Atomic Spectra
Atomic Spectra
Atomic Spectra
Balmer Series
In 1885 JJ Balmer identified the first such series in spectrum of hydrogen. This series is called Balmer series. It is in the
visible region of the electromagnetic spectrum. In 1896 J.R Rydberg expressed the Balmer results in the mathematical form as
1 . 4 4 - 4 1
A \ 2 2 n 'J
Where R H =1.0974 x107n?'1 and n = 3,4,5.........
R h is called Rydberg's constant. This formula is known as Empirical Formula. Later on,
many series have been discovered and they help in predicting the arrangement of the
electrons in different atoms. The Balmer series contain wavelengths in the visible Red Blue Blue Violet UV
region of the hydrogen spectrum. Green
The spectral lines of Hydrogen in the ultraviolet and infrared regions fall into several other series.
Lyman Series
The series which contains the wavelengths in the ultra violet region is called Lyman series. The empirical
formula for Lyman series is given by
1 ( 1 ■n
T = r h Z T -— \ Where n = 2,3,4......
k Vi n j
In infrared region following three spectral series have been found.
Paschen Series
The wavelengths of spectral lines in Paschen series is given by the formula
Where n = 4,5,6.
Brackett Series
The wavelengths of spectral lines in Brackett series is given by the formula
7 = ......
Pfund Series
The wavelengths of spectral lines in Pfund series is given by the formula.
1 ( 1 1
* = R hI 5 w J Where n = 6,7,8......
The existence of these regularities in the hydrogen spectrum shows that these regularities are also present in
the spectrum of other complex elements. This
proposes that atoms of different elements have definite regular structure.
Wavelength. X
Line spectrum of atomic
hydrogen only the Balmer
series lies in the visible
region of the
electromagnetic spectrum.
Helium was identified in the sun using spectroscopy before its was discovered on earth.
COLLEGE PHYSICS XII 381 ATOMIC SPECTRA
Postulate I:
Electrons are moving around the nucleus in circular orbits. As long as an electron remains in any of the
permitted orbit, no energy is radiated. These orbits are called discrete (quantized) stationary states of the atom.
Postulate II:
Only those orbits are allowed in which the angular momentum of an electron is an integral multiple of — i.e.
2n
where n = 1, 2, 3,... and n is called the principal quantum number, m and v are the mass and velocity of the orbiting
electron respectively and h is the Plank's constant.
Postulate III:
Whenever an electron jumps from a high energy state E n to a lower energy state E p , a photon of energy h f is
emitted, such that
hf = E n - E p
The orbital electrons have specific amount of energies where as free electrons may have any
I amount of energy.
ke2
Or (4)
m v:
In order to find vn we will use the'2nd postulate i.e.
h
mv" rn mn 2tt
_ nh
putting in equation (4)
0r V"” 2
ke
nh
m\
2nmr„
4 TT2km 2e 2r*
mn2h 2
n 2h 2
(4b)
4 n 2m e2k
COLLEGE PHYSICS XII 383 ATOMIC SPECTRA
AS h = 6.63x10'34J.S
m ■ 9.1x10"31K g
e = 1.6x10-19C
k = 9x10® Nm2C -2
Putting all these values In equation (5) we get
_____________ (g.63x1Q-34y ________
1 4xnr2 x 9.1 x 10_31x (i .6 x 10‘ 19/ x 9 x 109
r, - 0.053x1 O'9m
r, * 0.053 nm
so equation (5) can be written as
r„ * n 2 x 0.053 nm ------------------ (7)
uantized Energies
According to Bohr's second postulate, as long as an electron remains In any of the permissible orbit Its total energy
remains constant.
Since the total energy E n of electron In any orbit Is the sum of Its K.E and P.E so
£„ ■ K .E + P .E ---------------------- (8)
ke*
r. =
m vn
ke2
Or m v2
n=
kei
P.E. = - ( 10 )
So E =-— (d)
n n2
As h = 6.63 x 10_34J .S
m = 9.1x1 O'31K g
e = 1.6 x 10_19C
k = 9 x 1 0 9 Nm2C -2
Putting all these values in the equation (c), the value of f „ can be calculated
2tt2 x 9.1x 10~31 x(9x10s ]f x (l.6 x 10~,9)f
(6.63 x 10-34)2
Or £ 0 =2 .1 7 x1 0 18J
COLLEGE PHYSICS XII 385 ATOMIC SPECTRA
2.17 x 10-18 „
E 0 = -------------* T eV
1.6 x 10-19
E 0 = 13.6el/
Putting this value in equation (11)
En = - For n = 1,2,3...----------(12)
rr
The negative sign shows that much energy is required to remove the electron from the given orbit.
