2.

1 Bohrs atomic model

2.2 Quantum mechanical model 2.3 Electronic configuration
1

1 n2

At the end of this topic students should be able to:-

a) Describe the Bohrs atomic model. b) Explain the existence of electron energy levels in an atom. c) Calculate the energy of electron using: d) Describe the formation of line spectrum of hydrogen atom. e) Calculate the energy change of an electron during transition. f) Calculate the photon of energy emitted by an electron that produces a particular wavelength during transition.
2

g)perform calculations involving the rydberg equation for lyman, balmer, paschen, brackett and pfund series. h)calculate the ionisation energy of hydrogen atom from lyman series. i) state the weaknesses of bohr's atomic model. j) state the dual nature of electron using de broglie's postulate and heisenberg's uncertainty principle

BOHRS ATOMIC MODELS

In 1913, a young Dutch physicist, Niels Bhr proposed a theory of atom that shock the scientific world. The atomic model he described had electrons circling a central nucleus that contains positively charged protons.

Bhr also proposed that these orbits can only occur at specifically permitted levels only according to the energy levels of the electron and explain successfully the lines in the hydrogen spectrum.

BOHRS ATOMIC MODELS

Postulates
1.

Electron moves in circular orbits about the nucleus. In moving in the orbit, the electron does not radiate any energy and does not absorb any energy.

H Nucleus (proton)

1 1H

BOHRS ATOMIC MODELS

Postulates
ii) The energy of an electron in a hydrogen atom is quantised, that is, the electron has only a fixed set of allowed orbits, called stationary states. ( e can only exist on specific orbit,not between orbit)
[ orbit = stationary state = energy level = shell ]

H Nucleus (proton)

n=1

n=3
n=2
6

BOHRS ATOMIC MODELS

Postulates
3.

At ordinary conditions the electron is at the ground state (lowest level). If energy is supplied, electron absorbed the energy and is promoted from a lower energy level to a higher ones. (Electron is excited) Electron at its excited states is unstable. It will fall back to lower energy level and released a specific amount of energy in the form of light. The energy of the photon equals to the energy difference between the levels.

4.

Points to Remember

Ground state
the state in which the electrons have their lowest energy

Excited state
the state in which the electrons have shifted from a lower energy level to a higher energy level

Energy level
energy associated with a specific orbit or state

THE BOHR ATOM

The energy of an electron in its level is given by:

En

RH

1 n2

RH (Rydberg constant) or A = 2.18 10-18J. n (principal quantum number) = 1, 2, 3 . (integer) Note: n identifies the orbit of electron Energy is zero if electron is located infinitely far from nucleus Energy associated with forces of attraction are taken to be negative (thus, negative sign)

THE BOHR ATOM

Radiant energy emitted when the electron moves from higher-energy state to lowerenergy state is given by the difference in energy between energy levels:
E = Ef - Ei
E
Thus, where E i

RH

1 2 ni

RH

1 2 nf

RH

1 2 ni

Ef

RH

1 2 nf

RH

1 2 ni

1 2 nf

ni = initial orbit
nf = final orbit
10

THE BOHR ATOM

The amount of energy released by the electron is called a photon of energy.

A photon of energy is emitted in the form of radiation with appropriate frequency and wavelength.
where; h (Plancks constant) =6.63 = frequency 10-34 J s

E=h
Where;

c
c (speed of light) = 3.00 108 ms-1

Thus,

hc
11

Electron is excited from lower to higher energy level. A specific amount of energy is absorbed E = h = E1-E3 (+ve)

n =1

n=2 n=3 n=4

Electron falls from higher to lower energy level . A photon of energy is released. E = h = E3-E1 (-ve)
12

Energy level diagram for the hydrogen atom

n=
Potential energy n=4 n=3 n=2 Energy absorbed Energy released n=1
13

Example

Calculate: i) The E of an e- has when it occupies when it was at n=3 & n=4. ii) The E of the photon emitted when one mole e- of drops from the fourth E level to third E level. iii) The frequency & wavelength of this photon.
14

14

Solution :
En RH 1 n2

i) at n=3, E3 = -RH 1 = - 2.18 x 10-18 J 32 9 = -2.422 x 10-19 J at n=4, E4 = -RH 1 = - 2.18 x 10-18 J 42 16 = -1.363 x 10-19J
15

15

ii)

n=4

E = Ef Ei = E3 E4 = -2.422x 10-19J- (-1.363 x 10-19J) = -1.06 x 10-19J -ve sign indicates that E is released when e- falls.

n=3

E released by 1 mol of e-, E = -1.06 x 10-19J x 6.023 x 1023 mol-1 = - 63 843.8 Jmol-1 = -63.8438 kJmol-1

