ATOMIC STRUCTURE

History of the Development of Modern Atomic Structure

Scientists and Their Contribution to the Model of

an Atom
(History of the Atomic Theory: Summary)

1803 1897 1909 1913 1935 Today

solid electron Proton, e- orbit neutron Quantum
Particle nucleus nucleus: Atom
Random Planetary theory
placed model,
electrons quanta
Dalton Thomson Rutherford Bohr Chadwick Schrodinger
2
and others

1. John Dalton (1766 – 1844)

Postulates of Dalton’s Atomic Theory

 All matter is made of tiny indivisible particles called atoms.
 all the atoms of an element have identical mass while the atoms of different
elements have different masses
 Atoms of different elements combine in whole number ratios to form compounds
 Chemical reactions involve the rearrangement of atoms. No new atoms are created
or destroyed.

Limitations of Dalton’s Atomic Theory of Matter

(i) It failed to explain the existence of: electrons, protons and neutrons.
(ii) It fails to explain the existence isotopes. For example, Chlorine (Cl) has 2 isotopes
with the mass numbers of 35 and 37.

2. J.J. Thomson (1856 – 1940)

 Proved that an atom can be divided into smaller parts
 While experimenting with cathode-ray tubes, he discovered electrons
(Description of cathode-ray tubes is given in the reference material provided)
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 Postulates Thomson Atomic model
(i) He proposed the Plum Pudding Model which states that atoms mostly consist of
positively charged material with negatively charged particles (electrons) located
throughout the positive material
(ii) Stated that the atom is neutral because the negative and positive charges are equal in
magnitude

Limitations
 This theory failed to account for the position of the nucleus in an atom
 Thomson’s model failed to explain the scattering of alpha particles by thin metal
foils

3. Ernest Rutherford (1871 – 1937)

 Rutherford performed and experiment of scattering of α - particles by thin gold
foil. (See the detailed description of the experiment in the reference materials)
 He observed that majority α- particles passed through the foil straight.
 Few α particles were deflected by an angle less than 900.
 Very few α – particles were deflected by an angle 900 or more such as about
1800.
On the basis of these observations, he gave some conclusions regarding
structure of atom as follows.

Postulates of Rutherford’s atomic model:

(i) There should be large number of small empty spaces (gaps) inside the atom.
(ii) There should be positively charged nucleus at the centre the atom.
(iii) Electrons are revolving around nucleus in different orbits with high speed
such that electrostatic force of attraction between electrons and nucleus is
balanced by centrifugal force acting on electron.
(iv) The atom as a whole is electrically neutral. Since, number of electrons is
equal to number of positive charges, present inside the nucleus.
(v) Most of the mass and all the positive charge of an atom is concentrated in a
very small region called nucleus.

Limitations of Rutherford’s atomic theory

(i) It could not explain the discontinuous (line or band) atomic spectrum. Since,
Rutherford’s atomic model, expected continuous atomic spectra.
(ii) It could not explain the position, energy and distribution of electrons around
the nucleus.

4. Niels Bohr (1885 – 1962)

Bohr’s atomic model
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 • In 1913, Niels Bohr, a Danish physicist working in Rutherford’s laboratory,
proposed a quantum model for the hydrogen atom that seemed to answer
the question why atomic emission spectra of elements were discontinuous.
Postulates:
(i) Rutherford’s atomic model is accepted.
(ii) Nearly whole mass of atom is concentrated in the positively charged nucleus.
(iii) The electrons of an atom are revolving around the nucleus. In certain fixed
circular paths called ‘stationary orbits’. Each orbit was given a number, called
the quantum number

(iv) So long as an electron revolves in a permitted orbit, it doesn’t absorb or

radiate energy.
(v) an electron from lower orbit jumps to higher orbit on absorption of
Energy
(vi) Energy is radiated only when an electron from higher orbit jumps to
lower orbit.

(vii) The lowest allowable energy state of an atom is called its ground state.
When an atom gains energy, it is in an excited state

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 (viii) Hydrogen’s single electron is in the n = 1 orbit when it is in the ground
state. When energy is added, the electron moves to the n = 2 orbit.

Limitation of Bohr’s atomic Theory

(i) It couldn’t explain atomic spectrum of elements other than H and He.
(ii) It couldn’t explain the fine structure of spectral line.
(iii) Bohr couldn’t explain the wave particle dual nature of electron.
(iv) Bohr couldn’t explain arrangement of electrons in atom.

Exercise
State two postulates and two limitations of, Dalton’s, Thomson’s, Rutherford’s and
Bohr’s atomic models

5. The Quantum Mechanical Model (The Modern Atom)

The Bohr model of an atom was replaced with a more sophisticated modern model
called the quantum-mechanical or wave-mechanical model .

