CHM 101:BASIC CHEMISTRY

LECTURE NOTES

ABDUL-MUMEEN IDDRISU
BASIC CHEMISTRY I (CHM 101) – 2 CREDITS
INTRODUCTION: This course is a basic chemistry which will give an
understanding of basic principles, laws and theories of chemistry for first
year science students.
OBJECTIVES
Students will understand and apply concepts to solve problems using:
• Matter and Measurement
• Atoms, Molecules and Ions
• Students will predict, depict and describe:
• Electronic structure of atoms
• Elemental periodic properties
• Basic properties of chemical bonding
• Molecular geometry and theory of bonding
Students will understand and describe:
• Chemical bonding
• Chemistry of Selected groups of Elements
• Students will describe and calculate quantities for:
• Gas behaviour
• Stoichiometry and calculations with chemical formulas and
equations
• Reactions in aqueous solution
Students will understand and apply concepts to
solve problems using:
• Properties of Solutions
• Chemical Kinetics
• Students will describe and calculate quantities for:
• General Chemical Equilibria
• Acid-Base Equilibria
• Precipitation Equilibria
Students will predict, depict and describe:
• Thermodynamic Quantities and Relationships
• Oxidation and reduction reactions
• Students will understand and explain
• Chemical analysis
• Instrumental methods
• Chromatography
 COURSE CONTENT
Basic Chemistry
• Definition
• Sub-categories
• The Properties of substances
• Physical and chemical properties, pure substances
and mixtures
• Measurements and units
• The International System of Units, Extensive and
intensive properties
• Atomic structure and the periodic table
• Theories of the atomic structure (Dalton’s,
Thomson’s, Rutherford & Bohr’s)
• The structure of the hydrogen atom
• The structure of many electron atoms
• A survey of periodic properties
The chemical bond
– The ionic bond
– The covalent bond
– Coordinate or dative bond
– Deviation from the octet rule
– Hydrogen bond
– Metallic bond
– Chemistry of selected group of elements
States of matter
– Gaseous state
– The gas laws
– The kinetic molecular theory
– The liquid state
– The solid state
Solutions
– Types of solutions
– Modes of expressing composition (concentration) of solutions
– Solubility
– Colligative properties
Acids, bases and salts
• Definition of acids and bases
• Equlibria in solutions of acids and bases
• Hydrogen ion concentration and pH
• Salts as acids and bases
• Titration and pH curves
Chemical equilibria
• Description of Chemical equilibria
• Equilibrium Constant calculations
• Predicting direction of equilibria
• Heterogeneous equilibria
• Ionic equilibria
• Altering the position of equilibrium-Le Chatelier’s
principle
Acids, bases and salts
• Definition of acids and bases
• Equlibria in solutions of acids and bases
• Hydrogen ion concentration and pH
• Salts as acids and bases
• Titration and pH curves
Chemical equilibria
• Description of Chemical equilibria
• Equilibrium Constant calculations
• Predicting direction of equilibria
• Heterogeneous equilibria
• Ionic equilibria
• Altering the position of equilibrium-Le
Chatelier’s principle
Oxidation-reduction reactions
• Oxidation-reduction reaction
• Oxidation number
• Balancing oxidation-reduction reactions
Chemical Analysis
• Types of analysis
• Atomic Absorption Spectroscopy
• Chromatography
Recommended Books:
1. Silberberg, M. S. (2010). Principles of
General Chemistry, 2nd Edition. McGram Hill
Publications.
2. Sharma, K. K., & Sharma, L.L. (2012). A
Textbook of Physical Chemistry, Fifth Edition.,
Vikas Publishing House PVT Ltd.
3. Atkins, P.W. (1989). General Chemistry
(International Student Edition). Scientific
American Books.
4. Addae-Mensah, I., Asamaming, W. A.,
Bempah, O. A., & Yeboah, S. K. (1980).
‘A’Level Chemistry Volumes I & II. Afram
Publications (Ghana) Ltd.
METHODS OF INSTRUCTION AND ASSESSMENT

• Instruction: The main method of instruction will be lectures.

Students will be provided with lecture notes covering the
course content and also given references to read on their
own. Students must attend lectures regularly. Students will
be encouraged to ask questions and take an active part
during lectures. They will be encouraged to read the text and
lecture notes before the corresponding class meeting.

Assessment:
• Two quizzes 10 marks
• One mid-trim exams 15 marks
• One Final exams 75 marks
Grand total 100 mark
INTRODUCTION
Chemistry is the science that describes matter—its properties,
the changes it undergoes, and the energy changes that
accompany those processes.
• Organic chemistry: The chemistry of compounds of carbon
and hydrogen.
• Inorganic chemistry: The study of substances that do not
contain carbon combined with hydrogen.
• Analytical chemistry: The branch of chemistry that is
concerned with the detection or identification of substances
present in a sample (qualitative analysis) or with the amount
of each that is present (quantitative analysis).
• Biochemistry: is the study of the chemistry of processes in
living organisms.
• Physical chemistry: is the application of mathematical
theories and methods of physics to the properties of matter
and to the study of chemical processes and the
accompanying energy changes
MATTER AND ENERGY
• Matter is anything that has mass and occupies
space. Mass is a measure of the quantity of matter
in a sample of any material. The more massive an
object is, the more force is required to put it in
motion. All bodies consist of matter.
• Energy is defined as the capacity to do work or to
transfer heat. Some forms of energy include;
mechanical energy, light energy, electrical energy
and heat energy.
• Kinetic energy is the energy possessed by an object
by virtue of its motion.
• Potential energy is the energy an object possesses
because of its position, condition, or composition.
• The Law of Conservation of Matter: There is no
observable change in the quantity of matter during
a chemical reaction or during a physical change.
• The Law of Conservation of Energy: Energy cannot
be created or destroyed in a chemical reaction or in
a physical change. It can only be converted from
one form to another.
• The Law of Conservation of Matter and Energy:
The combined amount of matter and energy in the
universe is fixed.
• The Law of Definite Proportions (also known as
the Law of Constant Composition): Different
samples of any pure compound contain the
same elements in the same proportions by mass.
STATES OF MATTER
Matter can be classified into three states:
❑ The solid state: In this state substances
are rigid and have definite shapes.
❑ The liquid state: In this state the
individual particles are confined to a
given volume.
❑ The Gaseous state: In this state the
particles occupy all parts of any vessel
in which they are confined.
CHEMICAL AND PHYSICAL PROPERTIES
• The different of matter can be distinguished by their chemical and
physical properties.
• Chemical properties are exhibited by matter as it undergoes
changes in composition. These properties of substances are
related to the kinds of chemical changes that the substances
undergo.
• Physical properties are exhibited by all substances and can be
observed in the absence of any change in composition. Examples
of physical properties include; color, density, hardness, melting
point, boiling point, electrical and thermal conductivities. Some
physical properties of a substance depend on the conditions, such
as temperature and pressure, under which they are measured.
• Properties of matter can be further classified according to whether
or not they depend on the amount of substance present.
• Extensive properties depend on the amount of material present, e.
g volume and mass of a substance.
• Intensive properties are independent of the amount of material
examined e.g colour & melting point of a substance. All chemical
properties are intensive properties.
CHEMICAL AND PHYSICAL CHANGES
In any chemical change:
• one or more substances are used up (at least partially),
• one or more new substances are formed, and
• energy is absorbed or released.
• As substances undergo chemical changes, they
demonstrate their chemical properties.
A physical change:
• occurs with no change in chemical composition.
• physical properties are usually altered significantly
as matter undergoes physical changes
• may suggest that a chemical change has also taken
place.
• energy is released or absorbed
MIXTURES, SUBSTANCES, COMPOUNDS, AND ELEMENTS
• Mixtures are combinations of two or more pure
substances in which each substance retains its own
composition and properties. Almost every sample of
matter that we ordinarily encounter is a mixture.
• A heterogeneous mixture: is a mixture which is not
uniform throughout (one in which different portions of
the sample has recognizably different properties).
• A homogeneous mixture: is a mixture which has
uniform properties throughout (a solution).
• An important characteristic of all mixtures is that they
can have variable composition.
• In any mixture, (1) the composition can be varied and
(2) each component of the mixture retains its own
properties.
• A substance cannot be further broken down or
purified by physical means. A sub-
stance is matter of a particular kind. Each
substance has its own characteristic properties that
are different from the set of properties of any other
substance.
• A compound is a substance that can be
decomposed by chemical means into simpler
substances, always in the same ratio by mass.
• An element is a substance that cannot be
decomposed into simpler substances by chemical
changes.
UNITS OF MEASUREMENT
Mass and Weight
• Mass is the measure of the quantity of matter a
body contains. The mass of a body does not vary as
its position changes. The weight of a body is a
measure of the gravitational attraction of the earth
for the body, and this varies with distance from the
centre of the earth. The mass of a body is a more
fundamental property than its weight.
ATOMIC STRUCTURE
• Matter is made of particles whose properties determine the observable
characteristics of matter and its reactivity.
Dalton’s Atomic Theory:
• The first statement of an atomic theory based on experimental evidence
was that of John Dalton, published in 1807.
• It was based on the laws of chemical combination
Postulates of Dalton’s Atomic theory
• All matter is composed of atoms
• Atoms cannot be made or destroyed
• All atoms of the same element are identical
• Different elements have different types of atoms
• Chemical reactions occur when atoms are rearranged
• Compounds are formed from atoms of the constituent elements.
• However, modern atomic theory is more involved than Dalton’s theory but
the essence of Dalton’s theory remains valid.
• It has been shown that atoms can be destroyed via nuclear reactions but
not chemical reactions and also the existence of isotopes.
Thomson’s Atomic Theory
The theory proposed that:
• An atom consists of a sphere of positive charge
with negatively charged electron embedded in it.
• The positive and the negative charges in an atom
are equal in magnitude, due to which an atom is
electrically neutral. It has no overall negative or
positive charge.
• He proved his theory using the cathode ray tube.
• His work put forward a new theory that an atom
was made up of small particles-divisible. Thus he
discovered the electron.
Rutherford atomic model
Conclusions
• Only a positively charged and relatively heavy target
particle, such as the proposed nucleus could account
for such strong repulsion.
• The negative electrons that balanced electrically the
positive nuclear charge were regarded as travelling in
circular orbits about the nucleus.
• The electrostatic force of attraction between electrons
and nucleus was likened to the gravitational force of
attraction between the revolving planets and the Sun
• The Rutherford model was based wholly on classical
physics. This theory was superseded in a few years by
the Bohr atomic model, which incorporated some early
quantum theory.
Bohr's Model of the Atom
• Rutherford model of the atom could not explain why
electrons do not fall into the nucleus by taking a spiral path.
• Niels Bohr proposed the quantum theory of an atom. The
theory was based on the quantum theory of radiation.
• He retained the main postulates of Rutherford planetary
model & did some modification based on quantum physics.
• Bohr atomic model is also known as Rutherford-Bohr atomic
model.
• This model depicts the atom as a tiny, spherical body which
consists of a central nucleus and negatively charged particles
(electrons) revolving around the nucleus in a certain path
known as an orbit.
• He proposed some new postulate with same basis concepts
of Rutherford theory.
• He gave a new arrangement of electrons in the atom. The
electrons could revolve around the nucleus in only 'certain
orbits' (energy levels), each orbit having a different radius.
Major features of the model:
• Electrons orbit the nucleus in orbits that have a set size and energy.
• The energy of the orbit is related to its size. The lowest energy is found in
the smallest orbit.
• Radiation is absorbed or emitted when an electron moves from one orbit
to another.
• This model of the atom was able to explain the stability of the atom. It
also explained the phenomenon of atomic spectra and ionization of gases.
Limitations of the model:
• It could not explain those atoms which have more than one electron like
lithium, helium, etc. It was only applicable to the hydrogen atom.
• Bohr theory explained only spherical orbits. There was no explanation for
elliptical orbits.
• This model failed to explain Zeeman Effect (effect of magnetic field) and
stark effect (effect of electric field) on the spectra of atoms.
• Bohr model could not explain the uncertainty principle of Heisenberg.
• Bohr model was not related with classification and periodicity of
elements.
• The model can’t explain the intensity of spectrum line.
Definition of Terms:
Atomic Number (Z):
• The number of protons in an element is equal to its atomic
number.
Mass number (A):
• The mass number is the sum of the protons and neutrons in the
nucleus of an atom.
• Number of neutrons = A-Z
Isotopes:
• Atoms of the same element which have the same number protons
and electrons but different number of neutrons.
Isobars:
• Atoms which have the same mass number but different atomic
numbers.
Isotones:
• Atoms which have different atomic number and different atomic
masses but the same number of neutrons are called Isotones.
Quantum Numbers:
• The Bohr model was a one-dimensional model that
used one quantum number to describe the distribution
of electrons in the atom.
• The only information that was important was the size of
the orbit, which was described by the n quantum
number.
• Schrödinger's model allowed the electron to occupy
three-dimensional space.
• It therefore required three coordinates, or three
quantum numbers, to describe the orbitals in which
electrons can be found.
• The three coordinates that come from Schrödinger's
wave equations are the principal (n), angular (l), and
magnetic (m) quantum numbers. These quantum
numbers describe the size, shape, and orientation in
space of the orbitals on an atom.
An atomic orbital: describes a region of space in which there is a
high probability of finding the electron.
• Energy changes within an atom are the result of an electron
changing from a wave pattern with one energy to a wave pattern
with a different energy (usually accompanied by the absorption or
emission of a photon of light).
• Each electron in an atom is described by four different quantum
numbers. The first three (n, l, ml) specify the particular orbital of
interest, and the fourth (ms) specifies how many electrons can
occupy that orbital.
Principal Quantum Number ‘n’: This quantum number denotes the
principal shell to which the electron belongs. This is also referred
to as major energy level. The principal quantum number ‘n’ can
have non-zero, positive, integral values n = 1, 2, 3... increasing by
integral numbers to infinity. The letters K, L, M, N, O, P and Q are
also used to designate the energy levels or shells of electrons with
a n value of 1, 2, 3, 4, 5, 6, 7 respectively. There is a limited
number of electrons in an atom which can have the same principal
quantum number and is given by 2n2, where n is the principal
quantum number concerned.
Azimuthal Quantum number ‘l ’: may have all integral values
from 0 to n – 1, each of which refers to an Energy sublevel
or Sub-shell. The total number of such possible sublevels in
each principal level is numerically equal to the principal
quantum number of the level under consideration. These
sub-shells are also symbolised by letters s, p, d, f etc.
Example, for n = 1, l = 0, n = 2 , l = 0, l = 2-1 = 1. For a given
value of principal quantum number the order of increasing
energy for different subshells is s <p < d <f (except for H
atom)
Magnetic Quantum Number ‘m’: For each value of the
azimuthal quantum number ‘l’, the magnetic quantum
number m, may assume all the integral values between + l to
– l through zero i.e., + l, (+ l – l),... 0..., (– l + 1), – l. Therefore
for each value of l there will be (2l + 1) values of m.
Spin Quantum Number‘s’: There are two possible values of s
that are equal and opposite + ½ or – ½.
Worked example: List all possible values of l and m for n = 2.
Soln. n = 2. l = 0 and 1
When l=0 m=0
and l=1 m = + 1, 0, – 1