For n = 1 from equation (12)
13.6
= -13.6eV
(1f
This is called the normal or ground state energy of the H-atom. Similarly we can find the energies of the other orbits.
So the ionization energy of H- atom is 13.6 eV. And "the potential which causes the electron to move from the ground
state of an atom to infinite (ionized) is known as the ionization potential".
If we apply V volts to an electron of charge 'e' so that it escapes from its atom then
Ve = ionization energy = E „ - £.,
Ve = 0 -(-1 3 .6 )e V
Ve = 13.6eV
V = 13.6 Volts
Photon must have energy exactly equal to the energy difference between the two shells for excitation of an
atom but an electron with K.E. Greater that the required difference can excite the gas atoms.
CO LLEGE PHYSICS XII 386 ATOMIC SPECTRA
2rr2m k2e*
Where
h2
And
since f- ~ so
A E \ev)
he £0 (E o )
T n2 Ip2 J o n ■*
■0.28 n* 7
he ' 1 1 -0.38 n ■6
A E0 --- -T +- 7 - 0.54 n *5
L 0 P -0.85 n**
\
_1 E0 f'1 1
•1.51 n*3
A he
U 2 " 2J Patchin
Where p* 1,2,3,4... *
This equation shows that whenever an electronic jump (transition) takes place, result
Serial Limit
Is the emission of radiation. These emitted radiations of different wavelengths
constitute different spectral lines, which is the characteristic of the atom.
This energy level diagram Is made on scale by keeping lower energy (more negative)
at the bottom and higher energy at the top by using the equation
E .--^ e V For n ■ 1, 2, 3,4... 13.80
Lyman
n* 1
n*
The vertical lines between energy levels simply indicate the permissible electron jump
from one level to another.
■ROniJCriON nr X-RAYS I
An arrangement of producing X-rays is shown. It
consists of following important components.
Vacuum Tube:
A highly vacuumed tube is used to
envelope all the components inside it and is Low
called the X-rays tube. volUge
Cathode:'
Here the cathode Is heated by a filament
F, It emits electrons and they are accelerated
towards the anode T.
Anode:
The anode Is basically the target material which emits X-rays. Since during X-ray production, the anode is
heated to high temperatures so anode is made up of a metal of high melting point like cadmium, tungsten or
molybdenum. The usual method is to mount the target material on a hollow copper tube through which cold water Is
continuously circulated. Sometime air cooled target fitted with aluminum is also used.
High PD: A high potential difference (25 to 100 kV) Is maintained between cathode and anode.
If V is the potential difference between C and T, the kinetic energy with which the electron strike the target Is given by
K .E. ■ Ve ----------(1)
It Is possible that in a collision, the electrons in the innermost shell like K or L will be knocked out. Suppose that
one electron In the K shell is removed by producing a vacancy there. The electrons from the higher shell like L or M etc
Jump to fill this vacancy by emitting the energy in the form of electromagnetic radiations of very short wavelength (x-
rays). If the electron from L shell Jumps to K shell, then the K 0 X-rays photon is emitted with energy
hfk a ~ E L - E K ---------- ( 2 )
It is also possible that the electron from the M shell might also Jump to occupy the hole In the K-shell by emitting
a photon of energy
i -&K (3)
COLLEGE PHYSICS XII ATOMIC SPECTRA
HARACTERISTIC X-RAYS
Few of the fast moving electrons may strike the tightly bound electrons of the target atoms and their velocities are so
high that it may knock off the electron even from the inner most shell e.g. K shell, L shell etc. The electrons from the
higher shells may fill up vacancies so created by bombarding electrons.
Hence due to these electronic transitions the energy difference is radiated in the form of x-rays of very small but of
definite wavelengths (or frequencies). X-ray so produced have wavelengths depending
upon the target materials. The x-ray spectra in this case, consists of sharp lines which
are the characteristic of the target material and hence called the characteristic spectra
or line spectra. Let a high velocity electron knock off an electron from K-shell and
vacancy so created is being filled up by an electron of a nearer L-shell by emitting an x-
ray photon. This corresponds to K a line of K series. If the electronic jump occur from M-
shell, N-shell etc, then respectively K p,K r lines will be emitted.
