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01 03
—Classical Mechanics
C H A P T E R
FUNDAMENTAL PARTICLES
An atom consists of the two parts :
(a) Extremely small but dense central part called the nucleus.
(b) Extra nuclear part.
The size of nucleus is of the order 10–15 m and it contains positively charged protons and neutral
particles called neutrons. These particles are collectively called nucleons.
The charge and mass of these fundamental particles are given in the Table 1.1.
In CGS units, m is the mass of an electron in grams, e its charge in esu, v its velocity in cm sec–1, r the
radius of the orbit in cm, h the Planck's constant, E the energy in ergs, Z the atomic number and n is the
number of an integer having value 1,2,3 ...... representing the first, second, third, .... orbits respectively.
For first orbit of H atom (or He+ or Li2+ species) we have
h2 2 π2 Z2 e4 m 2 π e2
r1 = E1 = – and v1 =
4 π m Z e2 h2 h
and for nth orbit we have
E1 v1
rn = n2 × r1 En = – and vn =
n2 n
The difference between two energy states n2 (higher) to n1 (lower) is given by
ΔE = Ef – Ei
where Ef is the electronic energy in final state and Ei is the electronic energy in the initial state.
Using Equation (iii) it can be shown that
2 π2 Z2 e4 m
ΔE = –
h2
[ n1 – n1 ]
2
2
2
1
ΔE = 2 π Z 2e m
2 2 4
or
h
[ n1 – n1 ]
2
1
2
2
hc 2 π2 Z2 e4 m
or
λ
=
h2 [ n1 – n1 ]
2
1
2
2
= 2π Z e m
l 2 2 4
or
λ c h3
[ n1 – n1 ]
2 2
SOLVED PROBLEM 1. Calculate the velocity of the electron in the first Bohr orbit
(h = 6.625 × 10–27 erg sec ; r = 0.529 Å ; m = 9.109 × 10–28 g).
SOLUTION :
Formula used
nh
mvr =
2π
nh
or v =
2πmr
4 1 QUESTION BANK
Quantities given
n= 1 h = 6.625 × 10–27 erg sec r = 0.529 Å = 0.529 × 10–8 cm
Substitution of values
1 × 6.625 × 10–27 erg sec
We have v =
2 × 3.14 × (9.109 × 10–28 g) × (0.529 × 10–8 cm)
= 0.2189 × 109 cm sec–1
= 2.189 × 108 cm sec–1
SOLVED PROBLEM 2. Calculate the energy of transition involving n1 = 6 to n2 = 3 in a hydrogen
atom, given that Rydberg constant R = 109737.32 cm–1 and h = 6.63 × 10–34 J sec.
SOLUTION :
Formula used
hc
ΔE =
λ
∴
or = hcR [ n1 1
2
– 1
n2 2 ] ( 1
λ
=R [ n1
1
2
–
1
n2 2 ])
Quantities given
h = 6.63 × 10–34 J sec n1 = 6 n2 = 3
c = 3 × 1010 cm sec–1 R = 109737.32 cm–1
Substitution of values
SOLVED PROBLEM 3. Calculate the wavelength associated with an electron moving with a
velocity of 1 × 108 cm sec–1. Mass of an electron = 9.1 × 10–28 g.
SOLUTION :
h
Formula used λ =
mv
Quantities given
= 0.04772 × 10–6 cm
= 4.772 × 10–8 cm
SOLVED PROBLEM 5. Calculate the wavelength of first line in Lyman series of hydrogen spectrum.
(R, Rydberg constant = 109677 cm–1).
SOLUTION :
1
Formula used
λ
= R Z2
[ n1 2
1
–
1
n22 ]
Quantities given
R = 109677 cm–1 Z = 1 (for hydrogen atom)
n1 = 1 n2 = 2 (for 1st line in Lyman series)
Substitution of values
1
λ
= 109677 cm–1 × [ 11 2
–
1
22
]
= 109677 cm–1 × 0.75
= 82257.75 cm–1
1
or λ =
82257.75 cm–1
= 1.215 × 10–5 cm
= 1.215 × 10–5 × 108 Å
= 1215 Å
SOLVED PROBLEM 6. In the photoelectric effect experiment irradiation of a metal with light of
frequency 5 × 1020 sec–1 yields electrons with maximum kinetic energy 6.63 × 10–14 J. Calculate υ0,
threshold frequency of the metal.
SOLUTION :
Formula used
h υ = h υ0 + ½ m v2
or K.E., ½ m v2 = h υ – h υ0
= h (υ – υ0)
6 1 QUESTION BANK
Quantities given
KE = 6.63 × 10–14 J υ = 5 × 1020 sec–1 h = 6.63 × 10–34 J sec
Substitution of values
6.63 × 10–14 J = 6.63 × 10–34 J sec × (5 × 1020 sec–1 – υ0 )
6.63 × 10–14 J
or 5 × 1020 sec–1 – υ0 =
6.63 × 10–34 J sec
= 1 × 1020sec–1
υ0 = 5 × 1020 sec–1 – 1 × 1020 sec–1
= 4 × 1020 sec–1
SOLVED PROBLEM 7. The kinetic energy of a subatomic particle is 4.55 × 10–25 J. Calculate the
frequency of the particle wave. Planck's constant h = 6.62 × 10–34 kg m2 sec–1.
SOLUTION :
Formula used
m v2
Frequency, υ =
h
Quantities given
KE = ½ mv2 = 4.55 × 10–25 or m v2 = 2 × 4.55 × 10–25 J
h = 6.62 × 10–34 J sec
Substitution of values
9.10 × 10–25 J
We have υ =
6.62 × 10–34 J sec
= 1.37 × 10–9 sec–1
SOLVED PROBLEM 8. What is the frequency of emission spectrum when the electron in hydrogen
atom falls from 5th to 2nd orbit ?
SOLUTION :
Formula used
Quantities given
ΔE = h c R [ n1
1
2
–
1
n2 2
]
n1 = 5 n2 = 2 h = 6.625 × 10–34 J sec
c = 3 × 10 m sec
8 –1
R = 1.09677 × 107 m–1
Substitution of values
ΔE = (6.625 × 10–34 J sec) × (3 × 108 m sec–1) × (1.09677 × 107 m–1) ×
1
52
[–
1
22
]
= 21.798 × 10–34+8+7 × (0.04 – 0.25) J
= – 4.5776 × 10–19 J
ΔE
Now Frequency, υ =
h
4.5776 × 10–19 J
= –
6.625 × 10–34 J sec
= – 0.6909 × 1015 sec–1
= – 6.909 × 1014 sec–1
The negative sign simply indicates the loss of energy.