Worked example: Which of the following sets of quantum

numbers are not allowable and why?
(a) n=2 l=2 m=0 s = +1/2
(b) n=3 l=1 m=0 s = −1/2
(c) n=1 l=1 m=+1 s = +1/2
(d) n=2 l=0 m=–1 s=0
(e) n=3 l=2 m+2 s =−1/2
Soln
(a) Not allowable as l cannot have value equal to 2 when n = 2.
(b) Allowable
(c) Not allowable as l cannot have value equal to 1 when n = 1
(d) Not allowable as s cannot have value equal to 0.
(e) Allowable
Worked example: What designation are given to the orbitals having
(a) n=2 l=1
(b) n=1 l=0
(c) n=3 l=2
(d) n=4 l=3
Soln
(a) when n = 2 and l = 1 the orbital is 2p
(b) when n = 1 and l = 0 the orbital is 1s
(c) when n = 3 and l = 2 the orbital is 3d
(d) when n = 4 and l = 3 the orbital is 4f
ELECTRONIC CONFIGURATIONS & PERIODIC TRENDS
An electron configuration: This is a description of electron
arrangement within an atom. It indicates both population
and location of electrons among the various atomic orbitals.
Rules for Electron Configurations:
• Electrons occupy orbitals of the lowest energy available.
Pauli Exclusion Principle: states that no two electrons in the
same atom can have identical values for all four of their
quantum numbers.
Building-Up Principle (Aufbau Principle): Electrons are added
by successively filling subshells with electrons in a specific
order based on increasing energies of the subshells.
• The maximum number of electrons in any s subshell is two.
• The maximum number of electrons in any p subshell is six.
• The maximum number of electrons in any d subshell is ten.
• The maximum number of electrons in any f subshell is
fourteen.
Hund’s Rule: states that the electrons will occupy equivalent
orbitals singly, as far as possible with parallel spins.
Screening Rule: Electrons filling the inner shells have the
screening effect on the outer electrons against attraction by
the nucleus. This rule is responsible for the reason that every
ns orbital is filled earlier than the corresponding (n-1) d
orbital. Also 5s 5p an 6s orbital are filled before 4f orbital.
Ground State: This is the electron configuration associated
with the lowest energy level of the atom.
• Each electron in the atom or ion will be in the lowest energy
level possible.
Excited states: Configurations associated with electrons in
energy levels other than the lowest.
Core Electrons (Noble Gas Core): refer to the electrons within
the atom which have the same electron configuration as the
nearest noble gas of lower atomic number.
Valence Electrons: are those electrons in an atom outside the
noble-gas core.
Ground-state Electron Configuration of Elements
• For complicated atoms which may contain many
electrons and have many energy levels or orbitals, the
‘building up’ process for the electrons is governed by
the following rules:
Rule 1. Each electron shell can hold a maximum of 2n2
electrons where n is the shell number.
Rule 2. These electrons are accommodated in s,p , d andf
orbitals, the maximum number of electrons in each
type of orbitals being determined by its electron-
holding capacity (for s = 2,p = 6, d = 10 andf = 14).
Rule 3. In the ground state of an atom, the electrons tend
to occupy the available orbitals in the increasing order
of energies, the orbitals of lower energy being filled
first (Aufbau Principle).
• The increasing order of energy of various orbitals is as follows: 1s < 2s <
2p < 3s < 3p < 4s < 3d < 4p < 5s ...... The energy of an orbital is determined
by the sum of principal quantum number (n) and the azimuthal quantum
number (l). This rule is called (n + l) rule. There are two parts of this rule :
• The orbital with the lower value of (n + l) has lower energy than the
orbitals of higher (n + l) value.
(b) When two orbitals have same (n + l) value, the orbital with lower
value of n has lower energy. For example, let us compare the (n + l)
value for 3d and 4s orbitals. For 3d orbital n = 3, l = 2 and n + l = 5 and for
4s orbital n = 4, l = 0 and n + l = 4. Therefore, 4s orbital is filled before 3d
orbital. Similarly, for 4p and 5s orbitals, the (n + l) values are (4 + 1) and (5
+ 0) respectively. In this case 4p orbital has lesser value of n and hence it
has lower energy than 5d orbital and is filled first.
• Rule 4. Any orbital may have one or two electrons at the most. Two
electrons can occupy the same orbital only if they have opposite spins
(Pauli’s exclusion principle).
• Rule 5. When several orbitals of equal energy (degenerate orbitals) are
available, electrons prefer to occupy separate orbitals rather than getting
paired in the same orbital. Such electrons tend to have same spins
(Hund’s rule).
 Electronic Configurations
Electron Configurations of Anions- electrons are added
to the ground state electron configuration of the atom
by adding the extra electrons to the next highest
partially filled shell by following the Aufbau principle.
E.g N: 1s2 2s2 2p 3 N3-: 1s 2 2s2 2p 6 O: 1s 2 2s2 2p 4 O2-: 1s 2
2s2 2p 6
Electron Configurations of Cations –to obtain the
ground state electron configuration of a cation,
remove electrons from the orbital with the highest
principal quantum number. E.g Na: 1s2 2s2 2p 6 3s1 Na +:
1s2 2s2 2p 6 Mg: 1s2 2s2 2p 6 3s2 Mg2+: 1s 2 2s2 2p 6 , Fe:
1s2 2s2 2p 6 3s2 3p 6 4s2 3d 6 Fe 2+: 1s 2 2s2 2p 6 3s2 3p 6 3d 6 ,
Fe3+: 1s 2 2s2 2p 6 3s2 3p 6 3d 5
Electronic Configurations
Isoelectronic : These are atoms & ions that
possess the same number of electrons and
hence the same ground state electron
configuration . Ne, O2-, Na+ are isoelectronic,
they have identical electron configurations.

Paramagnetic : Atoms with unpaired electrons.

These are weakly attracted to a magnetic field.
Diamagnetic: Atoms with all paired electrons.
These are weakly repelled from a magnetic field.
The Periodic Table
• The representative elements (main group elements)
are the elements in Groups 1 (1A) through 17 (7A),
all of which have incompletely filled s or p subshells
of the highest principal quantum number.
• s-block elements
Group 1 (1A; the alkali metals) and Group 2 (2A; the
alkaline earth metals) are referred to as s-block
elements
• Group 1 - noble gas core + ns1 configuration e.g Li
[He] 2s 1, K [Ar] 4s 1
• Group 2 - noble gas core + ns2 configuration
• Be [He] 2s 2 , Ca [Ar] 4s2
The Periodic Table
• p-block elements
Group 13 (3A) elements through Group 18 (8A) are
referred to as p-block elements.
• Group 13 - ns2 np 1 configuration e.g B [He] 2s 2 2p1
• Group 14- ns 2 np 2 configuration e.g C [He] 2s2 2p2
• Group 15- ns 2 np 3 configuration e.g N [He] 2s2 2p3
• Group 16 - ns2 np 4 configuration e.g O [He] 2s 2 2p4
• Group 17 - ns2 np 5 e.g F [He] 2s2 2p5
• The p-block elements in the fourth period and beyond
will have the noble gas core together with (n-1)d10.
Br [Ar] 4s2 3d10 4p5
• In Group 18 (8A; the noble gases) the p subshell has just
been filled.
• Ar 1s2 2s2 2p6 3s2 3p6
 The Periodic Table
• Transition Elements, the d-block elements -a d
subshell is being filled & the principal quantum
number of the d subshell is always 1 less than the
period in which the element is located. E.g
Technetium
(Tc, atomic number = 43) is in the fifth period. Tc [Kr]
5s2 4d 5
• Inner Transition Elements, the f-block elements -an f
subshell is being filled & the principal quantum
number of the f subshell is always 2 less than the
period in which the element is located e.g Plutonium
(Pu, atomic number = 94) is in the seventh period. The
last electrons placed in the electron configuration
go into the 5f subshell.
The Periodic Table
The Periodic Table
Periodic Trends
Periodic Law: states that when the elements are arranged
by atomic number, their physical and chemical
properties vary periodically. i.e elements in the same
group (e.g., alkali metals: Li, Na, K, Rb, Cs) will have
similar chemical and physical properties.
Atomic Radius
• The atomic radius of an element can be defined as half
of the distance between the centres of two atoms of
that element that are just touching each other. Generally,
the atomic radius decreases across a period from left to
right and increases down a given group. Effective nuclear
charge increases across a period.
• The order of ionic radii size is: Cation < Atom < Anion
(Na1+ < Na < Na 1-)
Periodic Trends
Ionization Energy: The ionisation energy or ionisation
potential is defined as the energy required to completely
remove an electron from a gaseous atom or ion.
The first ionization energy: This is the energy required to
remove one electron from the parent atom.
The second ionization energy: This is the energy required to
remove a second valence electron from the univalent ion
to form the divalent ion
Ionization energies increase across a period from left to right
(decreasing atomic radius) and decrease down a group
(increasing atomic radius).
Exceptions to 1st ionisation trends
1) Xs2 > Xp1 e.g. 4Be > 5B
2) Xp3 > Xp4 e.g. 7N > 8O
Trends in Ionisation Energy
• Ionisation energies increase across a period from left to
right (decreasing atomic radius). e.g., Li to Ne. The reason
being that effective nuclear charge increases across a
period whilst atomic size decreases. Thus more energy is
required to remove an electron as you move from left to
right.
• Ionisation energies decrease down a group (increasing
atomic radius) e.g., Li, Na, K. The explanation is that as you
move down the group, atomic size increases and the
effective nuclear charge reduces as a result of the
shielding effect of the inner electrons.
• There are regular discontinuities in the increase trend
across a period e.g., Be to B, and N to O. For B less energy
is required to remove an electron from the 2p orbital as
compared to the 2s orbital in Be i.e Xs 2 > Xp1. For O, it is
easier to remove one of the paired electrons in 2p as
compared to removing the unpaired electron in 2p of N. i.e
Xp3 > Xp4.
Electron Affinity: of an element is the amount of energy
released when an electron is added to a gaseous atom
to form an anion.
X (g) + e− ⎯⎯→ X − (g) + EA
• The electron affinity of an element measures the ease
with which it forms an anion in the gas phase. Atoms
with stronger effective nuclear charge have greater
electron affinity. Electron affinity increases across a
period and decreases down a group. Exceptions
• Among nonmetals, however, the elements in the first
period have lower electron affinities than the elements
below them in their respective groups.
• Elements with electron configurations of Xs2, Xp3, and
Xp6 have electron affinities less than zero because they
are unusually stable.
Electronegativity:is a measure of the attraction of an
atom for the electrons in a chemical bond. Elements
with low ionization energies have low
electronegativities whilst those with high ionization
energies have high electronegativities.
Importance of Electronegativity
• In predicting the polarity of a particular bond. The
polarity of a bond, in turn, shows the way how the
bond would break when attacked by an organic reagent.
• In predicting the degree of ionic character of a covalent
bond.
• In predicting of inductive effects in organic chemistry.
• In understanding the shapes of molecules.
Periodic Trends
Summary of Periodic Table Trends
Moving across a period (Left → Right)
• Atomic radius decreases
• Ionization energy increases
• Electronegativity increases
Moving down a group (Top → Bottom)
• Atomic radius increases
• Ionization energy decreases
• Electronegativity decreases
COMPOUNDS: FORMULAS, NAMES AND MASSES

• In a chemical formula, element symbols and numerical

subscripts show the type and number of each atom
present in the smallest unit of the substance. There are
several types of chemical formulas for a compound:
• The empirical formula: This shows the relative number
of atoms of each element in the compound. It is the
simplest type of formula and is derived from the
masses of the component elements.
• The molecular formula: This shows the actual number
of atoms of each element in a molecule of the
compound. The molecular formula of hydrogen
peroxide is H2O2; there are two H atoms and two O
The structural formula: This shows the number of atoms and
the bonds between them; that is, the relative placement and
connections of atoms in the molecule. The structural
formula of hydrogen peroxide is H – O – O – H; each H is
bonded to an O, and the O’s are bonded to each other.
Names and Formulas of Ionic Compounds
• All ionic compound names give the positive ion (cation) first
and the negative ion (anion) second. Here are some points
to note about ion charges:
• Members of a periodic table group have the same ionic
charge; for example, Li, Na, and K are all in Group 1A and all
have a +1 charge.
• For A-group cations, ion charge = group number: for
example, Na is in Group 1A, Ba in Group 2A. (Exceptions are
Sn 2+and Pb2+)
• For anions, ion charge = group number minus 8: for example,
S is in Group 6A (6 - 8 = -2), so the ion is S-2.
Compounds Formed from Monatomic Ions:
• The name of the cation is the same as the name of the
metal. Many metal names end in -ium.
• The name of the anion takes the root of the nonmetal
name and adds the suffix -ide.
For example, the anion formed from brom ine is named
bromide (brom + ide). Therefore, the compound
formed from the metal calcium and the nonmetal
bromine is named calcium bromide.
Exercise: Name the ionic compound formed from the
following pairs of elements:
(a) Magnesium and nitrogen (b) Iodine and
cadmium
(c) Strontium and fluorine (d) Sulphur and cesium
In this and all other formulas,
• The subscript refers to the element preceding it.
• The subscript 1 is understood from the presence of the
element symbol alone (that is, we do not write Ca1Br2).
• The charge (without the sign) of one ion becomes the
subscript of the other:
Ca2+Br- gives Ca 1Br2 or CaBr2
• Reduce the subscripts to the smallest whole numbers
that retain the ratio of ions. Thus, for example, from the
ions Ca 2 and O2 we have Ca2O2, which we reduce to the
formula CaO.
• Exceptions: Compounds of the mercury (I) ion, such as
Hg2Cl2 and peroxides of the alkali metals, such as
Na2O2, are the only two common exceptions.
Compounds with Metals That Can Form More Than One
Ion
Compounds Formed From Polyatomic Ions
Oxoanions
• Most polyatomic ions are oxanions, those in which an
element, usually a nonmetal, is bonded to one or more
oxygen atoms. There are several families of two or four
oxoanions that differ only in the number of oxygen
atoms. The following simple naming conventions are
used with these ions.

a) With two oxoanions in the family:

