4.1 Atomic Spectra. Spectrum ~ display of component of a beam of radiation.

When white ray passes through a prism it forms rainbow colour. A continuous spectrum is spectrum composed of visible light of all wavelength while a discontinuous spectrum which the line spectrum represent the atomic emissions Productions of line spectrum depend on what types of element used and the visible light emitted also depend on it. Spectrophotometer is the instrument that is used to split and dispersed into individual wavelength. The study of line spectra can be used to Identify an element Determine the ionisation energy of an element Determine the arrangement of electrons in an atom of an element.

The main components of a typical spectrophotometer

Lenses/slits/collimaters narrow and align beam. Sample in compartment absorbs characteristic amount of each incoming wavelength. Computer converts signal into displayed data.

Source produces radiation in region of interest. Must be stable and reproducible. In most cases, the source emits many wavelengths.

Monochromator (wavelength selector) disperses incoming radiation into continuum of component wavelengths that are scanned or individually selected.

Detector converts transmitted radiation into amplified electrical signal.

7.3

4.2 The Atomic Emission Spectrum of Hydrogen In hydrogen, the atomic emission spectrum of hydrogen shows a few distinct series of line. These are the ultraviolet region Lyman series in visible Balmer series in . region. infrared Paschen series in region The diagram below shows the example of the line emission produced through the spectrophotometer.

4.2.1 Formation of atomic spectra. The absorption spectrum of a substance is a continuous spectrum of radiation produced by examining the substance through spectrophotometer. Hence, there is a absorption and emission process occur in the formation of spectra where
Absorption spectroscopy Occur when electron which is occupying at lower energy level (ground level / state) absorb light at a certain frequency. When enough energy is absorbed, electron is able to excite to a higher energy level. n=3 n=2 Emission spectroscopy Occur when electron which is located at a high energy level (after absorbed energy) released the energy in the form of radiation When energy is released, electron falls to the original ground state, emitting the radiation and hence give the spectrum n=3 n=2

n=1

n=1

The following characteristics of any series should be noted : The spectrum consists of discrete lines, each having its own discrete frequency.

1 1 = RH 2 2 n n 2 1 1

= wavelength (in m) n1 = series of the spectra line n2 = line where the emission of energy begin. RH = Rydberg constant = 1.097 x 107 m-1

The wavelengths represented by broken lines are called spectrum (plural : spectra) Each spectrum represents the wavelength (or frequency) in a series. The frequency emitted can be related to the spectral line by the Rydbergs Equation The value of n1 and n2 for the atomic spectrum of hydrogen are given in Table below
Series Lyman Balmer Paschen n1 1 2 3 n2 2, 3, 4 . 3, 4, 5 . 4, 5, 6 .

Example 1 : Calculate the wavelength of the first line of Lyman series

Example 2 : Calculate the wavelength of the third line of Balmer series

In Lyman series, n1 = 1 First line in series, so n2 = 1 1 1 1 = RH 2 n2 n 2 1

+1=2 1 1 7 1 = 1 . 097 10 2 2 1 2 = 122 nm

In Balmer series, n1 = 2 First line in series, so n2 = 2 + 3 = 5

1 1 = RH 2 2 n2 n1 1
1 1 7 1 = 1 . 097 10 2 2 5 2 = 434 nm

Example 3 : Calculate the wavelength of the forth Example 4 : Calculate the wavelength of the last line of Paschen series line of Balmer series

In Passchen series, n1 = 3 First line in series, so n2 = 3 1 1 1 = RH 2 2 n2 n1

+4=7

In Balmer series, n1 = 2 Last line in series, so n2 = 2 + =

1 1 = RH 2 2 n2 n1 1
1 1 7 1 = 1 . 097 10 2 2 2 = 365 nm

1 1 7 1 = 1 . 097 10 2 2 3 7 = 1005 nm

c (speed of light ) 3 .0 10 8 m s 1 Since frequency, f = ; f= ( wavelength ) m

Example 5 : Calculate the frequency of the second line of Paschen series Example 6 : Calculate the frequency of the last line of Lyman series

