6.02 × 1023 eV × 1.6 × 10–19
h n 2 = 9.343 × 104 J
(93) (B). For the information of 2 moles of He – H bonds it must
2 m e e 4 Z2
So the energy = – . 2 . provide,
h2 n (i) Energy of excitation of 1s2 to 1s1, 2s1
We known that the energy of the ground state (ii) Energy to produce 2 moles of H atoms.
Energy (i) is the difference between the promotion energy
22 e 4 22 m e e 4 to 1s1, 2p1 and the difference between this level and the
hydrogen atom = – =– = 13.62 eV..
h2 h2 1s1, 2s1 level.
60 IIT-JEE Chemistry
Structure of atom
hc 6.626 10 34 3 108 For He+ ion, Z = 2 and En = – 13.58 eV
E(1s2 1s1, 2p1) = = 13.6 4
58.44 10 9
So, n2 = n = 2.
= 3.4 × 10–18 J 13.58
E (1s1, 2p1 1s1, 2s1) Thus, He+ ion is in the 1st excited state.
Energy of photon emitted
hc
= = 6.626 × 10–20 × 3 × 108 × 485700 = 9.655 × 10–20 J
1 1 1
E(singlet) = (3.4 × 10–18 – 9.6555 × 1020) = 3.303 × 10–18 J = 13.6 Z2 1 2 eV = 13.6 × 4 1 = 40.8 eV
n n2 4
Energy (1) per mole
Energy of photon = I.P. of H + K.E. of photoelectron
3.303 1018 6.02 10 23 Thus, K.E. of photoelectron = 40.8 – 13.6 = 27.2 eV
= = 19.88 × 102 kJ
1000
h 6.625 1034
Energy (2) is 2 × 218 = 436 kJ mol–1 = =
Thus, each He – H bond must provide 2mE 2 9.11 1031 27.2 1.602 10 19
1 = 2.351 × 10–10 m = 2.351Å.
(19.88 × 102 + 436) = 1212 kJ mol–1 (96) (B). The minimum energy (E) required to eject an electron
2
per atom from metal surface is given by Planck’s quantum
(94) (A). Energy required per molecule in the following process theory as adopted by Einstein to explain photoelectric ef-
hv
may be given as O2 O + O* fect.
hc 6.626 10 34 3 108 hc 6.625 10 34 3 108
E0 = h0 = = = 8.63 × 10–19
E=
=
174 109 0 230 109
= 11.424 × 10–19 J molecule–1 For spectral line in Lyman series of H atom
Energy for, O O* is 3.15 × 10–19 J 1 1
Thus, energy for O2 2O will be = R 1 2
n
= 11.424 × 10–19 – 3.15 × 10–19
= 8.274 × 10–19 × 6.023 × 1023 × 10–3 kJ mole–1 For the 2nd longest wavelength transition, n = 3, so
= 498.3 kJ mol–1 1 8 8
= R = × 1.09677 × 107 m–1
h 9 9
(95) (C). =
2mE 9
or = = 1.025 × 10–7 m = 102.4 nm
h 2 (6.625 10 34 2
) 8 1.09677 107
E = = Energy of photon corresponding to this wavelength is as
2m 2.0.11 10 (3.329 1010 ) 2
2 31
given below
= 21.73 × 10–19 J = 13.58 eV
this is the K.E. of electron. c 6.625 10 34 3 108
E=h = = 1.937 × 10–18 J
Therefore, total energy = – 13.58 eV 1.025 10 7
Z2 K.E. of photoelectron = E – E0
En = – 13.6 × eV = 19.37 × 10–19 – 8.63 × 10–19 = 1.074 × 10–18 J
n2
EXERCISE - 2
(1) (ABC). Cathode rays consists of electrons which are fun- Ze2
1 Ze2
damental particles of matter. Hence, E = –
2 (40 ) r (40 ) r
(2) (ABC). The orbital angular momentum depends on the
value of and not on n.