• The ion with more O atoms takes the nonmetal root

and the suffix -ate.
phosphate
• The ion with fewer O atoms takes the nonmetal root
and the suffix –ite.
2- 2-
b) With four oxoanions in the family
• The ion with most O atoms has the prefix per-, the
nonmetal root, and the suffix –ate.
• The ion with one fewer O atom has just the root
and the suffix -ate.
• The ion with two fewer O atoms has just the root
and the suffix -ite.
• The ion with least (three fewer) O atoms has the
prefix hypo-, the root and the suffix -ite.
For example, for the four chlorine oxoanions, ClO 4- is
per chlorate, ClO 3- is chlorate, ClO 2- is chlorite, ClO- is
hypochlorite.
Hydrated Ionic Compounds
• Ionic compounds called hydrates have a specific number of
water molecules associated with each formula unit. In their
formulas, this number is shown after a centred dot. It is
indicated in the systematic name by a Greek numerical
prefix before the word hydrate. For example, Epsom salt has
the formula MgSO4.7H2O and the name is magnesium
sulphate heptahydrate. Gypsum has the formula CaSO4.2H2O
and the name is calcium sulphate dihydrate. The water
molecules, referred to as “waters of hydration,” are part of
the hydrate’s structure.
Qu. Give the systematic names for the formulas or the
formulas for the names of the following compounds:
(a) Fe(ClO 4)2 (b) Sodium sulphite (c) Ba(OH) 2.8H2O
(d) Cupric nitrate trihydrate (e) Zinc hydroxide (f)
LiCN
Acid Names from Anion Names
Acids are hydrogen-containing compounds and when naming
them and writing their formulas, they are considered as
anions connected to the number of hydrogen ions (H)
needed for charge neutrality. The two common types of
acids are binary acids and oxoacids:
• 1. Binary acid solutions form when certain gaseous
compounds dissolve in water. For example, when gaseous
hydrogen chloride (HCl) dissolves in water, it forms a
solution whose name consists of the following parts:
Prefix hydro- + nonmetal root + suffix -ic + separate word
acid
hydro + chlor + ic + acid
or hydrochloric acid. This naming pattern holds for many
compounds in which hydrogen combines with an anion that
has an -ide suffix.
2. Oxoacid names are similar to those of the oxoanions,
except for two suffix changes:
-ate in the anion becomes -ic in the acid
-ite in the anion becomes -ous in the acid
The oxoanion prefixes hypo- and per- are kept. Thus,
BrO4- is perbromate, and HBrO 4 is perbromic acid
IO2- is iodite, and HIO 2 is iodous acid
Qu. Name the following anions and give the names and
formulas of the acids derived from them: (a) Br-
(b) IO3- (c) CN- (d) SO42- (e) NO2-.
Qu. Write the formula for the name or name for the
formula of each acid:
(a) chloric acid (b) HF (c) acetic acid
(d) sulphurous acid (e) HBrO.
Names and Formulas of Binary Covalent Compounds
Binary covalent compounds are formed by the
combination of two elements, usually nonmetals.
Some common ones are: ammonia (NH 3), methane
(CH4) and water (H 2O), that we use their common
names, but most are named in a systematic way:
1. The element with the lower group number in the
periodic table is the first word in the name; the
element with the higher group number is the second
word. (Exception: When the compound contains
oxygen and any of the halogens chlorine, bromine and
iodine, the halogen is named first.)
2. If both elements are in the same group, the one with
the higher period number is named first.
3. The second element is named with its root and the
suffix -ide.
4. Covalent compounds have Greek numerical prefixes to
indicate the number of atoms of each element in the
compound. The first word has a prefix only when more
than one atom of the element is present; the second
word usually has a numerical prefix.
Qu. (a) what is the formula of carbon disulphide?
(b) What is the name of PCl5?
(c) Give the name and formula of the compound
whose molecules each consist of two N atoms and four
O atoms.
• Qu. Give the name or the formula for (a) SO3 (b) SiO2
(c) dinitrogen monoxide (d) selenium hexafluoride.
Molecular Masses from Chemical Formulas
The molecular mass (molecular weight) of a formula unit of the
compound is calculated as the sum of the atomic masses: i.e.
Molecular mass = sum of atomic masses
Molecular mass of H2O = (2 x atomic mass of H) + (1 x atomic
mass of O)
= (2 x 1.008 amu) + 16.00 amu = 18.02 amu
Ionic compounds are calculated in the same manner, but
because they do not consist of molecules, the term formula
mass is used for an ionic compound.
For barium nitrate, Ba(NO3)2 ,
Formula mass of Ba(NO 3)2
= (1 x atomic mass of Ba) + (2 x atomic mass of N) + (6 x
atomic mass of O)
= 137.3 amu + (2 x 14.01 amu) + (6 x 16.00 amu) = 261.3
amu
Stoichiometry of Formulas and Equations
The Mole
The mole (abbreviated mol) is the SI unit for amount of substance. It
is defined as the amount of a substance that contains the same
number of entities as there are atoms in exactly 12 g of carbon-12.
This number is called Avogadro’s number.
One mole (1 mol) contains 6.02210 x 1023 entities
Thus,
1 mol of carbon-12 contains 6.02210 x 1023 carbon-12 atoms
1 mol of H2O contains 6.02210 x 1023 H2O molecules
1 mol of NaCl contains 6.02210 x 10 23 NaCl formula units
The atomic mass of an element expressed in amu is numerically the
same as the mass of 1 mole of atoms of the element expressed in
grams. Examples
1 Fe atom has a mass of 55.85 amu and 1 mol of Fe atoms has a mass
of 55.85 g
1 S atom has a mass of 32.07 amu and 1 mol of S atoms has a mass of
32.07 g
A similar relationship holds for compounds: the molecular
mass (or formula mass) of a compound expressed in
amu is numerically the same as the mass of 1 mole of
the compound expressed in grams. Thus,
• 1 molecule of H2O has a mass of 18.02 amu and 1 mol
of H 2O (6.02210 x 1023 molecules) has a mass of 18.02 g
• 1 formula unit of NaCl has a mass of 58.44 amu and 1
mol of NaCl (6.02210 x 1023 formula units) has a
mass of 58.44 g
Molar Mass
The molar mass (M) of a substance is the mass per mole
of its entities (atoms, molecules or formula units).
Thus, molar mass has units of grams per mole (g/mol).
1. Elements: The molar mass of an element is found simply by
looking up its atomic mass in the periodic table.
Monatomic elements : The molar mass is the numerical value from
the periodic table expressed in units of grams per mole. For
example, neon is 20.18 g/mol, iron is 55.85 g/mol and sodium is
23.00 g/mol.
Molecular elements: The molecular formula is used to determine
the molar mass. For example, the molar mass of O 2 molecules is
twice that of O atoms.
2. Compounds: The molar mass of a compound is the sum of the
molar masses of the atoms of the elements in the formula
Molar mass (M) of SO2 = M of S + (2 x M of O) = 32.07 g/mol + (2 x
16.00 g/mol) = 64.07 g/mol
M of K 2S = (2 x M of K) + M of S = (2 x 39.10 g/mol) + 32.07 g/mol
= 110.27 g/mol
Converting Moles of Elements
For problems involving mass-mole-number relationships of
elements, keep these points in mind:

• To convert between amount (mol) and mass (g), use the

molar mass (M in g/mol).

• To convert between amount (mol) and number of entities,

use Avogadro’s number (6.022 x 10 23 entities/mol). For
elements that occur as molecules, use the molecular
formula to find atoms/mol.
• Mass and number of entities relate directly to number of
moles, not to each other. Therefore, to convert between
number of entities and mass, first convert to number of
moles. For example, to find the number of atoms in a given
mass,
1 mol 6.022 x 1023 atoms

No. of atoms = mass (g) x x

Steps in Balancing chemical Equations
• A chemical equation is a statement in formulas that
expresses the identities and quantities of the substances
involved in a chemical or physical change.
• To balance a chemical equation use the following steps

• Translate the statement into “skeleton” equation, i.e

chemical formulas arranged in an equation format with
reactants and products.
• Balance the atoms in the chemical equation (stoichiometric
coefficient)
• Adjust the coefficients to the smallest whole number ratio.
• Check that the equation is balanced.
• Specify the states of matter, i.e indicate the physical state of
each substance.
For example, write a balanced equation for a magnesium strip
that burns in oxygen to yield powdery magnesium oxide.
2Mg(s) + O 2(g) 2MgO(s)
CHEMICAL BONDING
• Chemical bonding may be defined as the phenomenon
involving the union of two or more atoms through the
redistribution of electrons in their outer shells, either
by sharing of electrons among themselves or by the
transference of electrons from one atom to another.
• The inert gases contain eight electrons except for
helium which contains two electrons, this configuration
represent a state of maximum stability and hence
minimum energy.
• Atoms of all other elements tend to acquire this stable
configuration of inert gases by either the transfer of
electrons from one atom to another or by mutual
sharing of electrons.
• A chemical bond is defined as a force that acts between
two or more atoms to hold them together as a stable
molecule.
Definition of terms
• Valence: is the number of bonds formed by an
atom in a molecule.
• Valence Electrons: The electrons in the outer
energy level of an atom are the ones that can take
part in chemical bonding. These electrons are,
therefore, referred to as the valence electrons.
• Bonding and Non-bonding Electrons: The valence
electrons involved in bond formation are called
bonding electrons. The remaining valence electrons
still available for bond formation are referred to as
non-bonding electrons.
Ionic or Electrovalent Bond: This bond is formed when
one or more electrons have been transferred from one
atom to another.
Properties of ionic substances
• Ionic compounds do not conduct electricity in solid
state but conduct electricity quite well when molten
• Ionic compounds show high melting and boiling
points
• The strong electrostatic forces between the ions
cause ionic crystals to be relatively hard.
The elements in the periodic table can be divided into:
• Electropositive elements-elements whose atoms give
up one or more electrons fairly readily
• Electronegative elements tend to take up electrons
• Elements which neither tend to gain or lose electrons
We can thus classify three types of bonding
• Electropositive element + electronegative element =
Ionic bond
• Electronegative element + electronegative element =
Covalent bond
• Electropositive element + electropositive element =
Metallic bond
Covalent Bond: A covalent bond is one produced by the
sharing of electrons by two atoms.
Rules for Covalent Bond Formation
• Normally two electrons pair up to form one bond
• The atomic orbitals on the bonding atoms must overlap
• For most molecules there will be a maximum of eight electrons in
the valence shell
• For elements with available d-orbitals, the valence shell can be
expanded beyond an octet
• Electron-electron repulsion will be minimised
General Characteristics of Covalent Compounds
• Covalent compounds have low molecular weights
• Solid covalent compounds posses crystalline lattices consisting of
separate molecules
• Covalent compounds have low melting and boiling points because
of weak intermolecular forces
• Some covalent bonds are polar in nature e.g H and Cl
• Covalent compounds are soluble in organic non-polar or weakly
polar solvents but insoluble in water and polar solvents
Polar Molecules & Polar Bonds
A polar bond is made when two atoms of different
electronegativities combine e.g HCl
Coordinate or Dative Bond: This is a kind of covalent bond
in which both the electrons in a covalent bond are supplied
by one of the bonded atoms.
Hydrogen Bond:
Intermolecular hydrogen bond: This is hydrogen bonding
occurring between two or more similar or different
molecules e.g HF, H 2O, NH3
Intramolecular hydrogen bonding: hydrogen bonding
occurring within a single molecule
Properties of the Hydrogen Bond
• Hydrogen bonds are formed between highly
electronegative atoms such as fluorine, oxygen and
nitrogen
• Hydrogen bond is comparatively weak.
• Hydrogen bond is different from covalent bond because
there is no sharing of electrons.
• Hydrogen bond is formed more easily when both atoms
are highly electronegative e,g N-H through O-H to F-H.
Application of Hydrogen Bonding
• Responsible for the relatively high melting and boiling
points of water and hydrogen fluoride
• Holding the strands of DNA together
• Responsible for making wood fibres more rigid
• Cotton, silk and synthetic fibres owe their tensile
strength to hydrogen bonding.
Intermolecular bonding - van der Waals forces
• Intermolecular attractions are attractions between one molecule
and a neighbouring molecule. The forces of attraction which hold
an individual molecule together (for example, the covalent bonds)
are known as intramolecular attractions
• Intermolecular forces exist between all atoms and molecules
except those of an ideal gas.
• Intermolecular forces depend on dipole moments
There are three types:
• Temporary dipole – induced dipole-arises when there is an
instantaneous dipole e.g H 2
• Permanent dipole – induced dipole-arises when a molecule with a
permanent dipole interacts with one which is symmetrical e.g H-Cl
and Cl-Cl
• Permanent dipole – permanent dipole-arises in molecules that
have permanent dipole e.g HCl and NH3
• The larger or heavier the atom or molecule the greater the
polarisability and the stronger the intermolecular forces
Intermolecular forces between non-polar molecules
are called London or dispersion forces
• Intermolecular forces are sometimes called van der
Waals forces.
The main types of intermolecular forces are:
• Van der Waals, which involve attractions between
induced dipole moments
• Attractions between permanent dipole moments
• Hydrogen bonds
The Metallic Bond
Properties of metals
• Most metals are:
• solids at room temperature
• Malleable i.e can be beaten into various shapes
• Ductile i.e can be drawn out into wires
• Good conductors of electricity
• Good conductors of heat
 LEWIS STRUCTURES
Lewis structure: A Lewis structure is a diagram showing how
electron pairs are shared between atoms in a molecule.
• A lone pair of electrons is a pair of valence electrons that is
not involved in bonding
• A double bond consists of two shared electron pairs
• A triple bond consists of three shared electron pairs
Procedure for writing Lewis Structures for Diatomic molecules
and ions
• Write the chemical symbols for the two atoms.
• Decide from their location in the periodic table how many
valence electrons each supplies.
• The sum of these numbers is the number of dots that must
appear in the Lewis structure
• Example in the case of carbon monoxide, CO, the C atom has
4 valence electrons and the O atom has 6 valence electrons
and so 10 dots must appear in the Lewis structure.
• The dots must be added to the structure in pairs so that
each atom (other than hydrogen) ends up with an octet
and all the dots are used.
• The same procedure is used to draw Lewis structure for
diatomic anions, but an additional electron is added for
each negative charge.
• If 16 electrons are available (Ne atoms), each atom can
have an octet without sharing.
• If 14 electrons are available (7 pairs of dots), each atom
can have an octet if it has 3 lone pairs and 1 shared pair.
E.g Cl2, F2
• If 12 electrons are available, each atom can have 2 lone
pairs and 2 bonding pairs e.g O2, S2
• If 10 electrons are available, the atoms complete their
octet by sharing 3 pairs and having 1 lone pair e.g N 2,
CO, CN-
Procedure for writing Lewis Structures for Poly
atomic molecules and ions
• The procedure is the same for diatomic molecules
• However you will need to identify the central atom
e.g CO2, OCO and not COO
• One clue is that the less electronegative atom is
often the central atom
• Another clue is that chemical formulas, especially
for simple ones, are often written with the central
atom first followed by the terminal atoms ( atoms
attached to the central atom). An exception is the
convention of writing acid formulas with hydrogen
at the front.
Steps
• Calculate the total number of electron dots to be used by
adding the number of valence electrons of all the atoms.
Each hydrogen atom supplies one electron. Each main-group
element supplies its group number of electrons. For a cation,
subtract 1 dot for each positive charge. For an anion, add 1
dot for each negative charge. Divide the number by 2 to
obtain the number of electron pairs
• Arrange the chemical symbols for each atom in the formula
so that the terminal atoms surround the central. Initially
hydrogen atoms should be attached to any oxygen atoms
present or if no oxygen is present, to the central atom.
• Use electron pairs to form single bonds linking each atom to
its neighbour. Then try to place any remaining electron pairs
around the atoms so as to complete the necessary octet. If
they are no enough electrons, use one or more of the lone
pairs to form double or triple bonds to the central atom.
A simple mathematical relationship can be used to draw
Lewis structures:
S=N-A
• S is the total number of electrons shared in the
molecule or polyatomic ion.
• N is the total number of valence shell electrons needed
by all the atoms in the molecule or ion to achieve noble
gas configurations (N x 8 number of atoms that are not
H, plus 2 x number of H atoms).
• A is the number of electrons available in the valence
shells of all of the (representative) atoms. This is equal
to the sum of their periodic group numbers. A must be
adjusted if necessary for ionic charges. Add electrons to
account for negative charges and subtract electrons to
account for positive charges.
• Examples PF 5, BF3, NO3- NO 2-
STATES OF MATTER
• There are three states of matter- solid, liquid and gaseous.
• The main difference in the three states lies in the
arrangements of atoms, molecules or ions constituting the
matter.
• In solids, the molecules are closely packed and are orderly
arranged. Solids have a definite shape and volume at a given
temperature and pressure.
• In the gaseous state, the molecules are not orderly arranged.
Gases have neither definite shape nor volume and fill
completely any container in which they are placed.
• In liqiuds, molecules are not as close as in the solid but are
much closer than are the molecules in a gas. A liquid has a
definite volume but no definite shape. It takes the shape of
the container.
• Note: The above distinction of the three states of matter is
not absolute.
NATURE OF INTERMOLECULAR FORCES
• There are two types of forces that a substance may possess:
• Forces of attraction (cohesive forces)
• Forces of thermal agitation (thermal forces)
• Thermal forces determine the tendency of molecules to
move. They depend on temperature and increase with
increase in temperature.
• There is always a competition between the thermal forces,
which tend to disorder the molecules and the cohesive
forces which tend to order them.
• For this reason, whether a given substance exists in the
gaseous, liquid or solid state will affect the imbalance
between these two opposing forces.
• The change of state can be caused by changing the
temperature.
• Increase temperature will result in increase in thermal
forces and vice versa. Solid to liquid to gas
GASEOUS STATE
• There are two types of gases:
• Ideal gas – it obeys the gas laws such as Boyle’s and
Charles’s law at all temperatures and pressure.
• Non-ideal or real gases – obey the gas laws only at low
pressures and high temperatures.
The general characteristics of all ordinary gases can be
summarised as follows:
• Gases can be compressed into smaller volumes
• Gases exert pressure on their surroundings
• Gases expand without limits
• Gases diffuse into one another
• The amounts and properties of gases are described in
terms of temperature, pressure, the volume occupied,
and the number of molecules present.
Parameters of a Gas
• A gas sample can be described in terms of four parameters
(measurable properties): Volume, Pressure, Temperature,
the number of moles
Boyle’s Law: states that for a given quantity (mass) of a gas at
constant temperature, the volume of the gas is inversely
proportional to the pressure exerted by the gas or at a given
temperature, the product of pressure and volume of a
definite mass of gas is constant.
Boyle’s Law may be expressed mathematically as
V ∝ 1/P (T, n are constant) or V = k × 1/P where k
is a proportionality constant.
PV = k
• If P 1, V1 are the initial pressure and volume of a given sample
of gas and P2, V2 the changed pressure and volume, we can
write
P 1V1 = k = P2V2 or P 1 V1 = P 2 V2
Charles’ Law: states that at constant pressure, the volume of a fixed
mass of a gas is directly proportional to its absolute temperature.
i.e V α T or (at constant pressure)
For a given volume V1 of a fixed mass at the absolute temperature T1,
the volume V2, at temperature T2 is given by the relationship
V1 /V 2 = T1 /T 2 or V1 /T 1 = V2 /T2 = k (a constant)
Combined gas Law
• Boyle’s Law and Charles’ Law can be combined into a single
relationship called the Combined Gas Law.
Boyle’s Law V ∝ 1/P (T, n constant)
Charles’ Law V∝T (P, n constant)
Therefore, V ∝ T/P (n constant)
• The combined law can be stated as: for a fixed mass of gas, the
volume is directly proportional to kelvin temperature and inversely
proportional to the pressure.
If k be the proportionality constant,
V = kT/P (n constant)
or PV/T = k (n constant)
It can be used to calculate the temperature, pressure or volume of a
given mass of a gas under varying conditions.