16

16

iii) Frequency, v = E = 1.06 x 10-19J h 6.63 x 10-34 Js = 1.599 x 1014 s-1 = 1.599 x 1014Hz # -ve sign of E is ignored because frequency is always +ve Wavelength, = c = 3.0 x 108 ms-1 v 1.599 x 1014 s-1 = 1.876 x 10-6 m = 1876 nm # 1 m = 109 nm
17

Exercises:
1) Calculate the energy of an electron in the second energy level of a hydrogen atom. (-5.448 x 10-19 J) 2) Calculate the energy of an electron in the energy level n = 6 of a hydrogen atom. 3) Calculate the energy change (J), that occurs when an electron falls from n = 5 to n = 3 energy level in a hydrogen atom. (answer: 1.55 x 10-19J)

4) Calculate the frequency and wavelength (nm) of the radiation emitted in question 3.

18

Emission Spectra

Continuous Spectra

Line Spectra

19

Continuous Spectrum
A spectrum consists all wavelength components (containing an unbroken sequence of frequencies) of the visible portion of the electromagnetic spectrum are present. It is produced by incandescent solids, liquids, and compressed gases.

20

Regions of the Electromagnetic Spectrum

21

FORMATION OF CONTINUOUS SPECTRUM

When white light from incandescent lamp is passed through a slit then a prism, it separates into a spectrum. The white light spread out into a rainbow of colours produces a continuous spectrum. The spectrum is continuous in that all wavelengths are present and each colour merges into the next without a break.

22

23

Line Spectrum (atomic spectrum)

A spectrum consists of discontinuous & discrete lines produced by excited atoms and ions as the electrons fall back to a lower energy level. The radiation emitted is only at a specific wavelength or frequency. It means each line corresponds to a specific wavelength or frequency.
Line spectrum are composed of only a few wavelengths giving a series of discrete line separated by blank areas

24

FORMATION OF ATOMIC / LINE SPECTRUM

prism

film

The emitted light (photons) is then separated into its components by a prism. Each component is focused at a definite position, according to its wavelength and forms as an image on the photographic plate. The images are called spectral lines.
25

Line Emission Spectrum of Hydrogen Atoms

26

26

FORMATION OF ATOMIC / LINE SPECTRUM

n= n=5 n=4 n=3 n=2

Radiant energy (a quantum of energy) absorbed by the atom (or electron) causes the electron to move from a lower-energy state to a higher-energy state. Hydrogen atom is said to be in an excited state (very unstable).

Energy

n=1

When an electrical discharge is passed through a sample of hydrogen gas at low pressure, hydrogen molecules decompose to form hydrogen atoms.
27

FORMATION OF ATOMIC / LINE SPECTRUM

n= n=6 n=5 n=4 n=3

When the electrons fall back to lower energy levels, radiant energies (photons) are emitted in the form of light (electromagnetic radiation of a particular frequency or wavelength)

Energy

n=2

Emission of photon
28

FORMATION OF ATOMIC / LINE SPECTRUM

n= n=5 n=4 Energy n=3 n=2

n=1

Emission of photon

Line spectrum Lyman Series

29

FORMATION OF ATOMIC / LINE SPECTRUM

n= n=5 n=4 Energy n=3 n=2

n=1

Emission of photon

Line spectrum Lyman Series

Balmer Series

30

Emission series of hydrogen atom

n=
E2

Pfund series
A 22 E3 A 32

E4

n=4 n=3

A 42

Brackett series

Paschen series
n=2 Balmer series
E1 A 12

n=1

Lyman series

31

Exercise: Complete the following table

Series

n1
1

n2

Spectru m region
ultraviolet Visible

Lyman
Balmer

2,3,4,
3,4,5, 4,5,6, 5,6,7, 6,7,8,

2
3

Paschen
Brackett

Infrared Infrared Infrared

32

4 5

Pfund

Example 1

The following diagram shows the line spectrum of hydrogen atom. Line A is the first line of the Lyman series. A B C D E
Line spectrum E

Specify the increasing order of the radiant energy, frequency and wavelength of the emitted photon. Which of the line that corresponds to : i) The shortest wavelength? Line E Line A
33

ii) The lowest frequency?

Draw the energy level diagram for corresponding line spectrum above.

33

E
iii)

n=6 n=5 n=4 n=3 n=2

C D

n=1
34

34

Example 2
W Y

Line spectrum

Balmer series

Describe the transitions of electrons that lead to the lines W, and Y, respectively.

