CHEM 111: FUNDAMENTALS OF

CHEMISTRY
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
and others
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 John Dalton (1766 – 1844)
Dalton’s Atomic Theory: Postulates
. All matter is made of tiny indivisible particles called atoms.
. Atoms of the same element are identical in their properties,
those of different elements are different.
. 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

It failed to explain the existence of: electrons, protons and
neutrons.
•It fails to explain the existence isotopes

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• Many scientists modified Dalton’s Atomic Theory and
contributed to understanding of the modern atomic
model.
 The Discovery of Electrons
J.J. Thomson (1856 – 1940)
 Proved that an atom can be divided into smaller parts
 While experimenting with cathode-ray tubes, he discovered
electrons

• 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
Limitation
 This theory failed to account for the position of the nucleus in
an atom
 Discovery of the Nucleus
Ernest Rutherford (1871 – 1937)
 Rutherford performed an experiment of scattering of α -
particles by thin gold foil.

 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
 Postulates of Rutherford’s atomic theory
(i) : of the atom
Proposed the NUCLEAR MODEL
(ii) There are large number of small empty spaces (gaps) inside
the atom.
(iii) There should be positively charged nucleus at the center the
atom.
(iv) 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.
(v) The atom as a whole is electrically neutral because number of
electrons is equal to number of positive charges (protons)
present inside the nucleus.
 Postulates of Rutherford’s atomic theory
Most of the mass and all the positive charge of an atom is concentrated
(i)

in a very small region called nucleus.

Limitations of Rutherford’s atomic theory
It could not explain the discontinuous (line or band) atomic spectrum.
It could not explain the position, energy and distribution of electrons
around the nucleus.
 Discovery of the Neutron: Chadwick

Chadwick (1935)

– Discovers neutron in nucleus

– Neutron is neutral
 Niels Bohr (1885 – 1962)
• Bohr’s atomic model
• proposed a quantum model for the hydrogen atom .
• 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 revolve 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)van electron from lower orbit jumps to higher orbit upon absorption
of Energy and energy is radiated only when an electron from higher
orbit jumps to lower orbit.
 The Bohr model
(vi) The lowest allowable energy state of an atom is called its
ground state. When an atom gains energy, it is in an excited state
 The Bohr model
(i) Limitation of Bohr’s atomic Theory
(ii) It couldn’t explain atomic spectrum of elements other than H and
He.
(iii) It couldn’t explain the fine structure of spectral line.
(iv) Bohr couldn’t explain the wave particle dual nature of electron.

(iv) Bohr couldn’t explain arrangement of electrons in atom.

• For these and other reasons, the Bohr model was replaced with a
more sophisticated modern model called the quantum-mechanical
or wave-mechanical model

Exercise
State the postulates and limitations of, Dalton’s,
Thomson’s, Rutherford’s and Bohr’s atomic models
 The Quantum Mechanical Model
(The Modern Atom)

• The Bohr model was discarded because it does not apply to all atoms

• Louis de Broglie (1892–1987) hypothesized that particles, including

electrons, could also have wavelike behaviors

• 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.

• Erwin Schrödinger treated electrons as waves and particles (wave-

particle duality) in a model called the quantum mechanical model
of the atom

• Bohr orbits were replaced with quantum-mechanical orbitals

 Quantum Numbers
• By solving the Schrödinger equation ((Hy = Ey ), we obtain a set of
mathematical equations, called wave functions (y )
• They 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, n, l, ml and ms
 The first three (n, l, ml) specify the particular atomic orbital (a
region of space in an atom in which there is a high probability of
finding an electron)
 the fourth (ms) specify an electron’s spin. There are two possible
directions of spin whose values are +½ ( )and −½ (.)
 Quantum Numbers
Principal Quantum Number (n): n = 1, 2, 3, …,
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)
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.
It 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:

Value of l 0 1 2 3 4 5

Letter s p d f g h

Example: The subshell with n=2 and l=1 is the 2p subshell;

if n=3 and l=0, it is the 3s so on
 Quantum Numbers

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).
• divides the subshell into individual orbitals which hold the
electrons
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).
 Quantum Numbers
The Pauli exclusion principle:
states that no two electrons in the same atom can have same values for all
four of their quantum numbers.
A maximum of two electrons can occupy the same orbital only if
they have opposite spins
Magnetism:
•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 whose atoms have paired electrons are not
attracted to magnets and are said to be diamagnetic.
•Atoms with more electrons that spin in one direction than another
are said to contain unpaired electrons. These substances are weakly
attracted to magnets and are said to be paramagnetic
 Quantum Numbers
Table 2: Allowed Quantum Numbers
Possible Maximu
Numb Maximu
values of l Possible values m no. of
Value of n Subshell er of m no. of
(l = 0 to n- ml (ml = -l, ..., 0, ..., +i) electron
(Shell) name orbital electrons
1) s per
s per shell
subshell
1 0 1s 0 1 2 2
2 0 2s 0 1 2
8
1 2p -1, 0, +1 3 6
3 0 3s 0 1 2
1 3p -1, 0, +1 3 6 18
2 3d -2, -1, 0, +1,+2 5 10
4 0 4s 0 1 2
1 4p -1, 0, +1 3 6
2 4d -2, -1, 0, +1,+2 5 10
32
3 4f -3, -2, -1, 0, 7 14
+1,+2, +3
Note: Each orbital can contain only two electrons
 Atomic Orbitals
• Each energy sublevel relates to orbitals of different shape.

s, p, d, f

s, p, d

s, p

s
 Shapes of Atomic Orbitals

• s sublevel:
 Shapes of Atomic Orbitals

• p sublevel:
 Shapes of Atomic Orbitals

• d sublevel: