List of good study habits

 Attend classes regularly and take careful notes.

 If possible, always review the topics you learned in the class.
 Think critically. Ask yourself if you really understand the meaning of a term.
 A good way to test your understanding is for you to explain a concept to a classmate.
 Do not hesitate to ask any question to your teacher

Lecture Note

Chemistry-I
GENERAL
CHEMISTRY
(PART-1)

www.mehedi360.wixsite.com/pciu
Text and Reference Books
1. “General chemistry: The essential concepts” by Raymond Chang & Jason Overby (McGraw-
Hill, 6th ed)
2. “General Chemistry” by Darrell D. Ebbing Steven D. Gammon (Houghton Mifflin Company,
9th ed).
3. “Physical Chemistry” by Peter Atkins and Julio de Paula (W. H. Freeman; 9th ed.)
4. “Modern Inorganic Chemistry” by- S.Z. Haider
5. “Concise Inorganic Chemistry” by-J.D. Lee
6. “Essential Physical Chemistry” by- B.S. bahl, G.D.Tuli, A. Bahl
 MID-TERM

1. Basic Concepts of Organic Chemistry

2. Introduction to organic chemistry
3. Hydrocarbons: Aliphatic & Aromatic
 CHAPTER-1
INTRODUCTION TO CHEMISTRY

► Lecture-01
Q 1: What is chemistry? Discuss the significant reasons to study chemistry.

We can define chemistry as the science of the composition and structure of materials and of the
changes that materials undergo. Chemistry deals with all materials, it is a subject of enormous
breadth. It would be difficult to exaggerate the influence of chemistry on modern science and
technology or on our ideas about our planet and the universe.

Significant reasons to study chemistry:

First, chemistry has important practical applications. The development of life saving drugs is
one, and a complete list would touch upon most areas of modern technology.

Second, chemistry is an intellectual enterprise, a way of explaining our material world.

Finally, chemistry figures prominently in other fields. Whatever your career plans, you will find
that your knowledge of chemistry is a useful intellectual tool for making important decisions.

Chemists began to look at the precise quantities of substances they used in their experiments.
From this work came the central principle of modern chemistry: the materials around us are
composed of exceedingly small particles called atoms, and the precise arrangement of these
atoms into moleculesor more complicated structures. Once chemists understood this central
principle, they could begin to fashion molecules to order. They could synthesize molecules; that
is, they could build large molecules from small ones.
 Q-02. Characterize gases, liquids, and solids in terms of motion of particles, shapes,
rigidity and compressibility.

Commonly, a given kind of matter exists in different physical forms under different conditions.
Water, for example, exists as ice (solid water), as liquid water, and as steam (gaseous water). The
main identifying characteristic of solids is their rigidity: they tend to maintain their shapes when
subjected to outside forces. Liquids and gases, however, are fluids; that is, they flow easily and
change their shapes in response to slight outside forces. These three forms of matter—solid,
liquid, gas—comprise the common states of matter.

Basis Gas Liquid Solid

Though particles can Particles move with
Particles have no
move but their kinetic high speed and they can
motion. They can only
energy cannot exceed exceed intermolecular
vibrate. Vibration
attractive forces. That’s force easily. Kinetic
Motion of particles increases with the
why see a boundary or energy is very high that
increases of
surface of a liquid. attractive forces are
temperature.
Ek  EI .F . insignificant.
Ek  0
Ek  EI .F .

Two different types of A given quantity of gas

A liquid has a fixed
shape are possible: will fit into a container
Shapes volume but no fixed
crystalline and of almost any size and
shape.
amorphous. shape.

Rigidity Very high Low Very low

Compressibility Very low low Very high
 Q 1: Write the classification of matter using a figure to illustrate the relationship
between them.

Classification of matte: We identify a matter by its various properties, which may be either
physical or chemical. A physical property is a characteristic that can be observed for a
material without changing its chemical identity. Examples are physical state (solid, liquid, or
gas), melting point, and color. A chemical property is a characteristic of a material involving
its chemical change. A chemical property of iron is its ability to react with oxygen to produce
rust.

Substances: Matter which has definite chemical identity i.e., chemical symbol or chemical
formula. Example: Water (H2O), Table salt (NaCl) etc.
Element: Substance formed by one type of atom.
Compound: Substances formed by different types of atom.
 The Importance of Chemistry

Chemistry, as a science, studies the composition and properties of matter. Chemistry also studies the reactions
between different chemicals, known as chemical reactions. Basic chemical reactions are always going on around us
as well as a more complex system of reactions, even just within our bodies. For example, as anyone sits down at his
computer and begins to type, his body undergoes a huge amount of chemical reactions to make his eyes and hands
move, and to make his brain think. This is an example of the Chemistry of biological processes. Some chemists
study these biological processes, while others may study different things. In general, all chemists do the following:

Chemists try to understand how the composition of substances affect the substance's properties.
Chemists seek to understand why and how substances change within chemical reactions.
Chemists try to understand and observe the underlying structure of matter.
Chemists attempt to understand why the properties that we observe with our senses occur in matter.

Of course, taking a first class in Chemistry does not mean you are going to become a chemist. However, Chemistry
is useful in all branches of science. Even for a non science major, chemistry can improve one's understanding of the
world around them, and in my experience, can help you win some arguments. Chemistry is used in Physics, Biology,
Engineering, Electronics, Pharmaceuticals etc. So you know what chemists do, in a very general sense. So you may
be wondering why chemistry is so important to all of the sciences. The answer is that all things are composed of
chemicals. This includes your hair, your water, your computer, and your dinner. Even living things are composed
entirely of chemicals. Everything you know is made of matter, and contains chemicals that are able to participate in
complex reactions. You can see why Chemistry is such a deep field of study. So, while scientific disciplines may
have varying interests, they all use chemistry, and today the lines between Physics, Biology, and Chemistry are more
hazy than ever.

Chemistry & Textile: Chemistry is absolutely essential for making clothes more affordable, versatile,
comfortable and creative. Several types of chemistry are responsible for the creation of fashion pieces,
including polymer, inorganic and organic chemistry. Without chemistry’s development of specialty fibres and
other components, the creative world of fashion could not be nearly as dynamic as it is today. In fact,
chemistry contributes 28% of the value of material input in clothing. Acrylics, nylon and polyester are all
synthetic fibres made from petroleum products, not to mention spandex made from polyurethane. From the
petroleum or natural gas naphta, the petrochemical industry manufactures several products like the ethyleneglycol,
terephthalic acid, dimethylterephthalate, acrylonitrile, adiponitrile and caprolactam. These are the hard-to-pronounce
products which originate the yarns and fibers of polyester, polyamide – better known as nylon, the acrylic fiber and
the spandex. With chemistry the possibilities are endless; dyes and pigments responsible for shining or
opaque coloured threads, socks that moisturise, sports clothes that deodorise and garments that kill bacteria.

A1. For each of the following, decide whether a physical or a chemical change is involved.
(i) melting of sodium chloride
(ii) burning of sulfur
(iii) dissolving of salt in water
(iv) rusting of iron
(v) burning of wood
(vi) evaporation of alcohol
A2. Describe each of the following as a physical or chemical property of each listed chemical
substance.
(i) baking soda reacts with vinegar
(ii) ice melts at 0°C
(iii) graphite is a soft, black solid
(iv) hydrogen burns in air
(v) chlorine is a green gas
(vi) iron can rust
 CHAPTER-1
INTRODUCTION TO CHEMISTRY

► Lecture-02

Q 1: Discuss the main points of Dalton’s atomic theory. Write the atomic symbols for
the elements having following atomic numbers: 3, 9, 12, 15, and 19 (Practice atomic
symbols for elements: 1-38).

