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The document discusses the principles of atomic structure, focusing on the successes and limitations of Bohr's model of the atom. It explains key equations related to electron behavior, quantization, and the line spectra of hydrogen and single electron ions. Additionally, it highlights the limitations of Bohr's model, including its applicability only to single electron systems and its inability to explain certain phenomena like fine structure and line splitting.

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Sona Kumar
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-lec-2

The document discusses the principles of atomic structure, focusing on the successes and limitations of Bohr's model of the atom. It explains key equations related to electron behavior, quantization, and the line spectra of hydrogen and single electron ions. Additionally, it highlights the limitations of Bohr's model, including its applicability only to single electron systems and its inability to explain certain phenomena like fine structure and line splitting.

Uploaded by

Sona Kumar
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Principles of Chemistry - CHEM 101

(Lecture 4)

Atomic structure

I. Success and Failure of Bohr’s Model

II. Interaction between Energy and Matter


Some Important Equations from Bohr Model
Angular Momentum Velocity of electron in an orbit

L = me vrn = n ZKe 2
Where,
Z = Atomic number
v= 1
h me r K=
Where, = 4 o
2 e = charge on electron
h = Planck’s constant = 6.625 x 10-34 J.s me = mass of electron

Radius of an orbit
n2
n = Principle Quantum No
rn = a0
Z rn = Radius of nth electron
Bohr’s radius (a0 )= 53 pm= 5.3×10−11m

Energy of ‘e’ in a single ‘e’ ion Energy of ‘e’ in H atom


Z2 RH
E n = − RH 2 En = − 2
n n
Success of Bohr’s Atomic Model

It successfully explained

1. Line Spectra of Hydrogen


2. Quantization in Atoms
3. Spectra of Single Electron Ions
=
4. Construction of Periodic Table

Also predicts on the limit of elements that


can possibly be discovered
 1 1 
Hydrogen atom series 
En = RH 2 − 2
n n 
 i f 

E
n
10
9
8
7
6
Pfund series
5

4 Brackett series (Far IR)

3
Paschen series (Near IR)

2 Balmer series (visible)

Lyman series (UV)


1
Ground state
2. Line Spectra of Single Electron hv  1 1 
Ions En = = RH Z  2 − 2 
2

 n n 
 i f 

For H

410.2 434.1 486.1 656.3

Spectra of H-Balmer Series

102.5 108.5 121.5 164.0

Spectra of Star Dust: Pickering


Spectra of Star Dust: Edward Pickering-1882

102.5 108.5 121.5 164.0

410.2 434.1 486.1 656.3

Spectra of H-Balmer Series


Bohr’s explanation
hv  1 1 
En = = RH Z  2 − 2 
2

 n n 
 i f 

For H: Z=1, ni = 2 and nf = 3, 4 5 and 6 Balmer lines

For He+: Z=2, ni = 2 and nf = 3, 4 5 and 6 Pickering lines

Divide each line of Balmer series by 4

Alfred Fowler-1914 Recorded Spectra of He+ in lab

What he found was that multiplication factor is


4.00160 and NOT 4.00000, as Bohr was claiming

Bohr came back with new number using


reduced mass of electron : 4.00163!
2. Quantization in Atoms
Franck-Hertz Experiment (1914)

Hg vapors

Hg atom
3. Quantization in Atoms
Franck-Hertz Explanation

1 eV
3 eV
4.9 eV
3. Quantization in Atoms
Franck-Hertz Explanation

5 eV
7.6 eV
9.8 eV
What is the highest possible Atomic Number
Element that can be discovered?
From Bohr’s model
n n 2 a0
mrn v = n v = and rn =
mrn Z
n Z Z
Substituting rn v=  2 =
m n a0 nma0
Solving for “Zmax” Z = Zmax when v = c where c is velocity of light

cma0
Z max = For n = 1

3  108 ms −1  9.1  10 −31 kg  53  10 −12 m
Z=
1.055  10 −34 J .s

Z max = 137
Limitations of Bohr’s Atomic Model

1. Applies only to single electron system


2. Can’t explain:
1. Fine structure of hydrogen
2. Line splitting
3. Anomalous Zeemann effect
1. Fine Structure of Hydrogen

410.2 434.1 486.1 656.3

410.2 434.1 486.1 656.3


Fine Structure
1. Fine Structure of Atom: Sommerfeld Quantization Rules

n defines the size of orbit l defines the shape of orbit

n = 2’
n=2

n=2
n=1
n=1
l = 0, circular orbital
l = 1, elliptical orbital

Orbit- circular Shell- Elliptical


Orbital Momentum Quantum Number (l): l =0 to n-1
2. Line splitting: Zeeman Effect (1890)
B=0 B0
l=1
n= 2
l=0

l=0 n= 1

Shell- Elliptical Line splitting


2. Magnetic Quantum Number: Sommerfeld
B
m defines orientation in space

+1

-1

n= 2 l=1 m = +1 m=0 m = -1
l=0
Magnetic quantum number, m = l, l-1, …0 … -l
2. Line splitting: ZeemanEffect (1890)

orbit shell orbital B=0 B0


n=2 l = 1 m =1, 0, -1

n=2 l=0 m=0

n=1 l=0 m=0

Shell Orbital
2. Line splitting: Zeeman Effect (1890)

orbit shell orbital B=0 B0


n=2 l = 1 m =1, 0, -1

n=2 l=0 m=0

n=1 l=0 m=0

Careful analysis revealed further splitting


Anomalous Zeeman Effect
2. Spin Quantum Number (s)
G. Uhlenbeck and S. Goudsmith- 1925

Na (1s22s22p63s1)

589.3 nm

589.0 589.6
2. Spin Quantum Number (s)

G. Uhlenbeck and S. Goudsmith- 1925

S = -1/2 S = +1/2

Spin magnetic angular momentum quantum number (s)


2. Spin Quantum Number (s)

Pauli exclusion Principle: Wolfgang Pauli-1925

“No two electron in an atom can have


same four quantum numbers”
Topics to be covered in the next Lecture:

1. Properties of Electromagnetic radiation


2. Photoelectric Effect

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