Solution
For W: transition of electron is from n=4 to n=2 For Y: electron shifts from n=7 to n=2
35

35

Exercise The following diagram depicts the line spectrum of hydrogen atom. Line A is the first line of the Lyman series. A Line spectrum B C D E E

Specify the increasing order of the radiant energy, frequency and wavelength of the emitted photon. Which of the line that corresponds to i) the shortest wavelength? Line E ii) the lowest frequency? Line A

36

Homework
Calculate En for n = 1, 2, 3, and 4. Draw a diagram showing how the energy, at different values of n, increases vertically and indicate by vertical arrows the electron transitions that lead to lines in: a) Lyman series b) Paschen series

37

Significance of Atomic Spectra

In Lyman series, the frequency of the convergence of spectral lines can be used to find the ionisation energy of hydrogen atom: IE = h The frequency of the first line of the Lyman series > the frequency of the first line of the Balmer series.
Line spectrum E

Balmer Series

Lyman Series

38

Exercise
E D Line spectrum C B A

Paschen series

Which of the line in the Paschen series corresponds to the longest wavelength of photon? Describe the transition that gives rise to the line.

Solution
Line A. The electron moves from n=4 to n=3.
39

EXERCISES
Calculate En for n = 1, 2, 3, and 4. Draw an energy level diagram and line spectrum for the transition of electron that lead to the formation of 4 lines in : a) Pfund series b) Paschen series

40

40

Rydberg Equation

Wavelength emitted by the transition of electron between two energy levels is calculated using Rydberg equation:
1

RH

1 2 n1

1 2 n2

where RH = 1.097 107 m-1 = wavelength Since should have a positive value thus n1 < n2

41

Exercise

Calculate a) the wavelength in nm b) the frequency c) the energy that associated with the second line in the Balmer series of the hydrogen spectrum.
1

Solution (a)
Second line of Balmer series: the transition of electron is from n2=4 to n1=2 1

= RH
=

n12

1 n22 m
1)

(1.097x107

1 22

1 42

109 nm = 4.86x10 7 m x 1 m = 486 nm

42

Solution (b)

Frequency, v = c = 3.0 x 10 8 ms-1

4.86 x 10-7 m
= 6.173 x 1014 s-1

Solution (c)
Energy, E = hv = 6.63 x 10 -34Js x 6.173 x 1014s-1 = 4.093 x 10 -19J
43

43

Example

Calculate the wavelength, in nanometers of the spectrum of hydrogen corresponding to ni = 2 and nf = 4 in the Rydberg equation.
Solution:

Rydberg equation:
1/ = RH (1/ni2 1/nf2) ni = 2 nf = 4 RH = 1.097 x 107m

1/ = RH (1/22 1/42) = RH(1/4-1/16) = 4.86m x 102 m = 486nm

44

Example
Use the Rydberg equation to calculate the wavelength of the spectral line of hydrogen atom that would result when an electron drops from the fourth orbit to the second orbit. Name the series of line Solution: formed.
1/ = RH (1/n1 2 1/n2 2) n1 = 2 n2 = 4
1/ = 1.097 x 107 (1/22 1/42) = 4.86 x 10-7 m = 486 nm *e dropped to the second orbit (n=2), >>> Balmer series
45

EXAMPLE 3

Calculate the wavelengths of the fourth line in the Balmer series of hydrogen.
n1 = 2 n2 = 6 RH = 1.097 x 107m-1

= RH

22

62

= 4.10 x 10-7 m

46

Different values of RH and its usage

1. RH = 1.097 1

107 m-1 1
2 n1

= RH

1
2 n2

n1 < n 2

RH = 2.18 x 10-18 J

RH

1 2 ni

1 2 nf

ni initial orbit
nf - final orbit
47

EXAMPLE 4

Calculate the energy liberated when an electron from the fifth energy level falls to the second energy level in the hydrogen atom. 1 1
2 n1

= RH

1
2 n2

1
=1.097 x 107 1

1 52

22

= 0.2303 X 107 m-1

48

E
E = (6.63

hc

10-34Js)X(3.00 108 ms-1) X (0.2303 X 107 m-1)

E = 4.58 x 10-19 J

49

EXERCISE 5

For Lyman series n1=1 and n2 = calculate; i ) Wavelength ii ) Frequency iii ) Wave number of the last line of hydrogen spectrum in Lyman series Wave number = 1/wavelength

Ans:

i) 9.116 x 10-8 m

ii) 3.29 x 1015 s-1 iii) 1.0970 x 107 m-1

50

The weakness of Bohrs Theory Bohr was successful in introducing the idea of quantum energy and in explaining the lines of hydrogen spectrum. His theory could not be extended to predict the energy levels and spectra of atoms and ions with more than one electron. His theory can only explain the hydrogen spectrum or ions contain one electron eg He+, Li2+. Modern quantum mechanics retain Bohrs concept of discrete energy states and energy involved during transition of electrons but totally reject the circular orbits he introduced.

