UN IT- I

ATOMIC STRUCTURE
_ _ _ _ __ _ __
CH AP TE R
_ j ,_ _ _ __
________
________

1.1 INT RO DU CT IO N
the ultimate particle of ,ru,ucr. Tho fir~,
Since long many attempts have been taken to know
theo ry abou t the structure of atom was prop osed by John Dalton in 1808 . AC<;ording 10 hl11
definite
isible particles called atoms. lfo did not 1my unything
theory, matter is made up of extremely smal~ indiv
t the inter nal structure of atom s and assumed atoms to be structureless particle. Howovcr, tho
abou
mson, Goldstein, Rutherford, Chndwick, Bohr. otc.
researches done by eminent scientists like J. J. Tho
ury shared that atom is not tho smn llest indivllliblo
in the later half of 19th century and early 20th cent
of still smaller particles like oloctrom, protons nnll
particle but has a complex structure and is made up
tomic particles are discovered but oloc tron, proton
neutrons, etc. At present about 35 different suba
cles because these are the main cornitituc:nt~ of nil
and neutron are regarded as the fundamental parti
atoms.
to explain the structure of atoir1 l.t'. , about
Various models are proposed by different scientists
ical model of atom wns proposod hy the following
the position ofelectron, proton and neutron. The class
.
models from time to time with some modifications
1. Rutherford's models of atom
2. Bohr's model of atom.
3. Bohr summerfeld model of atom
s i.e. ,
In all these model an atom is divided into two part
(a) nuclear part (b) E:utranuclear part. The nucl
ear part is present at the centre of the atom
h occu py a very small space and it is constituted by the protons and neutrons of tho atom. The
whic
large volume around the nucleus is called extr
anuclear part in which oloctrons 1uc revolving in
ditTcrcnt orbits.
1.1.1 Bohr's model of Atom
In order to overcome the drawbacks of Rutherfo
rd's model of atom and to explain the spoctrn
model of atom. His model is based on Ruth«ford'a
of hydrogm atan , Neil Bohr in 1913 proposed a new
radiation . The main postulate, or his modeJ are
model of atom and Planck's quantum theory of
pYeD belo w:
,.... ~ _ _ _ _ __ __ _ _ _ _ _ _
4
_ _ _ _ _ _ _ _ _ _ _~
__-__f_
C_~reM?
_ ,_:n-_w,_r -_ <;,,;::;i,,o{
f
-
n=4
l. An atom cons ists of a very smal l,
heav y posit ively charg ed nucleus_ in
its centr e. The electrons are revo lvmg
roun d the nucl eus in cert ain
perm itted circu lar path s calle d
orbi ts.
2. The energ y of these orbits are fixed or
defin ite arou nd the nucle us and are
calle d energy levels or stationary
states or shells. Thes e energ y levels
are numbered as 1, 2, 3, 4, ...... etc. or
des.\gnated as K, L, M, N, O .. .... etc. N
start ing from the nucle us. Fig. : 1.1 : Boh r's fiud cirCllUU Orbus
3. The ener gy leve l of the orbi ts
incre ases by incre asing the dista nce of the orbit s from . wbi b
the nucle us. The orbit s c are nearer
to nucle us poss ess lowe r energ y than the orbit s whic
h are away from the nucl eus.
~

(ABSORPTION SPECTRA)
(EMISSION SPEC TRA)
Fig. 1.2 : Excitation of electrons
4. As long as the elect rom are revo lving in a parti cular
orbit , they do not lose or gain energy.
5. Whe n an elect ron jump s (excites) from one energy
level to the other , at that time energy is
emitted or abso rbed discontinuously. The lowe r energ y
state of the dect ron is calle d ground
state or normal state and the high er energ y state of
elect ron is calle d its 8dl ed state. The
emission or abso rptio n of enel'gy takes place in the from
of quantas or photons.
Chan ge in energy, aE = E - E = hv
2 1
whe re E 1 and E 2 are the energies of the electron
in the lowe r and high er ener gy levels,
respe ctive ly.
( i) Whe n energ y is absorbed an elect ron jump s from lowe
r energy level to higher energy level
(Abt orpt ion spectra).
(ii) Wbt:n ener gy is emitted, an electron drop s from highe
l' ener gy level to lowe r energy level
(Emu1lon spectra).
6. The electronS revo lve in these circu lar orbit s in whic h
the angular momentum oftb c dcd! Oll is
8 who le number mult iple of~ .