1 Ze2
(3) (CD) or E = –
(4) (ABD). The energy of an electron in H-like atoms is given 2 (40 ) r
1 2 Ze2 1 1
by E = K.E. + P.E. = mv – (5) (AC). RZ2
2 (40 )r n12 n 22
From the stability of the circular motion of electron, we
1 1 5R
mv 2 Ze 2 x R 2 2
have = 2 3 36
r (40 ) r 2
IIT-JEE Chemistry 61
Structure of atom
tained.
1 36 108x
1 R 22 1 2 3R x3 (16) (A) (17) (D) (18) (D)
2 5 5 (19) (A) p,q, (B) p,q, (C) r, (D) s
For H atom 2nd lyman (20) (A) r, (B) s, (C) q, (D) p
(21) (A) r, (B) s, (C) p, (D) q
1 1 8 36x 32x 5
R 1 2 (22) (A) q, r , (B) p, s, (C) s, (D) q
2 9 9 5 5 32x
13.6 22
(6) (AB). Since it aborbs ‘n’ photons and it also emits exactly (A) B.E. of He+ atom = ; n 1, 2,3.........
n-photons therefore transition must have taken place from n2
1 to 2. Hence it can be 13.6 eV, 3.4 eV both
Energy of proton = 10.2 Z2 , where Z = 1, 2, 3, 4 (B) In 7 3 transition n = 7 – 3 = 4
(7) (ABC). Since B is in infrared region and A has more energy maximum number of spectral line observed
than B hence it will have lesser wavelength i.e. ultra violet,
4 (4 1)
visible or infrared region. = 10
2
z2 z2 It is line of Pashcen series hence infrared region
(8) (AB).B.E. of 4th state = 13.6 13.6 13.6 z 4
n2 42 (C) 5 1 : 10 lines
sample is Be3+ energy of electron in 3rd state. (D) Series limit of Balmer series is the last line i.e. 3.4 eV
state = 1.5 × 42 = 24 eV energy.
therefore 25 eV photon will cause ionisation. (23) (B) (24) (B) (25) (A)
(9) (BC). It is obvious from the fact. (26) (C) (27) (A) (28) (D)
(10) (ABD) (11) (ABC) (12) (ABCD) (29) (D) (30) (A) (31) (B)
(13) (A) (32) (A). (A) is not allowed, as the value of m must be ranging
(14) (C). According to Dalton’s atomic theory atoms can nei- between – 1 to +1.
ther be created nor destroyed and according to berzelius (33) (C). Orbital angular momentum for f orbital ( = 3)
hypothesis, under similar condition of temperature and pres- h h h
3(3 1) 12 12
sure equal volumes of all gases contain equal no. of atom. 2 2 2
(15) (E). We know that Absorption spectrum is produced when
white light is passed through a substance and transmitted h
light is analysed by a spectrograph. The dark spaces cor- (34) (A). The angular momentum must be a multiple of .
2
responds to the light radiation absorbed by the substance.
nh
And emission spectrum is produced by analysing the radi- L [where n = 1, 2, 3, 4, ........ for K, L, M, N shell
ant energy emitted by an excited substance by a spec- 2
trograph. Thus discontinuous spectra consisting of a se- respectively]
ries of sharp lines and separated by dark bands are ob-
EXERCISE - 3
(1) (a) Energy corresponding to 8205.8 Å Also energy used for breaking up to I2 molecule
6.626 x1034 x3 x108 240 x103
= 2.422 x 10–19 J = 1.572 eV = 3.984 × 10–19 cm
=
8205.8 x1010 6.023 x10 23
=
1 1 energy used in imparting kinetic energy to two iodine
E = E1H × Z2 2 2 atoms = [4.417 –3.984] × 10–19 J
n1 n 2 K.E. / iodine atoms = [(4.417 – 3.984)/ 2] × 10–19
1 1 E1H = 0.216 × 10–19 J
1.512 eV = E1H × (1)2 × 2 2 ; 1.512 eV =
3 9 (3) (i) KE of an electron in the orbits of hydrogen and hydro-
E1H = 13.608 eV gen like atoms = |Total energy| = 3.4 eV
Ionisation energy of hydrogen atom = 13.6 eV h h
34 8
(ii) = =
hc 6.626x10 x3 x10 p 2.mKE
(b) = = = 916 Å 6.626 1034
E 13.6 x1.602 x1019
=
(2) Energy given to I2 molecule 2 x 3.4 1.602 10 19 9.1 10 31
= 6.654 × 10–10 m = 6.654 Å
34 8
hc 6.626 x10 x 3 x10 (4) Wavelength of blue light () = 480 nm = 480 × 10–9 m
= = 10 = 4.417 10–19 J We know that frequency () is related to wavelength as :
4500 x10
62 IIT-JEE Chemistry
Structure of atom
c (8) If 0 be the threshold wavelength and be the work func-
× = c or =
hc 1242
Where c, velocity of light = 3.0 × 108 ms–1 tion 0 = = .
