UNIT 12: ATOMIC STRUCTURE

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12.1 Early Models of the Atom

12.1.1 Thomsons model of the atom In 1898, Joseph John Thomson suggested a model of an atom that consists of homogenous positively charged spheres with tiny negatively charged electrons embedded throughout the sphere as shown in figure 12.1a. The electrons much likes currants in a plum pudding. This model of the atom is called plum pudding model of the atom.

positively charged electron sphere Fig. 12.1a 12.1.2 Rutherfords model of the atom In 1911, Ernest Rutherford performed a critical experiment that showed the Thomsons model is not correct and proposed his new atomic model known as Rutherfords planetary model of the atom as shown in figure 12.1b.
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nucleus electron Fig. 12.1b

+Ze plop plop

-e

According to this model, the atom was pictured as electrons orbiting around a central nucleus which concentrated of positive charge. The electrons are accelerating because their directions are constantly changing as they circle the nucleus. Based on Maxwells electromagnetic theory, an accelerating charge emits energy. Hence the electrons must emit the e.m. radiation as they revolve around the nucleus. As a result of the continuous loss of energy, the radii of the electron orbits will be decreased steadily. This would lead the electrons spiral and falls into the nucleus, hence the atom would collapse as shown in figure 12.1c.

energy loss
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Fig. 12.1c

12.2 Bohrs Model of Hydrogen Atom

In 1913, Neils Bohr proposed a new atomic model based on hydrogen atom. According to Bohrs Model, he assumes that each electron moves in a circular orbit which is centred on the nucleus, the necessary centripetal force being provided by the electrostatic force of attraction between the positively charged nucleus and the negatively charged electron as shown in figure 12.2a. On this basis he was able to show that the energy of an orbiting electron -e depends on the radius of its orbit. This model has several features which r r are described by the postulates v FE (assumptions) stated below : +e 1. The electrons move only in certain circular orbits, called r STATIONARY STATES or ENERGY LEVELS. When it is in LEVELS one of these orbits, it does not radiate energy. energy Fig. 12.2a
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2. The only permissible orbits are those in the discrete set for which the angular momentum of the electron L equals an integer times

h/2 . Mathematically,

nh and L = mvr 2 nh or mvr = mvr = nh 2 where r : radius of the orbit m : mass of the electron L=

(12.2a)

3. Emission or absorption of radiation occurs only when an electron makes a transition from one orbit to another. The frequency f of the emitted (absorbed) radiation is given by

n : principal quantum number = 1,2 ,3 ,... h : planck constant h h = 2

where
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E = hf = E f Ei E f : final energy state Ei : initial energy state

(12.2b)
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Note : If

If 12.2.1 Bohrs Radius in Hydrogen atom

E negative value E positive value

Emission of e.m. radiation. e.m. Absorption of e.m. radiation. e.m.

Consider one electron of charge e and mass m moves in a circular orbit of radius r around a positively charged nucleus with a velocity v (Figure 12.2a). The electrostatic force between electron and nucleus contributes the centripetal force as write in relation below : FE = Fc centripetal force electrostatic force

kq1q2 mv 2 where q1 = e ; q2 = e = r2 r2 e mv 2 = (12.2c) 4 0 r nh From the Bohrs second postulate : mvr = 2

By taking square of both side of the equation, we get

and

k=

1 4 0

m2v 2 r 2 =
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n2h2 4 2

(12.2d)
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By dividing eq. (12.2d) and (12.2c), thus

mr =

n 2 h 2 0 e 2 n 2 h 2 0 r= ; n = 1,2,3,... me 2
h 0 me 2

(12.2e)

which r are radii of the permissible orbits for the Bohr atom. Eq. (12.2e) can be written as 2

r = a0 n 2 ; n = 1,2,3,...with a0 =

Where a0 is called the Bohrs radius of hydrogen atom. Bohr It is defined as the radius of the lowest orbit or ground state (n=1) and is given by 2

r = a0 (1) =
2

(6.63 10 ) (8.85 10 ) (9.11 10 )(1.60 10 )

34 12 31 19 2

a0 = 5.31 10 11 m
The radii of the orbits associated with allowed orbits or states n
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=
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2,3, are 4a0,9a0,, hence the atomic radius is quantized.