Dalton’s atomic theory: The main points of Dalton’s atomic theory are given below:

(i) All matter is composed of indivisible atoms. An atom is an extremely small particle of
matter that retains its identity during chemical reactions.

(ii) An element is a type of matter composed of only one kind of atom, each atom of a given
kind having the same properties.

(iii) A compound is a type of matter composed of atoms of two or more elements chemically
combined in fixed proportions. The relative numbers of any two kinds of atoms in a
compound occur in simple ratios.

(iv)A chemical reaction consists of the rearrangement of the atoms present in the reacting
substances to give new chemical combinations present in the substances formed by the
reaction. Atoms are not created, destroyed, or broken into smaller particles by any chemical
reaction.
Atomic Name of Atomic Name of
Symbol Symbol
number element number element
1 Hydrogen H 21 Scandium Sc
2 Helium He 22 Titanium Ti
3 Lithium Li 23 Vanadium V
4 Beryllium Be 24 Chromium Cr
5 Boron B 25 Manganese Mn
6 Carbon C 26 Iron Fe
7 Nitrogen N 28 Nickel Ni
8 Oxygen O 27 Cobalt Co
9 Fluorine F 29 Copper Cu
10 Neon Ne 30 Zinc Zn
11 Sodium Na 31 Gallium Ga
12 Magnesium Mg 32 Germanium Ge
13 Aluminum Al 33 Arsenic As
14 Silicon Si 34 Selenium Se
15 Phosphorus P 35 Bromine Br
16 Sulfur S 36 Krypton Kr
17 Chlorine Cl 37 Rubidium Rb
19 Potassium K 38 Strontium Sr
18 Argon Ar
20 Calcium Ca
 Q 1: What are the different kinds of particle present in an atom? Compare their
properties with each other.

 In atom there are two distinguished regions: nucleus and orbit. The center of an atom is
called nucleus. Nucleus is positively charged and contains most of the mass of an atom. The
circular path around the nucleus is called orbit.
 An atom contains three fundamental particles: electron, proton and neutron. Protons and
neutrons exist in the nucleus and electrons rotate in the orbit.
 Electron is a very light, negatively charged particle.
 Proton is a nuclear particle having a positive charge equal to that of the electron and a mass
more than 1800 times that of the electron.
 The neutron is also a nuclear particle having a mass almost identical to that of the proton but
no electric charge.
 An atom is normally electrically neutral, so it has equal number of electrons and protons. A
sodium atom has a nucleus of charge +11, and around this nucleus are 11 electrons (with a
charge of 11, giving the atom a charge of 0).

Nucleus

Electron

Orbit/ Shell

Carbon atom (Z=6)

Atomic particle Symbol Relative charge Relative mass Position

−
Electron e −1 1/1800u Orbit
Proton p +1 1u Nucleus
Neutron n 0 1u Nucleus
Note: 1u=1.66×10−24g
 Q 1: Define these terms: (i) atomic number, (ii) mass number, and (iii) isotope. What is
the nuclide symbol for the nucleus that contains 8 protons and 8 neutrons?

We characterize a nucleus by its atomic number and mass number. The number of protons in the
nucleus of an atom is called its atomic number. It is represented by Z. The identity of an atom
depends on Z. The atomic number of carbon atom is 6 (Z=6). Hence, it contains 6 protons at its
center and also in neutral atom there will be 6 electrons.

The mass number is the total number of protons and neutrons in the nucleus of an atom. It is
represented by A. For example mass number of carbon is 12 (A=12). So, total number of proton
and neutron is 12.

Isotopes are atoms whose nuclei have the same atomic number but different mass numbers; that
is, the nuclei have the same number of protons but different numbers of neutrons. Three isotopes
of carbon is given below-
12 13 14
C, C and C
6 6 6

For the given nucleus:

Atomic number, Z = 8
Mass number, A = (8 + 8) = 16
Nuclide symbol is-
16
O
8
Why does knowledge of atomic number enable us to deduce the number of electrons present in
an atom?

A nuclide is an atom characterized by a definite atomic number and mass number. For the
naturally occurring carbon nuclide as follows:
Mass Number 12
C
Atomic Number 6
 Assignment work

A3. Naturally occurring chlorine is a mixture of the isotopes Cl-35 and Cl-37. How many
protons and how many neutrons are there in each isotope? How many electrons are there in
the neutral atoms?
A4. An atom contains 11 protons and 11 neutrons. What is the nuclide symbol for the nucleus?
A5. Give the atomic symbol for each of the following elements.
a. potassium
b. sulfur
c. iron
d. manganese
 CHAPTER-2
STRUCTURE OF ATOM

► Lecture-03

Q 1: What is Rutherford’s α- ray scattering experiment? What are its conclusions?

Rutherford’s scattering experiment: Rutherford conducted a scattering experiment in 1911 to

find out the structure of atom. He bombarded a thin gold foil with positively charged stream of
α-particles (He2+). The conclusion of this experiment is given below:

Observation Interpretation
Most α-particles passed through the gold metal
Most of the space of an atom is empty
foil
Nucleus is positively charged which repeal the
Some α-particles are deflected by small angles
positively charged α-particles.
Most of the mass are concentrated in the
Few α-particles bounce back (one per million)
nucleus.
 Q 1: Discuss the postulates of Rutherford’s atomic model. Mention the drawbacks of
this model.
Q 1: The atom contains electrically charged particles, yet they are neutral.
The atom contains electrically charged particles, yet they are neutral.
Rutherford's nuclear model of atom: Rutherford proposed the nuclear model of atom.
According to this model:
(i) An atom consists of a tiny positively charged nucleus at its centre. The positive charge of the
nucleus is due to protons. The mass of the nucleus, on the other hand, is due to protons and
some neutral particles each having mass nearly equal to the mass of proton. This neutral
particle, called neutron.

(ii) The nucleus is surrounded by electrons that move around the nucleus with very high speed in
circular paths called orbits. Thus, Rutherford's model of atom resembles the solar system in
which the sun plays the role of the nucleus and the planets that of revolving electrons.
Electrons and the nucleus are held together by electrostatic forces of attraction.

(iii) The number of electrons in an atom is equal to the number of protons in it. Thus, the
total positive charge of the nucleus exactly balances the total negative charge in the atom
making it electrically neutral.

Drawbacks of Rutherford's Model:

(i) According to Rutherford's model, an atom consists of a positive nucleus with the electrons
moving around it in circular orbits. However it had been shown by J. C. Maxwell that
whenever an electron is subjected to acceleration, it emits radiation and loses energy.
Nucleus

+ Electron
e

Figure 1: Maxwell Concept

(ii) As a result of this, its orbit should become smaller and smaller and finally it should drop
into the nucleus by following a spiral path. This means that atom would collapse and thus
Rutherford's model failed to explain stability of atoms.

(iii) Another drawback of the Rutherford's model is that it says nothing about the electronic
structure of the atoms i.e., how the electrons are distributed around the nucleus and what
are the energies of these electrons. Therefore, this model failed to explain the existence of
certain definite lines in the hydrogen spectrum.
 Q 1: State the postulates of Bohr’s theory for hydrogen atom.
Q 1: Orbits are also called stationary states.

