AtomicStructure 1
AtomicStructure 1
AtomicStructure 1
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Atomic Structure
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What is an atom?
Democritus (Greek philosopher) believed that there was a smallest particle— “atomos”
(uncuttable, indivisible)—that made up all of nature.
Atom is the smallest part of an element that can take part in a chemical reaction. Atoms are
indivisible and unchanging. (Greek: atom = cannot be cut, i.e. indivisible).
1. Each element is composed of extremely small particles called atoms (tiny, indestructible, indivisible
unit particles)
An atom of the element of Oxygen An atom of the element of Nitrogen
2. All atoms of a given element are identical, but the atoms of one element are different from the atoms of
all other elements (size, shape, mass and other properties)
Nitrogen
Oxygen
3. Atoms of one element cannot be changed into atoms of a different element by chemical reactions,;
atoms are neither created nor destroyed in chemical reactions.
Oxygen Nitrogen
4. Compounds are formed when atoms of more than one element combine; a given compound always has
the same relative number and kind of atoms (1:1, 1:2, 1:3, 2:1, 2:3, etc.). Molecule is the smallest particle of
a compound.
VIDEO-1
Structure of Atom: Limitations of Daltons Atomic Theory
A subatomic particle is a unit of matter or energy that's the fundamental makeup of all matter.
After proposition of Dalton’s atomic theory, experiments of various scientists proved that the atom is
essentially built of three principal fundamental particles:
Electron
Proton &
Neutron
The proton & neutron constitutes the nucleus of the of the atom around which the electrons move in circular
paths.
Structure of Atom: Sub Atomic Particle - Electron (e–)
An electron is a massless particle which bears one unit of negative charge on it.
An electron is a subatomic particle which bears a charge of –1.60 x 10–19 coulombs (or 1 unit –ve charge)
and has a mass of 9.1 x 10–28g (or 1/1835 amu, which is taken to be equal to zero).
Electrons are the Common Universal Constituents of all Atoms
Sir J.J. (Joseph John) Thomson, an English Physicist, discovered electron in 1897 as the constituent of cathode
rays by the study of electric discharge in discharge tube. He constructed a glass tube which was partially
evacuated i.e. much of the air was pumped out of the tube. Then he applied a high electrical voltage between
two electrodes at either end of the tube. He detected that a stream of particle (ray) was coming out from the
negatively charged electrode (cathode) to positively charged electrode (anode). This ray is called cathode ray and
the whole construction is called cathode ray tube.
Structure of Atom: Subatomic Particles - Proton (p)
A sub atomic particle which bears mass equal to 1.672 x 10–24g (or 1 amu) and positive charge equal to + 1
(+1.60 x 10–19 coulombs) on it. In other words, a proton is a subatomic particle which bears one unit mass
and one unit of positive charge on it
In 1886 Eugen Goldstein noted that cathode-ray tubes with a perforated cathode emit a glow from the end
of the tube near the cathode. Goldstein concluded that in addition to the electrons, or cathode rays, that
travel from the negatively charged cathode toward the positively charged anode, there is another ray that
travels in the opposite direction, from the anode toward the cathode. Because these rays pass through the
holes, or channels, in the cathode, Goldstein called them canal rays. Since these canal rays travel in the
opposite direction from the cathode rays, they must carry the opposite charge.
Structure of Atom: Sub Atomic Particle - Neutron (n)
A sub- atomic particle which bears a mass equal to that of a proton (i.e. 1.674x 10–24g or 1 amu) and-has no
charge on it. For this reason a neutron is represented as 10n.
Sir James Chadwick, an English Physicist, discovered neutron in 1932. He used paraffin wax because it is a
hydrocarbon which is rich in hydrogen and so in protons. Chadwick measured the energy of the protons and
stated – gamma rays do not carry the amount of energy and momentum required to displace protons thus,
radiation coming from beryllium is not just electromagnetic in nature and must consist of particles. He named
particles discovered by him neutrons as they had no charge and their mass was almost equal to that of protons
Atom has a tiny dense central core or the NUCLEUS which contains practically the entire mass of the atom,
leaving the rest of the atom almost empty.
The entire positive charge of the atom is located on the nucleus, where electrons are distributed in vacant
space around it.