STRUCTURE OF ATOM – CLASSICAL MECHANICS 7
SOLVED PROBLEM 9. Calculate the energy difference, frequency and wavelength of light emitted
when the electron in a hydrogen atom undergoes transition from 4th energy level to 2nd energy level
(Rydberg constant = 1.09677 × 107 m–1).
SOLUTION :
Formula used
ΔE = h c R [ n1
1
2
–
1
n 22 ]
Quantities given
n1 = 2 n2 = 4 R = 1.09677 × 107 m–1 c = 3 × 108 m sec–1
Substitution of values
(6.625 × 10–34 J sec–1) × (3 × 108 m sec–1) × (1.09677 × 107 m–1)
ΔE =
( 21
2
–
1
42 )
= 21.798 × 10–34+8+7 × 0.1875 J
= 4.087 × 10–19 J
ΔE 4.087 × 10–19 J
Also frequency, υ = =
h 6.625 × 10–34 J sec
= 0.6169 × 1015 sec–1
= 6.169 × 1014 sec–1
c 3 × 108 m sec–1
and wavelength, λ = =
υ 6.619 × 1014 m
= 0.4532 × 10–6 m
= 4.532 × 10–7 m
SOLVED PROBLEM 10. If the energy difference between the ground state of an atom and its
excited state is 4.4 × 10–19 J, what is the wavelength of the photon required to produce this transition ?
SOLUTION :
Formula used
hc
ΔE = λ
hc
or λ =
ΔE
Quantities given
ΔE = 4.4 × 10–19 J h = 6.625 × 10–34 J sec c = 3 × 108 m sec–1
Substitution of values
(6.625 × 10–34 J sec) × (3 × 108 m sec–1)
λ =
(4.4 × 10–19 J)
= 4.517 × 10–34+8+19 m
= 4.517 × 10–7 m
8 1 QUESTION BANK
SOLVED PROBLEM 11. The electron in a hydrogen atom revolves in the second orbit. Calculate
(i) the energy of electron in this orbit (ii) radius of the second orbit and (iii) frequency and wavelength
of the spectral line emitted when this electron jumps to the ground state.
SOLUTION : (i) To calculate the energy of electron in 2nd orbit
Formula used
2 π2 m e4
En =
n2 h2
Quantities given
n = 2 e = 4.80 × 10–10 esu h = 6.625 × 10–27 erg sec m = 9.1 × 10–28 g
Substitution of values
2 × (3.14)2 × (4.8 × 10–10 esu)4 × (9.1 × 10–28 g)
E2 = –
22 × (6.625 × 10–27 erg sec)2
= – 3594.59 × 10–14 erg
= – 3.59459 × 10–14 erg
= – 3.5946 × 10–11 erg
(ii) To calculate the radius of 2nd orbit
Formula used
n2 h2
r2 =
Quantities given 4 π2 m e2
Quantities given
1
λ
= R [ n1
1
2
–
1
n 22 ]
n1 = 1 n2 = 2 R = 109677 cm–1
Substitution of values
1
λ
= (109677 cm–1) × [ 112
–
1
22
]
= 109677 × 0.75 cm–1
= 82257.75 cm–1
1
or λ = = 1.2157 × 10–5 cm
82257.57 cm–1
STRUCTURE OF ATOM – CLASSICAL MECHANICS 9
c 3 × 1010 cm
and frequency, υ = =
λ 1.2157 × 10–5 cm
= 2.4677 × 1015 Hz
SOLVED PROBLEM 12. According to Bohr's theory, the electronic energy of the hydrogen
atom in nth Bohr's orbit is given by En = – 21.76 × 10 Z J. Calculate the longest wavelength of
–19 2
n2
light that will be needed to remove an electrons from 3rd Bohr orbit of He+ ion.
SOLUTION :
Formula used
En = – 21.76 × 10–19 Z2
n2
Quantities given
Z =2 n = 3
Substitution of values
21.76 × 10–19 × 4
En = –
9
= – 9.671 × 10–19 J
Thus the energy required to remove an electron from 3rd Bohr's orbit of He+ ion is
9.671 × 10–19 J.
SOLVED PROBLEM 13. What transition in the hydrogen spectrum would have the same
wavelength as the Balmer transition n = 4 to n = 2 of He+ spectrum ?
SOLUTION :
Formula used
1
λ
= R Z2 [ n11
2
–
1
n2 2 ]
Quantities given (for helium atom)
Z=2 n1 = 2 n2 = 4
Substitution of values
1
λ1
= R × 4 × 1 – 1
4
[16
]
4R× 3
=
16
Quantities given (for hydrogen atom)
Z= 1
Substitution of values
1
λ2
= R×1 [ n1 –
1
2
1
n2 2
]
since λ1 = λ2
4R ×3
We have
16
= R × [ n11
2
–
1
n 22 ]
10 1 QUESTION BANK
3
or [ n1
1
2
–
1
n2 2 ]
=
4
SOLVED PROBLEM 14. Find out the number of waves made by a Bohr electron in one complete
revolution in its 3rd orbit.
SOLUTION :
Formula used
mvr = n h
Quantities given 2π
n= 3
Substitution of values
3h
mvr =
2π
or 2πr = 3 h ∴ h
= 3λ
mv [ λ =
mv ]
Hence three times the wavelength of electron is equal to the circumference of 3rd orbit. So the
electron makes three waves around 3rd orbit.
SOLVED PROBLEM 15. Iodine molecule dissociates after absorbing light of 4500Å. If one quan-
tum radiation is absorbed by each molecule, calculate the kinetic energy of iodine atom. (Bond
energy of I2 = 240 × 103 kJ mol–1).
