Principles of Chemistry - CHEM 101

Lecture 2

Atomic structure

I. Atom

II. Model of Atom

III. Failure of classical mechanics

IV. Introduction to quantum mechanics

Rutherford’s Model of Atom
Energy and Position of a Particle- Classical View

Classical
Energy of a Particle Position of a Particle

Energy can change We can precisely

continuously know the position
 Line Spectra of Atoms

410.2 434.1 486.1 656.3

Balmer Spectra of Hydrogen Atom

Line Spectra of Atoms
 Line Spectra of Hydrogen

Series
1 1 1 
 RH  2  2  n = 2, 3, 4, …  Lyman
 1 n 

1 1 1
 RH  2  2  n = 3, 4, 5, …  Balmer
  2 n 

1 1 1
 RH  2  2  n = 4, 5, 6 …  Paschen
  3 n 
 Bohr’s Hypothesis Combine Line Spectra and Rutherford

n3 E3

n2 E2

n1 E1
 Step-wise derivation of Bohr’s Energy

Goal is to calculate total energy of an electron in an atom

Total Energy = KE + PE

1
1. Calculate Kinetic Energy: KE  me v 2
2

q1  q2
2. Calculate Potential Energy PE 
4 0 rn

3. Orbits are fixed L  me vrn  n

 Bohr’s Atomic Model

Postulates:

1. Electrons move around nucleus in

circular orbits
Nobel Prize 1922

2. Orbital angular momentum, L, is quantized.

L  me vrn  n

3. Electrons in stable orbits do not radiate energy.

4. Electrons can change orbits by radiating,

absorbing radiation or through collisions
KE & ‘v’ from Orbit Stability Fc = centrifugal force
me = mass of electron
v = velocity of electron
Ze  e (Electrostatic)
r = radius of an electron
Fe   Z = charge on the nucleus
4 0 r 2 Fe = electrostatic force
e = charge on electron
KZe 2 K 
1
Fe   2
r 4 0

me v 2 (centrifugal)
Fc 
r
For a stable orbit magnitudes r e-
of Fc and Fe must be equal
Ze+
Fc  Fe
 Fc  Fe

Substituting values of Fc and Fe

mev2/r = KZe2/r2

2
ZKe 2 ZKe
and v  m r
2
v Eq 1
me r e

Substituting values of v2 in K.E equation

1 1 KZe 2 KZe2
K .E  me ( v )  me (
2
) K .E  Eq 2
2 2 me r 2r
PE from Coulomb's Law

2
KZe Fe
Fe   2 (electrostatic)
r Ze+ r e-

PE  Fe  r

2
KZe
PE   Eq 3
r
 Total energy of electron in an atom

ET  K .E  P.E Eq 4

2
ET = Total energy
We know K .E 
KZe
Eq 2
K.E = kinetic energy
2r P.E = potential energy

and
KZe2
P.E   Eq 3
r
Substituting values of K.E and P.E in Eq 4

KZe2 KZe2
ET  
2r r
2
KZe 2 KZe
ET   En   Eq 5
2r 2rn
 Angular momentum of electron in an atom is quantized

ZKe 2
L  me rn (v)  n Eq 6 since v  Eq 1
me rn

Substituting the value of v in Eq 6

2
ZKe
me rn ( )  n ZKe2 me rn  n
me rn

Squaring both sides of the above equation and rearranging for rn

n2 2 n = Principal quantum number

rn  Eq 7 n = 1,2,3,4,5…
ZKe 2 me
h = Planck’s constant
rn = radius of nth orbit
 Radius of nth orbit

n2 2 n = Principal quantum number

rn  Eq 7 n = 1,2,3,4,5… 
ZKe 2 me
h = Planck’s constant
rn = radius of nth orbit
Radius of first orbit of H atom, substitute
n= 1 and Z = 1 in Eq 7.

12  2
r1  = a0 = Bohr’s radius=5.29×10−11m
Ke 2 me

Eq 8 can be used to calculate

n2
rn  a0 Eq 8 the radius (rn) of any orbit of
Z any single electron atom or
ions. e.g. H or He+ or C+5 or U+91
 Total energy of an electron in the nth orbit is given by

2 n 2 2
En  
KZe
Eq 5 and rn  Eq 7
2rn ZKe2 me

Substituting the values of rn from Eq 7 into Eq 5

En  
ZKe 12
 
ZKe ZKe me
 2 2 
2
Z Ke me 2 2
 
2 2
RH 
Ke  m
2 2
e
2 rn 2 n n 2 2 2 2 2
2
Z
= E n   RH 2 Single e atom/ions
n
RH
En   2 Eq 9 For Z = 1
n H atom
Generalized energy formulation
 Absorption Spectra of Hydrogen

En  E2  E1
RH E
En   2
n
Substituting the value of E1 and E2 n2 E2

RH  RH 
E n   2    2 
n2  n1 
n1 E1
=

 1 1 
E n  RH  2  2 
 n1 n2 
 Hydrogen Spectra

Absorption spectra Emission spectra

E E

nf Ef nf Ef =Ei

ni Ei ni Ei =Ef

 1 1   1 1 
E n  RH  2  2  E n  RH  2  2 
n  n n 
 i n f   f i 
Hydrogen atom series  1 1 

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
 Bohr’s Atomic Model

RH
En   2
n

E  E2  E1
RH  RH 
E n   2    2 
= n2  n1 

 1 1
En  RH  2  2 
 n1 n2 
 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 limits of elements that

can be discovered
Hydrogen atom series  1 1 

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 hv  1 1 
En   RH Z  2  2 
2
Single Electron Ions  n n 
 i f 

For
H, Z=1

410.2 434.1 486.1 656.3

Spectra of H-Balmer Series

For
He+, Z=2

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 Balmer lines

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

Franck-Hertz Experiment (1914) IE (Hg) = 10.4 eV

Current (I)

9.8 V
4.9 V

5 10 15
Voltage (V)
 2. Quantization in Atoms

Franck-Hertz Explanation

1 eV
3 eV
4.9 eV
 2. 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

mrn v  n n 2 a0 n
and rn  v 
Z mrn
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
 2. Fine Structure of Hydrogen

410.2 434.1 486.1 656.3

410.2 434.1 486.1 656.3

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

n = 2’
n=2

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

Orbit- circular Shell- Elliptical

Orbital Magnetic Quantum Number (l): l = n-1
n defines the size of orbit l defines the shape of orbit
 2. Line splitting: Zeeman Effect (1890)
B=0 B0
l=1
n= 2
l=0

l=0 n= 1

Line splitting
Shell- Elliptical
 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. Magnetic
Line splitting:
Quantum
ZeemanEffect
Number: (1890)
Sommerfeld

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. Anomalous
3. Line splitting:
Zeeman
ZeemanEffect
Effect (1890)
(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”