Bohr's model: To overcome the defects of Rutherford's model, Niels Bohr in 1913 gave a
modification based on Quantum theory. The important postulates are:

(i) The electrons rotate around the nucleus only in certain selected circular paths called orbits.
These orbits are associated with definite energies and are called energy levels or shell. Shell
are numbered as 1, 2, 3, 4 etc. (starting from the nucleus) are designated as K, L, M, N ....etc.
(Figure 2).
M-Shell
Nucleus
L-Shell

K-Shell

+
n=1

n=2

n=3

Figure 2: Bohr's orbits

As long as an electron remains in a particular orbit, it does not lose or gain energy. This
means that energy of an electron in a particular orbit remains constant. Therefore, these
orbits are also called stationary states.

(ii) Only those orbits are permitted in which angular momentum of the electron is a whole
number multiple of h
2 , where 'h' is Planck's constant:
h
mvr  n ; where n  1, 2, 3,        
2

In other words, angular velocity of electrons in an atom is quantised.

(iii) If an electron jumps from one stationary state to another, it will absorb or emit
radiation of a definite frequency giving a spectral line of that frequency which depends upon
the initial and final levels. When an electron jumps back to the lower energy level, it radiates
same amount of energy in the form of radiation.
 Assignment work

A6. Naturally occurring chlorine is a mixture of the isotopes Cl-35 and Cl-37. How many
protons and how many neutrons are there in each isotope? How many electrons are there in
the neutral atoms?
A7. An atom contains 11 protons and 11 neutrons. What is the nuclide symbol for the nucleus?
A8. A bar of iron at high temperature is red. Is the light emitted from the glowing bar due to electrons
moving from low to high energy or dropping from a high energy to lower energy levels?
 ► Lecture-04
Mathematical Treatment of Bohr atom

de Broglie hypothesis

Matter waves are a central part of the theory of quantum mechanics, being an example of wave–
particle duality. De Broglie proposed that just as light has both wave-like and particle-like
properties, electrons also have wave-like properties. A relationship between the wavelength, λ
associated with an electron and its momentum, p, through the Planck constant, h is:
h

p
The relationship is now known to hold for all types of matter: all matter exhibits properties of
both particles and waves. Matter waves are referred to as de Broglie waves. The wave-like
behavior of matter is crucial to the modern theory of atomic structure and particle physics.

Q 1: Derive the de Broglie’s equation for the wavelength associated with a moving particle
of mass m and velocity v?

Derivation of de Broglie equation

Einstein relation
E  mc 2 (2)
Planck relation
E  h (3)
From above equation we get-
mc 2  h
hc  c 
or, mc     
2


or, h

mc
This equation is called de Broglie equation. For electron wc can replace the velocity term ‘c’
with ‘v’ as follows-

h h
  (4)
mv p

Q 1: Show that, the angular momentum, mvr, of an electron is an integral multiple of h/2π.

16. de Broglie reaffirms Bohr’s postulate

The wavelength associated with a moving particle is given by the equation

 h (5)

mv
where λ is the wavelength, h is Planck's constant, m is mass, and v is the velocity of the particle.

Fig. 1. Picture of electron orbitals, one of which is in phase, and the other out of phase.

Then, if r is the radius and 2πr the circumference of the circle occupied by the wave, we have
(6)
2r  n
The value n will be 1, 2, 3, etc.; therefore, Equations (5) and (6) may be combined as
nh (7)
2r  n 
mv
or, upon rearranging,
nh (8)
mvr 
2

17. Bohr's Theory of the Hydrogen Atom

Bohr pictured the hydrogen atom as a system consisting of a single electron with a charge
designated as e, rotating in a circular orbit of radius r about a nucleus of charge Ze. According to
Coulomb's law the electrostatic force of attraction Fe between the charges may be evaluated
mathematically as
Ze 2 (9)
Fe  2
r
By definition the magnitude of the centrifugal force Fc for an electron of mass m, with a velocity
in its orbit of v, and with an orbital radius of r,
is given as
mv 2 (10)
Fc 
r
In order that the electron's orbit may remain stable, it is necessary to assume that the two forces,
electrostatic and centrifugal, are equal and opposed to each other. From this assumption may be
deduced the following mathematical relationship,
Ze 2 mv 2

r2 r
2
or, Ze  mv 2 (11)
r
and, upon solving for v, we obtain
 Ze 2 (12)
v
mr
According to Bohr theory angular momentum may be described as-
nh
mvr 
2
where n represents an integer. If this equation is also solved for v, the result is
or, v  nh (13)
2mr
Equations (12) and (13) may be equated since they are equal to each other,

Ze 2 nh

mr 2mr
and, upon solving for r, we obtain
n2h2 (14)
r
4 2 mZe 2
Consequently the radius r0 of the smallest orbit for the hydrogen atom is
h2 (15)
ro 
4 2 me 2
The total energy En of the electron is the sum of its kinetic and potential energies. If the potential
energy of an electron is taken as zero when it is at an infinite distance from the nucleus, the value
at a distance r is given by —Ze2/r. This value may be obtained by integrating Equation (9)
between the limits of r and infinity. The negative sign indicates work must be performed on the
electron to transfer it to infinity. Therefore the total energy of the electron is
En  E k  E p
mv 2 Ze 2
 
2 r
Ze 2
Ze 2  Ze 2 
    mv 2 
2r r  r 
Ze 2

2r
Ze 2 4 2 mZe 2
 
2 n2h2
2 2 mZ 2 e 4
 En   (16)
n2h2

where En is the total energy of the electron in the orbit designated by thequantum number n.
Fig. 2: Origin of emission spectra of atomic hydrogen.

If we indicate the energy cf the higher level as En,2 and that of the lower as En,1, then the
difference may be expressed as
2 2 mZ 2e 4  1 1
E  E n  E n  2  2  2 (17)
2 1
h  n1 n2 
hc
E  h  (18)

Comparing equations (17) and (18) we get-
hc 2 2 mZ 2 e 4  1 1 
  2  2
 2
 n1 n2 
ho
1 2 2 mZ 2 e 4 1 1
or,   2  2
 h 3c  n1 n2 

1 1 1
  RH  2  2  (19)
  n1 n2 

Where, RH is the Rydberg constant ( RH  1.09678  10 2 nm 1 ).

18. Bohr Sommerfeld Model of Atom

Sommerfeld modified the Bohr Theory by adding elliptical orbits in order to explain the fine
structure. The electron travelling in elliptical orbits will have both the angular momentum and
the radial momentum. These momenta are also quantized in the units of h/2π. According to this
modification the electrons in any particular energy levels could have either a circular orbit or a
number of elliptical orbits about the nucleus. The mathematical relationship of the momentum of
the electron with the quantum conditions of the ellipticity of the orbit is given by
h h
mvr  k  l  l  1 (20)
2 2
Where l is denoted as the subsidiary quantum number. Thus the main energy level of electrons
may be considered as made up of one or more sub-levels. The number of subshells is limited by
quantum condition so that if n is the principal quantum numbers, then the number of subshells
will be equal to n. For n = 3, the number of possible subshells is 3. The symbol l may have
values from 0 to (n-1).

Fig 3. Bohr- Sommerfeld model showing the subshell in 4th orbit.

