Chapter one

Atomic structure

Theories about the atomic structure:-

(1) Demokrats:
He imagined the possibility of dividing any piece of matter to smaller parts until
it becomes an undividable fragment called atom
(2) Aristotle:
He said that all matter composed of water, air, dust and fire so we can change the
metal by changing the ratio of these components
(3) Boyle:
He defined the element as: The pure simple substance that can’t be changed into
simpler forms by the traditional chemical methods
(4) Dalton:
He said that each element is composed of very minute particles undividable
atoms that differs from an element to another
Compounds are formed due to the combination of atoms of different elements
Discovery of cathode rays:
Gases can conduct electricity in discharge tubes with a very low pressure
forming a potential difference of about 10000 volts between the electrodes and
invisible rays emits from the cathode called the cathode rays causing a
fluorescent glow on the tube wall
Properties of cathode rays:
(1) They consists of very fine negatively charged particles
(2) They move in straight lines
(3) They have thermal effect
(4) They are affected by both electric and magnetic fields
(5) They don’t differ either in behavior or in nature if the material of the
cathode or the used gas are changed
Thomson’s atom:
The atom is a sphere of uniform positive electricity surrounded by negative
electrons to be electrically neutral

Rutherford’s experiment:
In 1911 Geiger and Marsden performed a famous experiment according to
suggestion of Rutherford by
1 – Allowing alpha particles to hit a metallic plate lined with Zinc
 suphide (glows when hits with alpha rays)
2 – On placing a gold foil in the front of alpha rays he observed and
concluded the following:
Observation Conclusion
1- Most of alpha particles appeared 1- Most of the atom is a space not
in the same position before putting solid as explained by Dalton and
gold foil. Thomson.
2- A very small percentage of alpha 2- The atom has very small part
particles reflected back to appear as with very small volume but high
flashes on other side of sheet. density
3- Some flashes appeared on the 3- The dense part of the atom which
sides of 1st site. concentrates in it most mass has
same charge of alpha particle (+ve)
which called nucleus of the atom.

Rutherford’s atomic model:

1- The Atom:
It resembles the solar system in which electrons revolve around the central
nucleus in orbits as planets revolve around the sun.
2- The Nucleus:
It is much smaller than the atom. Located in the centre with (+ve) charge. There
is a big space between the nucleus and orbits of electrons, so most of the atom is
a space. Most mass of the atom is concentrated in the nucleus because it has the
greatest mass

3- Electrons:
1- Have negligible mass compared with the nucleus.
2- Number of electrons (-ve) equals the number of protons (+ve) so
the atom is electrically neutral.
3- Electrons revolve around the nucleus in fixed orbits and affected
by two forces equal in strength but in opposite directions, which
are:
a- The force of attraction between the nucleus and the electrons.
b- Centrifugal force due to velocity of electron around the nucleus.

Bohr's Theory
The atomic spectra
Studying the atomic spectra was the key in explaining the atomic structure
Atomic emission spectra:
1 – By heating gases or vapour of substances to a high temperature
or under low pressure in electric discharge tubes it emits light
2 – By using spectroscope we find that this light consists of a fixed
number of coloured lines called line spectrum.
He proved experimentally that the spectral line differs from one element to
another like finger prints

Bohr's Atomic Model:

Bohr's postulates:
1- A positively charged nucleus exists in the center of the atom.
2- Atom is electrically neutral as the number of protons equals the
number of electrons
3- Electrons revolve around the nucleus in orbits due to the
centrifugal and the attraction forces.
4- Electrons orbit the nucleus in a rapid movement without gaining
or losing energy.
5- Electrons orbit the nucleus only in a definite allowed energy
levels, so they can't be found at intermediate distance.
6- Each electron in the atom has a definite amount of energy
depending on the distance between the energy level and nucleus.
This energy increases as its radius increases.
7- It was found that the maximum number of energy levels in the
heaviest known atoms in their ground state ( unexcited ) is only
seven (K, L, M, N, O, P, Q). Each level has energy expressed by
a whole number called principle quantum number.
8- When the atom is excited by heating or by electric discharge
the electron will transfer to a higher energy level agrees with the
absorbed quantum.
The excited electron in the higher energy level is then unstable,
so it returns to its original level losing the same quantum of
energy, which it gained during excitation in the form of radiation
have definite wavelength and frequency

Disadvantages of Bohr's theory:

1 – He failed to explain the spectrum of any other element even that
of He except hydrogen (Simplest Electronic System).
2 – He considered the electron as a (-ve) particle only and did not
 consider that it also has wave properties.
3 – He postulated that it is possible to determine precisely both
speed and location of an electron at the same time.
This is experimentally impossible because the apparatus used
will change either speed or location of electron so the result
won't be accurate.
4 – He described the electron when moving in a circular planer orbit,
which means that hydrogen atom is planer. Later it was
confirmed that hydrogen atom has 3 dimensional co-ordinates

The principles of Modern Atomic Theory:

1 – The dual nature of the electron
The experimental data showed that the electron has a dual nature
a) It is a material particle.
b) It has wave properties.