Similarly if electrons jumps from higher shells to L-shell,
M-shell etc, then L-series [La,L p ,L Y—) M-series
(Af0,/lf/3)M(,...)will be emitted.
Due to their immense energy the x-rays can cause damage to living tissue. The absorbed x-rays break molecular
bonds and create highly reactive radicals (such as H and OH), which in turn can disturb the molecular structure of the
proteins and especially the genetic material. Young and rapidly growing cells are particularly affected. Due to this reason
x-rays can also be useful for selective destruction of cancer cells.
On the other hand a cell may be damaged due to x-rays bombardment, continue dividing and produces generation of
defective cells. Thus x-rays can cause a cancer. Excessive exposure to the x-rays can cause more serious damage to the body.
❖ X-rays are widely used in industry. They are used to detect defects in radio valves, tennis balls, rubber tyres and
presence of pearls in oysters.
❖ They are also used to test the uniformity of the insulating materials and quality of oil paintings.
❖ For engineering purposes they are used to check the cracks in the structure of metals.
❖ They are used to test the quality of welding, moulds and metal cuttings.
❖ They are also used to check the cracks in the boy of aeroplane and cars.
❖ For research purposes they are widely used to st-udy the structure of crystals, arrangements of atoms and molecules
in matter.
❖ X-rays are commonly used to detect the smuggling of precious metals, explosives and other contraband goods like
opium etc sealed in parcels and leather cases at the airports and custom posts.
In Atoms:
In atoms these limitations are much significant. To show this let us find that whether the electrons is present
inside the nucleus of the atom or not. To solve this we make use of equation (1) in a way to find the velocity of the
electron with in the nuclear dimensions i.e. 10~u m , Equation (1) can be written as
m AvAx m h
a h
Or mAx .............................. (2)
The constant values are given by
h = 6.63 x 10-34 J .s
m = 9.1.x 10~31/tg
. 6.63 x10~34
AV m------------rr------------ rr
9.1 x 1 0 '31x 5 x 10‘ 11
Av * 1 .4 6 x1 0 7ft)«-1
Note:
This speed of the electron Is less than the speed of light; therefore, It can exist In the atom but outside the nucleus.
20.5 LASER
The term LASER stands for Light Amplification By Stimulated Emission of Radiation. The laser Is a device which
produces very narrow beam of radiations having following properties.
❖ Intense
❖ Unidirectional
❖ Coherent
❖ Monochromatic
Laser of different power and application can be produced by using different materials.
CO LLEGE PHYSICS XII 391 ATOMIC SPECTRA
a) Normal Population
A normal population of atomic energy (Thermal Equilibrium)
states, with more atomic in the lower
energy state E1; than in the excited state E2. -----------— --------- e 3
----- --------------------Ej
-E,
A population inversion, in which the higher
b) Population Inversion
energy state has greater population than
the lower energy state. Ea---------
E 2----------- --------------
Ei ...................... ....
yA.-UrlaUdiJMsK
The key to laser is the presence of one or more excited
energy levels in many atoms whose lifetime may be
10~3 sec or more instead of usual 10'* sec. Such relatively
long lived states are called metastable states.
A medium which may be solid, liquid or gas is introduced
In a chamber. The chamber consists of two parallel
mirrors facing each other called optical cavity. One of the
mirrors is only partially silvered to allow the beam to
Fig 20.10
CO LLEG E PHYSICS XII 392 ATOMIC SPECTRA
Under normal conditions there are mostly few excited states in an atom, so special methods are used to increase the
number of excited states. This process is called the population inversion. A number of ways exist to produce a
population inversion. One of them is called Optical pumping. Here an external light source is used; some of whose
photons have the right frequency to raise the atoms to excited states that decay spontaneously into the desired
metastable state.
E 2 is the metastable state and transition from or to this state is difficult as compared to other excited states.
Hence instead of direct excitation to this state, the electrons are excited to higher level for spontaneous fall to
metastable state. t
In order to excite the atom to higher excited state (E3), let a photon of energy hf = E 3 - E , is incident on the atom so
that the electron moves from the first to the third energy state. Now the electron may decay directly to the ground state
but mostly it first decays from E 1to £ 2 (which is a metastable state). This eventually leads to the situation that the state
E 2 contains more atoms than state E , . This situation is called population inversion.
a) Normal Population
(Thermal Equillibrium) b) Population Inversion
A normal population of atomic energy states, with moraHA population inversion, in which the higher energy state
atomic in the lower energy state El, than in the excitedBhas greater population than the lower energy state,
state
Fig 20.11
Laser Action
Once the population inversion has been reached, the lasing action of
laser is simple to achieve. The atoms in the metastable state E 2 are bombarded
by photons of energy hf = E 2 - £ , , resulting the stimulated (induced) emission.