In Passchen series, n1 = 3 Second line in series, n2 = 3 + 2 = 5

1 1 = RH 2 2 n2 n1 1

In Lyman series, n1 = 1 last line in series, so n2 = 1 + =

1 1 7 1 = 1 . 097 10 2 2 1

1 1 1 1 1 1 = 1 . 097 10 7 2 2 = R H 2 2 n n 5 2 1 3

1 / = 7.80 x 105 m-1 f = c x (1 / ) = (3.0 x 108)(7.80 x 105) f = 2.34 x 1014 s-1

1 / = 1.097 x 107 m-1 f =c x (1 / ) =(3.0 x 108)(1.097 x 107) f = 3.29 x 1015 s-1

In 1900, Max Planck proposed the quantum theory. He mentioned that radiant energy was emitted in discrete packets or quantum Each quantum of energy emitted, E, is proportional to the frequency, f, of the radiation Where energy, E = Planck constant (h) x frequency (f) h = 6.63 x 10-34 J s

Energy , E = h ( Planck con tan ts )

c (speed of light ) ( wavelength )

Example 7 : Calculate the energy required to excite one electron to the fourth line in Passchen series In Passchen series, n1 = 3 Fourth line in series, n2 = 3 + 4 = 7

Example 8 : Calculate the energy required to excite one electron to the last line in Balmer series. In Balmer series, n1 = 2 Last line in series, n2 = 2 + =

1 1 = RH 2 2 n n 2 1 1
1 1 7 1 = 1 . 097 10 2 2 3 7
1 / = 9.95 x 105 m-1 f = c x (1 / ) = (3.0 x 108)(9.95 x 105) f = 2.99 x 1014 s-1 E = hf E = 6.63 x 10-34 x 2.99 x 1014 E = 1.98 x 10-19 J / e

1 1 = RH 2 2 n n 2 1 1
1 1 7 1 = 1 . 097 10 2 2 2
1 / = 2.74 x 106 m-1 f = c x (1 / ) = (3.0 x 108)(2.74 x 106) f = 8.23 x 1014 s-1 E = hf E = 6.63 x 10-34 x 8.23 x 1014 E = 5.45 x 10-19 J / e

4.3 Electronic Energy Levels Hydrogen emission spectrums consist of several series of discrete lines in different limited wavelength. This implies that hydrogen atoms do not emit light at of all possible energies but only emit light with certain amount of energy. Bohr made these assumptions to explain line in spectrum. Electron move in orbit around nucleus (like planet and sun) Energy of electron is quantised (only have certain energy). Electron closer to nucleus has lower energy and vice versa. Electron of atom will fill up the lowest energy level first. But when energy is given to the electron, it moves from a lower level to a higher level. This process is called excitation. If the energy loss from the excited level to original level, electron will emit electromagnetic radiation. This is what caused the emission of spectral lines. The convergence of spectral line show the difference between successive energy level become with increasing distance of the energy levels from the nucleus

Electron are not randomly distributed but are arranged in a series of shells or orbits which are situated at various distance from the molecules corresponding to differ E-level. Though Bohr theory proves its unsatisfactory when come to spectra of more complicated atoms. Thus Rydberg equation can only used for atoms or ions contain only 1 electron. For atom or ion with many electrons, the analysis of atomic spectra become more difficult.

Wavelength increase

Frequency increase

4.4

Calculate the Ionisation energy of Hydrogen from its Line Spectrum When energy level of the hydrogen spectrum increased, theres a possibility where it reaches the convergence limit of the energy level where n = When this occur, electron are not able to return to .., ground level the hydrogen atom is .., according ionised and eventually to the following equation H+ (g) + eEquation : H (g) For this to occur, a certain amount of energy is required. The energy required to remove one electron is called ionisation energy Here, a positive charged ion is formed. There are 2 methods of calculating ionisation energy of hydrogen through the line spectrum

Using Rydberg and Planck equations Supposed that electron at energy level n1 = 1 absorbed energy and it is excited. When reaches the convergence limit, n2 = , the wavelength can be calculated Using Rydberg equation n1 = 1 n2 =

1 1 = RH 2 2 n2 n1 1

1 1 7 1 = 1 .097 x 10 2 2 1

1 = 1 .097 x 10 7

For each electron, the energy absorbed can be determined using the Planck equation

