ATOMIC STRUCTURE

SUBTOPICS
• Concept of orbital’s
• Electronic configuration
• Discovery and properties of proton (positive rays)
• Quantum numbers
• Shapes of orbital’s
LEARNING OBJECTIVES
2.1. Describe discovery and properties of proton (positive rays)
2.2. Define photon as a unit of radiation energy.
2.3. Describe the concept of orbitals.
2.4. Distinguish among principle energy levels, energy sub-levels, and atomic orbitals.
2.5. Describe the general shapes of s, p, and orbitals.
2.6. Describe the hydrogen atom using the quantum theory.
2.7. Use the Aufbau Principle, the Pauli Exclusion Principle, and Hund’s Rule to write the
electronic configuration of the atoms.
2.8. Write electronic configuration of atoms.
Positive rays or canal rays. (Discovery of Proton by Goldstein, a German Physicist 1886)
In a discharge tube, atoms or molecules lose electrons forming positive ions. Typical
example is of ionization of Neon gas. (Ne – e- Ne+1). It is observed that the positive ions move
towards cathode in a discharge tube.

Fig. Positive particles moving towards cathode in a discharge tube.

Construction and Working: About one metre long tube was taken which was provided with a
perforated cathode as shown in the diagram. The electrodes were connected to a high voltage
battery. Atom being electrically neutral must contain equal number of positive and negative
particles. When electric current was passed through the gas under reduced pressure, some rays
are produced from cathode which travelled away from cathode. Such rays ionize the gas in the
middle of the discharge tube. They knocked out electron from the gas molecules. As a result
positive ions were produced, which start moving towards the perforated cathode.
M – e- M+1
 He – 2e- He+2
Since these rays passed through the canals (small holes) of cathode so they were also
called as “Canal rays”. Later on they were called Positive rays because they carried positive
charge.
Properties of positive rays:
1. Travel in straight line perpendicular to the anode surface.
2. Are deflected in electric field towards cathode showing that they are positively charged.
4. They produce flashes on ZnS plate.
e
5. Their ratio is smaller than that of an electron.
m
e e
6. The ratio depends upon the nature of the gas. The highest is obtained for Hydrogen
m m
gas is present in the tube.
7. The mass of a +ive particle is never less than that of a proton.
8. The positive particle obtained from H2 gas is the lightest among all the positive particles.
9. A particle obtained from positive rays is called proton, a name suggested by Rutherford.
10. The mass of a proton is 1836 times more than that of an electron.
DISTRIBUTION OF MASSES AND CHARGES
 An atom may consist of more than 100 subatomic particles.
 Out of these, three are called fundamental particles namely, electron, proton and
neutron.
 Number of protons in an atom is called proton number or atomic number (Z).
 The sum of number of protons and neutrons in an atom is called mass number or
nucleon number (A). A=Z+N
 Atomic masses are measured in a. m. u. (atomic mass unit)
1 a. m. u. = 1.66 x 10-27 kg.
Atomic nucleus is represented as A zX where Z, the charge number = number of
protons A, the mass number = number of protons + number of neutrons.
Charge/
Particle Relative charge Mass/Kg Mass (a.m.u) Place in atom
Coulomb
Proton + 1.6022  10-19 +1 1.6727  10-27 1.0073 In the nucleus
Neutron O O 1.6750  10-27 1.0087 In the nucleus
Outside
Electron - 1.6022  10-19 -1 9.1095  10-31 5.4858 10-4
nucleus

Plank’s quantum theory (Photon theory)

Maxwell Plank (1900) proposed a theory about nature of light.
POSTULATES
1. Energy is not emitted or absorbed continuously but in form of wave packets or quanta. In
case of light the quantum of energy is often called photon.
 2. The amount of energy associated with quantum of radiation is directly proportional to the
frequency () of radiation. i.e.
E  or E=h … (1)
where h = Plank’s constant and has a value of 6.625  10 JS.
-34

6.625  10-27 ergs

3. A body can emit or absorb energy only in terms of integral multiple of a quantum.
E=nh where n = 1, 2, 3
Now  1/
or  = c /
Where “” is wave length and “c” is the velocity of light, a constant quantity.
Putting the value of  in eq. (1), we get
E=hc/ … (2)
Thus greater the value of λ, smaller will be the energy.
Now … (3)
Where = wave number.
Putting the value of 1/  in eq. (2), we get,

Thus energy of radiation is directly proportional to the frequency.

