At ST Theory
At ST Theory
At ST Theory
ATOMIC STRUCTURES XI
Structure of Atom
Fundamental Particles:
1
M. P. I. ATOMIC STRUCTURES XI
separated by as much as two feet and the pressure in the discharge tube is
decreased progressively by removing the gas, a series of spectacular events
occur. An electric current begins to flow and at the same time beautiful light
through the gas between the electrodes are seen. If the pressure is further
reduced to 1/1,000,000 of an atmosphere, the light disappears completely and
there is only a greenish glow emanating from the glass in the region of the
anode (positive electrode). If the gas pressure is reduced still further, the
current ceases to flew. By a series of ingenious experiments, conducted mainly
by the British physicist J.J. Thomson, it was shown that originating near the
cathode (negative electrode) was a swiftly moving stream of charged particles
which moved across the void between the two electrodes. These charged
particles were first called cathode rays because of their origin at the cathode;
later they were given the name electrons by Johnstone stoney.
O e
O
O2 e
O2
O2
O2 e
(i) Cathode rays travel in a straight line : Cathode rays cast shadow of the
solid (mica cross) placed in their path as shown in Fig. 2.2. Furthermore, as
2
M. P. I. ATOMIC STRUCTURES XI
the shadow falls on the walls opposite to the cathode, it confirms that cathode
rays travel from cathode to anode in straight line.
(ii) Cathode rays are made up of material particles : When a light paddle
wheel of mica mounted on an axle is placed in the path of the cathode rays as
shown in the Fig.. The wheel begins to rotate on being hit by the electrons. This
indicates that the cathode rays are made up of material particles.
(iii) Cathode rays carry negative charge : When an electric field is applied to
a stream of cathode rays. they are deflected towards the positive plate of the
electric field as shown in Fig. This indicates that cathode rays carry negative
charges.
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M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
Left hand rule for electron deviation of electron from velocity vector to
magnetic field & Right hand rule for protons deviation of protons from velocity
vector to magnetic field.
(v) Cathode rays produce heating effect : When the cathode rays are allowed
to strike a thin platinum foil, it becomes red hot. This shows that cathode rays
produce heating effect.
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M. P. I. ATOMIC STRUCTURES XI
(viii) Cathode rays ionise the gas through which they pass : Cathode rays, on
collision with the atoms of gases, can eject electrons from them, and thus
ionization of the gas occurs.
(x) Cathode rays penetrate through the thin foils of aluminium metal These
rays penetrate through the thin Al foil when placed in the path of cathode rays.
(xi) The charge to mass ratio (elm) for the negatively charged particles in the
cathode is independent of the nature of the gas taken in the discharge tube or
the nature of the cathode.
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M. P. I. ATOMIC STRUCTURES XI
The value of e/m was found to be 1. 76 108 coulombs/g (1. 76 1011
coulombs/Kg). Two important conclusions can be drawn from this observation.
The first accurate determination of the charge of an electron (e) was made by
WA. Millikan (1909) by his famous oil drop experiment. The apparatus used by
him is shown in Fig. Small oil droplets are produced by an atorniser. The oil
drops enter the apparatus
through a small hole and
are allowed to fall under
gravitational force between
two charged metal plates.
The movement of a single
droplet is observed by a microscope. The space between two metal plates was
irradiated with X-rays. The X-rays ionised electrons from some of the air
molecules which in turn were caught by air droplets. As a result the oil droplet
becomes negatively charged by applying the electrical field on the droplet under
study, which balances the downward gravitational force, the droplet becomes
stationary. From the magnitude of the charge applied on the plate and the
mass of the droplet. the charge on the droplet was determined, which was
found to he 16 1019 coulombs.
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M. P. I. ATOMIC STRUCTURES XI
(iii) Determination of mass of electron: By knowing the value of elm ratio (by
J.J. Thomson’s experiment) and charge on the electron (by Millikan’s oil drop
method), it is possible to calculate the exact mass of a electron.
1
The mass of electron (91 10-28 g) is approximately th
1837
the mass of a hydrogen atom as shown below. However , the mass of electron is
so small that for all practical purposes , its value is considered negligible.
1 008
Mass of one atom of hydrogen = 1 67 1024 g.