12.2.2 Discrete Energy in Hydrogen atom The total energy E of the system is given by Kinetic energy of the electron

E = K +U

(12.2f)

Potential energy of the electron The potential energy, U of the electron is

U=

and the kinetic energy, K of the electron is

1 kq1q2 where q1 = e ; q2 = e and k = 40 r 2 e (12.2g) U = 4 0 r K=

K=

By substituting eq. (12.2c) into eq. (12.2h), thus

1 2 mv 2

(12.2h)

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1 e2 2 4 0 r e2 K= 8 0 r

(12.2i)

By substituting eq. (12.2g) and (12.2i) into eq. (12.2f), therefore the

e2 + 8 0 r 4 0 r 2 e (12.2j) E= 8 0 r Ze 2 In general, En = 8 0 r Z : atomic number where E= e2

total energy E of the system is

Equation of discrete energy in hydrogen atom only (12.2k)

From de Broglies relation, the electron is to be regarded as a wave, then its stable orbits in an atom are those satisfy the conditions of a standing (stationary) wave as shown in figures 12.2b, 12.2c, 12.2d , 12.2e and 12.2f. orbital

n=1

n=2

n=3

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Fig. 12.2b

= 2r1

2 = 2r2
Fig. 12.2c

3 = 2r3
Fig. 12.2d

n=4

n=5

4 = 2r4
Fig. 12.2e

5 = 2r5
Fig. 12.2f

If there are n waves in the orbital and is wavelength of wave properties of electron therefore

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n = 2rn (12.2l) th where rn : radius of the n orbit n = 1,2 ,3,... h Since = then eq. (12.2l) can be written as mv h n = 2rn mv nh mvrn = Bohrs second postulates Bohr 2

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The energy level of hydrogen atom is given by

En =

n 2 h 2 0 Ze 2 where Z = 1 and r = me 2 8 0 r (hydrogen atom) (1)e 2 En = n 2 h 2 0 8 0 me 2 4 me 4 me and E1 = = 13.6 eV En = 2 2 2 2 8 0 h 2 8 0 h n 13.6 eV E1 (12.2m) En = 2 or En = n2 n th where En : energy level of the n orbit(state) E1 : energy level of ground state n = 1,2 ,3,...

The negative sign means that work has to be done to remove the electron to infinity, where it is considered to have zero energy, i.e. the electron is bound to the atom.
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12.3 Energy Level of Hydrogen Atom

The energies of the electron in an atom can have only certain values. This values are called the energy level of the atom. The energy level of hydrogen atom can be calculated by using eq. (12.2m) which is 13.6 eV

En =

= 1, the ground state (the state of the lowest energy level) level 13.6 eV E1 = = 13.6 eV (1)2 13.6 eV = -3.39 eV When n = 2, the first excited state, E2 = 2

When n

n2

; n = 1,2,3,...

2 13.6 eV n = 3, the second excited state,E3 = = 1.51 eV 32 13.6 eV n = 4, the third excited state, E4 = = -0 .85 eV 42 13.6 eV electron is completely n = , E = =0 2 removed from the atom. ( )
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Figure 12.3a shows diagrammatically the various energy levels in the hydrogen atom.

En (eV ) 0.0 Free electron

0.54 0.85 1.51

Ionization energy is defined as the energy required by an electron in2 the ground state to escape completely from the attraction of the nucleus.

5 4 3

4th excited state 3rd excited state 2nd excited state

excited state

3.39

1st excited state is defined as the energy levels that higher than the ground state.

Excitation energy is defined as the energy required by an electron that raises it to an excited state from its ground state.

An atom becomes ion.

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13.6
Fig. 12.3a

Ground state

is defined as the lowest stable energy state of an 13 atom.

Example 1 : The electron in the hydrogen atom makes a transition from E2=-3.40 eV energy state to the ground state with E1= -13.6 eV. Calculate a. the energy in Joule, and b. the wavelength of the emitted photon. (Given h = 6.63 x 10-34 J s and c = 3.00 x 108 m s-1) Solution: a. The energy of the emitted photon is

E = E f Ei E = E1 E2 E = ( 13.6 ) ( 3.40 ) E = 10.2 (1.60 10 19 ) E = 1.63 10 18 J

b. The wavelength of the photon is

Negative sign means the energy is emitted.

E =

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hc hc = E = 1.22 10 7 m

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Example 2 : The lowest energy state for hydrogen atom is E1= -13.6 eV. Calculate the frequency of the photon required to ionize the atom. (Given h = 6.63 x 10-34 J s and c = 3.00 x 108 m s-1) Solution: An atom where its electron at ground state is raised to the zero energy level said to be ionized. The ionization energy is

The frequency of the photon required to ionize the atom is

E = E f Ei E = E E1 E = (0 ) ( 13.6 ) E = 13.6 (1.60 10 19 ) E = 2.18 10 18 J

E = hf E f = h f = 3.29 10 15 Hz
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Example 3 : A hydrogen atom emits radiation of wavelengths 121.5 nm and 102.4 nm when the electrons make transitions from the 1st excited state and 2nd excited state respectively to the ground state. Calculate: a. the energy of a photon for each of the wavelengths above; b. the wavelength emitted by the photon when the electron makes a transition from the 2nd excited state to the 1st excited state. (Given h = 6.63 x 10-34 J s and c = 3.00 x 108 m s-1) Solution: 1=121.5x10-9 m, 2=102.4x10-9 m a. The energy of the photon due to transition from 1st excited state to the hc ground state is