3.0 108 ms 1 3 1242
= 9 = × 1016 s–1 = 6.25 × 1014 s–1 For copper = 0 = = 276 nm
480 10 m 48 4.5
1242
1 For sodium = 0 = = 540 nm
Again, wave number, 4.5
1242
For caesium = 0 = = 654 nm
1 1 1.9
= 9 = × 108 m–1 = 2.08 × 106 m–1 (9) Energy of l orbit of H like atoms = 4Rh
480 10 m 48
= 4 × 2 .18 × 10–18 joule
Therefore, frequency = 6.25 × 1014 s–1 E1 for H = – 2.18 × 10–18 J
and wave number = 2.08 × 106 m–1 since EH like atoms = E1H × Z2
hc – 4 × 2.18 × 10–18 = – 2.18 × 10–18 × Z2
(5) Energy of photon, E = h =
Z=2
i.e, Atomic no. of H like atom is 2 or it is He+ ion.
Here, c = 3.0 × 108 ms–1
For de- excitation of electron in He+ from n2 = 2 to n1 = 1
In first case, = 800 nm = 800 × 10–9 m
hc
(a) E2 – E1 =
(6.626 10 34 Js) (3 108 ms 1 )
E1 = = 2.48 × 10–19 J Now E1 = 4Rh
800 10 9 m
In second case, = 400 nm = 400 × 10–9 m 4R h h1
E2 = – = – Rh E 2 2
4 n
(6.626 10 34 Js) (3 108 ms 1 )
E2 = = 4.91 × 10–19 J E2 – E1 = 3Rh = 3x 2.18 x 10–18 J
400 109 m
Ratio of energy of first and second radiations, hc
E2 – E1 =
E1 2.48 10 19 J 1
E2 =
4.97 10 19 J
=
2 6.625 x1034 x 3 x108
= = 303.89 × 10–10 m
E1 : E2 = 1 : 2 or E2 = 2E1 3 x 2.18 x1018
Thus, energy of the radiation with wavelength 400 nm is = 303.89 A.
twice that of the radiation of wavelength 800 nm.
(6) In any series the lines merge at the series limit. Here energy rH 0.529 x108
(b) Radius (r1) of H like atom = =
is maximum and wavelength of emitted line is minimum, so Z 2
the lines appear to merge. = 2.645 × 10–9 cm
Series limit for Balmer Series. (10) (i) The given expression for energy of an electron holds
1 1 1 101375 good only for one electron atoms (H, He+, Li2+ etc.)