 Solve the following questions

12. Derive the de Broglie’s equation for the wavelength associated with a moving particle of
mass m and velocity v?
13. Show that, the angular momentum, mvr, of an electron is an integral multiple of h/2π.
14. Deduce the following relation from Bohr’s theory-
2 2 Z 2 me 4
En  
n2h2
15. Derive an expression for the energy and radius of an electron in the n-th orbit of H-atom.
16. Write a short note on Bohr Sommerfeld model of atom.

Assignment work

A9. What is the frequency of violet light with a wavelength of 408 nm?
A10. The red spectral line of lithium occurs at 671 nm. Calculate the energy of one photon of this light.
A11. What is the wavelength of light emitted when the electron in a hydrogen atom undergoes a
transition from energy level n=4 to level n = 2?
A12. The first line of the Lyman series of the hydrogen atom emission results from a transition from the
n = 2 level to the n = 1 level. What is the wavelength of the emitted photon?
A13. Calculate the wavelength (in picometers) associated with an electron traveling at a speed of 2.19
106 m/s.
A14. The first line of the Lyman series of the hydrogen atom emission results from a transition from the
n = 2 level to the n = 1 level. What is the wavelength of the emitted photon?
 ► Lecture-05

19. Quantum numbers

Quantum Numbers: Numbers which are used to describe the position of electrons of an atom
are called quantum numbers. To describe the orbits, subshells, orbitals and spin of an electron
four quantum numbers are necessary, which are denoted by n, l, m and s.

n Orbit/ Shell

l Subshell

m Orbitals

s spin (+1/2 or -1/2)

(i) Principal quantum number (n): Quantum numbers used to describe the orbits are called
principal quantum numbers. It is represented by the ‘n’. The value of n can be 1, 2, 3, 4 etc.
For the first orbit n = 1 and it is known as K-shell. Second, as L-shell, third as M-shell, fourth
as N-shell and so on. The K-shell is the orbit nearest to the nucleus and next one is second or
L-shell and so on. The maximum number of electron in an orbit can be calculated from the
value of ‘n’ using 2n2 formula. From this formula it is seen that K, L, M and N shells can
accommodate 2, 8, 18, 32 number of electrons respectively.

(ii) Subsidiary quantum number (l): Each shell contains some subshell. Quantum numbers
used to describe the subshells are called subsidiary quantum numbers. It is represented by
the ‘l’. The values of ‘l’ depend on ‘n’. The values of ‘l’ are 0 to (n‒1).
Thus if-
n=l, l=0 (1 subshell: 1s)
n=2, l=0, 1 (2 subshells: 2s, 2p)
n=3, l=0, 1, 2 (3 sub-subshells: 3s, 3p, 3d)
n=4, l=0, 1, 2, 3 (4 sub-subshells: 4s, 4p, 4d, 4f)

When l=0, 1, 2, 3 then subshells are called s, p, d, f respectively. The maximum number of
electron in a subshell can be calculated from the value of l using 2(2l+1) formula. From this
formula it is seen that s, p, d and f type subshells can accommodate 2, 6, 10, 14 electrons
respectively.

 Orbits & orbitals

 Subshell Max
ℓ Shells containing it
label electrons
s 0 2 Every shell
p 1 6 2nd shell and higher

d 2 10 3rd shell and higher

f 3 14 4th shell and higher

(iii) Magnetic quantum number (m): Each subshell contains some orbitals. Quantum
numbers used to describe the orbitals are called magnetic quantum numbers. It is represented
by the ‘m’. The values of m are ‒l through zero to +l and thus there are (2l +1) values.

Thus when
l =0, m= 0 (only one orbital)
l =1, m= ‒1, 0, +1 (3 orbitals)
l =2, m= ‒2, ‒1, 0, +1, +2 (5 orbitals)
l =3, m= ‒3, ‒2, 1, 0, +1, +2, +3 (7 orbitals)

Table: Quantum numbers

Shell Subshell Orbitals
n =1,2,3,4…. l = 0 to (n − l) (m = −l to +l with 0)
1st orbit:
l=0 (1s) m=0 (1s)
n=1
l = 0 (2s)
m=0 (2s)
2nd orbit:

n=2 = 1 (2p)
m= −1,0,+1 (2px,2py,2pz)
l = 0 (3s)
m = 0 (3s)
3rd orbit:
m = −1,0,+1 (3px,3py,3pz)
= 1 (3p)
n=3
m = −2, −1,0,+1,+2
(3dxy, 3dyz, 3dzx, 3dx2-y2, 3dz2)
= 2 (3d)

(iv)Spin quantum number (s): The electron in the atom rotates not only around the nucleus but
also around its own axis and two opposite directions of rotation are possible (clockwise and
anti-clockwise). Therefore the spin quantum number can have only two values +1/2 or ‒1/2.
For each values of m including zero, there will be two values for s.
20. Importance of Four Quantum Numbers
To sum up, the four quantum numbers provide the following information:

1. ‘n’ identifies the shell, determines the size of the orbital and also to a large extent the energy
of the orbit.

2. There are n numbers of subshells in the n-th shell. ‘l’ defines the subshell and determines the
shape of the orbital. There are (2l+1) orbitals of each type in a subshell. To some extent l also
determines the energy of the orbital in a multi-electron atom.

3. ‘m’ designates the orientation of the orbital. For a given value of l, m has (2l +1) values, the
same as the number of orbitals per subshell. It means that the number of orbitals is equal to the
number of ways in which they are oriented.

4. ‘s’ refers to orientation of the spin of the electron.

21. Subshells & orbitals

‘s-type’ orbitals: For s‒subshell, l = 0 and m = 0 indicating that there is only one orbitals. s-
orbitals are spherical in shape. The electron cloud picture of 1s and 2s are shown below. All
orbits contain s-type subshell. Hence we found 1s, 2s, 3s…. for first, second, third…. shell
respectively.
2s
1s
+ nucleus

‘p-type’ orbitals: For p-subshell, l=1 and m = ‒1, 0, +1 indicating that there are three orbitals.
Except first orbit all orbital contain p-type subshell. Three p‒orbitals are named as px, py and pz.
Each p‒orbital has two lobes. Each p‒orbital is thus dumbbell shaped.

z z
y y

x= x

p = px + py + pz
‘d-type’ orbitals: For d-subshell, l = 2 , m = ‒2, ‒1, 0, +1, +2 indicating that there are five
possible orientations of electron cloud in a d‒subshell. Five d-orbitals are named as d xy, dyz, dzx,
dz2 and dx2−y2. First and second orbit do not contain d-subshell.
 y z z

x y x

dxy dyz dzx

y y

x x

dx2-y2 dz2

Solve the following questions

17. What are quantum numbers? Explain the importance of four quantum numbers to locate
the electrons in an atom.
18. Write short notes on (i) principal quantum number, and (ii) subsidiary quantum number.
19. How many electrons are possible in M-shell / N-shell / 3d subshell / 4f subshell?
20. Describe s, p, and d subshells with sketches of all orbitals showing the directional
characteristics.
21. What is the difference between an orbit and an orbital? Which of the orbitals namely 1p, 2s, 2p,
3f are not possible? Give reason for your answer.

