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CHAPTER 2 ATOMIC STRUCTURE

2.1 Bohrs Atomic Model 2.2 Quantum Mechanical Model 2.3 Electronic Configuration

CHAPTER 2 ATOMIC STRUCTURE

2.1 Bohrs Atomic Model

2.1

Bohrs Atomic Model

Learning Outcomes a) Describe Bohrs atomic model. b)Explain the existence of energy levels in an atom. c) Calculate the energy of an electron using: En = -RH(1/n2) , RH = 2.18 x 10-18 J of line spectrum of

d)Describe the formation hydrogen atom.

e) Calculate the energy change of an electron during transition using: E = RH(1/n12 _ 1/n2 2) where RH = 2.18 x 10-18 J
4 f) Calculate the photon of energy emitted by an

2.1

Bohrs Atomic Model

Learning Outcomes g)Perform calculation involving the Rydberg equation for Lyman, Balmer, Paschen, Brackett and Pfund series.

1/ = RH(1/n12 _ 1/n2 2) where RH = 1.097 x 107 m-1 and n1<n2

h)Calculate the ionisation energy of hydrogen atom from Lyman series. j) State the weaknesses of Bohrs atomic model. k) State the dual nature of electron using de Broglies postulate and Heisenbergs uncertainty 5 principle.

2.1

Bohrs Atomic Model

In 1913, a young Dutch physicist, Neils Bhr proposed a theory of atom that shook 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.
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2.1

Bohrs Atomic Model

Postulate 1

Electron moves in circular orbits around the nucleus. When moving in the orbit, the electron does not radiate or absorb any energy. H Nucleus (proton)
1 1

2.1

Bohrs Atomic Model

Postulate 2

The energy of an electron in a hydrogen atom is quantised, that is, an electron moving in an orbit can have only a certain amount of energy. n=1 n=3

H Nucleus (proton)

n=2
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2.1

Bohrs Atomic Model

Postulate 3

At ordinary conditions the electron is at the ground state (lowest level). If energy is supplied, electron absorbs the energy and is promoted from a lower energy level to a higher ones. The process is called excitation.
3)

Postulate 4
Electron at its excited state is unstable. It will fall back to lower energy level and releases a specific amount of energy in the form of light. The energy of the photon equals the energy difference between the levels.
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2.1

Bohrs Atomic Model

Points to Remember
lGround

state

The state in which the electrons have their lowest energy

lExcited

state

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

level

Energy associated with a specific orbit or state

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2.1

Bohrs Atomic Model

The energy of an electron in its level is given by: 1

E n = R H 2 n

RH = 2.1810-18 J (Rydberg constant) n (principal quantum number) = 1, 2, 3 (integer) .

Note: n determines the main energy level 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) 11

2.1

Bohrs Atomic Model

Radiant energy emitted when the electron moves from higher-energy state to lower-energy state is given by the difference in energy between energy levels:

E = Ef - Ei
1 1 E = R H 2 R H 2 n n f i
Thus,

where :

1 E i = R H 2 n i

1 E f = R H 2 n f

1 1 E = R H 2 2 n nf i

where, RH = 2.18 10values of RH ?? 2 -18 J

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2.1

Bohrs Atomic Model

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

h (Plancks constant) = 6.63 10-34 J E = h = frequency

A photon of energy is emitted in the form of radiation with appropriate frequency and wavelength.

c =

Thus,

hc E =
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c (speed of light) = 3.00108 ms-1

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 = 3n = 4

lectron falls from higher to lower energy level . photon of energy is released. E = h = E3-E1 (-ve)
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2.1

Bohrs Atomic Model

Energy level diagram for the hydrogen atom n =

Potential energy

n = 4 n = 3 n = 2 Energy absorbed Energy released n = 1

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2.1
Example 1 :

Bohrs Atomic Model

Calculate the energy of an electron in the second energy level of H a hydrogen atom. R = 2.1810-18 J (-5.448 x 10-19 J)

1 E n = R H 2 n
22) E2 = - 2.1810-18 J (1 / = 5.45 x 10-19 J

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2.1
Example 2 :

Bohrs Atomic Model

Calculate the energy of an electron in the energy level n = 6 of a hydrogen atom. (6.055 x 10-20 J)