So, it can be concluded that the energy of photon is related to frequency, wavelength and wave number.
The number of waves passing through a point per second is called Frequency. The distance between two
adjacent crests or troughs is called wavelength. It is expressed in 0A (Where 0A is an angstrom and one
Angstrom = 10-10m) or in nanometers (1 nanometer = 10 – 9 m).

The Quantum numbers and orbitals:

Schrodinger in 1926 gave an equation in which electrons are treated as moving with wave
like motion in the three-dimensional space around the nucleus. It differs from Bohr’s atomic
model in the sense that the electrons move in orbits. It also specifies the distance between the
electron and the nucleus.
The region or space around the nucleus in which the probability of finding the electron is
maximum is called an atomic orbital which are denoted as s, p, d and f.
The solution of Schrodinger’s wave equation gives certain mathematical integers. First three
quantum numbers are mathematical solution of Schrodinger wave equation.
Principal Quantum No. (n):
Significance: Determines the size of the orbit and the distance from the nucleus. Greater the
distance from the nucleus, larger will be the size of the orbit. The shells are named as,
If n = 1  K shell.
n = 2  L shell.
n = 3  M shell.
n = 4  N shell.
The no of electrons in various orbits are
 K = 2, L = 8, M = 18, N = 32.
The higher the value of n, the higher will be the energy of the electron and space
around the nucleus. The value of n can never be zero.
The Azimuthal Quantum No. (l) (Angular momentum quantum number)
It describes the shape of an orbital. Its value is always one less than that of value of
n. The various energy sub-levels (l) are s, p, d, f having at the most 2, 6, 10 and 14 electrons in
them respectively. They are designated as s for sharp, p for principal, d for diffused and f for
fundamental. The relationship between n and l is given below,
l = n –1
If, n = 1 (K), l = 0 (s), and e = 2
n = 2 (L), l = 0 (s) and 1 (p), and e = 2, 6
n = 3 (M), l = 0 (s), 1(p), and 2(d) and e = 2, 6, 10
n = 4 (N), l = 0 (s), 1(p), 2 (d) and 3 (f) and e = 2, 6, 10, 14
From here we conclude that the number of orbit gives the no of sub-shells.
. n = 1 (K) orbital = 1 s
n = 2 (L) orbitals = 2s, 2p
n = 3 (M) orbitals = 3s, 3 p, 3 d
n = 4 (N) orbitals = 4s, 4p, 4d, 4f.
The shapes of orbitals described by Azimuthal Quantum number are
s = spherical, p = dumbbell, d = sausage and f = complicated.
Magnetic Quantum No. (m): (Orbital orientation quantum number)
It explains the effect of an orbital in the magnetic field. It is related with Azimuthal
Quantum number as follows:
m=+l o –l
If l = o (s), m = o. It means that an s – orbital is spherical in shape because it is not
deflected in any particular direction on placing in an electric field.
If l = 1 (p), m = + 1, 0, –1. It means that a p–orbital can be deflected in three
directions on placing in a magnetic field. i.e. a p splits in to three degenerate orbitals in a
magnetic field.
orbital Px Py Pz
m value +1 -1 0

If l = 2 (d), then m = +2, + 1, 0, –1, –2. It means that a d–orbital can be deflected in
5–directions on placing in a magnetic field.
orbital dxy dyz dxz dx2 -dy2 dz2
m value -2 -1 +1 +2 0
If l = 3 (f), m = + 3, + 2, +1, 0, –1, – 2, –3. i.e. an f–orbital can be deflected in 7–direction in a
magnetic field.
Magnetic quantum number determines the orientation of orbital. Therefore, it is
also called Orbital orientation quantum number.
 Spin Quantum Number (s):
It describes the direction of spin of an orbital. In 1925 Goudsmit suggested that an
electron while moving in an orbital around the nucleus also rotates or spins about its own axis
 1
either in a clockwise or anti-clockwise direction. It may be 50% clockwise    () and 50%
 2
 1
anti-clockwise    ().
 2