51

1 n2

At the end of this topic students should be able to:1) Define the term orbital. 2) State all the four quantum numbers of an electron in an orbital. 3) Sketch the shape of s, p and d orbitals with the correct orientations.

52

Atomic Orbital

Definition
An orbital is a threedimensional region in space around the nucleus where there is a high probability of finding an electron.

53

ATOMIC ORBITAL

Orbital - region in space around the nucleus where there is a high probability of finding an electron.
Where electron can be expected to be found. Orbit the path of an e- as it travels round the nucleus of an atom.
54

QUANTUM NUMBERS
Quanta - discrete amounts of E that an eabsorbs as it moves up an E level or releases when it moves down to lower E level. The positions and orbits of e- referred as E state and described by 4 quantum numbers :

i. ii.

Principal quantum number (n) Angular momentum/Azimuthal quantum number (l) iii. Magnetic quantum number (m) iv. Spin quantum number (s)
55

PRINCIPAL QUANTUM NUMBER, n

- Determines the energy & size of an orbital.

- n is large size of atom is larger & distance e- from nucleus is greater. - The principal quantum number may have only integral values: n =1, 2, 3, , .
56

PRINCIPAL QUANTUM NUMBER, n

n
shell
Orbital size

1
K

2
L

3 M

4 N

Energy

increases

57

ANGULAR MOMENTUM QUANTUM NUMBER, l

Alternative name: Subsidiary / Azimuthal / Orbital Quantum Number - Indicates the shape of the atomic orbital, the types of orbitals, and the angular momentum of the electron. - The allowed values of l are 0, 1, 2,, (n 1). - Depends on value of n.
58

ANGULAR MOMENTUM QUANTUM NUMBER, l

Numerical value of l Symbol Orbital shape

0
1

s
p

spherical
dumbbell

2
3

d
f

cloverleaf
~
59

Example

Shell, n
2

Sub-shell, l
0
1 0 1 2

Called as
2s
2p 4s 4p 4d 4f

60

MAGNETIC QUANTUM NUMBER, m

Determines the orientation of orbital in space. Permitted value for m depend on the value of l. It has integer value ranging from l to +l . Indicates the maximum number of orbitals for a particular value of l. Example :
61

ELECTRON SPIN QUANTUM NUMBER, s

Determines the direction of spinning motions of an electron on its own axis. Clockwise or counter 1 clockwise. or - 1 + 2 2 The electron spin quantum number has a value of :

62

The relationship between the values of n, , and m

n 1 2

Orbital No. of m notati degenerat (<n) on (- m +) ed orbitals 0 1s 0 1 0 2s 0 1 1 2p 1,0,-1 3 0 3s 0 1 1 3p 1,0,-1 3 2 3d 2,1,0,-1,-2 5

63

Example

n
1
2 3

l
0

shap e
1s

m
0 0 -1, 0, 1 0 -1, 0, 1 -2, -1, 0, 1, 2 0 -1, 0, 1

s
1/2
1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2

No. of No. of orbital e1 1 3 1 3 5 1 3 5 2 8

0 1
0

2s 2p
3s

1 2 0 1 2 3

3p 3d 4s 4p 4d 4f

18

-2, -1, 0, 1, 2
-3, -2, -1, 0, 1, 2, 3

32
64

1/2

Exercise

State whether or not each of the following symbols is an acceptable designation for an atomic orbital. Explain what is wrong with the unacceptable symbols. (l < n)
a) 2d n=2

l=2 l=4 l=0 l=6

unacceptable

b) 6g
c) 7s d) 5i

n=6
n=7 n=5

acceptable
acceptable unacceptable
65

SHAPE OF ATOMIC ORBITALS

a)

s orbitals When l = 0 Spherical shape. As n increases, s orbital gets larger

Shape of s orbital with different n

66

SHAPE OF ATOMIC ORBITALS

b) p orbitals When l = 1 Dumbbell shaped Consists of 3 p orbital, each with the same size, shape and energy; they differ from one another only in orientation - px, py, and pz. Correspond m of -1, 0, and +1.
67

SHAPE OF ATOMIC ORBITALS

68

SHAPE OF ATOMIC ORBITALS

c) d - orbitals When l = 2, m = -2, -1, 0, 1, 2 The orbitals are: dyz, dxz, dxy, dx2-y2, dz2

69

70

1 n2

2.3 Electronic Configuration

At the end of this topic students should be able to:a. State Aufbou principle, Hunds rule and Pauli s
exclusion principle.

b. Apply the rules in (a) to fill electrons into atomic orbital.

c. Write the electronic configuration of atoms and monoatomic ions using spdf notation. d) Explain the anomalous electronic configurations of chromium and copper.