SOLUTION :
Formula used
hc
ΔE =
λ
Quantities given
h = 6.625 × 10–34 J sec c = 3 × 10–8 m sec–1 λ = 4500 Å = 4500 × 10 –10 m
Substitution of values
(6.625 × 10–34 J sec) × (3 × 108 m sec–1)
ΔE =
(4500 × 10–10 m)
= 4.416 × 10 J
–19
240 × 103
Now Bond energy of I2 per molecule = J/molecule
Avogadro's No.
240 × 103
= J/molecule
6.023 × 1023
3.984 × 10–19 J/molecule
=
Kinetic energy of iodine atoms =
Energy absorbed – Bond energy
4.416 × 10–19 J – 3.984 × 10–19 J
=
0.432 × 10–19 J
=
0.432 × 1019
∴ Kinetic energy per iodine atom = J
2
= 2.16 × 10 J–20
STRUCTURE OF ATOM – CLASSICAL MECHANICS 11
SOLVED PROBLEM 16. Calculate the wave number for the shortest wavelength transition in the
Balmer series of hydrogen atom.
SOLUTION :
Formula used
υ =
1
λ
= R [ n1 1
2
–
1
n 22
]
Quantities given
n1 = 2 n2 = ∝ R = 109677 cm–1
Substitution of values
υ = 109677 cm–1 [ 21 2
–
1
∝
]
= 109677 [ 1
4
– 0 ] cm –1
= 27419.25 cm–1
SOLVED PROBLEM 17. Calculate the energy emitted when electrons of 1.0 g atom of hydrogen
undergo transition giving the spectral line of lowest energy in the visible region of its atomic
spectrum. (R = 1.1 × 107 m–1).
SOLUTION :
Formula used
1
λ
= R [n1
1
2
–
1
n 22 ]
Quantities given
R = 1.10 × 107 m–1 For visible region we have Balmer series and
For Balmer series n1 = 2 n2 = 3 (lowest energy)
Substitution of values
1
λ
= 1.1 × 107m–1 × [ 21 2
–
1
32 ]
5
= 1.1 × 107 m–1 ×
36
= 0.15277 × 107 m–1
1
or λ =
0.15277 × 107 m–1
= 6.546 × 10–7 m
To calculate energy emitted
Formula used
hc
ΔE =
λ
Quantities given
λ = 6.545 × 10–7 m h = 6.625 × 10–34 J sec c = 3 × 10–8 m sec–1
Substitution of values
(6.625 × 10–34 J sec) × (3 × 108 m sec–1)
ΔE = 6.545 × 10–7 m
12 1 QUESTION BANK
= 3.037 × 10–34+8+7 J
= 3.037 × 10–19 J
Now energy emitted from 1 g atom of hydrogen
= 3.037 × 10–19 J × Avogadro's No.
= 3.037 × 10–19 × 6.02 × 1023 J
= 182.82 kJ
SOLVED PROBLEM 18. Calculate the wavelength of radiation emitted, producing a line in Lyman
series, when an electron falls from fourth stationary state in hydrogen atom. (R = 1.1 × 107 m–1)
SOLUTION :
Formula used
1
λ
= R [ n11
2
–
1
n2 2 ]
Quantities given
n2 = 4 n1 = 1 (Lyman series) R = 1.1 × 107 m–1
Substitution of values
1
λ
= (1.1 × 107 m–1) × [ 11 – 41 ]
2 2
1
× [1 –
16 ]
= 1.1 × 107 m–1
= 0.9696 × 10–7
= 9.696 × 10–8 m
1. Calculate the velocity of the electron in the first Bohr's orbit (h = 6.625 × 10–27 erg sec; r = 0.529 Å ;
m = 9.109 × 10–28 g).
Answer. 2.189 × 108 cm sec–1
2. Calculate the energy of transition involving n 1 = 6 to n2 = 3 in a hydrogen atom given that Rydberg constant,
R = 109737.32 cm–1 and h = 6.63 × 10–34 J sec.
Answer. 1.818 × 10–19 J
3. Calculate the radius of the third orbit of hydrogen atom (h = 6.625 × 10–27 erg sec ; m = 9.1091 × 10–28 g;
e = 4.8 × 10–10 esu).
Answer. 4.763 × 10 –8
STRUCTURE OF ATOM – CLASSICAL MECHANICS 13
4. Calculate the wavelength of the first line in Balmer series of hydrogen spectrum. (R = 109677 cm–1)
Answer. 1215 Å
5. What is frequency of a red light source having wavelength of 700 nm (nanometer) ? Calculate the energy of
a photon of light.
Answer. 4.28 × 1014 sec–1 ; 2.78 × 10–19 J
6. What is the frequency of emission spectra when the electron in a hydrogen atom falls from n6 orbit to n2
orbit ?
Answer. 7.30 × 1014 sec–1
7. A light beam has a frequency of 1.0 × 1012 Hertz. What is the wavelength of the beam in meters ? The
velocity of light is 3.0 × 108 m sec–1.
Answer. 3.0 × 104 m sec–1
8. Sound waves travel about 203 m sec–1 in air. What is the wavelength of the sound produced by a tuning fork
of 512 vibrations per second ?
Answer. 0.396 m
9. Calculate the loss of energy in Joules per mole of photons, when atoms release radiations at a frequency of
1012 sec–1.
Answer. 4 × 102 J mol–1
10. An electron in an atom drops to a lower energy level with the release of 5.0 × 1014 sec–1 radiations. What is
the loss of energy in J mol–1 ?
Answer. 2.0 × 105 J mol–1
11. Visible light is in the range of 4.0 × 1014 Hz to 7.5 × 1014 Hz. Calculate the range of visible radiation in meters.
Answer. 4 × 10 –7 m to 7.5 × 10–7 m
12. In hydrogen atom the energy of the electron in first Bohr's orbit is – 1312 × 105 J mol–1. What is the energy
required for the excitation of second Bohr's orbit ?
Answer. 9.84 × 105 J mol–1
13. The kinetic energy of an electron is 4.55 × 10–25 J. Calculate its wavelength (h = 6.6 × 10–34 kg m2 sec–1; m
= 9.1 × 10–31 kg)
Answer. 7.2 × 10–7 m
14. The reaction I 2 energy 2 I was brought about by light radiation. It was found that 151 kJ
mol–1 of light was required to dissociate the molecular iodine. Assuming that one quantum of light energy was
required to dissociate one molecule of iodine, calculate the energy in Joules in one quantum of light and the
wavelength of the light radiations in meters.