The electrons are moving in orbits or closed circular paths around the nucleus like planets around the sun.
Structure of Atom: (Rutherford’s Atomic Model)
Video - 2
In Rutherford's gold foil experiment, a beam of alphaαalpha particles that was shot at a thin sheet of gold foil. Most of the alphaαalpha particles passed straight
through the gold foil, but a small number were deflected slightly, and an even smaller fraction were deflected more than 900 degrees from their path
Structure of Atom: (Rutherford’s Atomic Model)
According to Maxwell’s electromagnetic theory, if a charged body rotates in an orbit around another
oppositely charged body, the former must radiate energy continuously and thereby lose kinetic energy
(getting slower in speed). So the electrons must gradually go in spiral motion and finally fall into the nucleus.
But practically it does not happen because then the atom would be unstable which it is not.
Since the process of radiating energy would go on continuously, the atomic spectra should also be
continuous and should not give sharp and well-defined lines as practically found.
Structure of Atom: Bohr’s Atomic Model
Rutherford’s nuclear atomic model simply stated the atom had a nucleus and electrons were
present outside the nucleus. It did not say anything about how and where the electrons are
arranged. It also could not explain why electrons did not fall into the nucleus. In 1913, Neils Bohr
proposed a new model of the atom which explained some of these things and also the emission
spectrum of hydrogen. Bohr’s theory was based on Planck’s quantum theory and was built on the
following postulates:
1. Electrons revolve round the nucleus in specific concentric circular orbits situated at definite
(i.e. fixed) distance from the nucleus and with a definite velocity.
The orbits are given the letter designation n and each is numbered 1, 2, 3 etc. (or K, L, M etc.) as
the distance from the nucleus increases.
2. As long as an electron remains in its specific orbit, it neither emits (i.e. radiates or loses) nor
absorbs (i.e. gains) energy.
Therefore, in a specific orbit the energy of a revolving electron remains constant or stationary.
Hence, the specific orbits available to the electron in an atom are referred to as Stationary energy
levels or simply Energy levels.
The energy associated with a certain energy level increases with the increase of its distance from
the nucleus.
Structure of Atom: (Bohr’s Atomic Model)
Structure of Atom: (Bohr’s Atomic Model)
3. An electron can move from one energy level to another by absorbing or emitting energy, but the
absorption or emission of energy can take place only in form of discrete quanta or photons.
When an electron resides in the lowest energy level — the energy level 1 (i..e. the orbit closest to the
nucleus), it is said to be in the ground state. Now, if energy is supplied to the electron residing in the energy
level 1, it will absorb the supplied energy in the form of quanta or photons and hence will jump to the
higher energy levels 2, 3, 4 --------etc. depending on the amount of energy absorbed by the electron. The
electron then is said to be in an excited state.
The quanta or photons of energy emitted or absorbed is the difference between the lower and higher
energy levels of atom, i.e., E = Ehigh –Elow
4. The angular momentum (mvr) of an electron orbiting around the nucleus is an integral multiple of
Planck’s constant divided by 2.
Angular momentum = mvr = n. h/2 Where, m = mass of electron; v = velocity of the electron; r = radius of
the orbit; n = 1, 2, 3, etc., and h = Planck’s constant.
Thus, according to this postulate, the angular momentum of a moving electron is quantized. The integer n in
the above equation can be used to designate an orbit and its corresponding energy level, and it is called the
atom’s principal quantum number.
Structure of Atom: (Bohr’s Atomic Model)
VIDEO-3
Structure of Atom: (Bohr’s Atomic Model)
1. Avogadro’s Number (N): Avogadro’s number is the number of molecules in a gram molecule or the
number of atoms in a gram atom of any substance. It is represented by the symbol N. The usually
accepted value for N is 6.023 x 1023.
2. Atomic Number (Z): The atomic number of an element is the number of protons in the nucleus of the
atom of that element. It is represented by Z. Since atom as a whole is electrically neutral, the atomic
number is also equal to the number of extraneuclear electrons.
Atomic Number (Z) = Number of protons (also = Number of electrons)
3. Mass Number (A): The mass number of an atom is the total number of protons and neutrons in the
nucleus of an atom.