6 02 10 23
7
M. P. I. ATOMIC STRUCTURES XI
1
or, Mass of an electron = Mass of one atom of H.
1837
9 65 104 coulomb
Avogadro’s number (NA) =
1 602 1019 coulomb
(iv) All forms of matter give out electrons when they are exposed to X-rays.
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M. P. I. ATOMIC STRUCTURES XI
He
Electrical
Energy
He e
Helium Helium Electron
atom ion
The same process would occur with the neon gas in the discharged tube,
but the canal rays will now be composed of positively charged neon atoms :
9
M. P. I. ATOMIC STRUCTURES XI
Ne
Electrical
Energy
Ne e
Neon Neon Electron
atom ion
Both helium and neon are monoatoinic molecules i.e., they are known to
consist of one atom per )lecule. In case of gas molecules consisting of two or
more atoms, such as nitrogen (N2), several reactions take place simultaneously.
decomposition of nitrogen molecules. Neutral nitro are also produced but these
are not associated with the either electrode.
Rutherford pointed out that the lightest particle bearing unit positive
charge was produced from the hydrogen gas. Therefore, each particle is a
hydrogen atom devoid of an electron, thus bearing a unit positive charge. This
lightest positive ray particle was named as proton. Later on it was found that
the mass of positive particle produced from all gases is the simple multiple of
the mass of the proton. Thus, proton is a fundamental constituent of atoms
of all elements bearing unit positive charge and having mass almost equal
to that of a hydrogen atom.
(iii) Anode rays are deflected by electric field towards negatively charged plate.
This shows that anode rays consist of positively charged particles.
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M. P. I. ATOMIC STRUCTURES XI
(v) The e/in ratio of the particles in the anode rays depends upon the nature of
the gas taken in the discharge tube.
(vi) (e/m)proton = 9.58 x 104 C/g; e = 1.602 x 10-19 C & mp = 1.6725 x 10-24 g.
Discovery of Neutron:
The lack of charge on the neutron is responsible for its great penetrating
power.
The lack of charge on the neutron is responsible for its great penetrating
power .
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M. P. I. ATOMIC STRUCTURES XI
the nuclei and electrons in the matter they are traversing. The interaction of
beryllium and alpha particles can be written as :
It is unstable particle & its half life = 20 min : 10 n 11 p 01e 00 e Antineutrino
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M. P. I. ATOMIC STRUCTURES XI
1. Positron: C.D. anderson-1932: It bears a unit positive charge & its mass
= mass of electron. It merges with an electron & emits electromagnetic
0
radiation. It is denoted by 1 e.
electroneutral particles.
4. Antiproton p : Serge 1956: It bears a unit negative charge & its masss
1
1
= mass of proton.
Note:
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M. P. I. ATOMIC STRUCTURES XI
It has been assumed that the nucleus remains stationary except for
rotating on its own axis. This would be true if the mass of the nucleus were
infinite, but the ratio of mass of an electrom to the mass of the hydrogen
nucleus is 1/1837.
The nucleus actually oscillates slight about the centre of gravity, and to
aloow for this the mass of the electron m is replaced by the reduced mass.
1 1 1
m1 m2
The reduced mass is always less than or equal to the mass of each body.
1 1 1 mm
m1 , m2 , and has the reciprocal additive property: 1 2
m1 m2 m1 m2
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M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
Observation:
Inferences:
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M. P. I. ATOMIC STRUCTURES XI
Moseley studies on the characteristic X-ray spectra for various target elements
using the X-ray diffraction technique.
When a target material (anticathode) was placed in the path of cathode rays. X-
rays Wavelengthbetween 0.1 20 A0 were produced.
Observation:
It was suggested by Moseley that the fast-moving cathode rays were able
to remove electrons from the inner-orbits (i.e. K, L, M etc) of an atom of anti
cathode due to collision. This creates vacancy in the innershells. Under the
influence of nuclear charges electrons from higher shells fall in those shells.
He found that the K freuquency line in the X-ray spectra from a particular
Moseley law:
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M. P. I. ATOMIC STRUCTURES XI
c
v Z, v v a Z b,
Atomic models:
iii. The positively charged matter is uniformly distributed in the atom &
negatively charged electrons are embedded in it.