Louis de Broglie
He hypothesized that particles, including electrons, could also have wavelike
behaviors. Electrons do not behave like particles flying through space. We cannot, in
general, describe their exact paths.
Heisenberg
The Heisenberg uncertainty principle states that it is fundamentally impossible to
know precisely both the velocity and position of a particle at the same time.
The only quantity that can be known is the probability for an electron to occupy a
certain region around the nucleus
Erwin Schrödinger
Schrödinger treated electrons as waves and particles (wave-particle duality) in a model
called the quantum mechanical model of the atom. The Schrödinger’s equation
applied equally well to elements other than hydrogen (unlike Bohr’s model).

• In this model, Bohr orbits were replaced with quantum-mechanical orbitals.

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Quantum Numbers
By solving the Schrödinger equation (H = E ), we obtain a set of mathematical
equations, called wave functions ( ), which describe the probability of finding
electrons at certain energy levels within an atom. Each electron in an atom is described
by four different quantum numbers. The first three (n, l, ml) specify the particular orbital
of interest, and the fourth (ms) specifies how many electrons can occupy that orbital.

1. Principal Quantum Number (n): n = 1, 2, 3, …, 8.

Specifies the energy of an electron and the size of the orbital. All orbitals that have
the same value of n are said to be in the same shell (level).
2. Angular Momentum (Secondary, Azimunthal) Quantum Number (l): Values of
range from l = 0 to n-1. Specifies the shape of an orbital with a particular principal
quantum number. The secondary quantum number divides the shells into smaller
groups of orbitals called subshells (sublevels). Usually, a letter code is used to
identify l to avoid confusion with n:

Table 1: Letters for different values of l (sublevels/subshells)

Value of l 0 1 2 3 4 5
Letter s p d f g h

The subshell with n=2 and l=1 is the 2p subshell; if n=3 and l=0, it is the 3s subshell,
and so on. The value of l also has a slight effect on the energy of the subshell; the
energy of the subshell increases with l (s < p < d < f).

3. Magnetic Quantum Number (ml): Values of ml = -l, ..., 0, ..., +l.

Specifies the orientation in space of an orbital of a given energy (n) and shape (l).
This number divides the subshell into individual orbitals which hold the electrons;
there are 2l+1 orbitals in each subshell. Thus the s subshell has only one orbital, the p
subshell has three orbitals, and so on.
4. Spin Quantum Number (ms): ms = +½ or -½.
Specifies the orientation of the spin axis of an electron. An electron can spin in only
one of two directions (sometimes called up and down).
The Pauli exclusion principle (Wolfgang Pauli, Nobel Prize 1945) states that no
two electrons in the same atom can have identical values for all four of their quantum
numbers. What this means is that no more than two electrons can occupy the same
orbital, and that two electrons in the same orbital must have opposite spins.
Because an electron spins, it creates a magnetic field, which can be oriented in
one of two directions. For two electrons in the same orbital, the spins must be
opposite to each other; the spins are said to be paired. These substances are not
attracted to magnets and are said to be diamagnetic. Atoms with more electrons that
spin in one direction than another contain unpaired electrons. These substances are
weakly attracted to magnets and are said to be paramagnetic.
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 Possible Maximum Maximum
Value of values of Possible values ml Number no. of no. of
Sublevel
n l ml (ml = -l, ..., 0, ..., + l) of electrons per electrons
name
(shell/ level) (l = 0 to orbitals sublevel/sub per
n-1) shell level/shell

1 0 1s 0 1 2 2
2 0 2s 0 1 2
1 2p -1, 0, +1 3 6 8
3 0 3s 0 1 2
1 3p -1, 0, +1 3 6
2 3d -2, -1, 0, +1,+2 5 10 18
4 0 4s 0 1 2
1 4p -1, 0, +1 3 6
2 4d -2, -1, 0, +1,+2 5 10
3 4f -3, -2, -1, 0, +1,+2, +3 7 14 32
Note: Each orbital can contain only two electrons

In Schrödinger’s model the shell is equivalent to Bohr’s orbit.

A shell is subdivided into subshells (sublevel) and subshells are subdivided into
orbitals.
.
The number of subshells that a shell contains is equal to the shell’s n number, for
example

Shell No (n) Number and name of sublevel

1 1 Sublevel ( 1s)
2 2 Sublevels (2s and 2p)
3 3 Sublevels (3s, 3p and 3d)
4 4 Sublevels (4s, 4p, 4d and 4f)
5 5 Sublevels (5s, 5p, 5d, 5f and 5g)
The energy of each subblevel increases with the letters s < p < d < f<g etc
Each sublevel is subdivided into atomic orbitals.

Atomic orbitals
An atomic orbital is a region of space in which there is a high probability of finding an
electron. All atomic orbitals in a given subshell (sublevel) have the same [Link] the
orbitals are said to be degenerate
The number of atomic orbitals in each sublevel increases with the energy of the
sublevel:

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Sublevel Number of atomic orbitals
s 1
p 3
d 5
f 7

Shapes of Atomic orbitals

S sublevel
S orbitals have a spherical shape.

p sublevel:

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d sublevel:
d orbitals have a clover-leaf shape

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