= 101375 2 = (ii) In multi - electron system energy of an electron is deter-
2 4 mined not only by 'n' but also by 'l'
= 3.9 × 10 cm
–5
h h
(7) Let x and y be the amounts of F and Cl atoms in the given (11) mv = v=
m
F IJ
mixture. Since the ionisation of atoms absorbs energy. we
G
2
1 h2
HK
can write. 1 1 h
mv2 = K.E. = m =
x (6.023 × 1023 mol–1) (27.91 × 10–22 kJ) 2 2 m 2 m2
+ y (6.023 × 1023mol–1 ) (20.77× 10–22 kJ ) = 272.2 kJ ......(1) 1 (6.626 10 34 ) 2
Since the addition of electron to atoms releases energy, we = ×
2 9.11 10 31 (4.7 10 10 ) 2
can write x (6.023 × 1023 mol–1) (5.53 × 10–22kJ )
+ y (6.023 × 1023 mol–1) ( 5.78 × 10–22 kJ) = 68.4 kJ.........(2) 0.218 2.18
= × 10–17 J/atom = × 10–18 J/atom
Solving for x and y, we get 2 2
x = 0.054 mol and y = 0.144 mol. = 1.09 × 10–18 J/atom
0.054 Energy for the ground state of H atom = 13.6 eV/atom
Percentage of F atoms = × 100 = 27.27 = 2.179 × 10–18 J/atom
0.144 0.054
photon of energy required for the ejection of electron
Percentage of Cl atoms = 100 – 27.27 = 72.73 = (2.179 + 1.09) × 10–18 J/atom = 3.269 × 10–18 J/atom.
IIT-JEE Chemistry 63
Structure of atom
Number of revolutions per second.
hc
(12) eV0 = – [ = work function]
1 v 0.729 108
= = =
1240.8 2r 2r 2 3.14 4.716 10 8
= – 0.5 = 3.63 eV
300 v
1240.8 = 2.4 × 1014 revolutions/sec
K.E. = hv – = – 3.63 = 2.57 eV
200
Stopping potential = 2.57 Volts (16) E - 46.12 kcal mol–1
(13) K.E. = h – h0 According to Bohr’s theory, E = Nh
hc
K.E. = – h0 E 46.12
or = = = 4.48 × 1014 cycles sec–1
Nh 9.52 1014
(6.63 10 34 J sec) (3 108 m / sec)
K.E. = – 7.52 × 10–19 J
3.60 10 8 m (17) v =
0.001
× 30,000 = 0.3 cm sec–1
= 4.77 × 10–18 J 100
(14) Here, h = 6.62 × 10–27 ergs According to uncertainty crinciple,
E3 = – 2.41 × 10–12 ergs
E2 = – 5.42 × 10–12 ergs h h
x.p ; x.v
E = E3 – E2 = – 2.41 × 10–12 + 5.42 × 10–12 4 4m
= 3.01 × 10–12 ergs 6.625 1027 7
Now we know that, E = h x × 9.1 × 10–28 × 0.3
4 22
E 3.01 10 12 3.01 x 1.93 cm.
= = 15
27 = 6.62 × 10 cycles/sec (18) (a) Energy of photon , E = W + KE = 1.82 + 0.73 = 2.55 eV
h 6.62 10 (b) The energy of an electron in nth orbit of hydrogen
c c atoms is given as
But = =
13.6 13.6eV
En = eV ; E1 = – 13.6 eV ; E2 = = – 3.4 eV
n2 4
3 10 6.62
10
or = = 6.6 × 10–5 cm E3 = – 1.51 ev , E4 = –0. 85 eV
3.01 1015
Obviously, the transition 2 4 leads to the release of
Since 1Å = 10–8 cm photon of energy 2.55 eV as
6.6 10 5 E = |E2 – E4| = 2.55 eV
= = 6.6 × 103 Å (19) K.E. of electron = h – h0
10 8
Radius of 3rd orbit = 32 × 0.529 × 10–8 = 4.761 × 10–8 cm hc hc 1240 nm.ev 1240 nm.ev
(15) = = – = 1.223 eV
400 660
nh nh
We know that mvr = or v = (20) u = 50m sec–1 = 50 × 102 cm sec–1, m = 150 g
2 2mr Putting these values in the relation
3 6.624 1027 h 6.625 10 27
=
2 3.14 (9.108 10 28 8
) (4.761 10 ) = =
mu 150 50 10 2
= 0.729 108 cm/sec = 8.83 × 10–33 cm
Since the above wavelength is much lesser than the wave-
2r
Time taken for one revolution = length of the visible region, it will not be visible.
