ludy lopy

Structure of Atom 12/1/2018

CErreel1d

My dear students, I hope that you have already gone through this chapter from

any of your text books. Now I shall highlight some portions of it.

You know about Rutherford's scattering experiment. It was once asked in the KVPY
exam why gold foil is used in this experiment. The answer is due to high malleability of
gold. Anyway this experiment showed for the first time that the atom has nucleus and
electrons occupy space around it. There were two drawbacks of Rutherford's nuclear model
of atom. This model could not explain the stability of atom and line spectrum of H-atom.
Both of these were successfully explained by Bohr's theory which is based on the formula
nh
mur =
27T

where of electron.
m = mass

=velocity of electron.
r= radius ofthe orbit
n= Principal Quantum Number = 1:2, 3, ..
h=Planck's constant =
6.626 x 10-34 JS

Problem: According to Bohr's theory, the angular momentum of an electron in Sth Orbit is
(A) 104 (B) 2.5 (C) 25 (D)
Ans. (B)

Explanation: angularmomentum (mvr)== 2.5

Photoelectric Effect:
Ejection of electron from surface of certain metals when exposed to a beam otf light. is
known as photoelectric effect.

incident radiation with

frequencyv

K.E of ejected photoelectron

A=hv-
 Work function (Ù) can be defined as minimum energy required to expel out a

photoelectron from the surface of metal.

Planck's Quantum theory states that energy of a radiation with v is h v.
Using Planck's Quantum Theory and conservation of energy Principle, Einstein
showed that kinetie energy of ejected
photoelectron hv
If v be the minimum
frequency (called, threshold frequency) to expel out
photoelectron from metal surface, then d =hv, and K.E. of
ë =hv -hv

Problem:
Inphotoelectric effect, the kinetic energy of photoelectrons increases linearly with the
(A) wave length
of incident light.
(B) frequency of incident light.
(C) velocity of incident light.
(D) atomic mass of an element.

Ans. (B)

Explanation:
E.ofe= hv- hvo
K.E. of e

Y m.x+C

hv0

Now let us discuss some concept and formulae regarding IE, Rydberg constant. series
etc. which are important to solve MCQ type problems.
 Total energy of electron
=
kinetic energy + Potential energy
7= atomic number

e e = electronic charge
21
r =radius of orbit
2 m= mass of electron
2 me4z2
n2h2 n= Principal Quantum Number

h Planck's constant

For electronic transition from Principal Quantum Numbern, to n, (n2> n1) we get
AE = E 2 - E

2n*metz2 22metz2
or, AE
AE =

ngh2 nh2
nh2

or, AE = 2-me 1 (1)

h2

lonization energy can be defined as minimum energy required to remove valence

electron to infinity froma free gaseous atom in its ground state (or lowest energystate).

Hence AE will be equal to IE when n2 > o

2tmetz2
Then AE =

nih2
for H-atom and other one electronic systenms for which Bohr's theory is applicable.

. IE =
(2T me*
h2

2m2me4
For H atom, IE = x 12 = 13. 6ev
h2

Similarly, forHet, IE = 13.6 x 22(Z =

2) = 54.4ev
for Li2+,IE = 13.6 x32(Z = 3) = 122.4ev

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AE 2
metz2 (1
h2
From above equation
Electronic transition
Name of series Spectrumn
UV
From aiten, =
2, 3, 4, ...
4 n1 Lyman
Balmer or Bohr Visible
From to71,,4,5, N 2 IR
rom e to 14.5. 6,-to n3 P'aschen
Brakett Far IR
From M4to n,5, 6, 7,..t n4
Far IR
From *5to n, 6, 7, 8, t h= 5
=
...
Pfund
Far IR
From n,=ó to n, = 7, 8,9,..ty n=6 Humphreys

from the red end

Problem: In Bohr series of lines of hydrogen spectrum, the third line
for Bohr Orbits
corresponds to which one of the following inter-orbit jumps of the electron
in an atom of hydrogen?
(A) 3 2 (B)5>2 (C)4-> (D)2>5
Ans. (B)
'red end' means longest wave length or from lowest AE value.
Considering increasing value of AE,
The 1st line is 2>3
The 2nd line is 2 >4
The 3rd line is 2>5

Rydberg Constant
AE = 2némeiz2(1_
h2 n
hy =27 me*z2
h2 n 0 =Wave numberwhich implies no. of
or, 27 met2
complete waves per unit length and bears the
h2
unit cm
2n2me z2(.
or, hCh3C R= Rydberg constant (its unit is as same as wave
or, -R(- no.)
where R 4 m e t z 2
h3C
For H-atom, Z=1,RH = 109700 cm-

