Chemistry Formulas

CHAPTER

02 STRUCTURE OF ATOM

 Thomson Model of Atom bombarded high energy a -particles from

(i) J.J. Thomson proposed a model in which radioactive source on thin foil (thickness 10-
7
atom was assumed to be uniform sphere m) of gold metal. The thin gold foil had a
with radius 10–8 cm of positive electricity circular flurescent ZnS screen around it.
(positive charge) with electrons embedded Whenever an a -particle struck the screen, a
into it in such a way as to give the most tiny flash of light was produced at that point.
stable electrostatic arrangement. He observed that:

(ii) In this model, the atom is visualized as a

pudding or cake of posiive charge with
raisins (electrons) embedded into it. This
model is also called the `raising pudding’
model. (i) Most of a -particles passed through the
(iii) The mass of atom is considered to be evenly gold foil undeflected.
spread over the atom acording to this (ii) A small fraction of a -particles was
model. deflected by small angles.
 Drawback of Thomson Model of Atom. This (iii) A very few a -particles (1 in 2000)
model of atom could account for the electrical bounded back, i.e., were deflected by
neutrality of atom, but it could not explain the nearly 180°.
results of gold foil experiment carried out by  Rutherford’s Conclusions regarding
Rutherford. Model of Atom:
 a -particles. They are positively charged (+2) (i) Most of space in atom is empty because
helium ions having high energy emittd during most of a -particles passed through the foil.
radio-active decay of unstable elements like (ii) The positive charge has to be concentrated
Uranium. It has +2 charge and mass 4u. ina very small volume that repelled and
 Rutherford’s a -Scattering Experiment deflected few positively charged a -
(Discovery of Nucleus). Rutherford particles. This very small portion of the
atom was called nucleus.
 Chemistry Formulas

(iii) The volume of nucleus is very small as (iii) The energy of quantum is directly
compared to total volume of atom. The proportional to the frequency (v) of the
radius of nucleus (10–13 cm) is about radiation.
1 Eµ v
of that atom (10–8 cm). If cricket
100, 000 E = hv
ball is nucleus then radius of atom will be
hc æ cö
about 5 km. E=  ç v = ÷ , where `c’ is
l è l ø
 Rutherford’s Nuclear Model of Atom:
(i) An atom consists of tiny positively charged verlocity of light and `l ' is wavelength
centre called nucleus. h’ is Planck’s constant, its value is 6.626 ×
(ii) The nucleus consists of protons and 10–34 Js.
neutrons called nucleons. According to Planck’s theory, energy is
(iii) Nucleons (proton and neutron) are much always emitted in integral multiple of hv,
heavier than an electron indicating that mass e.g., hv, 2hv, 3hv, etc.
of atom lies in its nucleus. The total number  Quantization. The restriction of a property to
of nucleons is termed as mass number. discrete values and not continuous values is
(iv) The electrons are outside the nucleus called quantization.
revolving around nucleus at high speed in  Hydrogen Spectrum. If a discharge is passed
certain fixed circular path called orbits in through hydrogen gas at a low pressure, some
the same manner as planets move around hydrogen, atoms are formed, which emit light
sun. in the visible region. This can be studied by
 Electromagnetic Spectrum. An arrangement using Spectroscope or Spectrometer, and is
of radiations of all kinds, electric and magnetic, found to comprise of series of lines of different
in order of decreasing frequency or increasing wavelength. The four lines can be seen by eyes,
wavelength is called electromagnetic spectrum but many more observed photographically in
which is shown in figure. ultraviolet region.
Electromagnetic radiations differ from one  Balmer Formula. In 1885, Balmar showed
another in wavelength or frequency. that the wave number n of any line in the visible
spectrum of atomic hydrogen could be given
by simple empirical formula
æ1 1 ö
n = R ç 2 - 2 ÷, R = 1.097373 ´ 107 m - 1
è2 n ø
where `R’ is Rydberg constant and `n’ has
values 3, 4, 5,........
 Lyman Series. When excited electrons in
hydrogen atoms fall from higher energy levels
 Planck’s Quantum Theory: to first energy level, the series of lines observed
(i) The energy is radiated or absorbed by a are called Lyman series. They are observed in
body not continuously but discontinuously ultraviolet region.
in form of small packets. æ1 1 ö
(ii) Each packet is called quantum. In case of Lyman n = R çè 2 - 2 ÷, n = 2,3, 4,5....
1 n ø
light, the quantum is called `photon’.
 Chemistry Formulas

