Physical

Chemistry
Atomic Spectra
1. A spectrum is a display of the components of a beam
of radiation.
2. The white light from the sun consists of a visible light
of all wavelengths and is called continuous spectrum.
3. However, if the source of light is from a discharged
tube which contains a gas, such as calcium vapor, a
spectrum which consists of a few colored lines on a
black ground is produced.
4. The discontinuous spectrum is called the line
spectrum/atomic emission spectrum/ atomic spectrum.
5. When elements in gaseous and atomic state is heated
to high temperature and low pressure in a discharge
tube, visible light is emitted.
6. Exp: neon  orange light, hydrogen reddish purple
light, sodium vapor -> yellow light.
7. The light emitted can be studied using spectroscope.
8. Spectroscope is used to disperse light into its
individual wavelength.
9. The study of line spectra can used to:
a) Identify an element
b) Determine the ionization energy of an element,
c) Determine the arrangement of electrons in an atom of
an element.
The Hydrogen Spectrum
1. A hydrogen discharge tube is a slim tube containing
hydrogen gas at low pressure with an electrode at
each end. If you put a high voltage across this (say,
5000 volts), the tube lights up with a bright pink glow.
2. If the light is passed through a prism or diffraction
grating, it is split into its various colors. What you
would see is a small part of the hydrogen emission
spectrum. Most of the spectrum is invisible to the eye
because it is either in the infra-red or the ultra-violet.
The Lyman series is a series of lines in the ultra-violet.
Notice that the lines get closer and closer together as
the frequency increases. Eventually, they get so close
together that it becomes impossible to see them
as anything other than a continuous spectrum.
That's what the shaded bit on the right-hand end of
the series suggests. Then at one particular point, known
as the series limit / converging limit, the series stops.
This is what the spectrum looks like if you plot it in terms
of wavelength instead of frequency:

Drawing the hydrogen spectrum in terms of wavelength

This is what the spectrum looks like if you plot it in terms of wavelength instead of frequency:

                                                                                                                                                                    
and just to remind you what the spectrum in terms of
frequency looks like:
 Wavelength of the lines is given:
                                       
RH is a constant known as the Rydberg constant,
1.097 x10^7 m-1

Balmer series
(Visible region)
Red Blue Indigo Violet
Hα Hβ Hγ Hδ
Wavelength decrease 
Frequency increases 
 Balmer series (Visible region)

n1 =2 (Balmer)
n2 = 3, 4, 5…

Series N1 start with n2 start with Region

Lyman 1 2,3,4… Ultraviolet
Balmer 2 3,4,5… Visible
Paschen 3 4,5,6… Infrared
Bracket 4 5,6,7… Infrared
Electronic Energy Levels
1. The hydrogen emmision spectrum consists of several
series of discrete line
2. Some assumptions of the lines in spectrum:
a) Electrons in an atom move in orbits around te
nucleus like the planet revolving around the
sun.
b) The energies of electrons are quantized.
c) To promote an electron from a ower energy
level to higher one, energy is needed
(excitation).
d) The electron at higher energy level is unstable.
It falls back and lose an amount of energy
exactly equal to the difference between the
two energy levels followed by emission of
spectral lines.
Tying particular electron jumps to individual lines in the spectrum
If an electron falls from the 3-level to the 2-level,
it has to lose an amount of energy exactly the same
as the energy gap between those two levels.
That energy which the electron loses comes out as light
(where "light" includes UV and IR as well as visible).
Each frequency of light is associated
with a particular energy by the equation:

                                                                    
 If you do the same thing for jumps down to the 2-level,
you end up with the lines in the Balmer series.
These energy gaps are all much smaller than in the Lyman series,
and so the frequencies produced are also much lower.

                                                                                  

             
 The significance of the infinity level
1. The infinity level represents the highest possible
energy an electron can have as a part of a
hydrogen atom.
2. So what happens if the electron exceeds that
energy by even the tiniest bit?
3. The electron is no longer a part of the atom. The
infinity level represents the point at which
ionization of the atom occurs to form a
positively charged ion.              
4. When there is no additional energy supplied to it, hydrogen's
electron is found at the 1-level. This is known as its ground
state.
5. If you supply enough energy to move the electron up to the
infinity level, you have ionized the
hydrogen.                                    
Defining first ionisation energy
Definition
The first ionization energy is the energy required to
remove the most loosely held electron from
one mole of gaseous atoms to produce
1 mole of gaseous ions each with a charge of 1+.
This is more easily seen in symbol terms.
                                            
If you can determine the frequency of the Lyman series limit,
you can use it to calculate the energy needed to move
the electron in one atom from the 1-level to the point of ionisation.
From that, you can calculate the ionisation energy per mole
of atoms.

a) The energy difference between the ground state (n=1) of the atom
and the excited state that corresponds to the converge limit of
the spectral line of hydrogen is the ionization energy of hydrogen.