Assignment work

A15. Give the values of the quantum numbers (n, l, and m) associated with the following
subshells: (i) 1s, (ii) 2p, (iii) 3d, and (iv) 4f subshells.
A16. What is the maximum number of electrons that can be present in the principal level for
which n =3?
A17. Determine the maximum number of electrons that can be found in each of the following
subshells: 3s, 3d, 4p, 4f, 5f.
A18. Draw diagrams of each of the following orbitals: 1s, 2px, 2pz, 3dxy, 3dx2-y2, 3dz2.
What is the maximum number of electrons in 5f and 3f energy levels?
 CHAPTER-3
ELECTRON CONFIGURATION & PERIODIC TABLE

► Lecture-06

14. Pauli's exclusion principle

Pauli's exclusion principle states that—no two electrons in an atom will have four quantum
numbers identical. In other word, in each of the orbital there will be only two electrons with
opposite spin. One of the important applications of Pauli’s principal is that it helps us to calculate
the maximum number of electron in an orbit or subshell.

number of maximum number of

subshell ℓ
orbital electron
s 0 1 2×1=2, s 2
P 1 3 2×3=6, p 6
d 2 5 2×5=10, d 10
f 3 7 2×6=14, f 14

15. Building up principle or (n+l) rule

This is also known as Aufbau principle. The principles states: electrons first occupy the lowest-
energy orbital available to them and enter into higher energy orbitals only after the lower energy
orbitals are filled. The relative energy of a subshell can be calculated from the (n+l) value where
‘n’ is principle quantum number and ‘l’ is the subsidiary quantum number. The lower the value
of (n+l) for an orbital, the lower is its energy. If two orbitals have the same (n+l) value, the
orbital with lower value of ‘n’ has the lower energy. Hence the order in which the orbitals are
filled is as follows:
1s→2s→2p→3s→3p→4s→3d→4p→5s→4d…….

1s n=1 (K - Shell)

2s 2p n=2 (L - Shell)

3s 3p 3d n=3 (M - Shell)

4s 4p 4d 4f n=4 (N - Shell)

5s 5p 5d n=5 (O- Shell)

6s 6p n=6 (P - Shell)

7s n=7 (Q - Shell)

16. Hund's Rule of Maximum Multiplicity

Hund's rule of maximum multiplicity states, that in filling p, d or f orbitals, as many unpaired
electrons as possible are placed before pairing of electrons with opposite spin is allowed. Pairing
of electrons requires energy. Therefore no pairing occurs until all orbitals of a given subshell are
half filled. This is known as Hund's rule of maximum multiplicity. It states that when electrons
enter subshell of fixed (n+l) values, available orbitals are singly occupied

17. Stability of Orbitals

According to Hund's rule atoms having half-filled or completely-filled orbitals are comparatively
more stable and hence more energy is needed to remove an electron from such atoms.

It may be noted that chromium and copper have five and ten electrons in 3d orbitals rather than
four and nine electrons respectively as expected. Therefore, to acquire more stability one of the
4s electron goes into 3d orbitals so that 3d orbitals get half-filled or completely filled in
chromium and copper respectively.

Chromium
Expected configuration: 1s2 2s2 2p6 3s2 3p6 3d4 4s2
Actual configuration: 1s2 2s2 2p6 3s2 3p6 3d5 4s1

Copper
Expected configuration: 1s2 2s2 2p6 3s2 3p6 3d9 4s2
Actual configuration: 1s2 2s2 2p6 3s2 3p6 3d10 4s1

18. Electron configuration

(Practice electron configurtaion for the elments having atomic number 1-40.)
 Solve the following questions

22. State the Pauli exclusion principle in the form relevant to atomic structure. Show how it leads to
the conclusion that in a given principal shell there can be only two s, six p, ten d, and fourteen f
electrons.
23 What is Pauli's exclusion principle? Explain the principle for He / Le / Be / B / C / N atom.
24. Describe (n + l) rule. Using a diagram show how electrons are distributed in different
subshells following this rule.
25. What is Hund’s rule? Show how it is used to specify in details electron configuration of the
elements from Li to Ne.
26. Write electron configurations for the elements of (i) second period, (ii) third period, (iii) 3d-
block, (iv) alkali metals, (v) alkaline earth metals, and (vi) halogens.

Assignment work

A19. Show the distribution of electrons in the atoms of X(12), Y(17), and Z(20). Identify the elements.
Predict their position in the periodic table and suggest some physical and chemical properties.
A20. Write the ground-state electron configuration for each atom (After each atom is its atomic
number in parentheses). Predict the position of these element in the periodic table and also
mention some properties: (i) Ca (20), (ii) S (16), (iii) Na (11), and (iv) Fe (26).
A21. Write an orbital diagram for the ground state of the iron atom.
General Chem note (final term) Page 30 of 48
 CHAPTER-6
Gaseous State

Q 1: Discuss the physical characteristics of gases. Starting with Boyle’s law, obtain an equation
(P1V1 = P2V2) for the final volume occupied by a gas from the initial volume when the pressure is
changed at constant temperature.

Answer-1

Physical Characteristics of Gases: Although gases are simple, both to describe and in terms of their internal
structure, they are of immense importance. All gases have the following physical characteristics:
 Gases assume the volume and shape of their containers.
 Gases are the most compressible of the states of matter.
 Gases will mix evenly and completely when confined to the same container.
 Gases have much lower densities than liquids and solids.
 The general form of an equation of state of gas is: V= f(P,T,n).

Boyle’s Law: Relating Volume and Pressure: According to Boyle’s law, the volume of a sample of gas at
a given temperature varies inversely with the applied pressure. That is-
1
V …………….(1)
P
where V is the volume, P is the pressure. Thus, if the pressure is doubled, the volume is halved. Let us
consider two different states of a gas at constant temperature as follows-

State-1 State-2
P1 , V1 P2 , V2

1
From Boyle’s law, we can write for state-1 V1  P
1

1
or, V1  K 
P1
…………….(2)
 P1V1  K
For state-2 we can write
1
V2 
P2
1
or, V2  K 
P2
 P2V2  K …………….(3)
From equation (2) and (3) we get
P1V1  P2V2 …………….(4)
Equation (4) is called Boyle’s relation.

General Chem note (final term) Page 31 of 48

 Q 2: Starting with Charles’s law show that (i) Vt = 0 (at – 273°C) and (ii) .

Answer-2

Charles found that for each degree rise in temperature, volume of a gas increases by 1/273 of the original
volume of the gas at 0°C. Thus if volumes of the gas at 0°C and at t°C are Vo and Vt respectively, then
t ………(1)
Vt  VO  VO
273
or, Vt  VO  273  t  ………(2)
 273 
From equation (2) we can see that the volume of the gas at – 273°C will be zero.
 273  273 
Vt  VO    VO  0  0
 273 
This means that gas will not exist. In fact all the gases get liquified before this temperature is reached. The
lowest hypothetical or imaginary temperature at which gases are supposed to occupy zero volume is called
absolute zero temperature. At this stage, we define a new scale of temperature such that t°C on new scale is
given by T = 273 + t. This new temperature scale is called the Kelvin scale or Absolute temperature scale.

State-1 State-2
t1 , V1 t2 , V2

From Charles’s law we can write for state-1

 273  t 1  ………………(3)
V1  VO  
 273 
For state-2 we can write:
 273  t 2  ……………(4)
V2  VO  
 273 
Dividing equation (3) by equation (4) we get
V1 273  t1 …………………(5)

V2 273  t 2
From Kelvin and Celcius scale relation we get
273+ t1=T1 and 273+ t2=T2
So we can write
V1 T1
 …………………(6)
V2 T2
From the above relation it is clear that
…………………(7)
V T
Equation (7) is the mathematical expression for Charles’ law, which states that pressure remaining constant,
the volume of a fixed mass of a gas is directly proportional to its absolute temperature.