1 E n = R H 2 n
/ 62) E6 = - 2.18 10-18 J (1 = -6.055 x 10-20 J

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2.1
Try this

Bohrs Atomic Model

(a)Calculate the energy change (J), that occurs when an electron falls from n = 5 to n = 3 energy level in a hydrogen atom. (answer: 1.1 x 1 -19 J) 55 10

E = R H 2 2 n nf i

E = 2.18 10-18 J [(1/52) (1/32)] = 6.055 x 10-20 J = 1.55 x 10-19 J

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2.1
Try this

Bohrs Atomic Model

( b)

Calculate the frequency and wavelength (nm) of the radiation emitted. (2.34 x 1014 s-1 , 1280nm) hc = 1.55 x 10-19 J = [6.63 10-34 J] E = [3.00108 ms-1 ] = [6.63 10-34 J][3.00108 ms-1 ] 1.55 x 10-19 J

c =
v
1014 s-1 = = 1280nm

2.34 x 1014 s-1

3.00108 ms-1 / 2.34 x

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2.1

Bohrs Atomic Model

Emission Spectra

Continuous Spectra

Line Spectra

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2.1 Bohrs Atomic Model 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.

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2.1 Bohrs Atomic Model Continuous Spectrum

Regions of the Electromagnetic Spectrum

 When white light from incandescent lamp is passed through a slit then a prism, it separates into a spectrum.

2.1 Bohrs Atomic Model Formation of the Continuous Spectrum

The white light spread out into a rainbow of colours produces a continuous spectrum.

The spectrum is continuous in that all wavelengths are presents and each colour merges into the next without a break.

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2.1 Bohrs Atomic Model The Line Spectrum (atomic spectrum)

Line spectrum is a spectrum consists of discontinuous and discrete lines produced by excited atoms and ions as the electrons fall back to a lower energy level.

The radiation wavelength or It means each wavelength or

emitted is only at a specific frequency. line corresponds to a specific frequency.

Line spectrum is composed of only a few wavelengths giving a series of discrete line separated by blank areas

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2.1 Bohrs Atomic Model Formation of the Line Spectrum

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.
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2.1 Bohrs Atomic Model Formation of the Line Spectrum

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 now said to be at excited state (very 26 unstable).

2.1 Bohrs Atomic Model Formation of the Line Spectrum

When an electrical discharge is passed through a sample of hydrogen gas at low pressure, hydrogen molecules decompose to form hydrogen atoms.
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2.1 Bohrs Atomic Model Formation of the Line Spectrum

Emission of photon

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)
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2.1 Bohrs Atomic Model Formation of the Line Spectrum

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2.1 Bohrs Atomic Model Formation of the Line Spectrum

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2.1 Bohrs Atomic Model Emission Series of Hydrogen atom

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2.1

Bohrs Atomic Model

Test yourself 1
Complete the following table Series n1 n2 Spectrum region ultraviolet Visible Infrared Infrared Infrared
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Lyman Balmer Paschen Brackett Pfund 4 5 2

2,3,4, 3,4,5,

4,5,6, 5,6,7, 6,7,8,

2.1

Bohrs Atomic Model

Test yourself 2
The following diagram depicts the line spectrum of hydrogen atom. Line A is the first line of the Lyman series.

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
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2.1

Bohrs Atomic Model

Test yourself 3
Describe the transitions of electrons that lead to the lines W, and Y, respectively.

Answer

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

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2.1

Bohrs Atomic Model

Try at home
Calculate En for n = 1, 2, 3, and 4. Make a one dimensional graph showing energy, at different values of n, increasing vertically. On this graph, indicate by vertical arrows transitions that lead to lines in a) Lyman series b) Paschen series

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2.1 Bohrs Atomic Model Significance of the 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 Balmer Series Lyman Series

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2.1
Example

Bohrs Atomic Model

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.
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Next Lecture

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2.1 Bohrs Atomic Model The Rydberg Equation

The wavelength emitted by the transition of electron between two energy levels is calculated by using the Rydberg Equation.