Answer. 2.51 × 10–19 J ; 7.92 × 10–7 m
15. Using Bohr theory, calculate the radius and velocity of the electron in tenth orbit of hydrogen atom.
Answer. 0.53 × 10–6 cm ; 21.9 × 107 cm sec–1
16. Calculate the frequency and energy associated with photons of radiations having a wavelength of 6000 Å.
Planck's constant = 6.625 × 10–27 erg sec.
Answer. 5 × 1014 cps ; 3.312 × 10–27 erg
17. Calculate the range of frequencies of visible light (3800 Å to 7600 Å)
Answer. 3.948 × 1014 cps to 7.894 × 1014 cps
18. Calculate the wave number of lines having frequency of 4.5 × 1016 cps.
Answer. 1.5 × 108 m–1
19. Calculate the energy in kcal mol–1 of photons of an electromagnetic radiations of wavelength 4000 Å.
Answer. 71.47 kcal mol–1
20. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the sodium atom. Calculate the
ionization energy of sodium in kJ mol–1 ; h = 6.6256 × 10–34 Joule sec.
Answer. 494.5 kJ mol–1
21. In a hydrogen atom, an electron jumps from 3rd orbit to first orbit. Find out the frequency and wavelength
of the spectral line.
14 1 QUESTION BANK
Answer. 1025.6 Å
22. Calculate the wavelength and energy of radiations emitted for the electronic transition from infinity (∝) to
stationary state of the hydrogen atom. (R = 1.09678 × 107 m–1 ; h = 6.625 × 10–34 Joule sec and
c = 2.9979 × 108 m sec–1)
Answer. 9.11 × 10–6 m ; 217.9 × 10–23 kJ
23. Calculate the wavelength in Å of the photon that is emitted when an electron in Bohr orbit n = 2 returns
to the orbit n = 1 in the hydrogen atom. The ionization potential in the ground state of hydrogen atom is
2.17 × 10–11 erg per atom.
Answer. 1220 Å
24. What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition n = 4 to
n = 2 of He+ transition ?
Answer. n = 2 to n = 1
25. A line at 434 nm in Balmer series of spectrum corresponds to a transition of an electron from the nth to 2nd
Bohr orbit. What is the value of n ?
Answer. n = 5
26. The electron energy in hydrogen atom is given by E = – 21.7 × 10–12/n2 ergs. 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 ?
Answer. – 5.42 × 10–12 erg ; 3.67 × 10–5 cm
27. The energy transition in hydrogen atom occurs from n = 3 to n = 2 energy level. (R = 1.097 × 107 m–1).
(i) Calculate the wavelength of the emitted electron (ii) Will this electron be visible ? (iii) Which spectrum
series does this photon belong to ?
Answer. 6564 Å ; Yes ; Balmer series
28. Calculate the energy emitted when electrons of 1.0 g of hydrogen undergo transition giving the spectral line
of lowest energy in the visible region of its atomic spectrum (R = 1.1 × 107 m–1; c = 3 × 108 m sec–1; h = 6.62
× 10–34 J sec)
Answer. 182.5 kJ
29. The energy of the electron in the second and third Bohr orbits of the hydrogen atom is – 5.42 × 10–12 erg and
– 2.41 × 10–12 erg respectively. Calculate the wavelength of the emitted radiation when the electron drops
from third to second orbit.
Answer. 6600 Å
30. A doubly ionized lithium atom is hydrogen like with an atomic number 3. (i) Find the wavelength of the
radiation required to excite the electron in Li from the first to third Bohr orbit (Ionization energy of hydrogen
atom is 13.6 eV) (ii) How many spectral lines are observed in the emission spectrum of the above excited
system ?
Answer. (i) 113.7Å (ii) 3
31. An electron beam can undergo diffraction by crystals. Through what potential should a beam of electrons be
accelerated so that its wavelength becomes equal to 1.54 Å.
Answer. 8.0459]
32. With what velocity should an α - particle travel towards the nucleus of a copper atom so as to arrive at a
distance of 10–13 meter from the nucleus of the copper atom ?
Answer. 6.318 × 106 m s–1
2 Structure of the Atom
—Wave Mechanics Approach
C H A P T E R
WAVE MECHANICS
According to "Wave Mechanical Theory' light exhibits both a wave and a particle nature under
suitable conditions. This theory was further extended to matter i.e. electrons, protons and atoms. The
new quantum mechanics which takes into account the particulate and wave nature of matter is termed
as wave mechanics.
DE BROGLIE EQUATION
de Broglie in 1924 proposed that matter (atoms, neutrons, protons, electrons, etc.) has dual character
i.e. it is associated with the properties of waves and their wavelengths λ is given by the relation
h h
λ= =
mv momentum
where m is the mass, v, the velocity of the particle and h the Planck's constant. de Broglie equation
has no significance for large objects.
HEISENBERG'S UNCERTAINTY PRINCIPLE
It is impossible to measure simultaneously both the position and velocity (or momentum) of a
microscopic particle with absolute accuracy or certainty. Mathematically,
h
Δx × Δ p >
_
4π
h
or Δx × m Δv >
_
4π
where Δx is uncertainty in position and Δp the uncertainty in momentum or Δv is the uncertainty in
velocity and m the mass of the particle. It also has no significance for large objects.
SCHRÖDINGER'S WAVE EQUATION
Schrödinger derived an equation based upon the idea of the electron as 'standing wave' around the
nucleus. This equation, known as Schrödinger's wave equation, is
d2ψ d2 ψ d2ψ 8 π2 m
+ + + ( E – PE ) ψ = 0
dx 2 dy 2 dz 2 h2
15
16 2 QUESTION BANK
where ψ is a mathematical function representing the amplitude of the wave, m the mass of the
particle, v, the velocity, E the total energy of the particle, P.E., the potential energy and x,y,z are three
space coordinates.
It may be noted that square of the wave function, ψ2, represents the probability of finding the
electron in different regions.
QUANTUM NUMBERS
According to modern theory of electronic structure an electron in an atom is specified in terms of
four quantum numbers which describe the probable location of the electron. The values of quantum
numbers govern its energy, orientation in space and its possible interaction with other electrons.