E=hf

E = h c 1/

E = (6.63 x 10-34)(3.0 x 108)(1.097 x 107) E = 2.182 x 10-18 J / e

Since this much energy is required to excite one electron, so for 1 mole of electron, the energy required

Since in 1 mol contain 6.02 x 1023 e, so Ionisation energy, H = E x NA = 2.182 x 10-18 J / e x 6.02 x 1023 = 1.313 x 106 J / mol + 1313 Hence, the ionisation energy of hydrogen is . kJ mol-1

4.5 Atomic Orbital Heinsberg uncertainty principle = position & momentum of an electron cannot be known with great precision but probability of finding an electron in a certain position can be calculated. high Orbital - the space within which theres a probability of electron finding an . The electron in the orbital is describe as occupying 3-D space around the nucleus. The nucleus is described as being surrounded by

Orbital boundary within which there is 95% (high) chances to find an electron

Type of orbital

Shape of orbital

Number of electron filled

Type of orbital

Shape of orbital

Number of electron filled

10

7 orbitals

14

Filling of orbitals in shell Electrons filled in the shell of an atom through occupation of orbitals in each shell The formula used to calculate the number of orbitals that can occupy each shell is No of orbitals in shell = n2 ; (n = the number of shell) Shell, n 1 2 3 4 No. of orbitals Type of orbitals Orbital in shell

n2 = 12 = 1 n2 = 22 = 4 n2 = 32 = 9 n2 = 42 = 16

s s,p s,p,d s,p,d,f

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

4.6 Electronic configuration Electronic configuration of an element is the expression on how the electrons inside the element filled in its orbitals accordingly There are 3 rules for assigning electrons to the orbitals of an atom in the ground state. 1. . Aufbau Principle 2. . Paulis Exclusion Principle 3. . Hunds Rule 1.The Aufbau Principle ~ e- occupy orbitals in the order of the energy levels of the orbitals. Orbital with the lowest energy are always occupied first. The arrangement of energy level from the lowest to the highest is shown in the diagram below

Energy level : 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p

2. The Pauli exclusion principle ~ 2 electron may occupy the same orbital but these 2 electrons must have opposite spin.

Opposite spin (Pauli exclusion principle) 3. The Hunds Rule ~ when electrons are placed in a set of orbitals with equal or degenerated energies, the electrons must occupy them singly with parallel spins before they occupy the orbital in pair In other words, an atom tend to have as many unpaired electrons as possible. Example : when filling in 3 electrons in p orbital

Same spin (cannot occur)

Element Hydrogen H Helium He Lithium Li Beryllium Be Boron B Carbon C Nitrogen N

No of e-

Orbital diagram ____ 1s ____ 1s ____ ____ 1s 2s ____ ____ 1s 2s ____ ____ ____ ____ ____ 1s 2s 2p ____ ____ ____ ____ ____ 1s 2s 2p ____ ____ ____ ____ ____ 1s 2s 2p

Electronic configuration

1 2 3 4 5 6 7

1s1 1s2 1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3

Element Oxygen O Fluorine F Neon Ne Sodium Na

Magnesium

No of e-

Orbital diagram ____ ____ ____ ____ ____ 1s 2s 2p ____ ____ ____ ____ ____ 1s 2s 2p ____ ____ ____ ____ ____ 1s 2s 2p ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s ___ ___ ___ 3p

Electronic configuration

8 9 10 11 12 13 14

1s22s22p4 1s22s22p5 1s22s22p6 1s22s22p63s1 1s22s22p63s2 1s22s22p63s23p1 1s22s22p63s23p2

Mg
Aluminium

Al
Silicon Si

____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s 3p

Element Phosphorous, P Sulphur S Chlorine Cl Argon Ar Potassium K Calcium Ca

No of e-

Orbital diagram

Electronic configuration

15 16 17 18 19 20

____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s 3p ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s 3p ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s 3p ____ ____ ____ ____ ____ ____ ____ ____ ____ 1s 2s 2p 3s 3p ____ ____ ____ ____ ____ ____ ____ ____ ____ ___ 1s 2s 2p 3s 3p 4s ____ ____ ____ ____ ____ ____ ____ ____ ____ ___ 1s 2s 2p 3s 3p 4s