Limitation of Thomson’s
Thomson’s atomic model:
Thomson’s atomic model failed to explain how the positive charge holds
on the electrons inside the atom. It also failed to explain an atom’s stability.
The theory did not mention anything about the nucleus of an atom.
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M. P. I. ATOMIC STRUCTURES XI
2. Some of the α-particles were deflected by the gold sheet by very small
angles, and hence the positive charge in an atom is not uniformly
distributed. The positive charge in an atom is concentrated in a very small
volume.
3. Very few of the α-particles were deflected back, that is only a few α-
particles had nearly 1800 angle of deflection. So the volume occupied by the
positively charged particles in an atom is very small as compared to the
total volume of an atom.
1. The positively charged particles and most of the mass of an atom was
concentrated in an extremely small volume. He called this region of the atom as
a nucleus.
2. Rutherford model proposed that the negatively charged electrons
surround the nucleus of an atom. He also claimed that the electrons
surrounding the nucleus revolve around it with very high speed in circular
paths. He named these circular paths as orbits.
3. Electrons being negatively charged and nucleus being a densely
concentrated mass of positively charged particles are held together by a strong
electrostatic force of attraction.
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M. P. I. ATOMIC STRUCTURES XI
energy from the motion of the electron which would come at the cost of
shrinking of orbits. Ultimately the electrons would collapse in the nucleus.
Calculations have shown that as per the Rutherford model, an electron would
collapse in the nucleus in less than 10-8 seconds. So Rutherford model
was not in accordance with Maxwell’s theory and could not explain the
stability of an atom.
One of the drawbacks of the Rutherford model was also that he did not
say anything about the arrangement of electrons in an atom which made
his theory incomplete.
Although the early atomic models were inaccurate and failed to explain
certain experimental results, they were the base for future developments in
the world of quantum mechanics.
Wave:
Electromagnetic radiations:
20
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
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M. P. I. ATOMIC STRUCTURES XI
Amplitude
Wavelength
Wavelength (λ) is the distance of one full cycle of the oscillation. Longer
wavelength waves such as radio waves carry low energy; this is why we can
listen to the radio without any harmful consequences. Shorter wavelength
waves such as x-rays carry higher energy that can be hazardous to our health.
Consequently lead aprons are worn to protect our bodies from harmful
radiation when we undergo x-rays. This wavelength frequently relationship is
characterized by:
c=λν (1)
Where
λ is wavelength, and
ν is frequency.
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M. P. I. ATOMIC STRUCTURES XI
Note: Wavelength tells you the type of light and Amplitude tells you about the
intensity of the light.
Frequency
E=hν (2)
Where
E is energy,
νν is frequency.
Period
Period (T) is the amount of time a wave takes to travel one wavelength; it
is measured in seconds (s).
Velocity
velocity=λν (3)
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M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
Electromagnetic spectrum
24
M. P. I. ATOMIC STRUCTURES XI
Radiation Types
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M. P. I. ATOMIC STRUCTURES XI
X-ray: A dentist uses X-rays to image your teeth, and airport security
uses them to see through your bag. Hot gases in the Universe also emit X-rays.
Gamma ray: Doctors use gamma-ray imaging to see inside your body.
The biggest gamma-ray generator of all is the Universe.
26
M. P. I. ATOMIC STRUCTURES XI
2 2 2 8 2 m
2 E V 0
dx 2 dy 2 dz 2 h
E ;
H Total energy operator called Hemilton operator
H
Ze 2
The potential energy at a distance r is given by V
4 0 r
2 2 2 8 2 m Ze 2
E 0
dx 2 dy 2 dz 2 h2 4 0 r
8 2 m Ze 2
2 E 0
h2 4 0 r
x r sin cos
y r sin sin
z r cos
r 2 x2 y2 z 2
27
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
The Max Born interpretation of Ψ is based on an analogy with the wave theory
of light in which the square of the amplitude of an electromagnetic wave is
interpreted as the intensity and therefore, in quantum terms, as the number of
photons present. The Born interpretation is that the square of the wave
function. i.e. Ψ2 is proportional to the finding the particle at each point in
space.
