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The third law of thermodynamics is sometimes stated as follows: The entropy of a

perfect crystal of any pure substance approaches zero as the temperature approaches absolute
zero. At zero temperature the system must be in a state with the minimum thermal energy.
Nernst heat theorem
The Nernst heat theorem says that as absolute zero is approached, the entropy change S
for a chemical or physical transformation approaches 0. This can be expressed mathematically as
follow

The above equation is a modern statement of


the theorem. Nernst often used a form that avoided
the concept of entropy.
Another way of looking at the theorem is to
start with the definition of the Gibbs free energy (G),
G = H - TS, where H stands for enthalpy. For a change
from reactants to products at constant temperature
and pressure the equation becomes

Graph of energies at low temperatures

In the limit of T = 0 the equation reduces to just G = H, as illustrated in the figure


shown here, which is supported by experimental data. However, it is known
from thermodynamics that the slope of the G curve is -S. Since the slope shown here reaches
the horizontal limit of 0 as T 0 then the implication is that S 0, which is the Nernst heat
theorem. The significance of the Nernst heat theorem is that it was later used by Max Planck to
give the third law of thermodynamics, which is that the entropy of all pure, perfectly crystalline
homogeneous materials is 0 at absolute zero.

PHASE RULE
The phase rule seeks to explain the equilibria existing in heterogeneous systems. It may
be stated as: "provided the equilibrium between any number of phases is not influenced by
gravity, or electrical, or magnetic forces, or by surface action and only by temperature,
pressure and concentration, then the number of degrees of freedom (F) of the system is related
to the number of components (C) and of phases (P) by the phase rule equation,
F=CP+2
for any system at equilibrium at a definite temperature and pressure."
Explanation of terms: (1) Phase: A phase is defined as "a homogeneous, physically distinct
and mechanically separable portion of system, which is separated from other such parts of the
system by definite boundary surfaces".
(2) Component: The term component is meant by "the smallest number of independent
variable constituents, taking part in the state of equilibrium, by means of which the composition
of each phase can be expressed in the form of chemical equation".
(3) Degree of freedom or variance: The term degree of freedom is meant by "the
minimum number of independently variable factors, such as temperature, pressure and
composition of the phases, which must be arbitrarily specified in order to represent perfectly
the condition of a system".
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ELECTRONIC THEORY OF VALENCY


The salient features of the electronic theory of valency are:
(i) The valency of an element depends upon the number of electrons in the outermost
orbit and these, are called "valency electrons". The remainder of the atom, excluding the
valence electrons, is called kernel of the atom.
(ii) Atoms of elements with 8 (or 2, if there is one orbit only) electrons in their valency
orbits are stable.
(iii) The atoms of other elements do not have a stable or inert gas electronic
configurations. They have a tendency to take part in chemical combinations, so that they may
also acquire a stable inert gas configurations with eight electrons (duplet, if one orbit only) in
their outermost shells. This may be either: (a) by the transference (gain or loss) of one or more
electrons from atom of one element to atom of another element, or (b) by the sharing of
electrons between the atoms.
According to their mode of formation, bonds may be classified as: (i) Ionic bond; (ii)
Covalent bond; (iii) Coordinate bond, and (iv) Metallic bond. In addition, there can be attractive
interactions, known as hydrogen bond and Vander Waals interactions.

Chemical Bonds - hold the atoms of elements together in a compound. Chemical bonds range
from covalent to ionic.