PRINCIPAL QUANTUM NUMBER
It denotes the principal shell to which the electron belongs. It also represents the average size of
electron cloud. The distance of the electron from the nucleus in hydrogen atom is given by
rn = 0.529 × n2 Å
where n is the principal quantum number. It can have integral values 1,2,3,4....... The maximum
number of electrons in the principal shell is equal to 2n2.
AZIMUTHAL QUANTUM NUMBER
It describes the angular momentum of the electron and defines the shape of the orbital occupied by
the electron. It is denoted by ' l ' and it can have all integral values from 0 to n–1. The total number of
sublevels in each principal level is numerically equal to the principal quantum number of that level. For
example,
n = 1 l = 0
n = 2 l = 0, l = 1
n = 3 l = 0, l = 1, l = 2
n = 4 l = 0, l = 1, l = 2, l = 3
The shape of the orbital is related to the azimuthal quantum number in the following manner :
l=0 l=1 l=2 l=3
s–subshell p–subshell d–subshell f–subshell
MAGNETIC QUANTUM NUMBER
It accounts for the splitting of the spectral line in a magnetic field (Zeeman effect). It gives the
orientation of the electron cloud and is denoted by m. For each value of l,m can have all integral values
between –l to +l through zero. For example,
l=0 m=0
l=1 m = –1, m = 0, m = +1
l=2 m = –2, m = –1, m = 0, m = +1, m = +2
l=3 m = –3, m = –2, m = –1, m = 0, m = +1, m = +2, m = +3
SPIN QUANTUM NUMBER
It accounts for the spin of the electron about its own axis. It is denoted by s and it can have either
+½ or –½ value depending upon whether the electron spin is clockwise or anticlockwise. The summary
of the four quantum numbers is given in Table 2.1.
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 17
TABLE 2.1 THE QUANTUM NUMBERS AND THEIR PERMITTED VALUES.
Quantum Number Designation Permitted Values
Principal Quantum Number n 1,2,3,4,..............
Azimuthal Quantum Number l 0,1,2,3,..............
Magnetic Quantum Number m –l,.....,0,.......+l
Spin Quantum Number s +1/2 or –1/2
1 2 – – – 2
2 2 6 – – 8
3 2 6 10 – 18
4 2 6 10 14 32
( n + l ) RULE
The energy of the electrons increases as the sum (n+l) increases, i.e. lower the value of (n+l) for an
electron in an atom lower is its energy.
For two electrons with same (n+l) value, the one with lower value of n has lower energy.
AUFBAU PRINCIPLE
In the ground state of an atom, the electron enters the orbital of lowest energy first and subsequent
electrons are added in the order of increasing energies. Fig. 2.1 shows the energy level scheme of filling
up of electrons in various orbitals.
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p
Figure 2.1
Aufbau order of filling up of electrons in various orbitals.
18 2 QUESTION BANK
The increasing order of energy of various orbitals is as follows :
1s < 2s < 2p <3s <3p <4s <3d <4p <5s .................
HUND'S RULE OF MAXIMUM MULTIPLICITY
Electrons are distributed among the orbitals of a subshell in such a way as to give maximum number
of unpaired electrons with the same direction of spin.
SOLVED PROBLEM 1. A neutral atom has 2K, 8L and 3M electrons. Predict from this (i) its
atomic number; (ii) total number of s-electrons; (iii) total number of p-electrons and (iv) total
number of d-electrons.
SOLUTION :
(i) Atomic number
Atomic number = No. of Protons = No. of electrons
=2+8+3
= 13
(ii) Total number of s-electrons
The electronic configuration of the atom with atomic number 13 is
1s2 2s2 2p6 3s2 3p1
Total no. of s-electrons = 2+2+2 [1s2, 2s2, 3s2]
= 6
(iii) Total no. of p-electrons
Total no. of p-electrons = 6 + 1 [2p6, 3p1]
= 7
(iv) Total no. of d-electrons
Total no. of d-electrons = 0 [ ∴ 3d is vacant]
SOLVED PROBLEM 2. The velocity of a ball bowled by Kapil Dev is 25 m sec–1. Calculate
the wavelength of the matter wave associated with the ball (mass of the cricket ball is 158.5 g;
h = 6.625 × 10–27 erg sec).
SOLUTION :
Formula used
h
λ=
mv
Quantities given
m = 158.5 g v = 25 m sec–1 = 2500 cm sec–1 h = 6.625 × 10–27 erg sec
Substitution of values
6.625 × 10–27 erg sec
λ =
158.5 g × 2500 cm sec–1
= 0.0000167 × 10–27 cm
= 1.67 × 10–32 cm
SOLVED PROBLEM 3. Give the orbital configuration and number of unpaired electrons in the
ground state for the following atoms :
(i) Nitrogen (At. No. 7)
(ii) Chlorine (At. No. 17)
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 19
(iii) Manganese (At. No. 25)
(iv) Cadmium (At. No. 48)
SOLUTION : The electronic configurations and number of unpaired electrons are as follows :
No. of unpaired electrons
(i) Nitrogen (At. No.7) = 1s 2s 2p1x
2 2
2p1z2p1y 3
(ii) Chlorine (At. No. 17) = 1s 2s 2p 3s 3p2x
2 2 6 2
3p2y 3p1z 1
2 2 6 2 6 2 5
(iii) Manganese (At. No. 25) = 1s 2s 2p 3s 3p 4s 3d 5
2 2 6 2 6 2 10 2 6 2 10
(iv) Cadmium (At. No. 48) = 1s 2s 2p 3s 3p 4s 3d 4s 4p 5s 4d 0
SOLVED PROBLEM 4. A particle having wavelength of 6.6 × 10–4 cm is moving with a velocity
of 106 cm sec–1. Find the mass of the particle. (Planck's constant = 6.62 × 10–27 erg sec)
SOLUTION :
Formula used
h
λ =
mv
h
or m=
vλ
Quantities given
h = 6.62 × 10–27 erg sec v = 106 cm sec–1 λ = 6.6 × 10–4 cm
Substitution of values
6.62 × 10-27 erg sec
m =
6.6 × 10-4 cm × 106 cm sec–1
= 1.003 × 10–29 g
SOLVED PROBLEM 5. What is the wavelength associated with a particle of mass 0.1 g moving
with a speed of 1 × 105 cm sec–1? (h = 6.6 × 10–27 erg sec)
SOLUTION :
Formula used
h
λ=
mv
Quantities given
h = 6.6 × 10–27 erg sec m = 0.1 g v = 1 × 105 cm sec–1
Substitution of values
6.6 × 10-27 erg sec
λ =
(0.1 g) × (1 × 105 cm sec-1)
= 66 × 10–32 g
= 6.6 × 10–31 g
SOLVED PROBLEM 6. Calculate the de Broglie wavelength for a ball of 200 g moving with a
velocity 3 × 1010 cm sec–1 and an electron moving with the same velocity. (Mass of electron = 9.109
× 10–28 g; h = 6.624 × 10–27 erg sec).