Ψ = a + ib then Ψ* = a – ib and
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M. P. I. ATOMIC STRUCTURES XI
* dx dy dz 1
*d 1 Where d dxdydz
29
M. P. I. ATOMIC STRUCTURES XI
r , , r . .
or
r , , R r . .
r R r n ,l
30
M. P. I. ATOMIC STRUCTURES XI
l ,m
m
The wave function can then be separated into three separate equations
each involving one variable r, θ and ϕ respectively.
Quantum numbers:
The wave equation provides more than one solution of Ψ, i.e. more than
one function satisfies this equation. Each wave function constitutes what is
known as an orbital in the atom. The function, besides depending upon the
corresponding independent coordinates, also depend on the three integral
numbers designated as n, l and m respectively. These numbers which
automatically emerge as we solve the Schrodinger equation, are known as
quantum numbers, since they represent the quantization of definite physical
31
M. P. I. ATOMIC STRUCTURES XI
properties about the electron in the atom. Principal, azimuthal and spin
quantum numbers are the solutions of Schrodinger wave equation.
2 2 mk 2 Z 2e4 n2 h2
En rn
n2 h2 4 2 mkZe 2
In a multi electron atom, the energy of the shell, besides depending upon
the quantum number n, is also determined by the quantum number l.
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M. P. I. ATOMIC STRUCTURES XI
h
L l l 1 h 6.625 x1034 J s
2
l = 0, 1, 2, ……., (n-1)
The maximum value of l is thus (n-1). With each value of l, a letter has
become associated, each corresponding to a different sublevel, or set of atomic
orbitals:
l= 0, 1, 2, 3, …….., (n-1)
s, p, d, f………
For a given value of n, the total allowed values of l are equal to n; these
represent various subshells within the principal quantum shell. For a one
electron system (such as H, He+, Li2+ etc), the various subshells within a
principal shell are degenerate, i.e. all have the same energy. For multi-electron
system, the energies of varius subshells within a principal shell increase with
increase in the value of l.
ml l cos ; 0 0
1800 ; i.e. m 2l 1
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M. P. I. ATOMIC STRUCTURES XI
An electron spin around its own axis, and thus spinning produces
angular momentum whose value is given by the expression:
h
s s s 1 Where s = Spin quantum number & has a value of ½.
2
h
Lz s Where “s” is either + ½ (Clockwise spin) or – ½
2
(Anticlockwise spin). The spin of the electron is genrally represented by an
upward arrow ↑ (+ ½ ) or a downward arrow ↓ (- ½ ).
34
M. P. I. ATOMIC STRUCTURES XI
35
M. P. I. ATOMIC STRUCTURES XI
The mathematical forms of the wave function that are solutions of the
wave equation for hydrogen like species are given as:
36
M. P. I. ATOMIC STRUCTURES XI
1. All the radial wave functions decay exponentlly with increase in r ; the
decay is slower for n = 2 and 3 than for n =1. Thus the likelihood of the
electron being further away from the nucleus increases with increase in n.
2. For n > 1, The wave function is zero in certain regions which are known
as nodes. As a general rule there are (n - 1) nodes in an s-atomic wave
function.
3. Node: The wave function is zero in certain region or where the probability
of finding of an electron is zero.
4. Radial nodes: Spherical region (surface) where the value of radial wave
function is zero, i.e. R r r 0 . Total numbers of radial nodes : n l 1
37
M. P. I. ATOMIC STRUCTURES XI
Radial nodes: n l 1
Anular nodes: l
3. d-orbitals: Each d-orbitals have two such plane where the value of
, 0 , Therefore number of nodal plane for d-orbitals is equal to two.
38
M. P. I. ATOMIC STRUCTURES XI
4. all f-orbitals have three angular nodes. These are combinations of nodal
planes and cones, depending on the particular f-orbitals.
39
M. P. I. ATOMIC STRUCTURES XI
40
M. P. I. ATOMIC STRUCTURES XI
First few radial wave functions for hydrogen (Z=1), R(r), n,l
1. S-orbitlas: Consider the radial wave functions for 1s, 2s and 3s orbitals:
32
z
1s wave function R1,0 2 e zr a0
a0
32
1 z zr zr 2 a0
2s wave function R 2,0 2 e
2 2 a0 a0
41
M. P. I. ATOMIC STRUCTURES XI
1 z
32
18 zr zr zr 3a0
2
Since the exponential factor for 2s-function has the term zr 2a0 as
in amplitude more slowly than the 1s-function. This is why 2s-electron tends to
stay away from the nucleus and has higher energy than that of 1s-electron.
zr
Besides this factor 2 introduces a new feature in the function for
a0
For large value of r, zr a0 2 , and the wave function is negative; and for
zr
r 2a0 z , zr a0 2 and the factor 2 is zero, the wave function R r 0 .
a0
that the wave function decreases even more slowly with increasing r. thus, the
3s-orbital is still further away from the nucleus.