Dalton’s Law of partial pressure

The law states that the total pressure exerted by a mixture of gases is
equal to the sum of partial pressures of the component gases
provided the gases do not react chemically with each other.
Hence the total pressure P of a mixture of gases A, B, C, is given by
the sum of their partial pressures, PA, P B, P C.
P = PA + P B + P C
Applying the ideal gas equation PA = n A RT/V , PB = n B RT/V , PA = n C RT/
V
Since the total pressure,
P = PA + P B + P C
Therefore P = nA RT/V + nB RT/V + nC RT/V
= (nA + n B + n C) RT/V
= nt RT/V
where nt = nA + n B + n C
PA = (nA/nt)P PB = (nB/nt)P PC = (nC/nt)P

Thus PA = XAP PB = XBP PC = XCP

In terms of mole fraction, the partial pressure of each
gas in a mixture of gases is equal to the mole
fraction of that gas multiplied by the total pressure.
The sum of all the mole fraction is unity, i.e .,
XA + XB + XC = 1
Avogadro’s Law: states that equal volumes of all
gases at the same temperature and pressure must
contain the same number of particles.
i.e V α n ( P, T constant) where n is the number of
moles of the gas.
Graham’s Law of Diffusion: states that at constant pressure
and temperature, the rate of diffusion of any gas is inversely
proportional to the square root of the density or the
molecular weight of the gas. i.e R α 1/√d or 1/√M
Effusion: is escape of a gas through a pinhole without
molecular collisions. The rate of effusion of a gas also
depends, on the molecular mass of the gas.
• For two gases with molecular masses M 1,M2 and rates of
diffusion R 1, R2, if the gases are at the same temperature and
pressure they must have the same molar volume Vm.
Hence R1/R2 = √d 2Vm/√d1Vm = √M2/√M1
Worked example: What is the relative rate of diffusion for
hydrogen molecules compared to those of oxygen at the
same temperature?
Solution: According to Graham’s law of diffusion
RH2/RO2 = √O2/√H2= √32/√2 = 4 M O2 = 32, MH2 = 2
• Thus the hydrogen molecules diffuse four times faster than
the oxygen.
The Ideal Gas Law
• This is a combination of Boyle’s law, Charles’ law
and Avogadro’s law which gives a relationship
between volume, pressure, temperature and the
number of moles of a gas sample.
V α nT/P or V = nRT/P or PV = nRT
From PV/RT = n = m/M = Vρ/M Thus P/RT =ρ/M
n is number of moles & R is the universal gas
constant and M is the molar mass.
R = 8.31441 JK-1 mol-1 = 0.082 litre atm/deg/mol =
8.314 x 107 ergs/deg/mol = 1.987 calories/deg/mol
The Kinetic Theory of Ideal Gases
The essential postulates of kinetic molecular theory of ideal gases are:
• Every gas consists of a very large number of tiny particles called
molecules, and molecules of the same gas are identical in all
respects.
• The molecules of a gas within a container are in the state of
constant rapid motion in all possible directions.
• The pressure of a gas results from the impacts of the molecules
upon the walls of the containing vessel.
• The molecules of a gas exert no appreciable attraction on each
other and behave as perfectly elastic bodies.
• The absolute temperature of a gas is the measure of the average
kinetic energy of all the molecules present in it and is directly
proportional to it.
• There is no effect of gravity on the motion of the molecules of a
gas.
• The molecules are very small as compared to the distances
between them and hence their actual volume is negligible as
compared to the volume of their container.
Deviation from Ideal Behaviour:
A gas is said to be ideal if it obeys the various gas laws, PV =
nRT. It has been found out that very few gases obey the ideal
gas equation only at low pressures and high temperatures.
At high pressures and low temperatures, there are marked
deviations from the ideal behaviour. The following
conclusions can be drawn:
• At low pressures and fairly high temperatures, real gases
show nearly ideal behaviour and the ideal-gas equation is
obeyed.
• At low temperatures and sufficiently high pressures, a real
gas deviates significantly from ideality and the ideal-gas
equation is no longer valid.
Causes of Deviations:
• Assumption that the volume occupied by the gas molecules
is negligible.
• The molecules do not exert any force of attraction on each
other.
However, these postulates are not strictly valid for the following
reasons:
Molecules of a gas do occupy some volume. At high pressures
the gas occupies a limited space as further compression is
resisted and the volume cannot be reduced.
Liquefaction of a gas is possible if there are forces of
attraction between the molecule
Modification of the Ideal Gas Equation:
• At low pressures, intermolecular attractions tend to slow
down and movement of the gas molecules. Therefore the
average kinetic energy, and hence the pressure exerted on
the walls of the container, becomes less than would be
predicted. A correction factor, n2a/V2, is introduced to
account for the total pressure, which thus becomes P + n 2a/
V2 .
• At high pressure, because of the large increase in the total
space occupied by the molecules, the total volume of the
gas is decreased by a factor, b, due to the actual volume of
the molecules. Hence the real volume of the gas becomes V
– nb.
Substituting the values of corrected pressure and volume in
the ideal gas equation, PV = nRT, we have
(P + an2/V2)(V – nb) = nRT
• This is known as van der Waals equation for n moles of a
gas. For 1 mole of a gas (n = 1), van der Waals equation
becomes
THE LIQUID STATE
• The molecules in a liquid are much closer to each other than
in gases, and the intermolecular forces are therefore greater.
The intermolecular forces that exist in liquids are called van
der Waals forces. These forces are electrical in nature and
result from the attraction of charges of opposite sign. The
principal kinds of intermolecular forces are: dipole-dipole
attractions, London forces and hydrogen bonding.
The nature of liquids can be discussed in terms of the kinetic
molecular theory on the basis of the following postulates:
• Liquids are practically incompressible.
• Liquids maintain their volume.
• Liquids have no characteristic shape but take the shape of its
container.
• Liquids diffuse because the molecules are in constant
random motion as a result that they have kinetic energy.
• Changes in temperature affect volumes of liquids. The
volume of a liquid increases with increasing temperature.
Vapour Pressure: The pressure exerted by a vapour in
equilibrium with a liquid at a given temperature is
called the vapour pressure or the equilibrium vapour
pressure of the liquid. The vapour pressure depends on
the nature of the liquid and on its temperature.
• Boiling Point: The boiling point of a liquid is defined as
the temperature at which vapour pressure of the liquid
becomes equal to the external pressure.
• Heat of Vaporization: This is the amount of heat
required to vaporise a mole of liquid to the gaseous
state. It is a measure of the attractive forces between
molecules in a liquid.
• Heat of Fusion: This is the amount of energy required
to melt one mole of solid to the liquid state at its
melting point.
Surface tension: the surface of a liquid tends to
contract to have the minimum surface area
possible. This force in the surface of a liquid is
called surface tension and is defined as the force
per unit length exerted at right angles upon a line
of unit length in the surface. Surface tension
decreases with increase in temperature.
• Viscosity: is defined as the resistance or opposition
to flow by liquids. Viscosity results due to the
internal frictional forces of the liquid. In general,
viscosity decreases with increase in temperature.
THE SOLID STATE
• In solids the attractive forces between the particles are
sufficient to overcome the translational energy and the
particles are forced to arrange themselves in a
characteristic geometric pattern i.e to form crystals.
• The particles, however, can vibrate and rotate around a
fixed point in this geometric pattern. The regular
geometric pattern of the units making up a crystalline
solid is called a crystal lattice.
• A lattice is a regular, three-dimensional arrangement of
equivalent points in space. The geometric properties of
the crystal lattice are summed up in the unit cell.
• The unit cell is the smallest portion of the crystal which
contains all the fundamental features of the crystal
without repetition. Thus the crystal lattice consists of a
regular three-dimensional arrangement of several units.
On the basis of the nature of forces that hold the particles together,
solids are classified into four main types i) metallic solids ii)
molecular solids iii) covalent solids and iv) ionic solids
• Metallic solids: These are solids the structures of which consist of
packed uniform spheres held together by forces of attraction
between positive ions and free moving electrons, e.g aluminium,
iron, magnesium, copper.
• Molecular Solids: In these, the binding forces may be van der
Waal’s forces or hydrogen bonding, and the lattice points are
occupied by molecules. The molecular solids are usually soft with
low melting points and are generally volatile e.g sugar, camphor,
naphthalene.
• Covalent Solids: The lattice points are occupied by atoms held
together by covalent bonds. They are normally hard, with high
melting points and are non-volatile, e.g diamond, silica (sand).
• Ionic Solids: The lattice points are occupied by positive and
negative ions held together by electrostatic forces. These crystals
are hard, brittle and have high melting points, sodium chloride,
magnesium sulphate
Fundamentals of solution stoichiometry
• Many environmental reactions and almost all
biochemical reactions occur in solution.
• A solution consists of a smaller amount of one
substance, the solute, dissolved in a larger amount of
another substance, the solvent.
• A solution may be gaseous, liquid or a solid of variable
composition within wide limits. For solutions in which
one component is a gas or solid and the other is a liquid,
the gas or solid is the solute and the liquid the solvent.
When both components are liquids present together in
different proportions, the major component is
considered the solvent and the minor component the
solute.
• The concentration of a solution is usually expressed as
the amount of solute dissolved in a given amount of
solution.
Dilution of Solutions
A concentrated solution (higher molarity) can be
converted to a dilute solution (lower molarity) by
adding solvent to it. As a result, the solution
volume increases while the number of moles of
solute remains the same. Thus, a given volume of
the final (dilute) solution contains fewer solute
particles and has a lower concentration than the
initial (concentrated) solution. A stock solution
(more concentrated solution) can be diluted using
the serial dilution formula to lower concentration.
Mdil x Vdil = no. of moles = Mconc x Vconc
i.e Mdil x Vdil = Mconc x Vconc
Stoichiometry of Chemical Reactions in Solution
• This involves preparing a solution by dilution approach as well as
the additional step of converting the volume of reactant or
product to moles.
• Step 1: balance the equation
• Step 2: find the number of moles of one substance
• Step 3: relate it to the stoichiometrically equivalent number of
moles of another substance
• Step 4: convert to the desired units.
• Worked example:
Calculating Amounts of Reactants and Products for a Reaction in
Solution
Specialized cells in the stomach release HCl to aid digestion. If they
release too much, the excess can be neutralized with an antacid
to avoid discomfort. A common antacid contains magnesium
hydroxide, Mg(OH) 2, which reacts with the acid to form water and
magnesium chloride solution. As a government chemist testing
commercial antacids, you use 0.10 M HCl to simulate the acid
concentration in the stomach. How many litres of “stomach acid”
react with a tablet containing 0.10 g of Mg(OH) 2?
Solution: Key principles
• Solubility refers to the amount of solute that dissolves
in a fixed amount of solvent at a given temperature.
• Dissolving involves enthalpy changes: heat is absorbed
to separate pure solute and pure solvent particles, and
it is released when they mix.
• The relative magnitude of these heats determines
whether the heat of solution is exothermic or
endothermic.
• In a saturated solution, the maximum amount of solute
has dissolved at a given temperature, and excess solute
and dissolved solute are in equilibrium.
• Because of the equilibrium nature of solubility, most
solids are more soluble in water at higher temperatures,
all gases are less soluble in water at higher
temperatures, and the solubility of a gas is directly
proportional to its pressure (Henry’s law)
• The concentration of a solution is expressed through
different concentration terms, including molarity, molality,
mass percent, volume percent, and mole fraction. These
terms are inter-convertible.
• The physical properties of a solution differ from those of the
solvent.
• Vapour pressure lowering, boiling point elevation, freezing
point depression, and osmotic pressure are called colligative
properties because they depend on the number, not the
chemical nature, of the dissolved particles.
• The vapour pressure above an ideal solution of a non-
volatile non-electrolyte is lowered by an amount
proportional to the mole fraction of the dissolved solute
(Raoult’s law).
• For a volatile non-electrolyte, the vapour has a higher
proportion of the more volatile solute than the solution
does. In a solution of a strong electrolyte, interactions
among ions cause deviations from ideal behaviour and, thus,
from the expected magnitudes of the colligative properties.
Heats of Solution and Solution Cycles
For one substance to dissolve in another, three events must
occur:
Step 1: Solute particles separate from each other. This step
involves overcoming intermolecular attractions, so it is
endothermic:
Solute (aggregated) + heat solute (separated) ΔHsolute > 0
Step 2: Solvent particles separate from each other. This step
also involves overcoming attractions, so it is endothermic:
Solvent (aggregated) + heat solvent (separated) ΔHsolvent >
0
Step 3: Solute and solvent particles mix. The particles attract
each other, so this step is exothermic:
Solute (separated) + solvent (separated) solution heat
ΔHmix < 0
• The total enthalpy change that occurs when a solution forms
from solute and solvent is the heat of solution (ΔHsoln),
which is the combination of the three individual enthalpy
changes to find it. The overall process is called a
thermochemical solution cycle and is yet another application
of Hess’s law:
ΔH soln = ΔHsolute + ΔH solvent + ΔH mix
Note: If ΔH soln is highly positive, the solute may not dissolve to
any significant extent in that solvent.
Heats of Hydration: In water,
ΔH soln = ΔHsolute + ΔH hydr
where ΔHhydr is the heat of hydration which is the enthalpy
change during solvation. Solvation is the process of
surrounding a solute particle with solvent particles.
The heat of solution (ΔHsoln) and entropy (S) are the two factors
that determine whether a solute dissolves in a solvent.
Types of mixtures:
• a. Homogeneous mixtures (true solution): the particles cannot be
separated from each other by mechanical means and the
composition is uniform all throughout. E.g salt or sugar in water
• b. Heterogeneous mixtures (coarse mixture): the particles are
present as large aggregates and can easily be separated from each
by simple mechanical methods. E.g mixture of sand and sugar.
• c. Colloidal solution: the particles are of intermediate size
between a homogeneous and a heterogeneous mixture. E.g milk
• Unsaturated solution: This is a solution in which the solute still
dissolves in the dissolving solvent at that temperature.
• Saturated Solution: is defined as one which is in equilibrium with
the excess of solid at a particular temperature. This is a solution
that contains as much solute as it can hold in the presence of the
dissolving substance at that temperature. Any more solute added
to the solution will not dissolve but remains as a solid.
• Supersaturated solution: This is a solution in which there is more
solute in the dissolving solvent than it should be at that
temperature. Such a solution is not stable and is very likely to form
a precipitate if the solution is slightly disturbed.
Types of Solutions (binary solutions)
• Gas/gas: All gases are infinitely soluble in one another. e.g
any mixture of gases, air (partial and total pressures
governed by Dalton’s law)
• Gas/liquid e.g ammonia in water, aerated water, oxygen in
blood
• Gas/solid: This is when gas dissolves in a solid, it occupies
the spaces between the closely packed particles. e.g
hydrogen in palladium
• Liquid/gas e.g vaporisation of a liquid into a gas
• Liquid/liquid e.g water in alcohol
• Liquid /solid e,g liquid benzene in solid iodine
• Solid/gas e,g sublimation of a solid to a gas
• Solid/liquid e.g sugar in water
• Solid/solid: solids diffuse so little and hence their mixtures
are usually heterogeneous, e.g gravel mixed with sand,
alloys; lead in silver, copper in nickel etc
Completely miscible liquids: These are liquid pairs which
dissolve in each other in all proportions and have no
saturation limit, e.g water-ethyl alcohol, benzene-
toluene, water-acetic acid, water-glycerol etc
• Completely immiscible liquids: These are liquid pairs
which do not dissolve at all in each other, e.g water-
mercury, water and oil
• Partially immiscible liquids: These are liquid pairs
which dissolve in each other only to certain limits, e.g
water-ether, water-phenol
The general observation is that liquids which have similar
chemical structure are completely miscible while liquids
which have different chemical structures are
completely immiscible.
Conditions That Affect Solubility
• In general, three major factors—pressure, temperature, and
the nature of the solute and solvent—influence the
solubility of a solute in a solvent. Not all these factors are
equally important in a specific instance.
• Pressure: It has been observed that changes in pressure
have little effect on the solubility of solid or liquid solutes in
a liquid solvent, but pressure has a much greater influence
on the solubility of a gaseous solute.
• Henry's Law: This law states that at any specified
temperature, the extent to which a gas dissolves in a liquid is
directly dependent upon the pressure of the gas or the
solubility of a gas (Sgas) is directly proportional to the partial
pressure of the gas (Pgas) above the solution:
S gas = kH x Pgas where kH is the Henry’s law
constant and is specific for a given gas-solvent combination
at a given temperature. With Sgas in mol/L and Pgas in atm, the
units of kH are mol/Latm.
• Temperature: In general, a change in temperature affects the
solubility of gaseous solutes differently than it does the solubility
of solid solutes, because the solubility of a gas in a liquid solvent
decreases with increasing temperature. With relatively few
exceptions, the solubility of solids in liquids increases with an
increase in temperature.
• The nature of solute and solvent: In general, the relative
solubilities of ionic substances are a measure of the magnitude of
the electrostatic forces that hold the crystals together.
Properties of Solutions
• Pure liquids have a set of characteristic physical properties
(melting point, vapor pressure at a given temperature, etc.).
Solutions in a solvent exhibit these same properties, but the
values differ from those of the pure solvent because of the
presence of the solute. Moreover, the change observed in these
properties in going from the pure solvent to a solution is
dependent only upon the number of solute molecules; these
properties are called colligative properties. The properties of a
solvent that show a predictable change upon the addition of a
solute are melting point, boiling point, vapor pressure, and
osmotic pressure
COLLIGATIVE PROPERTIES
Dilute solutions containing non-volatile solute exhibit the following
properties:
• Lowering of the Vapour Pressure
• Elevation of the Boiling Point
• Depression of the Freezing Point
• Osmotic Pressure
The essential feature of these properties is that they depend only on
the number of solute particles present in solution. A colligative
property may be defined as one which depends on the number of
particles in solution and not in any way on the size or chemical
nature of the particles.
• Melting and boiling points. Solutions exhibit higher boiling points
and lower melting points than the parent solvent. The increase in
boiling point and decrease in melting point is dependent upon the
number of solute particles in the solution. The greater the number
of solute particles (i.e., the concentration) the greater the boiling
point elevation and melting point depression.
• Vapour pressure: All liquids exhibit a vapour
pressure, the magnitude of which depends on the
temperature of the liquid. However, the vapour
pressure of a solution (at any temperature) is less
than that of the solvent.
• Osmosis: is the passage of a solvent through a
semipermeable membrane into a more
concentrated solution. A semipermeable
membrane may be defined as a material that
allows molecules of one kind to pass through it but
prevents the passage of other kinds of molecules or
allows the passage of different kinds of molecules
at different rates.
Trial Questions
Question: A sample of spirit contains 92% of ethanol by weight,
the rest being water. What is the mole fraction of its
constituents?
Answer: water = 0.182; ethanol =0.818
Question: Calculate the amount of Na+ and Cl– ions in grams
present in 500 ml of 1.5 M NaCl solution.
Answer. 17.3 g Na+ and 26.6 g Cl-
Question: Calculate the number of molecules of sugar present
in 1 ml of 10% sugar solution having density = 1.20 g /ml
Answer. 2.1 × 10 20
Question: Determine the Molality of a solution containing
86.53 g of sodium carbonate (mol mass = 105.99) per litre in
water at 20°C. The density of the solution at this
temperature is 1.0816 g / ml
Answer: 0.7547
Question: What is molarity and molality of a 13%
solution (by weight) of H 2SO4? Its density is 1.09 g/
ml.
Answer. (a) 1.44 M; 1.52 m
ACIDS, BASES AND SALTS
Arrhenius Concept: Arrhenius defined an acid as a
substance, which gives hydrogen ions (H +) in solution
and a base as a substance, which gives hydroxyl ions
(OH-) in solution. In this case the neutralization process
is simply
H+ + OH - = H2O
Bronsted-Lowry Concept: They defined acids and bases in
terms of proton transfer. An acid is a substance which
has a tendency to donate a proton and a base is
substance which has a tendency to accept a proton.
This can be illustrated by the general expression
Acid ↔ H + + Base
Thus, every acid has a base which is referred as the base
conjugate to the acid. Acids and bases can either be
neutral molecules or charged particles.
The general expression for all types of acid-base
reactions can be represented as
Acid 1 + Base 2 ↔ Acid2 + Base 1
Acid1-Base1 comprises one conjugate pair and Acid 2-
Base2 comprises the other conjugate pair.
Examples
Acid1 Base 2 Acid2 Base1
HCl + H 2O ↔ H 3O+ + Cl-
H 2O + NH3 ↔ +
NH4 + OH -