IONIC OR ELECTROVALENT BOND


An ionic bond is formed by the complete transference of one or more electrons from the
outermost energy shell (called, valency shell) of one atom to outermost energy shell of another
dissimilar atom, so that both acquire stable inert gas configurations. The atom which loses the
electrons becomes a positive ion (cation); while the other atom which gains electrons becomes
a negative ion (anion). These two oppositely charged ions combine, due to electrostatic forces of
attraction, to form an electrovalent or ionic compound.
Ionic bonding is a type of chemical bond that involves the electrostatic attraction
between oppositely charged ions. These ions represent atoms that have lost one or more
electrons (known as cations) and atoms that have gained one or more electrons (known as an
anions).
Conditions for the formation of ionic bonds: Formation of an ionic bond depends
upon ionization energy and electron affinity involved. One of the atoms should have low
ionization energy, so that only a small amount of energy is required to pull out an electron
from its outermost energy level. On the other hand, the other atom should have a high
electron affinity, so that it can readily accept an electron(s) in its outermost energy level.
Ionic Compounds - Electrons are transferred from one atom to another to form ionic
compounds, i.e. NaCl, MgCl2, CaO, etc.
Ionic compounds made up of anions and cations.
Cations - Atoms lose electrons to form + ions.
Anions - Atoms gain electrons to form - ions.
Ionization energy (E) of an element is defined as the energy required to remove the
most loosely bound electron from an isolated atom in the gaseous state, resulting in the
formation of a positive ion. Evidently, the smaller the value of ionization energy (E), the easier
is for the neutral atom to form cation. It is expressed in terms of either kcal/mol or kJ/mol or
electron volt/atom. The magnitude of ionization energy for an atom depends upon the factors:
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1.) Size of the atom: Ionization energy decreases with increase in atomic size.
2.) Charge on the nucleus: Ionization energy increases with increase in nuclear charge.
3.) Number of electrons: Ionization energy decreases with increase in number of electrons.
4.) Electronic arrangement: The more stable the electronic configuration, the greater is
the ionization energy.
Electron affinity gives a measure of the tendency of an atom to form anion. Just as
energy is required to remove an electron from an atom, energy is released when an electron is
added to a neutral atom. It is defined as the energy released, when a neutral atom in the gaseous
state takes up an extra-electron to form a negatively charged ion. Thus, electron affinity of an
atom measures the tightness with which it binds an additional electron to itself. It is expressed
in terms of kJ/mol.
Properties of ionic compounds:
(1) They are non-directional and cannot exhibit isomerism.
(2) They are non-conductor in solid state.
(3) They are conductor of electricity in molten state and in dissolved form in water.
(4) They are soluble in polar solvents (e.g., water), but insoluble in non-polar solvents
(e.g., benzene, CCl4).
(5) They possess high melting point and boiling point.
(6) They give ionic reactions.
(7) In solid state, each ion is surrounded by a definite number of oppositely charged ions.
(8) Their binding energy is very high.

COVALENT BOND
Covalent bond is formed by sharing of electrons in pairs between two atoms, both of
which make equal contribution of electrons. When each atom contributes one, two, or three
electrons such that two, four, or six electrons are shared in all, the union so-set up, is called single
or double or triple covalent linkage or bond respectively.
Covalent Compounds - Electrons are shared between atoms of different elements to
form covalent compounds (or molecules), i.e. H2, Cl2, N2, O2 etc.
A covalent bond is a chemical bond that involves the sharing of electron pairs between
atoms. The stable balance of attractive and repulsive forces between atoms when they share
electrons is known as covalent bonding.
Electro-negativity of the atom is defined as the ability of an atom to attract the shared
electrons pair towards itself. The greater the difference in electro-negativities of the two atoms
involved in covalent bonding, greater is the ionic character of the bond formed. Different atoms
have different tendencies to attract the bonding electron pair towards themselves. Greater the
ability of an atom to attract electrons in a bond, larger is the value of its electro-negativity. The
extent of the ionic character in a covalent bond depends on the relative attraction for electrons of
the bonded atoms.
Properties of covalent compounds:
(1) They are directional in nature.
(2) Their melting point and boiling point are low.
(3) They are non-conductor of electricity in fused as well as dissolved state.
(4) They are soluble in organic solvent, but, generally insoluble in water.
(5) They are non-polar in nature.
(6) They may exhibit isomerism.
(7) Their reactions are non-ionic in nature, involving molecules rather than ions.