[~•CUW mom mta m(m vr)• n" i; j

 CHAJ'TBR - l : A TOM IC S TRUCTURE

wh ere 'n' is any integer, J, 2, 3, ...

and ' h' is Pla nck 's con stan t, m is tbe
is the tan gen tial velo city of the rev mass of the electron. 11
olving elec tron and · r · is the rad ius
Thi s con cep t is kno wn as qua ntis atio of orb it.
n of ang ula r mo men tum.
1.1 .2 Expression for the nth orb
it of H-a tom or H-l lke spe cie s (Si ngl
Sup pos e an elec tron of cha rge e is
e ele ctr on sys tem )
revolving rou nd the nucleu s in circ
like spe cies hav ing ato mic num ber ular path of an ato m of H-
ma ss of the ele ctr on and v = tan
z. Let r is the ctist anc e betw een the
elec tron and nuc leus , m =
gen tial vel oci ty of the rev olv ing
nuc leu s= h . Du ring the mo tion of ele ctr on. Ch a r ge on the
the elec tron an elec tros tati c forc e of
exists between +ve cha rge of the nuc attr acti on (cen trip etal force)
leu s and neg ativ e cha rge of electron
am oun t of cen trif uga l forc es aris es . S imu ltan eously an equ al
(for ce awa y fro m the nuc leus ) w hich
aw ay fro m the nuc leu s. Bot h the keep the rev olving electron
abo ve forc e act in the opp osite ctire
keep the elec tron s to rev olv e uni form ly crio n to eac h other. Ln ord er to
round the nuc leu s,
Ele ctr ost atic force of attraction mu
st be equal to centrifugal force.
(a) Calculation of r
Ele ctro stat ic forc•e of attr acti on can
be obt ain ed from Cou lom b 's law
Ze xe
=--=--
Ze 2
r2 r2 ...( 1)

mv 2
Centrifugal forc e = - - ...(2)
r Fig. 1.3
Fro m eq0 (1) and (2) we get

mv2 Ze 2
-r -= 7
or, Ze 2
v2 = - ... (3)
mr
Ac cor din g to Bohr's postulates of atomic theory,
b
Angular momentum, mvr = n - or v = nh
21t 2rnnr
n2h2
oc, v2 = 41t2m2r2 ... (4)
From eqn (3) and (4), we have,

'h i n2 h 2
mr - 41t 2m 2 r 2

er.
r- ... (5)
' - 41t 2me 2Z
For H-atom in the ground state, n = 1,
Z = 1.
hl
... (6)

r.
6 U N'rYHRSlT'Y OctM I~ v - Gt.-1

lf the radius of the nth orbit is represented by r", then equa tion (5) can be writ ten as

n2h2
rn -- .. .(7)
41t 2 me 2 Z
Calculation of r in C.G S. unit :
We know, tile valu e of h = 6.62 6 x l 0-2' erg sec
m = 9. 1 x l 0-" g
e = 4.8 x 10-10 e.s.u .
Putting this values in Eq" (7) we get,

n 2 x(6. 626x 10-27 ergs /

rn = 4 X (3.14)2 X (9J X 10-2S g)(4.8 X }0-IO e.S. W . ) 2 XZ

0.529 X 10--8 X 0 2
= - - - - - - cm
z
2
r = 0.52 9xn A
I D z
For H-at om in the grou nd state n = 1, r
... (8)

0
= r 1, Z = 1.
Thu s, r 1 = 0.52 9 A.
Similarly, the valu e ofr in SJ. unit,
0

0.529 X }0- IO n 2
r =----- m ...(9)
D z
(b) Calculation of Energy
The total energy (E) of the revolving elec tron is equa
l to the sum of its pote ntial ener gy and
kinetic energy.
Thu s, E = P.E. + K.E.

-Ze2 1 2
= +-m v ... (10)
r 2
From equa tion (3) we have ,

Ze 2
mv 2= -
r
Subs titut ing the valu e of mv2 in equa tion (10), we
get,
-Ze 2 1 Ze 2 -Ze 2
E= --+
r 2 r 2r ...(11)
Putt ing the valu e of 'r' from equation (5) in equa tion
(11) we get,

a, ...(12)
 Thus., CDCrg) E of the cl~tron 111 the n.a orb11 can ~ "-Tlllcn ,h .
1 it· me' •
z· l

E • - . ( IJ)
•

For H-atom. Z -. I F
' .
Putting the value of n:, m. c, h in C. G S. unj 1 in the ~ ueLion ( I J), v..c get.
1
E •
, - 2. 18 x IO 11
-
z erg atom 1\
0 2
' n

I~ - 13.6 ' : : ev a1om 'fI erg ~ 6.2419 x 10" cv)