71

Representing Electronic Configuration

Method 1: Orbital diagram
1s

2s

2p

8 O:

box

platform
Concentric circle Method 2: spdf notation 8 O:

1s 2 2s 2 2p 4

72

Rules for Assigning Electrons to Orbitals

ii) Aufbau Principle
Electrons fill the lowest energy orbitals first and other orbitals in order of ascending energy.
The order of filling orbitals is: 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s

1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f

1s

2s

2p

73

Relative Energy Level of Atomic Orbitals

5s 4p 4d

3d
n=4 energy 4s 3p n=3 n=2 n=1 3s 2p 2s 1s n=2 n=1 2s 1s 2p energy n=4 4s 4p 4d

n=3

3s

3p

3d

Orbital energy levels in a many-electron atom

Orbital energy levels in the H atom 74

Rules for Assigning Electrons to Orbitals

ii) Pauli Exclusion Principle
No two electrons in an atom can have the same four quantum numbers (n, , m, s)

1s e(a)
a b

m (1, 0 , 0,

s
+ 1

e(b) e(c)

(1, 0 , 0,
1 0 0
+

2 1 2 1 2

)
75

Rules for Assigning Electrons to Orbitals

iii) Hunds Rule
Only when all the degenerate orbitals (a group of orbitals of identical energy e.g. three p-orbitals and five dorbitals) contain an electron do the electrons begin to occupy these orbitals in pairs. The electrons in half-filled orbitals have the same spins, that is, parallel spins.

2p

76

Exercise
Indicate which of the following orbital diagrams are acceptable or unacceptable for an atom in ground state. Explain what mistakes have been made in each and draw the correct orbital diagram: 1s 2s 2p 1s 2s ? 1s 2s 2p 2p

1s ? 1s 2s ? 2p 1s 2s 2p

?
2s 2p ?
77

Exercise
Draw electrons-in-boxes diagram of the electronic configuration of titanium, Ti (Z = 22). Also, write the groundstate electronic configurations for Ti and Ti2+ ion. 1s 2s 2p 3s 3p 4s

Ti:
3d

Ti: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 2 Ti2+: 1s 2 2s 2 2p 6 3s 2 3p 63d 2

78

Points to remember
The electronic configuration of atom or monatomic ion at ground state Distribution of electrons obeys Aufbau principle, Pauli exclusion principle and Hunds rule Each atomic orbital can only accommodate a maximum of 2 electrons Atomic orbital is a 3-D region in space around the nucleus where there is a high probability of finding an electron. Assigning electrons to subshells

s-orbital
p-orbitals d-orbitals

a max of 2 electrons (ns2)

a max of 6 electrons (np6) a max of 10 electrons (nd10)
79

The Anomalous Electronic Configurations of Cr and Cu

Cr and Cu have electron configurations which are inconsistent with the Aufbau principle. The anomalous are explained on the basis that a completely filled or halffilled orbital is more stable.

Element

Expected

Observed/actual

Cr (Z=24)
Cu (Z=29)

[Ar] 3d4 4s2

[Ar] 3d9 4s2

[Ar] 3d5 4s1

[Ar] 3d10 4s1

80

For Chromium : 24 eExpected : Cr = 1s2 2s2 2p6 3s2 3p6 4s2 3d4 24 Orbital diagram:
24Cr

= [ Ar ]

3d

4s

Observed : Cr = 1s2 2s2 2p6 3s2 3p6 4s1 3d5 24 Orbital diagram:
24Cr

= [ Ar ]

3d

4s
81

For Copper : 29 eExpected : Cu = 1s2 2s2 2p6 3s2 3p6 4s2 3d9 29 Orbital diagram:
29Cu

= [ Ar ]

3d

4s

Observed : Cu = 1s2 2s2 2p6 3s2 3p6 4s1 3d10 29 Orbital diagram:
29Cu

= [ Ar ]

3d

4s
82

 Orbitals that are halffilled (s1, p3 or d5) or completely filled (s2, p6 or d10) have extra stability due to the equal symmetrical distribution of charge around an atom.

83

z = 21

z = 30
84

Thinking question
1. How many 2p orbitals are there in an atom?

2. How many electrons can be placed in the 3d sub-shell?

85

3.What is the electron configuration of Mg?

4.What are the possible quantum numbers for the last (outermost) electron in Cl?

86

THE END

87