Mass Number (A) = Number of protons + Number of neutrons
In situations where it is unnecessary to differentiate between protons and neutrons, these elementary
particles are collectively referred to nucleons.
The number of neutrons can be determined by subtracting atomic number (Z) from the mass number
(A).
4. Isotopes: If an element can exist in more than one form with the same atomic number but different mass
number, then these forms are known as isotopes.
Examples: 8O16 (99.757%), 8O17 (0.039%), 8O18 (0.204%)
Structure of Atom: (Origin of Spectral Lines)
The emission line spectrum of hydrogen can be obtained by passing electric discharge through the gas
contained in a discharge tube at low pressure. The emitted light radiation is then passed through a
spectroscope to get the spectrum.
These four lines in the visible spectrum of hydrogen were named after him as the Balmer Series.
Structure of Atom: (Atomic Spectrum of Hydrogen)
In addition to Balmer series four other spectral series were discovered in the UV and IR regions of the
hydrogen spectrum, which also have been named after their discovers. Thus, in all, we have five spectral
series in the atomic spectrum of hydrogen.
1 Lyman Series UV
3 Paschen Series IR
4 Brackett Series IR
5 Pfund Series IR
Video - 4
Structure of Atom: (Quantum Numbers)
The principal quantum number denotes the distance of the electron orbit from the nucleus. In other
words, it represents the size of the electron orbit. It is expressed by the letter designation n.
Theoretically, the principal quantum number can have non-zero, positive, integral values up to infinity,
i.e. n = 1, 2, 3, …………... But practically only values 1 to 7 have so far been established for the atoms of
the known elements.
In a polyelectron atom or ion, the electron that has a higher principal quantum number is at a higher
energy level.
The letters K, L, M, N, O, P and Q are also used to designate the energy levels or shells of electrons with
an n value of 1, 2, 3, 4, 5, 6, 7 respectively.
n 1 2 3 4 ………
Shell K L M N ………
N
M
(1st Shell) (2nd Shell) (3rd Shell) (4th Shell) …….. L
K
Maximum number of electron in a shell: According to Bohr-Bury Scheme the
maximum number of electrons that a shell can hold is equal to 2n2 where n 1
is the number of shell: (1st shell = 2x12 = 2, 2nd shell = 2 x 22 = 8) 2
3
4
Structure of Atom: (Quantum Numbers )
Azimuthal or Subsidiary Quantum Number (l)
The subsidiary quantum number (l) is used to represent the subshells of which a given shell
(represented by a particular value of the principal quantum number, n) is composed.
The value of l depends on the value of n. For a given value of n, l can have the values from 0 to (n–
1), i.e. l = 0, 1, 2, 3, …………… (n–2), (n–1)
Thus, l can have n values.
The electronic configuration of an atom is written in terms of nlx notation where l indicates the
sub-shell. The subshells represented by the l values 0, 1, 2, 3, ……. are designated by small letters
s, p, d, f ……… respectively. The maximum number of electrons in a subshell is equal to 2(2l+1)
where l=0, 1,2,3 for s,p,d or f subshell respectively. The s subshell is the lowest energy subshell and
the f subshell is the highest energy subshell.
Each sub-shell represented by an l value has a definite shape. For example, the s sub-shell has
spherical shape, p sub-shell has dumb-bell shape, d sub-shell has a shape resembling four pears
with their stems pointed towards the nucleus. Subshells with higher l values have more complex
shapes. So, it can be said that: the values of l define the shape of the sub-shell.
Structure of Atom: (Quantum Numbers )
When an atom is placed in a strong magnetic field, each sub-shell (represented by l values) is further sub-
divided into sub-shells called orbitals. These orbitals actually represent the different three dimensional
space orientations that a particular sub-shell can assume. The magnetic quantum number (m) is used to
represent the orbitals of which a given sub-shell is composed.
The value of m depends on the value of l. For a given value of m, l can assume all the integral values between
+l and –l including zero.
i.e. m = +l, (+l-1), …..0….., (–l+1), –l.