General Chem note (final term) Page 32 of 48

 Q 3: What is molar gas volume. Derive the equation: P1V1/T1=P2V2/T2

Answer-3

One mole of any gas contains the same number of molecules and by Avogadro’s law must occupy the same
volume at a given temperature and pressure. This volume of one mole of gas is called the molar gas volume,
Vm. Volumes of gases are often compared at standard temperature and pressure (STP), the reference
conditions for gases chosen by convention to be 0°C and 1 atm pressure. At STP, the molar gas volume is
found to be 22.414 L/mol.
1
Boyle's Law : V  (at constant T and n)
P
Charles' s Law : V  T (at constant P and n)

Thus we can write-

1
V  T
P
KT
or, V  [Here, K is a proportional constant]
P
PV
or,  K …………….(1)
T
Let us consider two different states of a gas as follows-

State-1 State-2
P1 , T1 , V1 P2 , T2 , V2

Using equation (1) we can write for state-1

P1V1
 K …………….(2)
T1
And for state-2, we get
P2V2
 K …………….(3)
T2
Thus-
P1V1 PV
 2 2 …………….(4)
T1 T2
Equation (4) is a very useful equation and known as combined gas law.

General Chem note (final term) Page 33 of 48

 Q 4: Starting from Boyles’s, Charles’s, and Avogadro’s laws, obtain the ideal gas law, PV = nRT.
Calculate the value of R in L•atm•K-1•mol-1?

Answer-4

Let us summarize the gas laws we have discussed so far:

We can combine all three expressions to form a single equation for the behavior of gases:

or,
or, PV=nRT

where R, the proportionality constant, is called the universal gas constant. PV=nRT which is called the
ideal gas equation, describes the relationship among the four variables P, V, T, and n. An ideal gas is a
hypothetical gas whose pressure-volume-temperature behavior can be completely accounted for by the ideal
gas equation.

Before we can apply the ideal gas equation to a real system, we must evaluate the gas constant R. At 0°C
(273 K) and 1 atm pressure, many real gases behave like an ideal gas. Experiments show that under these
conditions, 1 mole of an ideal gas occupies 22.414 L. From Equation: PV=nRT, we can write

General Chem note (final term) Page 34 of 48

 Q 5: Give the postulates of kinetic theory. Show that the rms speed of molecules in a gas is
proportional to the square root of the temperature.

Answer-5

The kinetic theory of an ideal gas (a gas that follows the ideal gas law) is based on five postulates.

Postulate 1: Gases are composed of molecules whose size is negligible compared with the average distance
between them. Most of the volume occupied by a gas is empty space.

Postulate 2: Molecules move randomly in straight lines in all directions and at various speeds. This means
that properties of a gas that depend on the motion of molecules, such as pressure, will be the same in all
directions.

Postulate 3: The forces of attraction or repulsion between two molecules (intermolecular forces) in a gas are
very weak or negligible, except when they collide.

Postulate 4: When molecules collide with one another, the collisions are elastic. In an elastic collision, the
total kinetic energy remains constant; no kinetic energy is lost.

Postulate 5: The average kinetic energy of a molecule is proportional to the absolute temperature. From a
molecular point of view: the higher the temperature, the greater the molecular kinetic energy.

Kinetic equation for gas is given below-

1
PV  nmc 2 ……………….(1)
3

Here, P = Pressure of gas

V = Volume of gas

m = mass of gas molecule

n = Number of mole of gas

and compare equation (1) with PV=nRT. This conclusion is a major success of the kinetic model, for the

model implies an experimentally verified result. We now suppose that the expression for PV derived from

the kinetic model is indeed the equation of state of a perfect gas. That being so, we can equate the expression

on the right of equation (1) to nRT, which gives

1
nmc 2  nRT
3
3RT
c  ……………….(2)
Mr
The important conclusion to draw from equation (2) is that the rms speed of molecules in a gas is
proportional to the square root of the temperature.

General Chem note (final term) Page 35 of 48

 QUESTIONS

Part-A: Theoratical Problems

1. Discuss the physical characteristics of gases. Starting with Boyle’s law, obtain an equation (P1V1
= P2V2) for the final volume occupied by a gas from the initial volume when the pressure is
changed at constant temperature.
2. Starting with Charles’s law show that (i) Vt = 0 (at – 273°C) and (ii) V  T .
3. What is molar gas volume. Derive the equation:
P1V1 PV
 2 2
T1 T2
4. Starting from Boyles’s, Charles’s, and Avogadro’s laws, obtain the ideal gas law, PV=nRT.
Calculate the value of R in L.atm.K-1.mol-1 .
5. Give the postulates of kinetic theory. Show that the rms speed of molecules in a gas is
proportional to the square root of the temperature.

Part-B: Mathmatical Problems

6. A gas occupying a volume of 725 mL at a pressure of 0.970 atm is allowed to expand at constant
temperature until its pressure reaches 0.541 atm. What is its final volume?
7. You have a cylinder of argon gas at 19.8 atm pressure at 19°C. The volume of argon in the
cylinder is 50.0 L. What would be the volume of this gas if you allowed it to expand to the
pressure of the surrounding air (0.974 atm)? Assume the temperature remains constant.
8. A bacterial culture isolated from sewage produced 35.5mL of methane, CH 4, at 31°C and 753
mmHg. What is the volume of this methane at standard temperature and pressure (0°C,760
mmHg)?
9. An experiment calls for 3.50 mol of chlorine, Cl2. What volume will this be if the gas volume is
measured at 34°C and 4.00 atm?
10. The maximum safe pressure that a certain 4.00L vessel can hold is 3.50 atm. If the vessel contains
0.410 mol of gas, what is the maximum temperature (in degrees Celsius) to which this vessel can
be subjected?

Assignment work
A1. Explain why a helium weather balloon expands as it rises in the air. Assume that the temperature
remains constant.
A2. A gas in a closed-tube manometer has a measured pressure of 0.047 atm. Calculate the pressure in
mmHg.
A3. The volume of a gas is 5.80 L, measured at 1.00 atm. What is the pressure of the gas in mmHg if
the volume is changed to 9.65 L? (The temperature remains constant.)
A4. In an experiment, you fill a heavy-walled 5.00 L flask with methane gas, CH4. If the flask
contains 7.13 g of methane at 19°C, what is the gas pressure?
A5. A 2.50L flask was used to collect a 5.65g sample of propane gas, C 3H8. After the sample was
collected, the gas pressure was found to be 741 mmHg. What was the temperature of the propane
in the flask?
A6. Calculate the rms speeds of N2 molecules at 25°C and at 125°C.

General Chem note (final term) Page 36 of 48

 CHAPTER-7
Chemical Equilibrium

Q 11: Define chemical equilibrium. Write the mathematical expression of law of mass action.

Answer-11

Chemical equilibrium is the state of a reversible reaction when the rates of forward reaction become equal to
the rate of backward reaction. In another way we can define chemical equilibrium as the stage of a reaction at
which the concentration of reactants and products become fixed in reaction chamber is called chemical
equilibrium. Following two figures are used to illustrate chemical equilibrium.

Chemical Kinteics Chemical Equilibrium

Reactant
Concentration

rf

Rate of reaction
Equilibrium point
Equilibrium
stage

Product
rb
Time
Time

Figure 1: Change of concentration with time. Figure 2: Change of rate with time.