In general, the stronger an acid, the weaker is its

conjugate base and vice-versa. Order of decreasing
strength of some acids
HClO 4 > HBr > H2SO4 > HCl > HNO3
Lewis acid-base concept: An acid is an electron pair
acceptor (electrophile) and a base is an electron
pair donor (nucleophile). In the neutralization
process, a covalent bond is formed in which both
the electrons of the shared pair are provided by the
base.
Examples:
The reaction between boron trifluoride, BF3 and
ammonia, NH3
BF3 + NH3 → F 3B-NH3
The reaction between H+ and OH-
H + OH → H 2O
+ -
Hard and Soft Acids and Bases (HSAB) Theory is a qualitative
concept introduced by Ralph Pearson to explain the stability
of metal complexes and the mechanisms of their reactions.
• According to this theory, the Lewis acids and bases can be
further divided into hard or soft or border line types.
A hard acid is one in which the acceptor atom of the acid is
small, has a high positive charge and has no valence
electrons that can easily be shifted from their positions near
the nucleus. Examples are Li +, H3O+ and Al 3+
Soft acids have large acceptor atoms, zero or small positive
charge and several valence electrons, that can easily be
shifted or removed. Examples are Ag+, Hg 2+, etc
Hard bases are those that hold tightly to their valence
electrons such as OH - and F -.
Soft bases have positions of their valence electrons easily
shifted by positive charges in their neighbourhood or even
removed to other nuclei. Examples are I- and CO.
The Border line Lewis acids and bases have intermediate
properties.
• In short, Hard acids and bases are small and non-polarizable,
whereas Soft acids and bases are larger and more
polarizable.
• HSAB Principle: According to HSAB concept, hard acids
prefer binding to the hard bases to give ionic complexes,
whereas the soft acids prefer binding to soft bases to give
covalent complexes.
• The large electronegativity differences between hard acids
and hard bases give rise to strong ionic interactions.
• The electronegativities of soft acids and soft bases are
almost same and hence have less ionic interactions. i.e., the
interactions between them are more covalent.
• The interactions between hard acid - soft base or soft acid -
hard base are mostly polar covalent and tend to be more
reactive or less stable. The polar covalent compounds readily
form either more ionic or more covalent compounds if they
are allowed to react.
Ionisation of Water (Ionic Product of Water)
Water can behave as an acid and a base as shown below
H 2O + H2O ↔ H3O+ + OH-
Generally, the ionisation of water is represented by the
equation
H 2O ↔ H+ + OH-
The equilibrium constant is written as
K = [H+][ OH-]
[H 2O]

Kw = [H +][ OH-] where Kw =K[H2O] which is referred to as

the ionic product of water

Kw = 1 x 10 -14, at 25oC, CH+ x C OH- = 1 x 10 -14 gram ion per litre

An aqueous solution in which CH+ = COH- = 1 x 10 -7 is said to be
neutral. When C H+ > COH- the solution is acidic and when C H+ <
COH- , the solution is basic.
The ionic product principle is of great importance and can be applied to any
solution containing water for the calculation of concentrations of
hydrogen and hydroxyl ions.
The relationship between pKa, pKb and pKw
Consider a solution of a weak acid HA. A - is its conjugate base.
For the acid solution, HA + H 2O ↔ H 3O+ + A -
Ka = [H3O+][ A-]
[HA]
For the solution of the base, A - + H 2O ↔ HA + OH-

Kb = [HA][OH-]
[A -]

Therefore, KaKb = [H3O+][ A-].[HA][OH-]

[HA] [A-]

In an aqueous medium the product of [H 3O+][OH-] is always equal to 1 x 10-14 .

Hence for a conjugate acid-base pair
Ka Kb = K w = 1 x 10 -14 and since Kw is a constant, Ka α 1/Kb
The pH Scale
• The pH of a solution is defined as the negative logarithm to
the base 10 of the hydrogen ion concentration in gram ion
per litre.
pH = -log10 C H+
pOH = -log10 C OH-,
pKa =-log10 Ka,
pKw = -log10 Kw
• In any aqueous solution, the ionic product of water is
expressed as
Kw = C H+ x COH-
-log10 Kw = -log10 C H+ -log10 C OH-
pKw = pH + pOH
At 25oC, Kw = 10 -14
Hence, pH + pOH = 14
• For a neutral aqueous solution, pH = 7 while if the solution is
acidic, pH < 7 and if the solution is basic, pH >7.
pH of strong acids and bases
Strong acids dissociate completely in dilute solutions
HA + H2O → H3O+ + A-
+
The final [H3O ] is practically equal to the initial [HA].
Hence pH = -log 10[HA]
Similarly, for a strong base
B + H2O → BH + + OH - , pOH = -log10[B]
• Note: It is important to distinguish between a
concentrated acid and a strong acid. Concentration
refers to the number of moles of acid present per
litre of solutions; strength refers to the proton-
donating power of the acid molecules.
pH of weak acid and weak base solutions
A solution of a weak acid is an equilibrium mixture of the acid HA, H3O+ and the conjugate base A -
of the acid
HA + H 2O → H3O+ + A-
If a is the degree of ionisation of the acid, and C is its initial concentration (in mol dm -3 or mol/
litre), then the equilibrium concentrations of HA, H 3O+ and A - are C(1- a), Ca and Ca
respectively.
Then Ka = C2a2 = Ca2
C(1-a) 1- a
For weak acids, a will be very small and 1 – a ≈ 1

Therefore Ka = Ca 2 and a = √Ka/C

But [H3O+] = Ca
= C√Ka/C = √KaC

Therefore pH = -1/2 log KaC = 1/2pKa – 1/2log C

Similarly for a weak base it can be shown that

K b = C2 a 2 = Ca2
C(1-a) 1- a

where Kb is the base ionisation constant, and a the degree of ionisation of the base in water, and
pOH = 1/2pK b – 1/2logC
pH and Drug Action:
• A number of drugs are either weak acids or weak bases,
such as phenols, sulphonamides, alkaloids, e.g codeine and
barbiturates e.g phenobarbitone. The extent to which such
drugs are ionised depends on the pKa values and the pH of
the medium in which they are used.
• When the effect of pH on the toxic power of a drug is
investigated, the results often suggest that effective agent is
either (i) the non-ionised form, or (ii) the ionised form or (iii)
both forms of the drug.
Applications of pH
There are four main applications of pH determination
• Pharmaceutical applications
• Industrial applications
• Analytical applications
• Physiological applications
The Common ion effects: This is the suppression of
the degree of ionisation of a weak acid or base by
the addition of a common ion.