E1 =

The energy of the photon due to transition from 2nd excited state to the hc ground state is

1 E1 = 1.64 10 18 J

E2 =

2 E2 = 1.94 10 18 J
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b.

E3 E1 E2 E3 = E2 E1 E3 = 3.00 10 19 J

2nd excited state 1st excited state Ground state

Therefore the wavelength of the emitted photon due to the transition from 2nd excited state to the 1st excited state is

E3 =

hc 3 3 = 6 .63 10 7 m

Example 4 : The electron of an excited hydrogen atom make a transition from the ground state to the 4th excited state. Determine the energy absorbs by the atom. (Given h = 6.63 x 10-34 J s and c = 3.00 x 108 m s-1)

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Solution: a. By applying the equation of energy level in hydrogen atom,

13.6 eV n2 13.6 eV Ground state, n = 1 E1 = 12 E1 = 13.6 (1.60 10 19 ) J E1 = 2.18 10 18 J 13.6 eV E5 = 4th excited state, n = 5 52 E5 = 0.54 (1.60 10 19 ) J E5 = 8.64 10 20 J En =
Hence the energy absorbs by the atom is

E = E f Ei E = E5 E1 E = 2.09 10 18 J

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12.4 Emission Line Spectrum

The emission lines correspond to photons of discrete energies that are emitted when excited atomic states in the gas make transitions back to lower energy levels. Figure 12.4a shows line spectra produced by emission in the visible range for hydrogen (H), mercury (Hg) and neon (Ne).

Fig. 12.4a 12.4.1 Hydrogen Emission Line Spectrum Emission processes in hydrogen give rise to series, which are sequences of lines corresponding to atomic transitions as shown in figure 12.4b.
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n ( eV ) 0. 0 Free electron

5 4 3 2

0. 54 4th excited state *Pfund series 0. 85 3rd excited state *Brackett series 1. 51 2nd excited state Paschen series involves transitions that end with the Infrared range 2nd excited state. 3. 39 1st excited state Balmer series involves transitions ending with the Visible light range 1st excited state of hydrogen.

Lyman series Ultraviolet involves transitions that end with the range ground state of hydrogen. 13 . 6 Ground state 1 Fig. 12.4b *Brackett series involves transitions that end with the 3rd excited state. Infrared *Pfund series involves transitions that end with the range SF027 20 Simulation 4th excited state.

Figure 12.4c shows permitted orbits of an electron in the Bohr model of a hydrogen atom.

Fig. 12.4c : not to scale

Figure 12.4d illustrates the lines spectrum of Balmer series for hydrogen atom.

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Fig. 12.4d

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12.4.2 Wavelength of Emission Line Spectrum for Hydrogen atom If an electron makes a transition from an outer orbit (ni) to an inner orbit (nf), energy is radiated. The energy radiated can be calculated by using equation below:

E = E f Ei = En f Eni
4 4 me me E = 8 2 h2 n 2 8 2 h2 n 2 o f o i

Emission of e.m. e.m. radiation (you can ignore it)

E =

me4 1 1 2 2 2 2 8 o h n f ni

(12.4a)

Hence the wavelength of the photon emitted (energy radiated in form of e.m. radiation) is shown below. Since

E =

hc

hc me4 1 1 = 2 2 2 2 8 o h n f ni

then eq. (12.4a) can be written as

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me4 1 1 2 2 2 3 8 o ch n f ni
(12.4b)

1 1 = RH 2 2 n ni f
where

RH : Rydberd constant n f : final value of n ni : initial value of n

For Lyman series (nf=1) :

RH =

me4 = 1.0974 107 m 1 2 3 8 0 ch

Note:

For Balmer series (nf=2) :

1 1 = RH 2 2 1 n i 1 1 1 = RH 2 2 2 n i 1 1 1 = RH 2 2 3 n i 1

For Paschen series (nf=3) :

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For Brackett series (nf=4) :

For Pfund series (nf=5) :

To calculate the shortest wavelength in any line series, ni=. Example 5 : Determine the wavelength for a line spectrum in Lyman series when the electron makes a transition from n=4 level. (Given Rydberg constant ,RH = 1.0974 x 107 m s-1) Solution:

1 1 = RH 2 2 4 ni 1 1 1 = RH 2 2 5 n i 1

ni=4

By applying the equation of wavelength for Lyman series (nf=1), thus

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1 1 = RH 2 2 1 n i 1 1 1 = 1.0974 107 2 2 1 4 8 = 9.72 10 m 1

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Example 6 : The Balmer series for the hydrogen atom corresponds to electronic transitions that terminate at energy level n=2 as shown in the diagram below. E (eV ) n