1s22s22p63s23p3 1s22s22p63s23p4 1s22s22p63s23p5 1s22s22p63s23p6

1s22s22p63s23p64s1 1s22s22p63s23p64s2

1s22s22p63s23p63d14s2

1s22s22p63s23p63d24s2

1s22s22p63s23p63d34s2

1s22s22p63s23p63d54s1

1s22s22p63s23p63d54s2

1s22s22p63s23p63d64s2

1s22s22p63s23p63d74s2

1s22s22p63s23p63d84s2

1s22s22p63s23p63d104s1

1s22s22p63s23p63d104s2

Electron filling in orbitals at the same According to Hunds rule : .. energy level with single electron before pairing For the case of chromium, it has the valence electronic as 3d54s1 3d44s2 ... instead of . This is due to the extra stability achieved due to the equal / symmetrical distribution of charge around the atom within the half-filled (p3 and d5) orbital and full-filled orbital (p6 and d10) What happened before and after the electron filling in the 4s orbital can be explained by the diagram below

Position of 3 d and 4 s orbital before electron filling in ____ ____ ____ ____ ____ 3d ____ 4s

Position of 3d and 4s orbital after electron filling in ____ 4s ____ ____ ____ ____ ____ 3d

When this occurs, the 3rd electron is expected to be filled in 3d orbital (Aufbau principle). Until the 6th electron is filling in, a degeneration of orbital occur where now the energy level between 3d and 4s orbital are the same, thus one of the electron from the 4s jumped to 3d orbital. When this happened, an extra stability occur at the half-filled 3 d orbital has achieved. When the 7th electron is filled, it will be placed in 4s orbital

Position of 3 d and 4 s orbital before the 6th electron filling in ____ 4s ____ ____ ____ ____ ____ 3d

Position of 3d and 4s orbital after the 6th electron filling in

____ 4s ____ ____ ____ ____ ____ 3d

Same thing happened when comes to the case of copper. An extra stability is achieved when the orbital in 3 d is full-filled with electrons.
Position of 3 d and 4 s orbital before the 11th electron filling in ____ 4s ____ ____ ____ ____ ____ 3d ____ ____ ____ ____ ____ 3d Position of 3d and 4s orbital after the 11th electron filling in

____ 4s

1s 2s 3Li : . 1s 2s 2p 5B : .. 1s 2s 2p 7N : .. 1s 2s 2p 9F : 1s22s22p63s2 Mg : . 12
22s22p63s23p2 1s 14Si : .. 22s22p63s23p4 1s S : .
16

1s Li+ : 1s B3+ : . 1s 2s 2p N3- : . 1s 2s 2p F- : . 1s 2s 2p Mg2+ : .

Si4+ S222s22p6 1s : . 22s22p63s23p6 1s : 1s22s22p63s23p6 K+ : . 2 2 6 2 2 6 2 2 6 2

1s 2s 2p 3s 3p 4s 19K :
22s22p63s23p63d14s2 1s Sc : .. 21 22s22p63s23p63d34s2 1s V : .. 23
28

1s 2s 2p 3s 3p 3d Sc2+ : .
2 2 6 2 6

1 3

1s 2s 2p 3s 3p 3d V2+ : ..
Ni+
2

1s22s22p63s23p63d84s2 Ni : ..
2 2 6 2 6 10

1s 2s 2p 3s 3p 3d 4s 30Zn : .

22s22p63s23p63d84s1 1s : .. 22s22p63s23p63d10 1s 2+ Zn : ..

22s22p63s23p63d104s24p5 1s 35Br : .

Br-

22s22p63s23p63d104s24p6 1s : ..............

From the Periodic Table, elements can be classified accordingly to the block. Block of Periodic Table s-block Group of elements

Group 1 and 2 (Those with valence electron ns1 and ns2) Group 13 , 14 , 15 , 16 , 17 , 18 (Those with valence electrons ns2 np1, 2, 3, 4, 5, 6) Group 3 12 (Transition element with valence electron (n1)d1-10 ns2 ) Lanthanides and Actinides Series

p-block

d-block

f-block

Based on the valence electron, the Group of an element can determined.

be

Valence electron ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6

Group 1 2 13 14 15 16 17 18