Thus, m can have (2l+1) values. Thus
Value of l : 0 1 2 3 --------
Sub-shell : s p d f ----------
Max electron 2(2l+1) : 2 6 10 14
The maxim number of electrons that can be present in an orbital is 2. This means that an orbital can have
none, one or two electrons, but never more than two.
Structure of Atom: (Quantum Numbers )
An electron, while moving in an orbit round the nucleus, also rotates or spins about its own axis
(self-rotation) either in a clockwise direction or in an anticlockwise direction. The spin quantum
number (s) represents the direction of the spin or self-rotation of an electron about its own axis.
Since an electron can spin in either of the two directions, the spin quantum number (s) can have
two values, viz. +½ and –½. By convention, s= +½ is used to indicate clockwise direction and s = –½
to indicate anticlockwise direction.
The clockwise and anticlockwise directions are represented by and respectively. When there
are two electrons in an orbital, they spin in opposite directions and thus an electron pair in an
orbital is represented as .
Two electrons with the same sign of the spin quantum numbers are said to have parallel spins. In
contrast, two electrons with opposite signs of the spin quantum numbers are said to have opposite
spins, antiparallel spins or paired-up spin.
Structure of Atom: (The Atomic Orbitals )
Each orbital type has a unique shape
based on the energy of its electrons.
In 1925, Wolfgang Pauli, put forward an ingenious principle regarding the assignment of the four quantum
numbers to an electron. This principle imposes some restrictions as regards assigning the quantum numbers
to the electrons of an atom and hence the name ‘Puauli’s exclusion principle’. This principle can be stated as:
“No two electrons in an atom can have the same set of four identical quantum numbers.”
This means that two electrons of an atom may have, at the most, three same quantum numbers, but the
fourth one must be different.
This follows that ----
Every electron in an atom is different in total energy from every other electron and so there can be as
many electrons in a shell as there are possible arrangements of different quantum numbers.
An orbital can not accommodate more than two electrons.
Structure of Atom: (Pauli’s Exclusion Principle)
We know, the 1st shell of an atom has only one orbital --- 1s that contains two electrons. These two
electrons will have the same set of the first three quantum numbers, i.e. n=1, l=0 and m=0, but the fourth
quantum number will be different, i.e., either +½ or –½.
Electrons n l m s
1st Electron 1 0 0 +½
2nd Electron 1 0 0 –½
Let us suppose that the 1s orbital have three electrons so that: VIDEO- 6
n l m s
1st Electron 1 0 0 +½
2nd Electrons 1 0 0 –½
3rd Electron 1 0 0 ???
It is clear from the above illustration that the 3rd electron cannot be accommodated in the 1s orbital,
because there are only two possible values of the spin quantum number --- +½ and –½.
Structure of Atom: (Hund’s Rule of Maximum Multiplicity )
This is an empirical rule which states that: ‘Electrons are distributed among the degenerate orbitals of
a sub-shell (orbitals of equivalent energy such as 2px, 2py and 2pz) in such a way as to give maximum
number of unpaired electrons with the same direction of spin.’
Thus the orbitals available to a sub-shell are first filled singly with parallel spin before they begin to
pair. The following illustration shows the order of filling of electrons in the orbitals of n=1 and n=2
shells. (The orbitals are shown in circles and the electrons entering them by numbers 1, 2, 3 …..
according to their order of entering.)
Video - 7
Aufbau Principle: Construction Principle
Aufbau process or Aufbau principle is an empirical rule that governs the order of
‘filling’ or ‘building up’ of energy sub-shells of an atom with electrons (Aufbau is a
German expression meaning building up or construction). This rule states that:
VIDEO - 8
Aufbau Principle: Construction Principle
There are quite a few elements which show slight deviations from the standard pattern dictated
by Aufbau principle. The deviations involve placing of one or two electrons from ns orbitals to
(n–1)d orbitals. Actually, there is little energy difference between such s and d orbitals and the
deviations occur when the d level orbitals are either almost full (e.g. in Cu, Pd, Ag, Pt , and Au)
or half-full (Cr and Mo). The probable underlying reason of such deviations is the fact that a
completely filled (e.g. d10) or half-filled (e.g. d5) orbital is more stable than a nearly filled or
nearly half-filled orbital (e.g. d9, d8 or d4).
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Structure of Atom
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