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Problem:
In hydrogen atom, energy of first excited state is -3.4 ev. Find out the K.E. of electron
in the same orbit of' hydrogen atom-
(A)+3.4 ev (B) + 6.8 ev (C)- 13.6 ev (D)+13.6 ev
Ans. (A)
Total energy = kinetic energy + Potential energy

)+-) --32T
Total energy =-=-3.4 eu
. K.E. = Ze2 3.4 ev
2r

Problem: In a hydrogen atom, if the energy of an electron in the ground state is 13.6
ev, then that in the 2nd excited state is-
(A) 1.51 ev (b) 3.4 ev (C) 6.04 eu (D) 13.6 e
Ans. (A)
Remember three formulae:

E = , U , = a n d rn = roX

where E, energy of electron in the PQN n (Principal Quantum Number)

=velocity of electron in the PQN n
Tradius of nth orbit.
E, energy of in the Ist orbit.
Uvelocity of in the Ist orbit.
radius of Ist orbit of H-atom =
0.529 A
rBohr radius i.e.

Now apply the Ist formula. n=3 (2nd excited state.)

For 2nd excited state, n =3 -n= 2 (Ist excited state.)

13.6ev
E3 = 2 1.51eu n=I (ground state.)

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 Wave -particle duality
Some of the experimental phenomenon such as reflection, refraction, diffraction and
radiation. Again
interference can explained by the wave nature of the electromagnetic
be
nature of light.
black body radiation and photoelectron effect can be explained by particle
like radiation
Hence light has wave particle duality. Louis de Broglie proposed that matter,
wave length (^)
should also exhibit dual behavior and gave the following relation between
and momentum (P) of a material particle.

= mmass, v =velocityl

Problem: If the de Broglie wave length of the fourth Bohr's orbit of hydrogen atom is
4 A, the circumference of the orbit is -

(A) 4À (B) 4nm (C) 16A (D) 16 nm

Ans. (C)

Explanation:

No. of complete waves on revolution in the nth orbit

Circumference 27r

Wave length
h
2Ttr A=
de Broglie wave length mUI
mu

mur)
mur 2
Tx [:According to Bohrthecory,
n-PQN or Principal Quantunm Number

21t1 n

Or.27r= na= 4x 4Å = 16A

Heisenberg's Uncertainty Principle:

It states that it is impossible to determine simultancously the exact position and exact
momentum (or velocity) of an clectron.

Mathematically, it can be given as the following equation

4EX4t

Where, wtern h=
Ax x Ap 2 Ax=uncertainty in position.
4T

or,Ax x A(mv) 2
4Tt
Ap uncertainty in momentum.
or, Ax x Av > h Av uncertainty in velocity.
4TTm

Problem: In an atom an electron is moving with a speed of 600 m/s with an accuracy
of 0.005%.Certainty with which the position of the electron can be located is

(A) 1.52 x 104 m (B) 5.10 x 103m

(C) 1.92 x 10-3 m (D) 3.84 x 10-3 m
Ans. (C)

Explanation: Ax 2 ,
4tmAu

6.626 x 10-34JS
4x 3.14x 9.1 x 10-31kg x 600ms-1x
100

=
1.92 x 103 m

Page 8
 Schrodinger wave equation
This equation is written as
HY =E
where H is a mathematical operator called Hamiltonian operator.
E is total energy of the system and y is wave function for an electron.
With reference to this context, |4"|2is knowm as probability density

Problem:
The Schrodinger wave equation for H-atom is

ao ao

where a is Bohr's radius. If the radial node in 2s be at r, then find r, in ternms of a,

Answer: At node, probability of finding electron is zero,

/2s12= 0 at the radial node

. (2-=0
327T

: 2- = 0
ao

Or, ro = 2a0

Page 9
 Quantum numbers and orbitals
Solving Schrodinger wave equation. Quantum numbers were obtained.
These are-

1) Principal Quantum Number n which has values I(K), 2(L), 3(M), 4(N), 5(O),
6(P). 7(O). lt gives concept of size of orbit.