Examples:
CH3COOH + H2O ↔ H3O+ + CH3COO-
The equilibrium will shift to the left by an increase in
the concentration of acetate ions or hydrogen ions.
Similarly, the equilibrium
NH 4OH ↔ NH 4+ + OH -
will also shift to the left by an increase in the
concentration of ammonium ions or hydroxyl ions.
Buffer Solutions
• These are solutions which are resistant to change of pH
when some acid or base is added to them.
1. Buffer action of solutions containing a mixture of weak
acid and its highly ionisable salt, such as acetic acid and
sodium acetate.
H3O+ + CH 3COO- ↔ H 2O + CH3COOH
• When hydrogen ions are added to this solution in the
form of some acid, HCl, they will combine with the
acetate ions to form more unionised acetic acid.
• When some base is added such as sodium hydroxide,
the hydroxyl ions added will be removed by the
reaction with acetic acid
OH - + CH 3COOH ↔ CH 3COO- + H2O
• Thus, again the solution will maintain a constant pH.
2. Buffer action of solutions containing a mixture of weak base and
its highly ionisable salt, such as ammonium hydroxide and
ammonium chloride.
H 3O+ + NH 4OH ↔ NH 4++ 2H 2O
• Addition of acid is removed by ammonium hydroxide and hence
no change in pH.
• When a base is added, the hydroxyl ions are removed by reacting
with ammonium ions to form unionised ammonium hydroxide.
OH- + NH 4+ ↔ NH4OH
3. Buffer action of solutions containing salt of weak acid and a weak
base, such as ammonium acetate.
• Such a solution will contain excess of both ammonium ions and
acetate ions. If some acid is added, the hydrogen ions added will
be removed by reaction with acetate ions and if some base is
added, the added hydroxyl ions will be removed by ammonium
ions as shown
H 3O+ + CH 3COO- ↔ CH3COOH + H 2O
Thus, in both the cases, the solution will not change its pH.
Calculation of pH values of buffer solutions
Consider a buffer solution containing a mixture of acetic acid and sodium
acetate. Let C1 and C2 be the initial concentrations of the acid and salt
respectively. The pH value for this solution can be calculated from
knowledge of the ionisation constant of the weak acid as follows:
The equilibrium expression for the dissociation of the acetic acid for the
buffer solution is
K a = [CH3COO-][H +]
[CH 3COOH]

[H +] = Ka [CH3COOH]
[CH 3COO-]

[H +] = Ka [Acid]
[Salt]
Thus -log10 [H+] = -log 10 Ka + log10 [Salt]
[Acid]
pH = pKa + log10 [Salt]
[Acid]
Buffer Capacity: the capacity of a buffer is the amount of acid
or base that may be added before the buffer loses its ability
to resist change in pH.
Uses of buffer solutions:
• Buffer solutions find numerous applications in the fields of
analytical, pharmaceutical and biological systems.
• Used for preparing standard solutions of definite pH values
which are insensitive towards the addition of small
quantities acids and alkalis.
• Citric acid is used for stabilising milk of magnesia
• Penicillin preparations are stabilised by the addition of
sodium citrate or aluminium hydroxide.
• Sulphonamide preparations usually contain sodium
bicarbonate, sodium acetate or sodium citrate which acts as
buffers.
• Blood is maintained at a pH of about 7.4 by buffers in the
plasma. The plasma contains carbonic acid, carbonate and
sodium salts of phosphoric acid as buffers.
Hydrolysis:
• When an acid reacts with a base in aqueous solution,
neutralisation takes place.
i.e Acid + Base = Salt + Water
• Neutralisation is complete when strong acids and
strong bases react.
• In all other cases, the final solution will not be neutral
and is either basic or acidic.
• The acidity or basicity of a final solution is due to the
tendency of the salt formed by neutralisation to react
with water thereby partially reversing the process of
neutralisation.
• The partial reversal of neutralisation due to the
reactions of the salt with water is known as hydrolysis.
1. Salts of strong acids and strong bases: they do not undergo
hydrolysis and the solutions of such types of salts are neutral, e.g
HCl + NaOH → NaCl + H2O
2. Salts of weak acids and strong bases: they undergo hydrolysis to
give basic solutions, e.g CH 3COONa
CH3COO- + H 2O ↔ CH 3COOH + OH -
The presence of OH - make the solution alkaline
3. Salts of strong acids and weak bases: they undergo hydrolysis to
give acidic solutions, e.g NH4Cl
NH4+ + 2H 2O ↔ NH 4OH + H 3O+
(unionised)

The presence of H 3O+ makes the solution acidic.

4. Salts of weak acids and weak bases: they undergo hydrolysis to
gives solutions that are neutral, basic or acidic depending on the
relative strength of the acid and base, e.g
CH 3COO- NH4 + + H2O ↔ CH 3COOH + NH 4OH
(feebly ionised) (feebly ionised)
CHEMICAL EQUILIBRIUM
• Reversible Processes: All chemical reactions are
reversible, i.e they proceed in both directions. When
the extent of the reverse reaction is negligible, it is
regarded as an irreversible reaction. Consider, for
example, a simple reaction of the type
A+B↔C+D
(double arrow indicate that the reaction is reversible)
Equilibrium law and equilibrium constant
Consider a general reaction of the form
aA + bB +… ↔ cC + dD+….
Kc = [C]c [D]d...
[A] a [B] b...
where K c is the equilibrium constant.
Free energy & Equilibrium constant
A relationship between the free energy change in the standard state
for a reaction and the thermodynamic equilibrium constant is
given by
ΔGϴ = -RT In Ka
where Ka is the equilibrium constant.
For gases at low pressure and dilute solution, Ka can be replaced by
Kp (equilibrium constant in terms of partial pressures) and Kc
(equilibrium constant in terms of molar concentrations)
respectively.
Relationship between Kp and Kc:
It is possible to obtain a relationship between Kp and Kc at any
temperature provided the gases in the reaction obey the ideal gas
laws.
For ideal gases, PV = nRT
P = (n/V) RT where V is the volume occupied by n moles of gas
at the temperature T. But n/V is equal to the molar concentration
C, therefore
P = CRT,
Substituting P into equation 1 we have
K p = CC c(RT)c.CD d(RT)d...
CA a(RT)a.CB b(RT)b....

= C C c.CD d (RT)c + d
C A a.CB b (RT) a + b

= C Cc.CD d (RT)(c + d...) - (a +b + ...)

CA a.CB b

But Kc = C C c.CD d
CA a.CB b

Hence , Kp = Kc (RT) Δn
The Le-Chatelier Principle
• This principle is useful in determining the effect of
variation in temperature, pressure and concentration
on the position of equilibrium of a reversible reaction.
• Le Châtelier’s principle states when a chemical system
at equilibrium is disturbed, it reattains equilibrium by
undergoing a net reaction that reduces the effect of the
disturbance.
The Effect of Pressure: Changes in pressure have
significant effects only on equilibrium systems with
gaseous components. Pressure changes can occur in
three ways:
• Changing the concentration of a gaseous component
• Adding an inert gas (one that does not take part in the
reaction)
• Changing the volume of the reaction vessel
• An increase in the pressure of a gaseous mixture at
equilibrium will cause a decrease in the volume.
Therefore the system will move in such a manner as to
favour smaller volume. E,g
N2 (g) + 3H 2 (g) ↔ 2NH 3 (g) ΔHϴ = -92 kJ
• Hence an increase in pressure favours the formation of
ammonia.
The Effect of Temperature: For endothermic reactions,
which absorb heat, an increase in temperature will
favour the forward reaction whilst for exothermic
reaction a decrease in temperature will favour the
forward reaction.
The Effect of Concentration: If the concentration of one
of the components of the system is increased, the
equilibrium will change in such a so as to decrease the
concentration of that particular component.
The Effect of a Catalyst: A catalyst does not alter the
value of the equilibrium constant for any reversible
reaction but rather speeds up the attainment of
equilibrium.
Types of chemical Equlibria: There are two types of
equilibria:
Homogeneous equilibria in which only one phase
occurs. For example, a system containing only gases
or a single liquid or solid phase.
Heterogeneous equilibria in which more than a
single phase appears. For example, equilibrium
between solid and gas, liquid and gas, solid and
liquid, solid and solid, immiscible liquids.
Equilibrium constant for step-wise reactions
If a reaction proceeds through one or more intermediate
steps, then the equilibrium constant for the overall
reaction is related to the equilibrium constants of the
component steps.
Example
Fe + CO 2 = FeO + CO; K 1 = [FeO] [CO]
[Fe] [CO 2]
FeO + H 2 = Fe + H2O; K2 = [Fe] [H2O]
[FeO] [H2]
The overall reaction is
CO2 + H2 = CO + H 2O; K 3 = [CO] [H2O]
[CO2] [H2]
Thus K 3 = K1 K 2
Equilibrium in heterogeneous system
• Heterogeneous reactions involve two or more
different phases, ie solid/liquid, solid/gas, or liquid/
gas mixtures.
• By convention the activity of a pure solid or liquid
may be taken as unity at all temperatures.
Thus for reaction
CuO(s) + H 2(g) ↔ Cu(s) + H 2O(g)
The equilibrium constant,
Ka = AH2O and Kp = PH2O
A P
H2 H2
The Solubilty product:
When a sparingly soluble salt such as barium sulphate or
silver chloride is agitated with water until the solution is
saturated, the equilibrium which is established
between the solid phase and the completely
dissociated salt solution is expressed as
BaSO4 (s) ↔ Ba2+ (aq) + SO 42- (aq) and
AgCl (s) ↔ Ag + + Cl- (aq)
K = [Ba2+] [SO 42-] K = [Ag+] [Cl -]
[BaSO 4(s)] [AgCl(s)]
K [AgCl(s)] = constant
• This constant is known as the solubility product and is
denoted as Ksp.
Ksp = K [AgCl(s)] = [Ag +] [Cl -] and for BaSO4,
Ksp = [Ba2+] [SO 42-]
In general, the equilibrium expression for the
dissolution of any salt AnBm, yielding n positive ions
of A and m negative ions of B is given by
A nBm (s) ↔ nA m+ + mBn-
This gives the general expression for the solubility
product as
Ksp = [Am+]n [Bn-]m
where Ksp is constant at a given temperature
Example:
The solubility product of BaCrO 4 is 2.0 x 10-10 at 25 oC.
Calculate the molarity of the BaCrO4 solution.
Solution: BaCrO4, being a sparingly soluble salt,
dissociates as
BaCrO 4↔ Ba+2+ CrO42-
2+ 2-
Ksp = [Ba ] [CrO4 ]
Let x g be the solubility of BaCrO 4 per litre. Then
[Ba2+] = [CrO42-] = x g ion/litre
-10 2
2.0 x 10 = x × x = x
x = √2.0 x 10-10 = 1.45 x 10-5 g mol/litre
Hence, the molarity of this solution is 1.45 x 10-5 g
mol/litre
CHEMICAL KINETICS
This is the study of rates of chemical reactions.
The Rate of a chemical reaction
Let us consider a hypothetical reaction,
A + B → C +D
• The rate of a reaction may be defined as the decrease in the
concentration of A or B with time. The rate may also be defined in
terms of the increase in the concentration of C or D with time.
rate = - d[A] or - d[B]
dt dt

rate = + d[C] or + d[D]