- - f 1rnh.' )
= - 13.1279 ><, 10 x Z c:rg mol 1
12 2
( , ,. L,. ~ ~
'- , -
I0
)
a· -- _ -10~-r
Cakulatioo of cocr-gy of H-atom in k.J/mol (S.J. unit),
1
- IO
E -- -1312 ~
I E = - - kJ moI- 1
• nJ
1.1.3 Bohr's Model and Spectra of H-atom
According to Bohr's model, as long as the electrons are in a particular energy level (orbit) they
dooo( emit or absorb energy. But wbai some extra energy is supplied to the atom from outside soun-cs.
its elcctroo gru excited to the higher state. The higher state of an electron (n,) ls umtabl(, so, It
ttturm back to the eround state (n,) by emitting energy lo the form of photons of ll&bt of
some deflnJte "avelength "blcb gives rile to emission spectrum or line spectrum. This
~gy is equal to the difference of energies of the electrons in n, orbit and o orbit.
1
6.£ = Energy of the electron in the n, orbit (higher energy state) - Energy of the electron
in n 1 orbit (ground energy state).
er, ~ "" E2 - E 1 •• • (14)
There arc diffcrcnt energy levels around the nucleus. Thus, this spectrum comlsta of a tarae
number or Unn called fine 1tructure which can be grouped together Into ftve series 1. c.
Lyman series, Balmer series, Pascheo series, Brackett series and Pfund series.
Calculadon or frequency (v) ud wave number (v) of spectral lines :
From equation (12), we have,
2 ◄
and E = - 21t me
2
n22h2

2 4
er, dE _ 2n me (-1 __1J
- h2 n2I n22 ... ( 15)
 I
UN1VERS1n a n.M,~'l"'R v _ GE.1

From Planck 's quantum theory of radiation, we have,

6E = hv, where v = frequency of radiation.

hv =
2
2n me (-1 __
h2
I
4
J
2
D1 n 22

or,
v _ 21t me (-1 __
2
I) 4

2 ...(16)
- h3 n n2 I
I 2
28
Putting the value of n, m, e and bin the above equation i.e., 1t = 3. 14, m = 9.108 x I 0- g, e::: 1

4.8 X I 0- 10 esu and h = 6 .626 x 10-21 erg sec, we get,

v = 3.2906 x 10 15 (~-~)
n1 n2
s- 1 or Hz

- V
We have, wave number ( v)=- ... (17)
c
where c = velocity of light.
Thus, equation ( 16), may be written as,

v= 21t
2
me
4
(-• __ l J ... (18)
ch 3 o 2I o 22

ThuS, __
v- 3.2906xl0 ( 1 l
- - -10- - -2- - -
15
Jcm_ 1

3xl0 n I o22

= 1.0976 x 105 ( ~ - ~ ] cm- 1

n1 n2

Cl',
J I
-v=R,. ( 2--2
n1 0 2
J cm- 1
...(19)

or, I - (I IJ
,. =v=R11 - 2 ----;-
n, n2
where, v=- I
A ... (20)

2 2
where R, 1 is a constant known as Rydberg constant, and is equal to 2n me
ch 3
i.e., 1.0976 x I 0 5 cm- 1
Using the relation ( 19) or (20), the different spectral ·
(I) Lyman Sena senes can be obtained.

In rhjs series, n 1 1, n, • 2. 3, 4, .. ... i.e. excited electron etums b

111

10 ground s tate (n .. J ). Thh spectral line appears

In the u~t vi ack from higher energy states
r adJarion (2000 - 2800A). ra olet region ~f electromagoedc
 l ' 11,\ P'll• R - I : A roM1c Srnun l J"R E
9

(ii) Balmer Series

In this series n 1 = 2, °i = 3, 4, 5, ..... i.e. the excited electron drops from higher energy stat es 10
the second energy level (n = 2), this spectral line appears in the visible rce;ion of electromagnetic
radiation (3800 - 7600A).
(iii) Paschen Series
In this series n, = 3, °i = 4, 5, 6 ..... , i.e. an excited electron drops from higher energy ~latcs 10
third energy state (n = 3). This series appears in the Infrared region of electromagnetic radiation
(7600 - 106 A).
(iv) Brackett Series
In this series, n 1 = 4 and f½ = 5, 6, 7, .... This series appears in the I. R. region or
electromagnetic radiation.
(v) Pfund Series
In this series, n 1 = 5 and n., = 6, 7, 8. This series appears in the I.R. region of electro
magnetic radiation. -
(vi) Humphrey Series
In this series, n, = 6 and n2 = 7, 8. This series also appears in the I.R. region of
electromagnetic radiation.
The above possibilities by which the e:ectrons fall back from higher energy level (excited state)
to lower energy level are given in the fig. 1.4.
n=8
n=7
n=6
l
HUMPHRE y
:s SERIES
.8 n=5 PFUND
E
:, SERIES
C
0
C: 0)
En=4 Q)
:,
c BRACKETT a::
SERIES a::
"'tT
:,