 Balmer Series. When excited electrons in (ii) When an electron moved form one orbit to
hydrogen atoms fall from higher energy levels another, it either radiates or absorbs energy.
to second energy level, teh series of lines If it moved towards nucleus, energy is
observed is called Balmer series. They are radiated.
observed in visible region.
hc
DE = E 2 - E1 = hv = .
æ1 1 ö l
Balmer n = R çè 2 - 2 ÷, n = 3, 4,5....
2 n ø
- 1312
Paschen Series. When excited electrons in En = kJ mol- 1for H - atom

n2
hydrogen atoms fall from higher energy levels
to third energy level, we observe Paschen - 2 p 2 mZ2e 4
En = for other atom
series. They are observed in infra-red region. n2h 2
æ1 1 ö - 1312 ´ 103 J mol - 1
Paschen n = R çè 2 - 2 ÷, n = 4,5, 6, 7.... En = for H - atom
3 n ø n2
 Brackett Series. When excited electrons in
hydrogen atoms fall from higher energy levels - 2.173 ´ 10- 18 J / atom
En =
of fifth energy level, we observe Brackett series. n2
The are also observed in infra-red region of For Hydrogen like species
spectrum.
- 1312
Brackett En = ´ Z2 kJ mol - 1 ,
n2
æ1 1 ö where `Z ' is atomic number.
n = R ç 2 - 2 ÷, n = 5, 6, 7,8....
è4 n ø
Pfund Series. When excited electrons hc æ1 1ö

DE = E 2 - E1 = - 1312 ç 2 - 2 ÷ kJ mol - 1
inhydrogen atoms fall from higher energy levels l è n 2 n1 ø
of fifth energy level, Pfund series is observed.
They are also found in infra-red region of n2h 2 1
rn = 2 2 Þ rn µ n 2 or rn µ
spectrum. 4 p me Z Z
æ1 1 ö rn = 0.0529 n 2 nm for H-atom, where `n’ is
Pfund n = R ç 2 - 2 ÷, n = 6, 7,8,9....
è5 n ø
energy level, rn is radius of nth orbit.
 Rydberg Formula.

1 æ1 1 ö 0.0529n 2
n= = R H ç 2 - 2 ÷, rn = , where `Z ' is atomic number.
l è n1 n 2 ø Z
Where n is wave number, `l ' is wavelength, (For H-like atom)
RH is Rydberg constant, n1 is lower energy level, Radius of various nuclei = 1.4 × 10–13 cm ×
n2 is higher energy level. RH = 109679 cm–1. A1/3
 Bohr’s Theory: 2 p e 2 Z 2.188 ´ 106 ´ Z - 1
(i) An electron did not radiate energy if it Vn = = ms
nh n
stayed in one orbit and therefore did not
(iii) The angular momentum of orbits in which
slow down
electron revolves must be integral multiple
 Chemistry Formulas

h quantised values can be expressed in terms of

of , where `h’ is quantum number. They are used to get
2p
complete information about electron. i.e.,
Plank’s constant (h = 6.6262 × 10–34 Js) location, energy, spin, etc.
nh  Principal Quantum Number. It specifies the
mVr = , where, n = 1, 2,3, 4,....
2p location and energy of an electron. It is the
measure of the effectiv volume of the electron
Thus, energy of orbits is fixed. Therefore,
cloud. It is denoted by `n’. Its possible values
these orbits are called energy levels. Bohr’s
are 1, 2, 3, .... for K, L, M, N....
theory provides an explanationfor atomic
spectra of hydrogen.  Angular Momentum Quantum Number. It
is also called `azimuthal quantum number’. The
(iv) The energy of orbit closest to the nucleus
quatised values of orbital angular momentum
is lowest whereas energy of orbit far away
cna be specified in terms of angular momentum
from the nucleus is highest.
quantum number. It determines the shape of the
(v) As we go higher, diffrence in energy of orbital. It is denoted by `l’. The permitted values
energy levels goes on decreasing. of `l’ are 0, 1, 2, etc., upto n – 1, `l’ can bave
 Achievements of Bohr’s Theory: value equal to zero unlike `n’. The maximum
(i) It could successfully explain the stability of value of `l’ is equal to n – 1, e.g., if value of n is
atom 6. l can have values 0, 1, 2, 3, 4, 5 represent s,
(ii) It could explain spectrum of hydrogen and p, d, f, g, u orbitals.
unit-electron species.
h
(iii) It could help to calculate energy and velocity mVr = l (l + 1) , where mVr is angular
2p
of electrons in various energy levels.
moment.
(iv) It helped to calculate radius of various
 Magnetic Quantum Number. An electron
energy levels in hydrogen and hydrogen like
having angular momentum produces a magnetic
species.
field which can be observed. The observed
 Zeeman Effect. The splitting of spectral lines magnetism shows the quantised nature and is
in strong magnetic field is called Zeeman effect. described by magnetic quantum number. It is
Itis associated with magnetic quantum number. denoted by `mi’ and its value depends on value
 Stark Effect. The splitting of spectral lines in of `l’ since magnetism is due to angular
electric field is called Stark effect. momentum. It determines the magnetic
 Drawbacks of Bohr’s Theory: orientation of an orbital, i.e., the direction of
(i) It could not explain spectrum of multi- orbital relative to magnetic field in which it is
electron atoms. placed. Its permitted values are –l to +l
(ii) It could not explain Zeeman and Stark including zero, e.g., when l = 1, then m = –1,
effect. 0, +1. It has total number of values equal to 2l
(iii) It could not explain shape of molecules. + 1.
(iv) It was not in accordance with Heisenberg’s m= n(n + 2) Bohr Magneton
uncertainty principle.
where `m' is magnetic moment and `n’ is
 Quantum Numbers. Atomic orbitals can be
specified by giving their corresponding energies number of unpaired electrons.
and angular momenta which are quantised (i.e., `s’ orbitals are of `1 type, `p’ orbitals are of 3
they can bave some specific values). The types, `d’ orbital are of 5 types. `f’ orbitals are
of 7 types, `g’ orbitals are of 9 types and `u’
 Chemistry Formulas