dt dt
• Thus, the rate of a reaction depends on the concentration of the
reactant. The rate also depends on the physical state of the
reactants, the medium, the temperature, the presence of a
catalyst and the pH.
Units of Rate
• Reactions rate has the units of concentration
divided by time. Concentrations are expressed in
moles per litre (mol/litre or mol/1 or mol 1–1) but
time may be given in any convenient unit second
(s), minutes (min), hours (h), days (d) or possible
years.
Therefore, the units of reaction rates may be:
mole/litre sec or mol 1–1 s-1
mole/litre min or mol 1–1 min–1
mole/litre hour or mol 1 –1 h–1 and, so on
Factors affecting rates of reactions
1. The physical state of the reactants
2. Effect of concentrations (or pressures)
3. Effect of temperature
4. Effect of a catalyst
5. Effect of the medium
6. Effect of pH
The order of a chemical reaction
• The rate of a chemical reaction in any instance is dependent
on the concentration of the reactants.
rate α [reactants]n
• The above expression is known as the rate law and the
exponent n is defined as the order of the reaction.
When n = 1, reaction is first order
When n = 2, reaction is second order
When n = 3, reaction is third order
• The rate-law expression for a reaction in which A, B . . . are
reactants has the general form.
rate = k[A]p[B]q . . .
• The constant k is called the specific rate constant (or just the
rate constant) for the reaction at a particular temperature.
Note: The order of a chemical reaction cannot be obtained
from the stoichiometry of the chemical equation but from a
mathematical analysis of the experimental data.
It is important to remember the following points about this
specific rate constant, k.
• Once the reaction orders are known, experimental data
must be used to determine the value of k for the reaction at
appropriate conditions.
• The value of k determined is for a specific reaction,
represented by a balanced equation.
• The units of k depend on the overall order of the reaction.
• The value of k does not change with concentrations of either
reactants or products.
• The value of k determined does not change with time.
• The value of k determined refers to the reaction at a
particular temperature and changes if the temperature is
changed.
• The value of k determined depends on whether a catalyst is
present.
Interpretation of the Rate Law
For a hypothetical reaction
A+B+C products,
the rate law is determined to be
rate = k[A][B] 2
Predict the reaction rate when the following
concentration changes are made?
(a) The concentration of A is doubled without changing
the concentration of B or C.
(b) The concentration of B is doubled without changing
the concentration of A or C.
(c) The concentration of C is doubled without changing
the concentration of A or B.
(d) All three concentrations are doubled simultaneously.
Solution
Note: changing concentrations does not change the value of k.
(a) The rate is directly proportional to the first power of [A]. No
change to [B] or [C]. Doubling [A] (means increasing [A] by a
factor of 2) causes the reaction rate to increase by a factor of
21 = 2 i.e the reaction rate doubles.
(b) The rate is directly proportional to the second power of [B].
No change to [A] or [C]. Doubling [B] (means increasing [B]
by a factor of 2) causes the reaction rate to increase by a
factor of 2 2 = 4.
(c) The reaction rate is independent of [C], so changing [C]
causes no change in reaction rate.
(d) Doubling all concentrations would cause the changes
described in (a), (b), and (c) simultaneously. The rate would
increase by a factor of 2 due to the change in [A], by a factor
of 4 due to the change in [B], and be unaffected by the
change in [C]. The result is that the reaction rate increases
by a factor of 21 x 2 2 = 8
Questions:
Qu. 1. A chemistry student desires to prepare one litre of a solution buffered
at pH 9.00. How many grams of ammonium chloride have to be added to
one litre of 0.20 M NH 3 to make such a buffer. pK b value of ammonia is
4.75 in the equation
NH 3 + H 2O NH 4+ + OH -
Ans. 19.2 g NH4Cl
Qu 2. The pH of a buffer solution containing 0.5 mole/litre of CH 3COOH and
0.5 mole/litre CH3COONa has been found to be 4.76. What will be the pH
of this solution after 0.1 mole/litre HCl has been added to the buffer?
Assume that the volume is unchanged. K a = 1.75 × 10 – 5 .
Ans. 4.58
Qu 3. The solubility of CuBr is found to be 2.0 × 10 – 4 mol/l at 25°C. Calculate
Ksp value for CuBr.
Ans. 4.0 x 10 -8 mol2 L-2
Qu 4. Calculate the solubility of NiCO 3 in moles per litre and grams per litre.
The value of K sp for NiCO 3 = 1.4 × 10– 7.
Ans. 3.7 x 10 -4 mol/l and 0.044 g/l
Qu 5 Calculate the K sp for Bismuth sulphide (Bi2S3 ), which has a solubility of
1.0 × 10 -15 mol/L at 25°C.
Ans. Ksp = 1.08 x 10 -73
THERMODYNAMICS: is the study of the flow of heat or any other
form of energy into or out of a system as it undergoes a physical or
chemical transformation..
THERMODYNAMIC TERMS
System and Surroundings:
• A system is that part of the universe which is under
thermodynamic study and the rest of the universe is surroundings.
• The real or imaginary surface separating the system from the
surroundings is called the boundary. A system can also be defined
as any part of the universe which is chosen for thermodynamic
consideration.
• The system might be simple or complex e.g a container of
chemicals ready to react, a biological cell, an electrochemical cell,
or a simple vessel of gas.
• The regions outside the boundaries of the system are termed the
surroundings. A system and its surroundings constitute the
universe.
• A system can be classified as an open, closed or isolated system.
Isolated System:
An isolated system is one that can transfer neither matter nor
energy to and from its surroundings. Here the boundary is
both sealed and insulated; no interaction is possible with the
surroundings. A substance, say boiling water, contained in a
thermos flask, is another example of an isolated.
Closed System
A closed system is one which cannot transfer matter but can
transfer energy in the form of heat, work and radiation to
and from its surroundings. Here the boundary is sealed but
not insulated. A specific quantity of hot water contained in a
sealed tube.
Open System
An open system is one which can transfer both energy and
matter to and from its surroundings. Hot water contained in
a beaker placed on laboratory table is an open system.
Thermodynamic Functions or Variables: are parameters used
to define a system e.g mass, volume, temperature, pressure,
work, heat, enthalpy, entropy and free energy.
A system can be defined by four variables namely pressure,
volume, temperature and mass.
State functions: those whose initial and final values are not
path dependent e.g temperature (T), pressure (P), volume
(V), enthalpy (H), entropy (S), internal energy (E), and free
energy (G).
Non state functions: Those whose initial and final values are
path dependent e.g work (w), heat (q) and energy.
Properties of a System:
a. Extensive properties:
b. Intensive properties:
State of a system
• A thermodynamic system is said to be in a certain
state when all its properties are fixed. The
fundamental properties which determine the state
of a system is pressure (P), temperature (T), volume
(V), mass and composition.
• For a pure gas, the composition is fixed
automatically. The remaining state variables P, V, T
are interrelated in the form of an algebraic
relationship called the Equation of State.
Thus for one mole of a pure gas, the equation of state
is :
PV = RT
• An important characteristic of a state variable (or
state function) is that when the state of a system is
altered, the change in the variable depends on the
initial and final states of the system.
ΔT = Tfinal – Tinitial = 25ºC
The way in which the temperature change is brought
about has no effect on the result.
Equilibrium and Non–equilibrium states:
• A system in which the state variables have constant
values throughout the system is said to be in a
state of thermodynamic equilibrium
• A system in which the state variables have different
values in different parts of the system is said to be
in a non-equilibrium state.
The Criteria for Equilibrium
• The temperature of the system must be uniform and must
be the same as the temperature of the surroundings
(thermal equilibrium).
• The mechanical properties must be uniform throughout the
system (mechanical equilibrium). That is, no mechanical
work is done by one part of the system on any other part of
the system.
• The chemical composition of the system must be uniform
with no net chemical change (chemical equilibrium).
• If the system is heterogeneous, the state variables of each
phase remain constant in each phase.
Thermodynamic Processes
• When a thermodynamic system changes from one state to
another, the operation is called Process. These processes
involve the change of conditions (temperature, pressure and
volume).
The various types of thermodynamic processes are:
Isothermal Processes: These are processes in which the temperature
remains fixed. This is often achieved by placing the system in a thermostat
(a constant temperature bath).
For an isothermal process dT = 0
Adiabatic Processes: These are processes in which no heat can flow into or
out of the system. Adiabatic conditions can be approached by carrying
the process in an insulated container such as ‘thermos’ bottle. High
vacuum and highly polished surfaces help to achieve thermal insulation.
For an adiabatic process dq = 0
Isobaric Processes:These are processes which take place at constant
pressure. An example of such a process is heating of water to its boiling
point and its vaporisation which take place at the same atmospheric
pressure.
For an isobaric process dp = 0
Isochoric Processes: These are processes in which the volume remains
constant. An example is heating of a substance in a non-expanding
chamber.
For isochoric processes dV = 0.
Cyclic Process: This is when a system in a given state goes through a number
of different processes and finally returns to its initial state, the overall
process is called a cycle or cyclic process.
Thermodynamic Equilibrium: This is when the observable
properties of the system are not undergoing any change
with time. This term implies three types different
equilibrium which must be attained simultaneously. These
are:
Mechanical Equilibrium: when there are no macroscopic
movements within the system itself, or of the system with
respect to its surroundings.
Chemical Equilibrium: For a system consisting of more than
one substance, if the composition does not vary with time.
Thermal Equilibrium: This is when the temperature of the
system is uniform and is same as the temperature of the
surroundings.
Reversible and Irreversible Processes: A reversible process is
one which is carried out infinitesimally slowly so that the
system is at all times in equilibrium with its surroundings.
In an irreversible process the system does not remain in
equilibrium with its surroundings throughout.
Heat and Work: In thermodynamics, work (W) is energy
transferred by means of mechanical link between a system
and it surroundings whereas heat is energy transferred by
thermal conduction and radiation when there is a
temperature difference between a system and its
surroundings.
The First Law of Thermodynamics or The law of conservation
of energy: This law states that energy can be transferred but
never created or destroyed.
Internal Energy (E): This is the energy associated with a system
by virtue of its molecular constitution and the motion of its
molecules or the total of all the possible kinds of energy of a
system.
ΔE = EB – E A
Thus the first law of thermodynamics is given by the equation
ΔE = q – W
where ΔE is change in internal energy, q is the heat transferred
and W is the work done.
Calorimetry: is the study of heat transfer during physical
and chemical processes. A calorimeter is a device for
measuring energy transferred as heat. The change in
temperature, ΔT, of the calorimeter is proportional to
the heat that the reaction releases or absorbs.
Thus q = CΔT where C is the calorimeter
constant and can be measured electrically by passing a
constant current, I, from a known potential difference,
V through a heater for a known period of time, t, then
q = IVt
Example: If we pass a current of 10.0 A from a 12 V
supply for 300 s, then the energy supplied as heat is, q
= (10.0 A) × (12 V) × (300 s) = 3.6 × 104 AVs = 36 kJ, bec
1 AVs = 1 J
If the observed rise in temperature is 5.5 K, then the
calorimeter constant is C = 36 kJ / 5.5 K= 6.5 kJ K-1
Heat Capacity (c): The heat capacity of a system is
defined as the quantity of heat required to raise
the temperature of the system by one degree.
c = q/dT
Heat capacity at constant volume c v: At constant
volume, w = 0
Hence dE = qv = c vdT
cv = qv/dT = dE/dT

Heat capacity at constant pressure c p: At constant

pressure, w = PdV
i.e dE + PdV = dH = qp = cp dT
Thus cp = qp/dT = dH/dT
Heat Content or Enthalpy (H): The sum of the internal
energy of the system plus the product of the pressure
of the gas in the system and its volume or the total heat
content of a system at constant pressure is equivalent
to the internal energy E plus the PV energy.
i.e H = E + PV at constant pressure
For a change in enthalpy, ΔH, we have
ΔH = ΔE + Δ(PV)
ΔH = ΔE + PΔV + VΔP
Since pressure is kept constant, ΔP = 0
ΔH = ΔE + PΔV
ΔH = q p
Hence the change in enthalpy of a system is equal to the
heat given to the system at a constant pressure.
ΔH= Hfinal – Hinitial and q is heat
THERMOCHEMISTRY: This deals with enthalpy changes
accompanying chemical reactions or the study of
energy transferred as heat during the course of
chemical reactions.
• Since different substances have different heat contents
the total energy of the products of a reaction is
generally different from that of the reactants.
• Thus, in any chemical change, energy usually in the
form of heat is evolved or absorbed. If heat is given out
the reaction is said to be exothermic and the value of
the enthalpy change involved is by convention negative
( i.e ΔH = - ve). If heat is absorbed the reaction is said
to be endothermic and the value of the enthalpy
change is positive (i.e ΔH = +ve).
Standard State: In thermochemistry, temperature of 25 oC (298
K) and pressure of 1 atm are generally used as the standard
conditions for all substances (pure solids, liquids and ideal
gases). The standard state is defined at pressure of 1 atm at
any specified temperature. The symbols g, l, and s indicate
whether the substance taking part in the reaction is gas,
liquid or crystalline solid, respectively. For a general reaction
represented as
Reactants Products
For this reaction the internal energy change and the enthalpy
change are given by
ΔE = Eproducts – Ereactants
ΔH = Hproducts – Hreactants
• If the reactants and the products are in the standard state,
the heat transferred is called the standard heat for that
reaction and ΔE and ΔH for such reactions are symbolised
by ΔEϴ and ΔHϴ respectively.
Enthalpies of physical change: The standard enthalpy
change that accompanies a change of physical state
is called the standard enthalpy of transition ΔtrsHϴ.
Examples
The standard enthalpy of vaporisation, ΔvapHϴ, is the
enthalpy change per mole when a pure liquid at 1
bar or 1 atm vaporises to a gas at 1bar as in
H 2O(l) → H 2O(g) ΔvapHϴ(298K) = +40.66 kJmol-1
The standard enthalpy of fusion, ΔfusHϴ, is the
enthalpy change accompanying the conversion of a
solid to liquid, as in
H2O(s) → H 2O(l) ΔfusHϴ(298K) = +6.01 kJmol-1
Enthalpies of chemical change: There are two ways of reporting the
change in enthalpy that accompanies a chemical reaction.
One way is to write the thermodynamic equation, a combination of a
chemical equation and the corresponding change in standard
enthalpy:
CH4 (g) + 2O 2 (g) → CO 2 (g) + 2H 2O (l) ΔHϴ = -890 kJ
ΔHϴ is the change in enthalpy when reactants in their standard states
change to products in their standard states.
Pure, separate reactants in their standard states → pure, separate
products in their standard states
Alternatively, is to write the chemical equation and then report the
standard reaction enthalpy, Δ rHϴ. Thus, for combustion of reaction
we write
CH 4 (g) + 2O 2 (g) → CO 2 (g) + 2H 2O (l) ΔrHϴ = -890 kJ
For the reaction, 2A + B → 3C + D, the standard reaction enthalpy is
｛
ΔrHϴ = 3Hϴm(C) + Hϴm(D) ｝-｛ ｝
2Hϴm(A) + Hϴm(B)
In general,
ΔrHϴ = ∑vHϴm - ∑vHϴm where v is stoichiometric coefficients
Products Reactants
The Laws of Thermochemistry: The first law was given by Lavoisier and
Laplace in 1780. It states that the quantity of heat which must be
supplied to decompose compound into its elements is equal to the heat
evolved when the compound is formed from its elements. For example,
H 2 (g) + 0.5 O 2 (g) = H 2O (l) ΔH = -285.8 kJ
H 2O (l) = H 2 (g) + 0.5 O 2 (g) ΔH = +285.8 kJ
Hess’s Law: The standard enthalpy of an overall reaction is the sum of the
standard enthalpies of the individual reactions into which a reaction may
be divided.
• The individual steps need not be realisable in practice: they may be
hypothetical reactions, the only requirement being that their chemical
equations should balance. The importance of Hess’s law is that
information about a reaction of interest, which may be difficult to
determine directly, can be assembled from information on other
reactions.
Some applications of Hess’s law are:
1. Formation reactions of some compounds
2. Calculation of lattice energies of ionic crystals
3. Study of multistep reactions
4. Determination of calorific values of food and fuels
Standard enthalpies of formation:
The standard enthalpy of formation, Δ fHϴ, of a substance is the
standard enthalpy for the formation of the compound from its
elements in their reference states. Example, the standard enthalpy
of formation of liquid benzene at 298K is given the reaction
6 C (s, graphite) + 3 H 2 → C 6H6 (l) ΔfHϴ = +49.0 kJ mol -1
The reaction enthalpy in terms of enthalpies of formation is given by
ΔrHϴ = ∑vΔfHϴ - ∑vΔfHϴ where v is stoichiometric coefficients
Products Reactants
Example: the standard reaction enthalpy of
2HN 3 (l) + 2 NO (g) → H2O2 (l) + 4 N 2 (g)

｛｝ ｝ ｛
is calculated as follows:
ΔrHϴ = Δ fHϴ (H2O2,l) + 4Δ fHϴ (N2,g) - 2Δ fHϴ (HN 3,l) + 2 ΔfHϴ
(NO,g)
｛-
= ｝｛ ｝
187.78 + 4(0) - 2 (264.0) + 2 (90.25) kJmol -1
= -896.3 kJmol-1
HN3(l) = Hydrazoic acid, also known as hydrogen azide or azoimide
Heat of Solution: This is the amount of heat evolved when one
mole of the solute is dissolved in a specified amount of
solvent.
Heat of Neutralisation: This is the change in enthalpy when
one gram equivalent of an acid is neutralised by one gram
equivalent of a base in dilute solution.
Heat of Combustion: The heat of combustion of a compound
or element is the change of heat content when one mole of
it is burnt in oxygen at constant pressure.
Bond Energies: This is the average amount of energy per mole
necessary to rapture a particular bond in a molecule and
thus effect a complete separation of the resulting atoms or
radicals from one another. Bond energy and bond
dissociation energy are equivalent only for diatomic
molecules. Note: when a bond is broken it is given a plus
sign and when a bond is formed it is given a minus sign.
Uses of bond energies:
• Comparing the strength of bonds
• Understanding structure and bonding
• Estimating the enthalpy changes in reactions
(most important application)
• Understanding the mechanisms of chemical
reactions
Example: Using the bond energies given, calculate
the heat of formation of dimethyl ether from its
elements from the reaction below:
2C(s) + 3H2(g) + 0.5O2 = H 3C-O-CH3 (g)
H-H = 436 kJ mol -1, O=O = 494 kJ mol-1, C(s)-C(g) =
720 kJ mol-1, C-H = 412 kJ mol-1, C-O = 360 kJ mol -1
Solution:
Total bond energy of Total bond energies of
reactants products
3 H-H = 3 (436)= 1308 kJ 6 C-H = 6 (412) = 2472 kJ
0.5 O=O = 0.5(494) = 247 kJ 2 C-O = 2 (360) = 720 kJ
2 C(s)-C(g) =2(720) = 1440 kJ = 3192 kJ
= 2995 kJ
The heat of this reaction is given by:
ΔHϴ = -3192 + 2995 = -197 kJ mol -1
The Born-Haber Cycle:
• The Born-Haber cycle makes use of Hess’s law to
calculate lattice energies. The lattice energy is the
energy change when one mole of a crystal is
formed from its component ions in the gaseous
state.
• The Born-Haber cycle can be used for the
determination of electron affinities of elements
which are difficult to determine by other methods.
The Born-Haber cycle helps rationalize the
existence of certain compounds.
Example: By using Born Haber cycle for the formation
of silver chloride, calculate the lattice enthalpy of
silver chloride from the following data.
Enthalpy of atomization of Ag(s): 284 kJ/mol
1st ionization energyof Ag(g): 731 kJ/mol
Enthalpy of atomization of Cl2(g): 122 kJ/mol
1st electron affinity of Cl(g): -349 kJ/mol
Enthalpy of formation of AgCl(s): -127 kJ/mol
Solution:
ΔHLE° = ΔHa°(Ag)+ ∑ΔHIE°+ ΔHa°(Cl2)+ ΔHea° -
ΔHf°
= 284 + (731+ 122) + (-349) – (-127)
= 788– (-127)
= 915KJmol-1
Entropy and Spontaneous Change
• A process which proceeds of its own accord without
any outside assistance, is termed a spontaneous or
natural process. The reverse process which does not
proceed on its own is referred to as a non-spontaneous
or unnatural process. In general, the tendency of a
process to occur naturally is called the spontaneity. A
spontaneous change is a change that has a natural
tendency to occur without having to be driven by some
external influence or a spontaneous change is a change
that does not require work to be done to bring it about.
E.g of a spontaneous physical change is the cooling of a
block of hot metal to the temperature of its
surroundings. A spontaneous chemical change is the
formation of magnesium oxide when magnesium burns
in oxygen.
Criteria of spontaneity
• Some important criteria of spontaneous physical and
chemical changes are listed below.
• A spontaneous change is one-way or unidirectional. For
reverse change to occur, work has to be done.
• For a spontaneous change to occur, time is no factor. A
spontaneous reaction may take place rapidly or very
slowly.
• If the system is not in equilibrium state (unstable), a
spontaneous change is inevitable. The change will
continue till the system attains the state of equilibrium.
• Once a system is in equilibrium state, it does not
undergo any further spontaneous change in state if left
undisturbed. To take the system away from equilibrium,
some external work must be done on the system.
• A spontaneous change is accompanied by decrease of
internal energy or enthalpy (ΔH).
Entropy is the measure of chaos or disorder in a closed
system.
The thermodynamic definition of entropy: The
thermodynamic definition of entropy concentrates on
the change in entropy dS that occurs as a result a
process.
ΔSsurr = q surr / Tsurr
The Standard molar entropy S ϴ: of a substance is the
entropy per mole of the pure substance at 1 atm
pressure.
The standard reaction entropy for any reaction is the
difference between the entropy of the reactants in
their standard states and the entropy of the products in
their standard states:
ΔSϴ = S ϴ (products) - Sϴ (reactants)
Worked Example: Calculate the standard reaction
o
entropy for the synthesis of 2 mol NH3 (g) at 25 C in
the reaction
N 2(g) + 3H2(g) = 2NH3(g)
Solution: The reaction is
N2(g) + 3H2(g) = 2NH3(g)
The standard reaction entropy is therefore
ΔSϴ = Sϴ(products) - Sϴ(reactants)
ΔS = 2 × S (NH3,g) -[1 × S (N2,g) + 3 × S (H2,g) ]
o o o o