The law of mass action which stated as follows: The rate of a chemical reaction is proportional to the ‘active
mass’ of each of the reactants present in the system. active mass means the molar concentration or of any
term proportional to this such as partial pressure in case of gases.

Mathematical Expression of Law of Mass Action

Let us consider a simple reversible reaction of the type
A+B C+D
Let [A], [B], [C] and [D] represent the molar concentration of A, B, C and D respectively at any instant.
According to the law of mass action the rate of the forward reaction at any instant is proportional to the
concentrations of A and B. Then
rf   A   B 
or, rf  k1 A   B  . . . . . . . . . . . .(1)

where, k1 is a constant, called the velocity constant or specific rate constant. The speed of the reverse
reaction, i.e., the one in which A and B are formed from C and D at any instant is proportional to [C] and
[D]. Hence
rb   C    D 
or, rb  k 2  C    D  . . . . . . . . . . . .(2)
where, k2 is the rate constant of the backward reaction.

At equilibrium the rate of the forward reaction is equal to the rate of the backward reaction. That is,

General Chem note (final term) Page 37 of 48

rf  rb
 k  A   B  k  C    D
1 2

k1  C    D
or,   K . . . . . . . . . . . .(3)
k 2  A   B 
Equation (3) may be rearranged in the form
K
 C    D
 A   B 
where, K is called the equilibrium constant for the above reaction. K is equal to the ratio of the rate constants
for the forward and the backward reaction.

Q 12: Define Kc and KP. Derive the equation relating KC and KP.

Answer-12

There are two was to express equilibrium constant: (i) molar equilibrium constants (denoted by K C) (ii)
partial pressure (denoted by KP) used for gaseous phase reactions. The equilibrium-constant expression for a
reaction is an expression obtained by multiplying the concentrations or partial pressures of products, dividing
by the concentrations or partial pressures of reactants, and rising each concentration term to a power equal to
the coefficient in the chemical equation. For a general reversible reaction represented by
aA + bB cC + dD
where A, B, C, and D denote reactants and products, and a, b, c, and d are coefficients in the balanced
chemical equation. Mathematically we can define Kc and KP for the above general reversible reaction as
follows:
[C ]c  [ D]d CCc  C Dd
Kc  
[ A]a  [ B]b C Aa  C Bb
and
Pc  Pd
K P  Ca Db
PA  PB
Relation between Kc and KP :
Let us consider this equilibrium in the gas phase:
aA bB
in which a and b are stoichiometric coefficients. The equilibrium constant Kc is
[ B ]b C Bb
Kc  
[ A]a C Aa
and the expression for KP is
Pb
K P  Ba
PA
in which PA and PB are the partial pressures of A and B. From ideal gas equation:
PV  nRT
n
 P  RT  CRT
V
Here, C is the concentration of gas. Hence,

General Chem note (final term) Page 38 of 48

 p A  C A RT and p B  C B RT
Substituting these relations into the expression for KP, we obtain

Kp 
 C B RT  b
C Bb   RT 

b

C Bb
  RT 
b a

 C A RT  a
C A   RT 
a a
CA a

 K p  K c  RT  ............(1); in which Δn = b ‒ a
n

= moles of gaseous products -moles of

gaseous reactants

Q 13: Discuss the uses of equilibrium constant. Write three ways to alter the equilibrium composition
of a gaseous reaction to increase the yield of product.

Answer-13

Ways in which an equilibrium constant can be used are discussed below:

1. Qualitatively interpreting the equilibrium constant. By merely looking at the magnitude of K c, you can
tell whether a particular equilibrium favors products or reactants.

2. Predicting the direction of reaction. Consider a reaction mixture that is not at equilibrium. By
substituting the concentrations of substances that exist in a reaction mixture into an expression similar to the
equilibrium constant and comparing with Kc, you can predict whether the reaction will proceed toward
products or toward reactants (as defined by the way you write the chemical equation).

3. Calculating equilibrium concentrations. Once you know the value of Kc for a reaction, you can
determine the composition at equilibrium for any set of starting concentrations.

Changing the Reaction Conditions: Obtaining the maximum amount of product from a reaction depends
on the proper selection of reaction conditions. By changing these conditions, you can increase or decrease the
yield of product. There are three ways to alter the equilibrium composition of a gaseous reaction mixture and
possibly increase the yield of product:

1. Changing the concentrations by removing products or adding reactants to the reaction vessel.

2. Changing the partial pressure of gaseous reactants and products by changing the volume.

3. Changing the temperature.

Note that a catalyst cannot alter equilibrium composition, although it can change the rate at which a product
is formed and affect the result.

QUESTIONS

General Chem note (final term) Page 39 of 48

 Part-A: Theoratical Problems
13. Define chemical equilibrium. Write the mathematical expression of law of mass action.
14. Define Kc and KP. Derive the equation relating Kc and KP.
15. Discuss the uses of equilibrium constant. Write three ways to alter the equilibrium composition of
a gaseous reaction to increase the yield of product.

Part-B: Mathmatical Problems

16. Consider the following equilibrium process at 700°C:

Analysis shows that there are 2.50 moles of H2, 1.35×10‒5 mole of S2, and 8.70 moles of H2S
present in a 12.0L flask at equilibrium. Calculate the equilibrium constant Kc for the reaction.
17. What is the KP at 1273°C for the reaction

if Kc is 2.24×1022 at the same temperature?

18. The equilibrium constant KP for the reaction
2SO3(g) 2SO2(g) + O2 (g)
is 5.0×10‒4 at 302°C. What is Kc for this reaction?
19. Consider this reaction:
N2 (g) + O2 (g) 2NO (g)
If the equilibrium partial pressures of N2, O2, and NO are 0.15 atm, 0.33 atm, and 0.050 atm,
respectively, at 2200°C, what is KP?

Assignment work
A7. Write equilibrium constant expressions for Kc and for KP, if applicable, for these processes:

A8. The equilibrium constant ( Kc) for the reaction

is 4.17×10‒34

at 25°C. What is the equilibrium constant for the reaction

at the same temperature?

General Chem note (final term) Page 40 of 48

 CHAPTER-8
Acid–Base Equilibria

Q 20: Discuss the modern concepts of acids and bases using various concepts.

Answer-13
Arrhenius Concept Brønsted–Lowry Concept Lewis Concept
Substances/chemical
Substances/chemical Substances/chemical species that
species that produce H+
species that can donate a can accept an electron pair is called
Acid when dissolved in water is
proton is called acid. acid.
called acid.
Example: HCl, NH4+ Example: AlCl3, BF3
Example: HCl, H2SO4
Substances/chemical
Substances/chemical Substances/chemical species that
species that produce OH-
species that can accept the can donate an electron pair is called
Base when dissolved in water is
proton is called base. base.
called base. ‒
Example: NH3, Cl Example: NH3, OH‒
Example: NaOH, Ca(OH)2

In 1923 G. N. Lewis proposed a definition of acid-base behavior in terms of electron-pair donation and
acceptance. The Lewis definition is perhaps the most widely used of all because of its simplicity and wide
applicability, especially in the field of organic reactions. Lewis defined a base as an electron-pair donor and
an acid as an electron-pair acceptor.