Fig: Two different spins of electrons and their magnetic fields

This is also called self-rotation. This spinning of electron is associated with a magnetic field and
hence a magnetic moment.
Principal quantum Relative energies
number (n) Number of subshells Number of orbitals
of subshells
n=1 1 – subshell (s) s 1-orbital
n=2 2 – subshell (s) s< p 4-orbitals
n=3 3 – subshell (s) s< p< d 9-orbitals
n=4 4 – subshell (s) s< p< d< f 16-orbitals
The volume of space in which there is a 95% chance of finding the electron is called orbital.
No.of electrons in a shell =2n2
No.of electrons in a sub-shell= 2(2l+1)
Total no. of orbitals in a shell= n2
Relative order of stability of orbitals d5<p3<d10<<p6
ENERGY AND SHAPES OF ORBITALS
Number of subshells are equal to given principal quantum number and their relative energies are
S < p < d < f.
(i) Shapes of s-orbitals:
s-orbital is spherical in shape and is represents by a circle (cut of sphere). Higher the value of ‘n’
for s-subshell, greater will be its size.
Example
2s is larger in size than 1s.
Nodal Surface or Nodal Plane
The probability of finding the electron is zero between
two orbitals. This plane is called Nodal plane or Nodal
surface.
(ii) Shapes of p-orbitals
 Each p-orbital has two lobes in dumbel
shape.
 These lobes are either oriented along
x-axis (px,m=+1)), y-axis(py, m=-1)
or z-axis (pz ,m=0)
 The size of p-orbital increases with
increase in its ‘n’ value.
Example
3px orbital is larger in size than 2p x but
both have same shape.
(iii) Shapes of d-orbitals
 Each d-orbital has four lobes or two
Dumbel in sausage shape.
 These lobes are either oriented
along x-axis, y-axis and z-axis
 The size of d-orbital increases with
Increase in its ‘n; value.
ELECTRONIC DISTRIBUTION

Auf-bau principle
The electrons should be filled in energy sub shells in order of increasing energy values.
The electrons are first placed in
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s and so on.
Pauli’s exclusion principle
Two electrons in the same orbital must have opposite spins.
It is impossible for two electrons residing in the same orbital of a poly electron atom to have the
same values of four quantum numbers.
Hund’s rule
 If degenerate orbitals are available and more than one electron is to be placed in them,
they should be placed in separate orbitals with the same spin rather than putting them in
the same orbitals with opposite spins.
NOTE:
Half-filled and completely filled sub-shells, are more stable e.g. Cr and Cu.
Electronic configuration of some elements
Element Atomic Number Electron configuration Notation
Hydrogen 1 1s1
Helium 2 1s2
Lithium 3 1s22s1
Beryllium 4 1s22s2
Boron 5 1s22s22p1x2p0y2p0z

Carbon 6 1s22s22p1x2p1y2p0z

Nitrogen 7 1s22s22p1x2p1y2p1z

Oxygen 8 1s22s22p2x2p1y2p1z

Fluorine 9 1s22s22p2x2p2y2p1z

Neon 10 1s22s22p2x2p2y2p2z

Sodium 11 [Ne]3s1
Magnesium 12 [Ne]3s2
Aluminum 13 [Ne]3s23p1x3p0y3p0z

Silicon 14 [Ne]3s23p1x3p1y3p0z

Phosphorus 15 [Ne]3s23p1x3p1y3p1z

Sulphur 16 [Ne]3s23p2x3p1y3p1z

chlorine 17 [Ne]3s23p2x3p2y3p1z

Argon 18 [Ne]3s23p2x3p2y3p2z

Potassium 19 [Ar]4s1
Calcium 20 [Ar]4s2
Scandium 21 [Ar]4s23dxy1 3dyz0 3dxz0 3dx2 −0 y23dz20
Titanium 22 [Ar]4s23dxy1 3dyz1 3dxz0 3dx2 −0 y23dz20

Vanadium 23 [Ar]4s23dxy1 3dyz1 3dxz1 3dx2 −0 y23dz20

Chromium 24 [Ar]4s13dxy1 3dyz1 3dxz1 3dx2 −1 y23dz21

Manganese 25 [Ar]4s23dxy1 3dyz1 3dxz1 3dx2 −1 y23dz21

Iron 26 [Ar]4s23dxy2 3dyz1 3dxz1 3dx2 −1 y23dz21

Cobalt 27 [Ar]4s23dxy2 3dyz2 3dxz1 3dx2 −1 y23dz21

Nickel 28 [Ar]4s23dxy2 3dyz2 3dxz2 3dx2 −1 y23dz21

Cooper 29 [Ar]4s13dxy2 3dyz2 3dxz2 3dx2 −2 y23dz22

Zinc 30 [Ar]4s23dxy2 3dyz2 3dxz2 3dx2 −2 y23dz22

Gallium 31 [Ar]4s23d104p1𝑥4p0y4p0z

Germanium 32 [Ar]4s23d104p1𝑥4p1y4p0z

Arsenic 33 [Ar]4s23d104p1𝑥4p1y4p1z

Selenium 34 [Ar]4s23d104p2𝑥4p1y4p1z

Bromine 35 [Ar]4s23d104p2𝑥4p2y4p1z

Krypton 36 [Ar]4s23d104p2𝑥4p2y4p2z