= 2 × 192.5 J/K – (191.6 + 3 × 130.7 J/K)

= -198.7 J/K
The second law of thermodynamics: A spontaneous
change is accompanied by an increase in the total
entropy of the universe.
• The total entropy change, the sum of the changes in the
system and its surroundings, is
Δ Stotal = ΔS + ΔSsurr
ΔS is the change in the system
But ΔSsurr = - ΔH/T
ΔStotal = ΔS - ΔH/T
-T ΔStotal = ΔH – T ΔS
Gibbs free energy, G = H - TS
When a process takes place at constant temperature, the
resulting changes in enthalpy and entropy produce a
change in free energy of
ΔG = ΔH – T ΔS
Thus -T ΔStotal = ΔG
The standard reaction free energy ΔGϴ for a reaction is the
difference between the free energy of the products and that
of the reactants in their standard states:
ΔGϴ = G ϴ(products) - G ϴ(reactants)
• The standard free energy of formation ΔGϴf of a compound
is the standard reaction free energy per mole for its
formation from its elements.
Worked Example: To calculate the standard Gibbs energy of
the reaction
CO (g) + ½ O 2 (g) → CO 2 (g) at 25 oC
Solution:
｛ ｝
ΔrGϴ = ΔGϴf (CO2,g) - ΔGϴf (CO,g) + ½ ΔGϴf (O 2,g)
｛ ｝
= -394.4 kJ mol -1 - (-137.2) + ½ (0) kJ mol-1
= -257.2 kJ mol -1
OXIDATION-REDUCTION REACTIONS
• Oxidation-reduction reactions or redox reactions involve the
transfer of electrons from one species to another.
• The species which loses electrons is said to be undergoing
oxidation and it is referred to as a reductant or reducing
agent. Oxidation leads to an increase in oxidation number.
• O I L–O x i d a t i o n I s L o s s o f e l e c t r o n s .
• The species which gains electrons is said to be undergoing
reduction and it is referred to as an oxidant or oxidising
agent. Reduction leads to a decrease in oxidation number.
• R I G–R e d u c t i o n I s G a i n o f e l e c t r o n s .
• The oxidation and reduction steps take place simultaneously,
and the total number of electrons lost in the oxidation step
being equal to that gained in the reduction step.
Oxidation number
• The oxidation number of an element indicates the
number of electrons lost, gained, or shared as a
result of chemical bonding.
Rules for Assigning Oxidation Numbers
• The oxidation number of an atom in the elemental state is
zero.
• The oxidation number of a monatomic ion is equal to its
charge.
• The algebraic sum of the oxidation numbers in the formula
of a compound is zero.
• The oxidation number of hydrogen in a compound is +1,
except when hydrogen forms compounds called hydrides
with active metals, and then it is -1.
• The oxidation number of oxygen in a compound is -2, except
in peroxides when it is -1, and when combined with fluorine
it is+2.
• The algebraic sum of the oxidation numbers in the formula
for a polyatomic ion is equal to the charge on that ion.
• Note: Some elements can exhibit several different oxidation
states.
Balancing redox reactions (Half-reaction method or
Ion-electron method)
• In this method, the oxidation and reduction steps
of the redox reactions are considered separately.
• Determine the oxidation and reduction steps.
• Proceed to balance the two equations obtained
separately in the following manner.
• If the reaction is taking place under acidic
conditions, then to the side of the equation which
has an excess of oxygen atoms, add two H + for
every oxygen atom in excess and balance this with
one molecule of H2O on the opposite side.
• If the reaction is taking place under alkaline
conditions, then for every oxygen atom in excess,
add one molecule of H 2O to the same side and
balance this with two OH- ions on the other side of
the equation.
• Balance the rest of the atoms present and check for
electrical balance as well.
• Multiply the two balanced equations by numbers
such that the number of electrons lost in the
oxidation step equals the number of electrons
gained in the reduction step.
• Add the modified equations, cancelling terms
common to both sides of the final equation.
CHEMICAL ANALYSIS
This is the resolution of a chemical compound into its
proximate or ultimate parts i.e the determination of its
elements or the foreign substances it may contain.
There are basically two types of chemical anaysis
1. Qualitative analysis: This deals with the determination of
the constituent or constituents in a sample.
2. Quantitative analysis: This deals with the determination
of how much of a given substance is in a sample.
Types of Analysis:
There are important factors needed to be considered when
selecting the method of analysis:
1. the essence of the information needed
2. the amount of sample available & the proportion of the
constituent to be determined
3. The purpose of which the analytical data are required.
The different types of chemical analysis are:
1. Proximate analysis: In this method the amount of each
sample is determined with no concern as to the actual
compounds present
2. Partial analysis: This deals with the determination of
selected constituents in the sample
3. Trace constituent analysis: This is a specialised instance of
partial analysis where the interest is in determining
specialised components in minute quantity
4. Complete Analysis: In this method, the proportion of each
component of the sample is determined
Common Techniques
In quantitative inorganic analysis, the main techniques
involved are:
1. The quantitative performance of suitable chemical
reactions and either measuring the amount of reagent
needed to complete the reaction, or ascertaining the
amount of reaction product obtained
2. Appropriate electrical measurements ( e.g potentiometry)
3. The measurement of certain optical properties (e.g
absorption spectra)
4. A combination of optical or electrical measurements and
and quantitative chemical reaction (e.g amperometric
titration).
Gravimetric Analysis:
• This involves the selective separation of the analyte by
precipitation followed by the weighing of the precipitate.
In this method, the substance being determined is
converted into an insoluble precipitate which is collected
and weighed.
• The principle behind gravimetric analysis is that the mass
of an ion in a pure compound can be determined and then
used to find the mass percent of the same ion in a known
quantity of an impure compound.
• In order for the analysis to be accurate, certain conditions
must be met:
i. The ion being analyzed must be completely precipitated.
ii. The precipitate must be a pure compound.
iii. The precipitate must be easily filtered.
• In the case of electrogravimetry, electrolysis is carried out
and the material deposited on one of the electrodes is
weighed.
• A typical example of a gravimetric analysis is the
determination of chloride in a compound. The first process
is to find a cation that forms an insoluble compound with
chloride. Typical cations are Ag +, Pb 2+, and Hg 22+ . These
cations form insoluble chlorides and can be easily filtered.
E.g Ag+(aq) + Cl-(aq) AgCl(s)
Titrimetric (Volumetric) Analysis:
• In this method, the substance to be determined is allowed
to react with an appropriate reagent which is added as
standard solution. The volume of the solution needed for
complete reaction is determined.
• Reactions which employ this method include:
a) neutralisation (acid-base) reactions;
b) complex-forming reactions;
c) precipitation reactions; oxidation-reduction reactions
Volumetry is concerned with measuring the volume of gas
evolved or absorbed in a chemical reaction.
Electrical methods involve the measurement of current,
voltage or resistance in relation to the concentration of a
certain species in solution.
Examples include; voltametry (measurement of current at a
micro-electrode at specified voltage); coulometry
(measurement of current and time needed to complete an
electrochemical reaction or generate sufficient material to
react completely with a specified reagent; potentiometry
(measurement of the potential of an electrode in
equilibrium with an ion to be determined; conductimetry
(measurement of the electrical conductivity of a solution).
Optical methods: these are dependent on:
1. The absorption of radiant energy and the measurement
of the amount of a particular wavelength absorbed by the
sample
2. The emission of radiant energy and the measurement of
the amount of energy of a particular wavelength emitted.
Absorption methods are classified according to the
wavelength involved as:
a. Visible spectrophometry (colorimetry)
b. Ultraviolet spectrophometry
c. Infrared spectrophotometry
Atomic Absorption Spectroscopy:
• Atomic absorption analysis involves measuring the
absorption of light by vapourised ground state atoms and
relating the absorption to concentration. The incident light
beam is attenuated by atomic vapour absorption according
to Beer’s law.
• The law states that the amount of light emerging from a
sample is diminished by three physical phenomena:
a. The amount of absorbing material in its pathlength
(concentration)
b. The distance the light must travel through the sample
(optical pathlength, b)
c. The probability that the photon of that particular
wavelength will be absorbed by the material (absorptivity
or extinction coefficient, ε)
Beer Lamberts Law , A = ε b c
A = absorbance (-)
ε = molar absorptivity with units of L mol-1 cm -1
b = path length of the sample (cuvette)
c = Concentration of the compound in solution, expressed
in mol L-1
Deviation of Beer Lambert law
1. Deviations in absorptivity coefficients at high
concentrations (> 0.01M) due to electrostatic interactions.
2. Scattering of light due to particulates in the sample
3. Fluoresecence or phosphorescence of the sample
4. Changes in refractive index at high analyte concentration
5. Non-monochromatic radiation
If the sample concentration is too high to permit accurate
analysis in linearity response range, there are three
alternatives that may help bring the absorbance into the
optimum working range:
1) sample dilution
2) using an alternative wavelength having a lower absorptivity
3) reducing the path length by rotating the burner hand.
• The process of atomic absorption spectroscopy (AAS)
involves two steps:
1. Atomization of the sample
2. The absorption of radiation from a light source by the
free atoms
• The sample which is either a liquid or a solid is atomized in
either a flame or a graphite furnace. Hence upon the
absorption of ultraviolet or visible light, the free atoms
undergo electronic transitions from the ground state to
excited electronic states.
Atomic Emission Spectroscopy: This involves the submission
of a sample to heat or electrical treatment so that atoms
are raised to excited states causing them to emit energy.
The intensity of the emitted energy is then measured.
Some of the common techniques are:
a. Emission Spectrography; this involves subjecting the
sample to an electrical arc or spark and the light emitted
is examined.
b. Flame photometry: A solution of the sample is injected
into a flame and the light emitted is investigated.
Fluorimetry: In this method a suitable substance in solution
is (commonly a metal-fluorescent reagent complex) is
excited by irradiation with visible or ultraviolet radiation,
and the characteristic emitted radiation is then examined.
Instrumental Methods: These are methods dependent on
the measurement of an electric property and those based
upon determination of the extent to which radiation is
absorbed or upon assessment of the intensity of emitted
radiation.
CHROMATOGRAPHY
• This is the process through which constituents of a mixture
are separated and analyzed by physical means through an
adsorption or partition process.
• Chromatography is based on two principles; the ability of
different organic molecules to (i) adsorb onto a surface to
different degrees and (ii) to partition between two phases
to different degrees.
• Chromatographic methods depend on the use of two
phases; a stationary and a mobile phase.
• Separation of components in a mixture depend on the
movement of the mobile phase relative to the stationary
phase, and the extent to which the individual components
are held by the stationary phase.
• Chromatographic can further be classified into two general
classes:
a. for separation of lipophilic (fat loving) substances and
b. Hydrophilic (water loving) substances
• If the stationary phase is a solid the process is called an
adsorption chromatography. In this technique the
separation depends on the distribution ratio of the
solutes between the mobile and the stationary phases.
• If the stationary phase is a liquid it is called partition
chromatography. In this technique, the extent of
separation depends on the difference in the partition
coefficients of the various solute components.
• However, in ion-exchange chromatography the separation
does not depend strictly on either partition or adsorption.
Types of Chromatography
Chromatography techniques are roughly classified on the
basis of purpose for which they are used and the methods
involved. Some examples include:
a. Column chromatography
b. Paper chromatography
c. Thin layer chromatography
d. Ion-exchange chromatography
e. Gas chromatography
Column Chromatography: This is an example of adsorption
chromatography. In this method, the stationary phase or
adsorbent is usually a solid (alumina or silica gel). The
column usually comprises of a glass tube and a tap at the
end. A solution of the impure substance is introduced at
the top of the column and the solvent run over it. The
components are separated based on their adsorption rates.
Paper Chromatography: This method involves the use of
strips of filter paper. The stationary phase is the moisture
in the paper and separation depends on the differential
partition of the solute between the stationary water phase
and the mobile chromatographic solvent.
Thin layer chromatography: In this method, the adsorbent
(silica gel or alumina) is made into a slurry with water and
applied as a thin film on glass plates.
The plates are activated by heating at about 100 to 250 oC.
The material to be purified is applied to the plate and the
separation of individual components occurs as the mobile
phase percolates through the stationary phase.
Ion-exchange chromatography: In ion-exchange
chromatography, an insoluble high molecular weight
polymer in the form of organic resins containing an ionic
group is used as the ion-exchanging material. The
exchange group can be cationic or anionic.
Gas chromatography: This is a technique for separating
chemical substances that relies on differences in
partitioning behavior between a flowing mobile phase and
a stationary phase to separate the components in a
mixture. The sample is carried by a moving gas stream
(mobile phase) through a tube packed with a finely divided
solid or liquid (stationary phase).