32
1 Z Zr Zr 2 a0
2p-wave function 2,1 e
2 6 a0 a0
42
M. P. I. ATOMIC STRUCTURES XI
32
4 Z Zr Zr Zr 3a0
3p-wave function 3,1 6 e
81 6 a0 a0 a0
Inspection of the radial wave functions for the 2p-orbitals reveals that no
nodes exist at finite values of r. The function R(r) is zero at r = 0 as compared to
Zr
the 2s-wave function which is zero at r . Thus for 2p-wave functions a
a0
Note that R2r has maximum value at the nucleus and that nodes
appear for n 1 . Another important point to note that R2r is never negative; a
43
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI
is spherically symmetric.
symmetric
significant difference. Analogous plots of R, and R2 can be drawn for the 2p, 3p
and 3d orbital electrons.
4 4
dV r dr r 3
3
r
r+dr
3 3 dr
4 4 r
dV r 3 3r 2 dr 3rdr 2 dr 3 r 3
3 3
44
M. P. I. ATOMIC STRUCTURES XI
4
dV r 3 3r 2dr 3rdr 2 dr 3 r 3
3
4
dV 3r 2 dr 3rdr 2 dr 3
3
4
dV 3r 2 dr
3
dV 4 r 2 dr
45
M. P. I. ATOMIC STRUCTURES XI
d
If r rm. p.
dr
4 r 2 R 2 0
the electron from the nucleus is found weighting each possible distance with
the probability that the electron will be found at that distance.
1
Penitration effect : ns np nd nf
ravg
Energy of orbitals:
46
M. P. I. ATOMIC STRUCTURES XI
47
M. P. I. ATOMIC STRUCTURES XI
Thus one lobe of the orbital has a different sign from that of the other.
This is also true for Px and Py orbitals.
48
M. P. I. ATOMIC STRUCTURES XI
The plots of the angular wave function against and give three
dimensional surfaces for each l and m value and are called orbitals. These plots
give the definite geometry of orbitals.
3. d-orbitals:
49
M. P. I. ATOMIC STRUCTURES XI
Note:
50
M. P. I. ATOMIC STRUCTURES XI
Electronic configuration:
1. Aufbau Principle:
2 0 2 , hence energy of 1s 2 s
d. If two orbitals have same value of n l , the orbital having lower n value
1s 2 s 2 p 3s 3 p 3d 4 s 4 p 4d 4 f
5 s 5 p 5d 5 f 6 s 6 p 6 d 6 f 7 s 7 p
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M. P. I. ATOMIC STRUCTURES XI
a. No two electron in an atom can have the same value for all the four
quantum numbers.
b. Two electrons in a given orbital have same values of n, l & m , but differ in
their spin quantum number.
c. An orbital can not accommodate more than two electrons.
d. The capacity of S, P, d and f sub-shells are 2, 6, 10 and 14 electrons
respectively. i.e. 4l 2
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M. P. I. ATOMIC STRUCTURES XI
g. Electrons of same spin are present in sub-shell then they exchange their
positions release energy called exchange energy. The number of exchanges that
can take place is maximum when the sub-shell is either half-filled or
completely filled. Greater is the exchange energy, maximum will be the
stability.
h. Anomalous configuration is observed in the following cases:
Ru 44 : Kr 4d 7 5s1 , Rh 45 : Kr 4d 8 5s1
Pd 46 : Kr 4d 10 5s 0 , Ag 47 : Kr 4d 10 5s1
Gd * 64 : Xe 4 f 7 5d 1 6 s 2 , Tm* 69 : Xe 4 f 13 6 s 2
Pt * 78 : Rn 4 f 17 5d 9 6 s1 , Au 79 : Rn 4 f 13 5d 10 6 s1
53
M. P. I. ATOMIC STRUCTURES XI
54