The Usanovich definition includes all reactions of Lewis acids and bases and extends the latter concept by
removing the restriction that the donation or acceptance of electrons be as shared pairs. The complete
definition is as follows: An acid is any chemical species which reacts with bases, gives up cations, or accepts
unions or electrons, and, conversely, a base is any chemical species which reacts with acids, gives up unions
or electrons, or combines with cations.

General Chem note (final term) Page 41 of 48

 Q 21: What are Ka and Kb? Explain mathematically, how Ka and Kb are related?

Answer-13
Acid ionization constant (Ka):The acid ionization constant, is the equilibrium constant for the ionization of
an acid.
HB + H2O H3O+ + B

[H 3O  ]  [ B  ]
Ka  ………….(1)
[ HB]  [ H 2 O]

Base ionization constant (Kb): The base ionization constant, is the equilibrium constant for the ionization
of a base.
B + H2 O HB + OH
[ HB]  [OH  ]
Kb  ………….(2)
[ B  ]  [ H 2 O]
If we multiply Ka with Kb we get-

[H 3O  ]  [OH  ]
K a  Kb  ……….(3)
[H 2O]2
K a  Kb  K w
Kohlrausch and Heydweiller (1894) found that the most highly purified water that can be obtained possesses
a small but definite conductivity. Water must therefore be slightly ionised in accordance with the equation:
H2O H+ + OH (old concept)
H+ + H2O H3O+
2 H2O H3O+ + OH (modern concept)

Applying the ‘Law of mass action’ to this equation, we obtain, for any given temperature:
[H 3O  ]  [OH  ]
 K w ……….(4)
[ H 2 O ]2

Comparing equationn (3) with (4) we get-

K a  Kb  K w

Taking logaritham on both side we get

log K a  log K b  log K w
or,  log K a  log K b   log K w
We define pH and pOH as
pK a   log K a , pKb   log K b , and pK w   log K w
Hence,
pK a  pKb  pK w

General Chem note (final term) Page 42 of 48

 Q 22: What is meant by the pH of a solution? Derive a relation between pH and pOH.

Answer-13

The Hydrogen Ion Exponent: pH

A very convenient method was proposed by S. P. L. Sorensen (1909). He introduced the hydrogen ion
exponent pH defined by the relationships:
pH   log[H 3O  ]   log[H  ]

or, [ H  ]  10  pH
The quantity pH is thus the logarithm (to the base 10) of the reciprocal of the hydrogen ion concentration, or
is equal to the logarithm of the hydrogen ion concentration with negative sign. This method has the
advantage that all states of acidity and alkalinity of dilute solutions can be expressed by a series of positive
numbers between 0 and 14.

Relation between pH and pOH:

In pure water or in dilute aqueous solutions, the concentration of the undissociated water may be considered
constant. Hence:
K w  [ H 3O  ]  [OH  ]
 [ H  ]  [OH  ] ( [ H 3O  ]  [ H  ] )
 1  10 14
where Kw is the ionic product of water.
K w  [ H 3O  ]  [OH  ]  1  10 14

Taking logaritham on both side we get

log[H 3O  ]  log[OH  ]  log(1014 )  14
or ,  log[H 3O  ]  log[OH  ]  14

We define pH and pOH as

pH   log[H 3O  ]   log[H  ]
and, pOH   log[OH  ]
Hence,
pH  pOH  14

General Chem note (final term) Page 43 of 48

 Q 23: What is buffer solution? Write some importance of buffer system in our life. Derive Henderon-
Hasselbach equation for buffer system.

Answer-13

78. Importance of Buffer Solutions:

The resistance of a solution to changes in hydrogen ion concentration upon the addition of small amounts of
acid or alkali is termed buffer action; a solution which possesses such properties is known as a buffer
solution. It is said to possess 'reserve acidity' and 'reserve alkalinity'. A buffer solution is a solution of (1) a
weak acid or a weak base and (2) its salt; both components must be present. The solution has the ability to
resist changes in pH upon the addition of small amounts of either acid or base. Buffers are very important to
chemical and biological systems. The pH in the human body varies greatly from one liquid to another; for
example, the pH of blood is about 7.4, whereas the gastric juice in our stomachs has a pH of about 1.5. These
pH values, which are crucial for the proper functioning of enzymes and the balance of osmotic pressure, are
maintained by buffers in most cases.

Henderon-Hasselbach Equation: Consider a buffer made up of a weak acid HA and its conjugate base A.
The acid-ionization equilibrium is
HA H+ + A
and the acid-ionization constant is
[ A ] [H  ]
Ka 
[ HA]
[ HA]
or, [H  ]  K a  
[A ]
[ HA]
or, log[ H  ]  log K a  log
[ A ]
[ HA]
or,  log[ H  ]   log K a  log 
[A ]
The left side equals the pH. You can also simplify the right side. The pK a of a weak acid is defined in a
manner similar to pH and pOH.

pKa= ‒ logKa
The previous equation can be written
[ HA]
pH  pK a  log
[ A ]
[HA] = [acid ] and [ A ] = [salt ]
[ acid ]
or, pH  pK a  log
[ salt ]
[ salt ]
 pH  pK a  log ---------------(3)
[acid ]
This is the equation used to calculate the pH of a buffer solution; it is known as the Henderson–Hasselbalch
equation. By putting all the value on right hand side,we can obtain the pH of buffer solutions.

General Chem note (final term) Page 44 of 48

 QUESTIONS

Part-A: Theoratical Problems

20. Difine acid and base using various concepts.
21. What are Ka and Kb? Explain mathematically, how Ka and Kb are related?
22. What is meant by the pH of a solution? Derive a relation between pH and pOH.
23. What is buffer solution? Write some importance of buffer system in our life. Derive
Henderon-Hasselbach equation for buffer system.

Part-B: Mathmatical Problems

24. A solution is 0.020 M HNO3 (nitric acid). What is the hydronium ion concentration at
25°C? What is the hydroxide ion concentration at 25°C?
25. An antiseptic solution at 25°C has a hydroxide-ion concentration of 8.4×10‒5M. Is
the solution acidic, neutral, or basic?
26. A solution of washing soda (sodium carbonate, Na2CO3) has a hydroxide ion
concentration of 0.0040 M. What is the pH at 25°C?
27. A sample of vinegar has a hydronium ion concentration of 7.5×10 ‒3M. What is the
pH of the vinegar?
28. The pH of a cup of coffee (at 25°C) was found to be 5.12. What is the hydronium ion
concentration?
29 A detergent solution has a pH of 11.63 at 25°C. What is the hydroxide ion
concentration?

Assignment work
A9. A solution of lye (sodium hydroxide, NaOH) has a hydroxide ion concentration of
0.050 M. What is the pH at 25°C?
A10. Some lemon juice has a hydronium ion concentration of 5.0×10‒3M. What is the pH
of the lemon juice?
A11. A 1.00L aqueous solution contained 5.80 g of NaOH. What was the pH of the
solution at 25°C?

General Chem note (final term) Page 45 of 48

 Chemical Bonding (Part-2)

Modern Theories of Chemical Bonding

30. Define lattice energy. Draw a Born Haber cycle for NaCl / MgO / CaCl2.

31. Write short note on VBT and MOT. Apply VBT for the following inorganic compounds: PCl 5, SF6, IF7,
XeF4, and XeF6.

32. Compare VBT and MOT. Draw a MO diagram for the following compounds: H2, He2, B2, N2, O2 and F2

General Chem note (final term) Page 46 of 48