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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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-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
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
where
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(12.2b)
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Note : If
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
and
k=
1 4 0
m2v 2 r 2 =
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n2h2 4 2
(12.2d)
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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
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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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)
U=
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
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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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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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.
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
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.
13.6
Fig. 12.3a
Ground state
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 =
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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
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
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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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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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.
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
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
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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 =
Note:
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
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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
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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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min
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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
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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
4p 3d 4s 3p 3s
Energy level
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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