orbitals are of 9 types and `u’ orbitals are of 11 energies, i.e., orbital having lowest energy will
types. be filled first and the orbital having highest energy
 Spin Quantum Number. It indicates the will be filled last.
direction in which electron revolves. Spin is  Stability of Half Filled and Completely
magnetic property and is also quantised. It has Filled Orbitals. (i) Symmetrical distribution
two permitted values +1/2 and –1/2. It is of electrons. It is well known that symmetry
denoted by `s’. leads to stability. Half filled and completely filled
orbitals are symmetrical, therefore, more stable.
h
Spin moment = s(s + 1) . (ii) Exchange Energy. When two or more
2p electrons with same spin in the degenerate
 Pauli Exclusion Principle. No two electrons orbitals, they can exchang their positions and
in an atom can have the same four quantum energy released is called exchange energy.
numbers. It can also be stated as—An orbital Greater the number of exchanges, greater will
can bave maximum two electrons and they must be exchange energy and more will be stability.
be of opposite spin quantum numbers. In case of half filled and completely filled
 Aufbau principle. Electrons are filled in the orbitals, maximum number of exchanges are
various orbitals in the increasing order of their possible, therefore, it leads to maximum stability.

Table : Quantum Number and their Significance

Quantum Number Symbol Restrictions Range of values Significance

Principal quantum n Positive integers 1, 2, 3... Identifies shell, determines
number size and energy of orbital,
number of orbitals in the
2
nth shell = n
Azimuthal quantum l Positive integers 0,1,2,...(n–1) Identifies subshell; deter-
number or Angular less than n Total possible mines shape of the orbital,
momentum quantum values = n energy of orbital in a
number multi-electron atom along
with n and ortbial angular
momentum i.e.
l (l + 1)h / 2 p
Magnetic quantum mi Integers between –l to +l including Determines orientation
number –l and +l 0. Total possible the orbital
values = (2l + l)
Magnetic spin ms Half integers + 1/2 or –1/2 Determines orientation of
quantum number +1/2 or –1/2 the spin.]
 Chemistry Formulas

 The atomic theory of matter was first proposed  A body that emits and absorbs all frequencies
by John Dalton is called as black body
e  Photo electric effect : Ejection of electron
 = 1.758820 ´ 1011 c/kg from a metal surface takes place when a pho-
mc
ton of energy greater than the threshold en-
FORMULAE AND CONCEPTS ergy strikes an electron in the atom
 The atomic theory of matter was first pro-  According to photo electric effect
posed by John Dalton
h  W  K.E
e Where; h  energy of photon
  1.758820  1011 c / kg
me K.E. = kinetic energy of emitted electron
 Mass of electron W = Work function
e  Work function (W) : The energy required to
me   9.1094  1031 kg over come the attractive forces on the elec-
e / me
tron in the metal
 J.J. Thomsons atomic model is also called is  h  W  K.E (or) h
'water melon' or 'plum pudding' or Raisin Pud-
ding model 1
 h0  K.E (or) h  h0  m e v 2
 Atomic number (Z) = Number of protons in 2
the nucleus of an atom = Number of electrons
here 0  Threshold frequency
in a neutral atom
 Mass number (A) = Number of (Z) + number  Energy of one mole of photon = energy 
of neutrons (n) Avagadro number
 Nucleons = The protons and neutrons present  Rydberg equation
in the nucleus are collectively known as nucle-
1 1 1
ons   RH  2  2 
  n1 n 2 
 Isobars = Atoms with same mass number but
different atomic number
22me4
Examples of Isobars 14 14 RH  where R = 109677 cm-1
6 C and 7 N Ch 3
 Isotopes are Atoms with same atomic num-  E  E 2  E1  h
ber but different mass number
E 2  energy of outer orbit
Example of isotopes is 1 H1 , 1D 2 , 1T 3
E = energy of inner orbit
1
 Wave number  