SOLUTION :
Formula used
h
λ=
mv
20 2 QUESTION BANK
Quantities given
(i) For the ball
m = 200 g v = 3 × 1010 cm sec–1 h = 6.624 × 10–27 erg sec
Substitution of values
6.624 × 10–27 erg sec
λ=
200 g × 3 × 1010 cm sec–1
= 1.04 × 10–39 cm
(ii) For the electron
m = 9.109 × 10–28 g v = 3 × 1010 cm sec–1 h = 6.624 × 10–27 erg sec
Substitution of values
6.624 × 10–27 erg sec
λ =
9.109 × 10–28 g × 3 × 1010 cm sec–1
= 0.24239 × 10–9 cm
= 2.4239 × 10–10 cm
SOLVED PROBLEM 7. If an electron is accelerated by 100 volts, calculate the de Broglie
wavelength associated with it. Also calculate the velocity acquired by the electron. (Mass of
electron = 9.1 × 10–28 g; h = 6.62 × 10–27 erg sec).
SOLUTION :
(i) To calculate wavelength
Formula used
√
150
λ= Å
V volts
Quantities given
V = 100 volts
Substitution of values
√
150
λ= Å
100
= √ 1.5 Å
= 1.2247 Å
= 1.2247 × 10–8 cm
(ii) To calculate the velocity
Formula used
h
λ=
mv
h
or v=
mλ
Quantities given
m = 9.1 × 10–28 g h = 6.62 × 10–27 erg sec λ = 1.2247 × 10–8 cm
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 21
Substitution of values
6.62 × 10–27 erg sec
v =
(9.1 × 10–28 g) × (1.2247 × 10–8 cm)
= 0.594 × 109 cm sec–1
= 5.94 × 108 cm sec–1
SOLVED PROBLEM 8. Calculate the wavelength of a particle of mass 1.5 g moving with a
velocity of 250 m sec–1.
SOLUTION :
Formula used h
λ = mv
Quantities given
h = 6.625 × 10–27 erg sec m = 1.5 g v = 250 m sec–1 = 25000 cm sec–1
Substitution of values
6.625 × 10–27 erg sec
λ =
1.5 g × 25000 cm sec–1
= 0.1766 × 10–27–3 cm
= 0.1766 × 10–30 cm
= 1.766 × 10–31 cm
SOLVED PROBLEM 9. Calculate the wavelength of an electron of mass 9.1 × 10–28 g moving with
a velocity of 4.2 × 106 cm sec–1 (h = 6.62 × 10–27 erg sec).
SOLUTION :
Formula used
h
λ =
mv
Quantities given
h = 6.62 × 10–27 erg sec m = 9.1 × 10–28 g v = 4.2 × 106 cm sec–1
Substitution of values
6.62 × 10–27 erg sec
λ =
(9.1 × 10–28g) × (4.2 × 106 cm sec–1)
= 0.1732 × 10–27+28–6 cm
= 0.1732 × 10–5 cm
= 1.732 × 10–6 cm
= 1.732 × 10–8 m
SOLVED PROBLEM 10. Calculate the momentum of a particle which has de Broglie's wavelength
of 0.10 nm. (h = 6.6 × 10–34 kg m2 sec–1).
SOLUTION :
Formula used
h
λ =
mv
h
or momentum, mv =
λ
22 2 QUESTION BANK
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 λ = 0.1 × 109 m
Substitution of values
6.6 × 10–34 kg m2 sec–1
Momentum =
0.1 × 10–9 m
= 6.6 × 10–24 kg m sec–1
SOLVED PROBLEM 11. An electron is moving with a kinetic energy of 4.55 × 10–25 J. Calculate de
Broglie wavelength for it. (mass of the electron = 9.1 × 10–31 kg; h = 6.6 × 10–34 kg m2 sec–1).
SOLUTION :
(i) To calculate the velocity of the electron
Formula used
K.E.= ½ m v2
or v2 = 2 × K.E.
m
Quantities given
K.E. = 4.55 × 10 –25 J m = 9.1 × 10–31 kg
Substitution of values
2 × 4.55 × 10–25 kg m2 sec–2
v2 =
9.1 × 10–31 kg
= 1 × 106 m2 sec–2
or v = √ 1 × 106 m2 sec–2
= 1 × 103 m sec–1
(ii) To calculate the wavelength of the electron
Formula used
h
λ =
mv
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 m = 9.1 × 10–31 kg v = 1 × 103 m sec–1
Substitution of values
6.6 × 10–34 kg m2 sec–1
λ =
9.1 × 10–31 kg × 1 × 103 m sec–1
= 0.7253 × 10–34+31–3 m
= 0.7253 × 10–6 m
= 7.253 × 10–7 m
= 725.3 nm
SOLVED PROBLEM 12. Calculate the de Broglie's wavelength of an electron travelling with a
speed of 20% of light.
SOLUTION :
Formula used
h
λ =
mv
Quantities given
h = 6.625 × 10–34 kg m2 sec–1 m = 9.1 × 10–31 kg
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 23
20 × 3 × 108
v = 20% of c = m sec–1 = 0.6 × 108 m sec–1
100
Substitution of values
6.625 × 10–34 kg m2 sec–1
λ =
(9.1 × 10–31 kg) × (0.6 × 108 m sec–1)
= 1.2133 × 10–34+31–8 m
= 1.2133 × 10–11 m
= 12.133 × 10–12 m
∴
= 12.133 pm [ 1 pm = 10–12 m]
SOLVED PROBLEM 13. Compare the relative de Broglie wavelength of an atom of hydrogen and
an atom of oxygen both moving with the same velocity.