-0
111n=3
I

PASCHEN
~
H

E SERIES
~
.£
'ii
>
a,
-n=2
>-
~
BALMER SERIES (Visible region)
a,
C:
UJ

n=1
LYMAN SERIES (U.V. regt0n)
Fig. 1.4 : The origin of H-spectrum
Note (I) fn each series, the most prominent line has the longest wavelength. It is caJ~cd a-
line and the next one is called J}-lioe and so on. The intensity and separation of
lines decrease regularly with decreasing wavelength. At the shortest w_avclength
en~ llna crowd together and form the series limit. Different series and its rela t ed
poinu are given below,
( 11,\l' I I I' • I I\ IOM I(' SI l'I IC-I I :kl I1

~; 1.4 Advantages (Importance) of Bohr's Model

!'hr liohr's moclcl or alorn successfu lly explained the fo llowing facts :
( I) Stability of atom :
t\ccord111g to Bohr's concept, an electron does not lose or ga in energy when it revolves in a
purticulur orhil . As it docs not lose uny energy, the question of its fal ling on the nucleus docs not
nri:-c und ntom is suid to he stab le. Thus, Bohr's theory explained the inadcquency of Rutherford's
mo<lr l or atom.
(2) Explanation for Negative value of energy :
Wht.'11 an electron is present at infinity distance from the nucleus, the energy of the electron is
takCfl to be zero as there is no force of attraction between the eleclrnn a11d nucleus. But, when an
clC(;tron approaches close towards the nucleus it experiences force of attraction by the nucleus and
energy is released. As a result of which energy of the electron decreases and it becomes lower than
·, .cro, i.e. negative.
()) Bohr's thc,«)ry and idea of quantisation :
According to Bohr. the electron in H-alom, can have energy,
- 1311.8
E= 2
kJ mo1- 1,
n
· n' is a whole number, i.e. 1,2,3 ... ..... When an electron gains or loses energy, it does so in such
a way that 'n' has a value which is a whole number. In other words, electron does not gain or
lose energy in a continuous manner but in jumps. This means that energy is emitted or absorbed
when an electron jumps from one energy level to other (just like crossing steps of a ladder).
Thus the energy of an electron is quantised.

1.1 .5 Limitations of Bohr's model of atom

Some of the limitations of Bohr's model are :
0J, Bottr's theory successfully explained the observed spectra for hydrogen atom and hydrogen like
atoms. (e.g. He', Li ,.. , etc), but it could not explain the spectral series for the atoms having
multiple electrons.
(2) Bohr's model also could not explain the structure of atoms having multiple electrons except
. -- hydrogen atom or H-like atoms.
(3) Bohr in his model described that the orbits are circular in nature, but later on Sommerfeld
- suggested that the orbits are elliptical in nature.
(4) There was no satisfactory justification for the assumption that the electron can rotate only in
~ h
those orbits in which the angular momentum of the electron is an integral multiple of- , i.e. , he
21t
could not give any explanation for using the quantisation of angular momentum and it was
introduced by him arbitrarily.
(5) Bohr's theory could not say anything about the geometry and shape of the molecules.
0i ~~~•s theory co~1ld not explain the splitting of a single spectral line into a group of ~losely
spaced spectral Imes called fine structure when passed under the influence of magnetic field
(Zeeman effect) or electric field (Stark effect)
 -- -. :
si,
ug ge st ed by dc •l lr og lic ) w h, cl, " 't:Rc
cs (s
el co ul d no t sa tisf y the wave mec hani ar ac te r. ll oh r co ns ulc, "'I clc'c tro.,,
( ") Bo hr 's mod ch ar ac ter i.e. particle and
wave ch
rron ha s du al
thi:y
· on ase di
at th ccre
elsc te pa rti c les .
fi ni te di st an ce from th e nuclcu , '"'"
d at a de
th at an el ec tron in an atom is locate ei se n be rg 's u nc er toint y pr icipJ,
jJ i) Bohr assumed nst 11
it w ith a de f, n ite velocity. Th is is agai d m om entum (or vcIIJocitiJ
•s revo Ivi ng ar ou nd e «ac t po si tion an
is irn po s~ l~ o.<!_eter~ne bolh th
which states th
o f~ ~
at it
t~ ~ ! Y: and w,
er s on ly pa rt ic le na tu re or elec tron
nsid
e m od els fa ile d on the ground that it co er n th eo ry o f at omic structure.
But all th es hich give rise to m od
nature o f electron w