2) Azimuthal or orbital angular momentum Quantum number Pwhich has values

0 to (n-1). It gives concept ofshape of orbital.
e.g. For n =1, f=0(ls)
Forn 2 , f=0, 1 (2s, 2p)
For n 3. =0, 1, 2 (3s, 3p, 3d)
Forn=4, f=0, 1, 2, 3, (4s, 4p, 4d, 41) etc.
s-orbital is spherically symmetrical, p-orbital is of dumb-bell shape. d orbital is

four-cusped hypocycloid.

which gives concept of orientation of orbital

3) Magnetic Quantum number > m

and it has values from +/ to -/

e.g For -0 (s-orbital) =>m=0 (one orientation) spherically symmetrical

For =1 p-orbital) =m=+1,0, - 1 (Three orientations p- P,, P)

along x.y and 7 axes respectivel

For 2 (d-orbital)=m = +2, +1, 0, -, -2 (ive orientations
For
dya, d,e, dyy, dyz, dye). along s and y aves, along avis, on the w plane
On the y/ plane and on the xz plane respectively

For -3 (f-orbital) =m= +3, +2, +1,0,-1., -2,-3

Seven orientations =/fyt,f,1, fayzsl x(y?-z2)/y(-x*),Jz(a- y*)

4) The fourth quantum number is spin Quantum number (s) which has valuest
It is associated with spin of electron. This quantum number is not obtained by solving

Schrodinger wave equation.

Page 10
 Boundary surface diagrams of atomic orbitals

() S orbital

x X

Px Px P

Along axes

dr-y dz2

- y

On the xy plane On the yz plane On the xz plane

NOTE: Here the signs'+' or ' ' imply sign of wave function and not the charges.
Pauli Exclusion Principle
According to this principle: No two s in an atom can have the same set of four
quantum numbers.
This principle can also be stated only two
as: s may exist in the same orbital and
these electrons must have opposite spin.

Note:
The particles those follow Pauli Exclusion Principle, called Fermions.
are Example
electron, proton, neutron.
The particles those do not follow Pauli Exclusion Principle, are called Bosons.
Fxamnle - nhoton meson
Hund's Rule of maximum spin Multiplicity
It states: pairing of ë in the orbitals belonging to the same subshell (that is orbitals of
equal energy or degenerate orbitals) does not take place until each orbital belonging to that
subshell has got singly occupied.

Totalspin S= 2(++2(-)=0 Totalspin S=3(+)+1-) =1

Spin Multiplicity
Spin Multiplicity
2S+1
= 2 x0+1 = 2S+1=2 x1+1 =3
This Configuration is correct as it bears maximum

This Configuration is incorrect spin Multiplicity (25+1) value. Hence this rule is
called rule of maximum spin multiplicity.

Remember that filled or half-filled sub-shells are extra-ordinarily stable due to

() symmetrical distribution of electrons and
(2) Exchange energy

Filling of orbitals in atoms

The filling of into the orbitals of different atoms takes place according to the autbau
principle which is based on the Pauli's exclusion principle, the Hundu's Rule and relative
energies of the orbitals.

Page 12
Aufbau Principle
In the ground state (or lowest energy state) of the atoms, the orbitals are filled in order

of their increasing energies which may be remembered by using the method given below:

*********
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**** *a*n sesen * * * *sau"anar****ss
n**mranmon*

wwR*ama**** *******
*nnunennnasn**** *****

ruou umuanpanmnmuxe* unsuaosama mn

s* an:

ansns

Electronic configuration:
Mg(12) 1s22522p 3s2
Mg2+12 - 2 = 10e 1s22s22p

C 17 +1= 18e1s22s22p 3s23p

Elec. Configuration of Cu2+
Cu(29) 1s22s22p 3s23p°4s23d°

As
4s1 3d10 (Sable filledelec.config)
3d10
3d10 4s' (Energy of 3d orbital becomes lower than 4s)
Cu2t 3d°
Electronic configuration of cr2+
Cr24)1s22522p°3s23p 4s23d
 4s 3d5 (Sable halffilled elec.config)

3d5 4s' (lEnergy of 3d orbital becomes lower than 4s)

Cu2t 3d
Someimportant electronicconfiguration.
Sc2 3d'
Ti2+ 3d2
v2+ 3d3
Cr2 3d*
Mn2t 3d5
Fe2t 3d6
Co2 3d"
Ni2 3d8
Co2 3d°
Zn* 3d10
NOTE
Presence of unpaired makes a species paramagnetic (i.c. feebly attracted by magnetic

field) whereas absence ofimpaired makes a species diamagnetic (i.e. repelled by

magnetic field

Denivatin otBokns frm ula

TI
TT= n x Broglie)
nh
mUY=
2T

Page 14