The photons so produced are monochromatic (same frequency) and coherent (in
phase). They are reflected back and forth between the mirrors to stimulate more
and more excited atoms to emit photons. As the process continues, the number
of photons multiplies to produce an intense mono-chromatic beam of radiation.
elium Neon Lase
It is most common type of laser used in physics laboratories. Its discharging tube is filled with 85% helium and 15% neon
gas. Here neon is the lasing or active medium. By chance, helium and neon have nearly identical metastable states,
respectively located 20.61 eV and 20.66 eV level..
The high voltage electric discharge excites the electrons in some of the helium atoms to 20.61 eV level.
Population Inversion:
Neon
In this laser population inversion in neon is achieved by direct collisions Helium
Metastable ■r — Metastable ■ 000^00
with same energy electrons of helium atoms. Thus excited helium atoms collide
'/WiotSn
with neon atoms, each transferring its own 20.61 eV of energy to an electron
along with 0.05 eV of K.E. from the moving atoms. As a result, the electrons in
neon atoms are raised to the 20.66 eV state. In this way a population inversion 20.61 eV 20 66 eV
16.70 eV
is sustained in the neon gas relative to an energy level of 18.70 eV.
Stimulated Emission: Ground
Ground
Spontaneous emission from neon atoms causes the laser action and State State
stimulated emission causes electrons in the neon to drop from 20.66 eV to the
Fig 20.12
18.70eV level and red laser light of wavelength 632.8 nm corresponds to 1.96 eV energy.
COLLEGE PHYSICS XII 393 ATOMIC SPECTRA
❖ Laser beams are used as surgical tool for welding detached retinas.
❖ This narrow intense beam of laser can be used to destroy tissue in a localized area.
❖ Using laser tiny organelles in the living cells are destroyed to check the behavior of cell in the absence of organelle.
❖ The narrow intense beam of laser can be used to destroy cancerous and pre-cancerous cell.
❖ The heat of the laser seals off capillaries and lymph vessels to prevent spread of the disease.
❖ A laser beam can also be used to drill tiny holes in the hardest material like steel or diamond.
♦> The precise straightness of laser beam is used to check the lining up of equipment especially in inaccessible
locations.
❖ A high power laser is used to induce nuclear fusion reaction.
❖ Laser can.be used as range finder over large distances.
❖ It can be used for telecommunication along optical fibers.
❖ Laser beam can be used to generate three dimensional images of objects in a process called holography.
k •> Laser is used to break stones in gall blader and kidney. The device is known as Lithotripmeter.
/
COLLEGE PHYSICS XII 394 ATOMIC SPECTRA
IMPORTANT FORMIJLE
ATOMIC SPECTRA Quantized Radii:
Lyman Series n 2h 2
1 f 1 1 " Atr2m e2k
X * R h I i ’ n’
Balmer Series r< =
4 tr 2me2k
i- R < ' --L ] r0 = n V ,
* - * " ( ¥ n’ j
rn - rn 4r1t 9r1f 16r1t.
Paschen Series
Quantized velocity
l_ o f i 1' 2 trke2
A H 32 n2 Vn ' nh
Brackett Series Quantized Energies
f 1
1] 1 f 2rr2m k 2e 4 )
II
3~l
3n
i - * U2 n2J l h2 j
Pfund Series 2rr2mk 2eA
*„ =
1 -R ( 1 1 '
l M[ ? nJ
Second postulate of Bohr's theory E = ——
n n2
( h ' 13.6
2rr. E„=- eV For n = 1,2,3..,
n*
Third postulate of Bohr's theory Hydrogen Emission Spectrum:
hf = E „ - E p * 1 _1_
X-Rays: a - r * ,P ‘ _2
Mka ~= E,
C L ~- EUK
,
Mkp - Eh E
GLOSSARY
Ionization Potential The energy needed to remove the electron from an atom or molecule to infinite distance
Laser Light amplification by stimulated emission of radiation
Spectroscopy The branch of physics, which deals with the investigation of wavelengths and intensities of
electromagnetic radiations emitted or absorbed by atoms, is called spectroscopy.
Excitation Potential The energy needed to move electron from the ground state to any required state.