1- De Broglie principle:
Every moving body (such as electron or the nucleus of an atom or whole
molecule)is associated with (accompanied by) a wave motion (or matter waves)
which has some properties of light waves.
The matter wave motion differs from electromagnetic waves

2- The Heisenberg uncertainty principle: (quantum mechanics)

It is practically impossible to determine both position and the velocity of the
electron exactly (precisely) at the same time. We can only say that it is probably
to a greater r lesser extent to locate the electron in this or in that place. This is to
speak in terms of probability seems to be more precise.

3- The wave equation for motion of electron inside the atom:

(Schrodinger wave mechanics theory): He applied the ideas of Blanck, Einestein,
De Broglie and Heisenberg so he shows that:
It is possible to determine the allowed energy levels of the electron and define
the region of space around the nucleus where it is most probable to find the
electron in each energy level.

Electron Cloud:
Area of space around the nucleus where there is a great probability for finding
electrons in all direction and all positions.
Quantum Numbers:
These numbers define the volume of space where there is maximum probability
of finding electrons. Besides, they define the energy, shape and direction of
orbital.
1- Principle Quantum Number (n).
2- Subsidiary or orbital Quantum Number (L).
3- Magnetic Quantum Number (ml).
4- Spin Quantum Number (ms).

1- Principle Quantum Number (n):

Bohr had used this number to define the following:
1- Order of principle E. levels their number in the heaviest known
atom in the ground state is seven.
2- Number of electrons required to fill a given energy level = two
times the square of the level no (2n2).
-1st energy level K is filled with 2 electrons
-2nd energy level L is filled with 8 electrons
-3rd energy level M is filled with 18 electrons
-4th energy level N is filled with 32 electrons
But this rule does not apply to the last three levels (O, P, and Q). However, the
atom becomes unstable if no of electrons exceeds 32 electrons on any level.

2- Subsidiary Quantum Number (L):

1- Used to detect the number of sub levels in each energy level.
2- The energy sub levels take the symbols s, p, d, f. this is shown by
the scientist Somerfield. When he used a spectroscope which
has a high resolving power, he found that the single line (which
represents electron transition between two different energy levels)
is indeed a number of fine spectral lines which represents
electron transition between very near energy levels (sublevels).
3- Number of sublevels in each energy level = order of principle
energy level (n).
-1 energy level K has 1 sub level 1s
st

-2nd energy level L has 2 sub level 2s, 2p

-3rd energy level M has 3 sub level 3s, 3p, and 3d
-4th energy level N has 4 sub level 4s, 4p, 4d, and 4f
N.B:
Energy of sub levels of same E. level is not equal.
f>d>p>s

(3) The magnetic quantum number (ml):

1- It represents the number of orbital within an energy sublevel and
their direction in space.
2- Sublevel (S) has one orbital of spherical symmetrical shape.
3- Sublevel (P) has 3 orbitals.
Each orbital (Px,Py,Pz) is perpendicular to the other two.
Also the electron cloud of each orbital takes the form of 2 pears
meeting head to head
4- Sublevel (d) has 5 orbitals.
5- Sublevel (f) has 7 orbitals.
6- Orbitals of the same sub level are equal in energy and shape.
Ex: px = py = pz
7- Number of orbitals in each energy level = square order of energy
level = n2.

4- Spin quantum number (ms):

Detects the direction in which the electron spins around its axis during its
rotation around the nucleus.
Each orbital can be saturated by 2 electrons, one electron spins around its axis
clockwise while the other electron spins anti – clockwise in order to from 2
opposite magnetic fields to decrease the force of repulsion between them which
keep the atom stable.
It has only two possible values +1/2 or –1/2

Principle of distributing electrons:

(1) Pauli’s exclusion principle:
It is impossible for 2 electrons in the same atom to have the same 4
Quantum numbers

(2) Aufbau (building – up) principle:

Electrons occupy energy sublevels in an ascending order according
to increasing energy where the lowest energy sublevel are filled
 first
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s <
5f < 6d < 7p

(3) Hund's rule:

No electron pairing takes place in a given sublevel until each orbital
contains one electron

Remarks:-
1- Electrons are preferred to be unpaired before pairing according to
Hund's rule on pairing electrons in the same orbital, because they
will repel decreasing stability of the atom.
2- Electrons prefer to be paired with another electron than to transfer to
a higher sub-level
3- The spin of single electrons must be in the same direction because
this gives the atom more stability.

Examples:
(1) Na11
1s2, 2s2, 2p6, 3s1

(2) K19
1s2, 2s2, 2p6, 3s2, 3p6, 4s1