v
EXERCISE - 4
(1) = 0.9696 × 10–7 metre (2) 0.216 × 10–19 J (13) (C) (14) (A)
(3) n = 27.2 × 1018 (15) (A) (16) (B)
(17) (C)
e2 98.18 kJ, 10.93 × 1014 sec–1 or Hz
(a) T. E. =
h (18)
(4) , (b)
40a 0 e2 m
(19) (C) (20) (A)
(21) (B) (22) (D)
4 0 a 0 (23) (C) (24) (D)
(5) (B) (6) (D) (25) 22.85 nm (26) (B)
(7) 27419.25 cm–1 (8) 63.3 volt (27) 6.625 × 10–32 m (28) (A)
(9) 4+
23V (10) (A) (29) a-q, b-p, c-r, d-s (30) (B)
(11) 6.32 × 108 cm/sec (12) (A) (31) (A) q, (B) s, (C) p, q, r (D) p, q, r
64 IIT-JEE Chemistry
You might also like
- 10 - A Text Book On Engineering MechanicsNo ratings yet10 - A Text Book On Engineering Mechanics17 pages
- GUJCET Physics Paper Ch-5 (EM) (GSEBMaterial - Com)No ratings yetGUJCET Physics Paper Ch-5 (EM) (GSEBMaterial - Com)27 pages
- Chemistry Chapter 2 Structure of Atom Class 11 Notes - FREE PDFNo ratings yetChemistry Chapter 2 Structure of Atom Class 11 Notes - FREE PDF50 pages
- Lecture Electrostatics Physics Raj Sahu SirNo ratings yetLecture Electrostatics Physics Raj Sahu Sir42 pages
- Assignment - Thermodynamics - Chemistry - Class 11th NEET - Mukesh Sir - Mukesh KumarNo ratings yetAssignment - Thermodynamics - Chemistry - Class 11th NEET - Mukesh Sir - Mukesh Kumar23 pages
- Class Xi Chemistry Nit 2: Tructure of AtomNo ratings yetClass Xi Chemistry Nit 2: Tructure of Atom131 pages
- Soalan Ramalan Fizik SPM2020 (Skema Jawapan)No ratings yetSoalan Ramalan Fizik SPM2020 (Skema Jawapan)8 pages
- Wave Optics: Prove Law of Reflection Using Huygen's PrincipleNo ratings yetWave Optics: Prove Law of Reflection Using Huygen's Principle5 pages
- (2087) Lecture Notes 1 Atomic Structure eNo ratings yet(2087) Lecture Notes 1 Atomic Structure e53 pages
- Class XI - C (2024-25) PHYSICS SYLLABUS (Science Stream)No ratings yetClass XI - C (2024-25) PHYSICS SYLLABUS (Science Stream)10 pages
- Rotational Motion - Miscellaneous SolutionsNo ratings yetRotational Motion - Miscellaneous Solutions16 pages
- Elicit: Distinguish Mechanical and Electromagnetic WavesNo ratings yetElicit: Distinguish Mechanical and Electromagnetic Waves3 pages
- Exercise (S-1) : Definitions of Kinematics VariablesNo ratings yetExercise (S-1) : Definitions of Kinematics Variables5 pages
- Structure of Atom Class 11 Chemistry CBSE BoardNo ratings yetStructure of Atom Class 11 Chemistry CBSE Board5 pages
- The Mysterious World of Fundamental Particles - Cosmic BeginningsFrom EverandThe Mysterious World of Fundamental Particles - Cosmic BeginningsNo ratings yet
- All 118 Elements In The Universe?: Atomic Map Of The World? Navigating The Periodic Table?From EverandAll 118 Elements In The Universe?: Atomic Map Of The World? Navigating The Periodic Table?No ratings yet