1 1 = 1 R H 2 2 n2 n1
Where RH = 1.097 107 m-1 = wavelength Since should have a positive value thus n1 < n2
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2.1 Bohrs Atomic Model The Rydberg Equation

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

Solution (a) Second line of Balmer series: the transition of electron is from n = 4 to n = 2 So, n2=4 and

1 1

1 22
) 1

= (1.097 107

1 22

1 42

= 4.86 107
= 486

109 nm 1 m
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2.1 Bohrs Atomic Model The Rydberg Equation

Example :

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

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= 4.10 x 10-7 m
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2.1 Bohrs Atomic Model The Rydberg Equation

Different values of RH and its usage 1. RH = 1.097 107 m-1 2. 3. 1 = RH 4. 5. 6. 7. 8. 9. RH = 2.18 x 10-18 J 10. E = R

1
2 n1

1
2 n2

n1 < n2

1 1 2 H n2 n f i

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Sampai sini

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EXAMPLE 2

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

1 1

= RH

1
2 n1
1

1
2 n2
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hc E =
E = (6.63 10-34 Js)X(3.00108 ms-1 ) X (0.2303 X 107 m-1 )

=1.097 x 107

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E = 4.58 x 10-19 J = 0.2303 X 107 m-1

(or by directly using the energy difference formula)
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Exercise 6
Calculate what is; i ) Wavelength ii ) Frequency iii ) Wave number of the last line of hydrogen spectrum in Lyman series (Wave number = 1/wavelength)

For Lyman series; n1 = 1 & n2 = Ans: i.9.116 x10-8 m ii.3.29 x1015 s-1 iii.1.0970 X 107 m-1
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SOLUTION
1 =1.097 x 107 1 1

i)

12

= 1.097 X 107 m-1

= 9.116 X 10-8 m

ii) V = c =3.00 X 108 ms-1 = 3.29 X 1015 s-1 9.116 X 10-8 m

iii) Wave number =
1

= 1.097 X 107 m-1

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Ionization Energy
Definition : Ionization energy is the minimum energy required to remove one mole of electron from one mole of gaseous atom/ion. M (g) M+(g) + e H = +ve

The hydrogen atom is said to be ionised when electron is removed from its ground state (n = 1) to n = .

At n = , the potential energy of electron is zero, here the nucleus attractive force has no effect on the electron (electron is free from nucleus). 47

Example
n1 = 1, n2 =

= RH (1/ni2 1/nf2) = 2.18 X 10 -18 (1/12 1/ 2) = 2.18 X 10 -18 (1 0) = 2.18 X 10 -18 J

Ionisation energy = 2.18 X 10 -18 J x 6.02 X 1023 mol-1 = 1.312 x 106 J mol-1 = 1312 kJ mol-1

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Finding ionisation energy experimentally:

Convergent limit 1 st line

Ionisation energy is determined by detecting the wavelength of the convergence point

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Example

10.97 10.66

10.52

10.27

9.74

8.22

wave number (x106 m-1 )

The Lyman series of the spectrum of hydrogen is shown above. Calculate the ionization energy of hydrogen from the spectrum.

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Solution = hc/ =h x c / = h x c x wave no. = 6.626 x 10-34 J s x 3 x 108 m s-1 x 10.97x 106 m-1 = 218.06x 10-20 J = 2.18 x 10-18 J

Ionisation energy = 2.18 X 10 -18 x 6.02 X 1023 J mol-1 =1.312 x 106 J mol-1 = 1312 kJ mol-1

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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.
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Point to Ponder
Davisson & Germer observed the diffraction of electrons when a beam of electrons was directed at a nickel crystal. Diffraction patterns produced by scattering electrons from crystals are very similar to those produced by scattering X-rays from crystals. This experiment demonstrated that electrons do indeed possess wavelike properties.

Thus, can the specified???

position

of

wave

be

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de Broglies Postulate
In 1924 Louis de Broglie proposed that not only light but all matter has a dual nature and possesses both wave and corpuscular properties. De Broglie deduced that the particle and wave properties are related by the expression:

h = Planck constant (J s) m = particle mass (kg) = velocity (m/s) = wavelength of a matter wave
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Heisenbergs Uncertainty Principle

It is impossible to know simultaneously both the momentum p (defined as mass times velocity) and the position of a particle with certain.

Stated mathematically,

x p

Where x = uncertainty in measuring the position p = uncertainty in measuring the momentum = mv h = Planck constant
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