  h = planck's constant
 = frequency
C  Angular momentum of an electron
 Frequency    
 nh
mvr  where n = 1, 2, 3 (n = principal
 Energy associated with a photon; is given by 2
E  nh quantum number)
 h = planck's constant  According to coulomb's law, electro static
force of attraction between nucleus and the
 6.6256  1034 J.S  6.6256  10 27 erg.sec
electron (in hydrogen atom)  e 2 / r 2
 Chemistry Formulas

 Centrifugal forces acting away from the nucleus  Heisenberg's uncertainty principle states that
it is impossible to determine simultaneously the
mv 2
is equal to  exact position and momentum of an electron.
r
 th h
Radius of n orbit x.p   n  1, 2,3, 4 
n
n2h2
rn  here x  uncertainty in position.
42 me 2
p  uncertainty in momentum
rn  0.529  10 8 n 2 cm or rn  0.529n 2 A0 for electron line particle
 Potential energy  e 2 / r h
x.p   here n  4 
2 n
1 2 e
Kinetic energy = mv   Schrodinger wave equation
2 2r
 2   2   2  82 m
e2    2  E V    0
Total energy (E) = x 2 y 2 z 2 h
2r
 Wave function  should satisfy the following
k conditions.
 Energy of an electron En  2
n (i)  must be continous
22 me 4 (ii)  must be finite
Where K  (iii)  must be single valued at any point
h2
(iv) The probability of finding the election over
21.72  1012 the space from  to  must be equal
 En  ergs / atom
n2 to one
 The three dimensional space around the
21.72  10 19 nucleus in an atom where the probabitlity of
 Joules / atom
n2 finding an electron is maximum is called an
13.6 atomic orbital.
 eV / atom  Principal quantum number (n) determines size
n2
and energy of the orbit.
 Splitting of spectral lines under the influence
of electric field is called as stark effect.  The values possible for principal quantum num-
ber (n) are 1, 2, 3, 4 ........... 
 Splitting of spectral lines under the influence
of magnetic field is called as zeeman effect.  Azimuthal quantum number defines three di-
mensional shape of the orbital.
 According to de Broglie
 The values possible for Azimuthal quantum
h h number are 0, 1, 2,............ (n -1)
 
mv p  The number of orbitals in a given sublevel
In a constructive interference n  2r  2l  1
(or)  Magnetic quantum number (m) gives informa-
tion about spatial orientation of the orbital.
nh  The values possible for magnetic quantum
mvr 
2 number are
 Chemistry Formulas

m1  l ,   l  1 ,   l  2  .........  1, 0,1.........  l  2  ,  l  1 , l
 Values of 'l' 0 1 2 3 4 5
Subshell notation s p d f g h
Number of orbitals 1 3 5 7 9 11

 Spin quantum number (s) given an idea about  Number of radial nodes  n  l  1
the spin of the electron
 Total number of nodes = Number of radical
 Spin quantum number (s) can take the values nodes + number of angular nodes
1 1
of  and   (l )   n  l  1  n 1
2 2
 Aufbau principle : In the ground state of the
 Electron radial probabitlity distribution func-
atoms orbital are filled in the order of their
tion (D) is equal to 4r 2 dr  2 increase in energies.
 The distance at which the maximum probabil-  Order of energy of orbital
ity of finding an electron increases with increase
1s  2s  2 p  3s  3 p  4s  3d  4 p  5s.........
in the value of principal quantum number.
 Paulis exclusion principle :
 For 1s orbital the maximum probability is at
0.530A No two electrons have same set of four quan-
tum numbers.
For 2s orbital the maximum probability is at
about 2.60A  Hund's rule :
 Size of the orbital increases in the order Pairing of electrons in the orbitals belonging
to the same subshell (p, d or f) does not take
1s  2s  3s  4s............
place until all the orbitals are singly occupied.
 The total number of peaks appearing in the
 Anamalous electronic configuration
radial distribution curves for 's' orbital is equal
to principal quantum number (n) Chromium (24) : - 1s 2 2s 2 2 p 6 3s 2 3 p 6 4 s1 3d 5
 The surface at which the probabitlity of find-
Copper (29) : - 1s 2 2s 2 2 p 6 3s 2 3 p 6 4s1 3d 10 .
ing an electron is zero is called as radial node.