SOLUTION :
Formula used
h
λ =
mv
h
For hydrogen atom λ1 = .... (i)
m1 v
h
For oxygen atom λ2 = [∴ v is the same] ... (ii)
m2 v
Dividing (i) by (ii), we have
λ1 h m v
= × 2
λ2 m1 v h
m2
= m
1
λ1 16 m1
or = m [ ∴ at. mass of O = 16 × at. mass of H]
λ2 1
or λ1 : λ2 = 16 : 1
SOLVED PROBLEM 14. A good baseball pitcher can throw a 130 g baseball at a speed of 92 km
–1
hr . What is the de Broglie wavelength in meters produced by the moving baseball ?
SOLUTION :
Formula used
h
λ =
mv
Quantities given
h = 6.625 × 10–34 kg m2 sec–1 m = 130 g = 130 × 10–3 kg
5 ∴ 5
v = 92 km hr–1 = 92 × m sec–1 [ 1 km hr–1 = m sec–1]
18 18
Substitution of values
6.625 × 10–34 kg m2 sec–1
λ =
(130 × 10–3 kg) × (25.55 m sec–1)
= 0.001994 × 10–34+3 m
= 0.001994 × 10–31 m
= 1.994 × 10–34 m
24 2 QUESTION BANK
SOLVED PROBLEM 15. Calculate the product of uncertainty of displacement and velocity of a
moving electron having a mass of 9.1 × 10–31 kg (h = 6.6 × 10–34 kg m2 sec–1).
SOLUTION :
Formula used
h
Δx × m Δv =
4π
h
or Δx × Δv =
4πm
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 m = 9.1 × 10–31 kg
Substitution of values
6.6 × 10–34 kg m2 sec–1
Δx × Δv =
4 × 9.1 × 10–31 kg × 3.14
= 0.05774 × 10–34+31 m2 sec–1
= 5.774 × 10–5 m2 sec–1
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 m = 9.1 × 10–31 kg Δv = 5.7 × 105 m sec–1
Substitution of values
= 0.0103 × 10–34+31–5 m
= 0.0103 × 10–8 m
= 1.03 × 10–10 m
SOLVED PROBLEM 17. What are the possible l and m quantum numbers for an electron n = 3
quantum level of an atom ?
SOLUTION :
Here n = 3
∴
∴ l = 0,1 and 2 [ l = 0,1 ...... n–1]
and when l = 0 m=0
l = 1 m = – 1, 0, + 1
l = 2 m = –2, –1, 0, + 1, +2
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 25
SOLVED PROBLEM 18. The electronic configuration of an atom in the ground state is 1s2 2s2 2p6.
Give the four quantum numbers of the electron in last orbital.
SOLUTION :
The given electron configuration is 1s2 2s2 2p6
or 1s2 2s2 2px2 2py2 2pz2
∴ The last electron is in 2pz orbital
For 2pz orbital n = 2, l = 1, m=1 and
s = + ½ or – ½
SOLVED PROBLEM 19. Arrange the electrons in the following list in order of increasing energy.
n l m s
(a) 3 2 –1 +½
(b) 4 0 0 –½
(c) 4 1 1 +½
(d) 2 1 –1 –½
SOLUTION :
(n + l) values in respect of above electrons are
(a) 3+2=5
(b) 4+0=4
(c) 4+1=5
(d) 2+1=3
∴ Increasing order of energy is (d) < (b) < (a) < (c)
SOLVED PROBLEM 20. Deduce the possible set of four quantum number when n = 3
SOLUTION :
For n = 3 l = 0,1 and 2
When l=0 m=0 s = +½ or –½
l=1 m = –1 s = +½ or –½
m=0 s = +½ or –½
m = +1 s = +½ or –½
l=2 m = –2 s = +½ or –½
m = –1 s = +½ or –½
m=0 s = +½ or –½
m = +1 s = +½ or –½
m = +2 s = +½ or –½
26 2 QUESTION BANK
SOLVED PROBLEM 21. Arrange the electrons represented by the following sets of quantum
numbers in the decreasing order of energy.
(a) n= 4 l = 0 m = 0 s = +½
(b) n= 3 l = 1 m=0 s = –½
(c) n= 3 l = 2 m=0 s = +½
(d) n= 3 l = 0 m=0 s = –½
SOLUTION :
The (n + l) values of above electrons are as follows :
(a) n=4 l=0 m=0 s = +½ n+l=4 (4s)
(b) n=3 l=1 m=0 s = –½ n+l =4 (3p)
(c) n=3 l=2 m=0 s = +½ n+l=5 (3d)
(d) n=3 l=0 m=0 s =–½ n+1=3 (3s)
Thus the decreasing order of energy is 3d > 4s > 3p > 3s
SOLVED PROBLEM 22. Calculate the wavelength of a 200 kg drum rolling at a speed of 30 km per
hour.
SOLUTION :
Formula used
h
λ=
mv
Quantities given
30 × 103
h = 6.6 × 10–34 kg m2 sec–1 m = 200 kg v = 30 km hr–1 = m sec–1
60 × 60
= 8.33 m sec–1
Substitution of values
6.6 × 10–34 kg m2 sec–1
λ =
200 kg × 8.33 m sec–1
= 3.96 × 10–37 m
SOLVED PROBLEM 23. Calculate the momentum of a particle which has a de Broglie wavelength
of 110Å.
SOLUTION :
Formula used
h
λ =
mv
h
or mv =
λ
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 λ = 110 Å = 110 × 10–10 m
Substitution of values
6.6 × 10–34 kg m2 sec–1
mv =
110 × 10–10 m
= 6 × 10–26 kg m sec–1
STRUCTURE OF THE ATOM – WAVE MECHANICS APPROACH 27
SOLVED PROBLEM 24. By applying de Broglie's equation, calculate wavelength associated
with the motion of the earth, a ball and an electron. Following data is given :
Mass of earth = 6.0 × 1024 kg.
Mass of ball = 0.1 kg
Mass of electron = 9.1 × 10–31 kg
Velocity of orbital motion of the earth = 3 × 104 m sec–1
Velocity of the ball = 100 m sec–1
Velocity of the electron = 1.0 × 106 m sec–1
h = 6.6 × 10–34 kg m2 sec–1
In case of which of these three objects, will the wavelength be measurable ?