Rydberg Equation: n1 = 1, and n2 = ∞

1/λ = 1.097 x 10^7 ( 1/1 – 1/∞2)

= 1.097 x 10^7 m^-1
E = hc/λ = 2.18 x 10^-18 J
Ionization energy = 2.18 x 10^-18 J per electron
= 2.18 x 10^-18 x (6.02 x 10^23) J/mol
= 1313 kJ/mol
 Finding the frequency of the series limit graphically
Here is a list of the frequencies of the seven most widely spaced lines
in the Lyman series,
together with the increase in frequency
as you go from one to the next.

                                                            
Both lines point to a series limit at about 3.28 x 1015 Hz.
 We can work out the energy gap between the ground state and
the point at which the electron leaves the atom by substituting
the value we've got for frequency and looking up the value of
Planck's constant from a data book.

                      
                                
That gives you the ionisation energy for a single atom.
To find the normally quoted ionisation energy, we need to multiply
this by the number of atoms in a mole of hydrogen atoms
(the Avogadro constant) and then divide by 1000 to convert it
into kilojoules.

                                                                                           
 Factors affecting the size of ionisation energy
Ionisation energy is a measure of the energy needed to pull
a particular electron
away from the attraction of the nucleus.
A high value of ionisation energy shows
a high attraction between the electron and the nucleus.
The size of that attraction will be governed by:
The charge on the nucleus.
The more protons there are in the nucleus, the more positively charged
the nucleus is, and the more strongly electrons are attracted to it.
The distance of the electron from the nucleus.
Attraction falls off very rapidly with distance. An electron close to
the nucleus will be much more strongly attracted than one further away.
The number of electrons between the outer electrons and the nucleus.
Consider a sodium atom, with the electronic structure 2,8,1.
If the outer electron looks in towards the nucleus,
it doesn't see the nucleus sharply. Between it and the nucleus there are
the two layers of electrons
in the first and second levels. The 11 protons in the sodium's nucleus
have their effect cut down by the 10 inner electrons.
The outer electron therefore only feels a net pull of approximately
1+ from the centre. This lessening of the pull of the nucleus by
inner electrons is known as screening or shielding.
Succesive Ionization Energy
Energy E kJ/mol lg E
Levels
lg IE against number of electron
1 494 2.69

2 4560 3.66 6
3 6940 3.84 5
4 9540 3.98 4
5 13400 4.13
3 Series1

lgIE
6 16600 4.22
2
7 20100 4.30
1
8 25500 4.41
0
9 31600 4.50
0 2 4 6 8 10 12
10 135000 5.13
number of eletron removed
11 177800 5.25
Atmic Orbitals
Hydrogen's electron - the 1s orbital

1. In the hydrogen case, the electron can be found anywhere

within a spherical space surrounding the nucleus.
2. The diagram shows a cross-section through this spherical
space.
3. 95% of the time (or any other percentage you choose),
the electron will be found within a fairly easily defined region
of space quite close to the nucleus.
4. Such a region of space is called an orbital.
1. Electron can ocuppy 4 types of orbitals, known as s, p,
d and f
2. The first energy level (n=1) contains one atomic orbital
(1s). S orbital is spherical in shape.
3. The second energy level (n=2) has two sublevels with
4 atomic orbitals: 2s, 2px, 2py, 2pz.
4. (n=3) has orbitals: 3s, 3px, 3py, 3pz, 3dxy, 3dzx, 3dyz,
dz2, dx2-y2
5. Each orbital can occupy 2 electrons
The Arrangement of Electrons
• Aufbau principle: Electron occupy orbitals in the order of the
energy levels of the orbitals.
• Pauli Exclusion Principle: Only two electrons may occupy the
same orbital and these two electron must have opposite spin.
• Hund’s Rule: When electrons are placed in a set of orbitals
with equal energy level, the electrons must occupy them singly
with parallel spins before they occupy the orbital in pair.

4s 3d

3p
3s
2p
2s
1s
Electronic configuration

Elements Proton 1s 2s 2px 2py 2pz

No
H 1
He 2
Li 3
Be 4
B 5
C 6
N 7
O 8
F 9
Ne 10
Electronic configuration of D-block Elements
• Scandium (Sc)
• Itanium (Ti)
• Vanadium (V)
• Chromium (Cr)
• Manganese (Mn)
• Iron (Fe)
• Cobalt (Co)
• Nickel (Ni)
• Coper (Cu)
• Zinc (Zn)

Before being filled with electrons, the 4s orbitals is energetically

Stable than 3d orbitals.
After the 4s is filled with electrons, the 4s are repelled to a
Higher energy level.
Electronic configuration and The Periodic Table
• The s-block elements: Group 1 and Group 2 elements with
general electronic configuration: ns1 and ns2, n is the shell of
highest principal quantum number.
• The p-block elements: Group 13-18 with general electronic
configuration: ns2 np1 …
• The d-block elements: Group 2- 13, has d orbitals
Transition elements: elements in which the d orbitals are
partially occupied.
P 3S2, 3P6
Q 4S2, 4P5
R 3S2, 3P6, 4S2
S 1s2, 2s2, 2p6, 3s3, 3p6, 4d3, 4s2
T 1s2, 2s2, 2p6, 3s3, 3p6, 4d3, 4s2 4p6