6 5 4 3 2

0. 0 0. 38 0. 54 0. 85 1. 51

3. 40

Calculate a. the longest-wavelength, and b. the shortest-wavelength photon emitted in this series. (Given Rydberg constant ,RH = 1.0974 x 107 m s-1) Solution: nf=2 The equation of wavelength for Balmer series is

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1 1 = RH 2 2 2 n i 1

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a. The longest-wavelength photon results from the transition from n = 3 to n = 2 (Balmer series). Thus

max

1 1 = RH 2 2 2 3

or

max = 6.56 10 7 m

Emin = E f Ei = E2 E3 Emin = ( 3.40 ) ( 1.51) Emin = 1.89 1.60 10 19 Emin = 3.02 10 19 J hc = 3.02 10 19 J

max

b. The shortest-wavelength photon results from the transition from n = to n = 2 (Balmer series). Thus

min

1 1 = RH 2 2 2

or

min = 3.65 10 7 m
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Emax Emax Emax Emax hc

= E f Ei = E2 E = ( 3.40 ) (0 ) = 3.40 1.60 10 19 = 5.44 10 19 J = 5.44 10 19 J

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min

12.5 Many Electrons Atomic Model

12.5.1 Limitations of Bohrs Model The Bohrs theory predicts successfully the energy levels of the hydrogen atom but fails to explain the energy levels of more complex atoms. can explain the spectrum for hydrogen atom but some details of the spectrum cannot be explained especially when the atom is placed in a magnetic field. cannot explain the Zeeman effect. Zeeman effect is defined as the splitting of spectral lines when the radiating atoms are placed in a magnetic field. Figure 12.5a shows the zeeman effect. 2p Energy Levels Transitions 1s No magnetic field Magnetic field Fig. 12.5a Spectra
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12.5.2 Utilises 4 quantum numbers: Principal quantum number, n: Specifies the main energy level and corresponds to the number n in the Bohr atomic model where n = 1,2,3,... Orbital (azimuthal) quantum Number, l : (azimuthal) Specifies the angular momentum of electron, where

l = 0,1,2,..., (n 1)
= 1, l = 0 For n = 2, l = 0 and 1 For n = 3, l = 0,1 and 2
Magnetic quantum number, ml : Specifies the orientation of the electron orbitals in a magnetic field and plays an important part in explaining the Zeeman effect E.g : a. l For n

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= 0, ml = 0 b. l = 1, ml = -1,0,+1 c. l = 2, ml = -2,-1,0,+1,+2

ml = l ,(l 1),...,0,1,..., (l 1),+l

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Spin quantum number, ms: Electron spins when put in a magnetic field and have a magnetic moment because of this spin. Its value is given by Specify whether the spin aligned 1 ms = with, or counter to, an applied 2 magnetic field. 12.5.3 Pauli Exclusion Principle States No two electrons in an atom can have the same set of four No quantum numbers. numbers. It is needed in describing the electron configuration of multi-electron atoms. Example 7 : Write down the set of quantum number for electron with principal quantum number n=2. Solution: When n=2; l = 0,1; ml=0,-1,0,+1; ms = , , , The following set of quantum numbers are, therefore, possible :

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(2,0,0,+) ; (2,0,0,-) (2,1,-1, +); (2,1,-1, -) (2,1,0, +); (2,1,0, -) (2,1,1, +); (2,1,1, -)

There are 8 electron states with n = 2 and these form the L shell
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or in table form :

Note : Table 12.5a shows the electron quantum states in the first four shell.

n 2 l 0 1 ml 0 -1 0 +1 m s + - + - + - + -
Subshell 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f Number of electron 2 2 6 2 6 10 2 6 10 14 32 18 8 Shell

n
1 2 2 3 Table 12.5a 3 3 4 4 4
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l
0 0 1 0 1 2 0 1 2 3

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

K L M

N
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The total number of electrons in all the shells equal to Z, the atomic number. Hence the electron configuration for various elements can be written as shown below in table 12.5b. Element He Be C O Ne Mg Si S Ar Ca Atomic Number (Z) 2 4 6 8 10 12 14 16 18 20 1s2 1s22s2 1s22s22p2 1s22s22p4 1s22s22p6 1s22s22p63s2 1s22s22p63s23p2 1s22s22p63s23p4 1s22s22p63s23p6 1s22s22p63s23p64s2 Table 12.5b
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Electron Configuration

Figure 12.5b shows the energy levels for various subshell.

4p 3d 4s 3p 3s

Energy level

Maximum electron in shell

2p n = 2 2s

n = 1 1s
Fig. 12.5b Example 8 : (exercise) Write down the set of quantum number of electron in form of table for nitrogen atom with atomic number, Z=14.

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THE END
Next Unit
UNIT 13 : X-rays

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