SOLUTION :
Formula used
h
λ =
mv
(i) For earth
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 m = 6.0 × 1024 kg v = 3 × 104 m sec–1
Substitution of values
6.6 × 10–34 kg m2 sec–1
λ =
6.0 × 1024 kg × 3 × 104 m sec–1
= 3.66 × 10–63 m
(ii) For ball
Quantities given
h = 6.6 × 10–34 kg m2 sec–1 m = 0.1 kg v = 100 m sec–1
Substitution of values
ISOTOPES
The atoms of an element which have the same atomic number but different atomic masses or
mass numbers are called Isotopes. They have the same number of protons (or electrons) and different
number of neutrons. They have same position in the periodic table. Isotopes have similar chemical
properties as they have the same electronic configuration. However, they differ in respect of physical
properties which depend on their atomic masses. Examples of isotopes are
1
H1 1
H2 1
H3
Hydrogen Deuterium Tritium
12 13
6
C 6
C 6
C14
8
O 16 8
O 17
8
O 18
92
U 234 92
U 235 92
U 238
10
Ne 20 90.92
10
Ne 21 0.26
10
Ne 22 8.82
Thus we have
20 × 0.9092 = 18.18
21 × 0.0026 = 0.055
22 × 0.0882 = 1.94
20.175
∴ The atomic mass of Neon is 20.175
29
30 3 QUESTION BANK
RATE OF DIFFUSION
The rate of diffusion is inversely proportional to the square root of its atomic mass (Graham's Law)
√
i.e. 1
Rate of Diffusion ∝ Molecular mass
Thus when a mixture of two isotopes is allowed to diffuse through a porous partition, the lighter
isotope passes through more rapidly than the heavier one.
DETERMINING THE NUMBER OF ELECTRONS, PROTONS AND NEUTRONS
The isotopes of an element are characterised by different number of neutrons in the nucleus. The
number of neutrons in the nucleus is equal to the difference between mass number (A) and the atomic
number (Z) i.e.
Number of neutrons = Mass number – Atomic number
= A–Z
WHAT ARE ISOBARS ?
The atoms which have the same mass number but different atomic numbers are called Isobars. They
have different number of protons (or electrons) and neutrons but the sum of protons and neutrons is
the same. Examples are :
18
Ar 40 19
K40 20
Ca40
No. of Protons 18 19 20
No. of Neutrons 22 21 20
Sum of Protons and Neutrons 40 40 40
6
C 14 7
N15 8
O 16
No. of Protons 6 7 8
No. of Neutrons 8 8 8
Sum of Protons and Neutrons 14 15 16
Isotones have different physical and chemical properties.
COMPARISON OF ISOTOPES, ISOBARS AND ISOTONES
The comparison of Isotopes, Isobars and lsotones is given in the Table 3.1.
TABLE 3.1. COMPARISON OF ISOTOPES, ISOBARS AND ISOTONES
Name Mass number Atomic number No. of neutrons Examples
(A) (Z) (A– Z)
SOLVED PROBLEM 1. Calculate the relative atomic mass of an element which consists of the
following isotopes with the indicated relative abundance.
Isotope Isotopic mass Natural abundance
1 28 92.0
2 29 5.0
3 30 3.0
SOLUTION :
The atomic mass of an ordinary isotopic mixture is the average of the determined atomic masses
of individual isotopes. Thus
28 × 0.92 = 25.76
29 × 0.05 = 1.45
30 × 0.03 = 0.90
Total 28.11
Thus the atomic mass is 28.11 amu
SOLVED PROBLEM 2. Chromium, Cr, has following isotopic masses and fractional abundances :
Mass Number Mass (amu) Fractional abundance
50 49.9461 0.0435
52 51.9405 0.8379
53 52.9407 0.0950
54 53.9389 0.0236
SOLUTION :
Multiplying each isotope by its fractional abundance, we have
49.9461 amu × 0.0435 = 2.17 amu
51.9405 amu × 0.8379 = 43.52 amu
52.9407 amu × 0.0950 = 5.03 amu
53.9389 amu × 0.0236 = 1.27 amu
Total 51.99 amu
Thus the atomic mass of chromium is 51.99 amu
SOLVED PROBLEM 3. Calculate the atomic mass of boron, B, from the following data :
Isotope Atomic mass (amu) Fractional abundance
5
B 10 10.013 0.1978
11
5
B 11.009 0.8022
SOLUTION :
Multiplying each isotope by its fractional abundance, we have
10.013 amu × 0.1978 = 1.9806 amu
11.009 amu × 0.8022 = 8.8314 amu
Total 10.8120 amu
Thus the atomic mass of Boron is 10.8120 amu
32 3 QUESTION BANK
SOLVED PROBLEM 3. Naturally occuring boron consists of two isotopes whose atomic masses
are 10.01 and 11.01. The atomic mass of naturally occuring boron is 10.81. Calculate the percentage of
each isotope in natural boron.
SOLUTION :
Let the percentage of isotope with atomic mass 10.01 be A.
∴ the percentage of isotope with atomic mass 11.01 = 100 – A
A × 10.01 + (100 – A) × 11.01
Now the atomic mass =
100
10.01 A + 1101 – 11.01A
10.81 =
100
or 11.01 A – 10.01 A = 1101 – 1081
or A = 20
Hence the percentage of isotope with atomic mass 10.01 = 20
and the percentage of isotope with atomic mass 11.01 = 80
1. Magnesium has naturally occuring isotopes with the following masses and abundances.
Isotope Atomic mass (amu) Fractional abundance
24
MG 23.985 0.7870
12
25
MG 24.986 0.1013
12
26
MG 25.983 0.1117
12
Calculate the atomic mass of magnesium.
Answer. 24.31 amu
2. Silver has two naturally occuring isotopes with atomic masses 106.91 and 108.90 amu. The atomic mass of
silver is 107.87 amu. Calculate the fractional abundances for these two isotopes.
Answer. 0.518 ; 0.482
3. Calculate the fractional abundances for the two naturally occuring isotopes of copper. The masses of the
isotopes are 62.9298 and 64.9278 amu. The atomic mass of copper is 63.546 amu.
Answer. 0.692 ; 0.308]