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COORDINATE OR DATIVE BOND


It is special type of covalent bond in which the shared electrons are contributed by one
atom only; while the other atom accepts their sharing without any contribution of electrons.
Thus, coordinate valency involves one-sided sharing of electrons. The atom which contributes
electron-pair (called lone-pair) for sharing is called the donor; while the other atom which shares
these, is called accepter.

HYDROGEN BOND
When hydrogen atom is covalently bonded to a strongly electronegative and small-sized
atom (such as nitrogen, oxygen and fluorine), the shared electron pair between the hydrogen
atom and the strongly electronegative atom lies much more nearer to the electronegative atom.
This consequently, results in the development of partial ionic character in the covalent bond,
with a fractional positive charge on the hydrogen atom, and a fractional negative charge on the
electronegative atom. This attractive force between hydrogen atom and electronegative atom
leads to the formation of a weak bond, called hydrogen bond or Hydrogen Bridge.
Thus, the attractive force which binds hydrogen atom of one molecule with
electronegative atom (such as F, N, O) of another molecule of the same substance, is known as
hydrogen bond. The hydrogen bond may be:
(1) Intermolecular, i.e., involving the electrostatic forces of attraction between
hydrogen atom and an electronegative element of two different molecules.
(2) Intramolecular, i.e., involving the electrostatic force of attraction between
hydrogen atom and an electronegative atom, both present in the same molecule.

HEISENBERG'S UNCERTAINTY PRINCIPLE


However, in the case of moving small particle (e.g., electron), its position and velocity at a
given instant cannot be determined with absolute velocity. Consequently, we cannot talk of
trajectory of a moving electron. Werner Heisenberg (1927) put forward this fact in the form
of Heisenberg's uncertainty principle, which is a direct consequence of the dual nature of
matter and radiation. It states that "it is impossible to determine both position and momentum of
a body simultaneously with perfect accuracy".
Mathematical expression: An experiment can measure both position and momentum
only within certain limits of accuracy. These limits are specified by the uncertainty principle
(due to Heisenberg's), according to which - "Given an object, the error in position of the object
(no matter how small) multiplied by the error in momentum of the object (no matter how large
or how small) must be greater than or equal to Planck's constant divided by 4". Or
mathematically:

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PAULI EXCLUSION PRINCIPLE


On the basis of wave mechanics, Wolfgang Pauli (a German physicist) in 1925 put
forward Paulis exclusion principle in order to explain the atomic spectra and atomic
structure of certain elements. It state that "two electrons in the same atom cannot have set of all
the four quantum numbers identical". In other words, two electrons in the same atom can have
upto three quantum numbers identical, but the fourth is always different.
Explanation: The four quantum numbers of an electron identify the electron in an atom.
So it follows that if all the four quantum numbers of two electrons in the same atom are identical,
then the two electrons would become indistinguishable. Hence, in the same atom, two electrons
may have at the most three quantum numbers identical, but the fourth quantum number must be
different.
Application: By applying the exclusion principle, the maximum number of electrons that
can exist in any quantum shell (or major energy level) can be computed. According to this rule
"the number of electrons that can enter each energy level is equal to the number of sets of
combinations of values of the four quantum numbers".

VALENCE BOND THEORY FOR COVALENCE


Heitler and London concept:
(i) For the formation of a covalent bond, two combining atoms must come closer to each other so
that the orbital of one overlaps with that of the other.
(ii) Overlapping orbitals must have: (a) unpaired electron, (b) antispin electrons.
(iii) Due to overlapping, a new localized bond orbital is formed, in which the probability of
finding electron pair is maximum.
(iv) Formation of covalent bond is due to:
(a) Electrostatic attraction between nuclei and the so-accumulated electron clouds,
(b) Attraction between spins of antispin electrons.
(v) Greater the extent of overlapping more will be the attraction, bond energy and stability of
bond.
(vi) Greater the overlapping, lesser is the bond length.
Extension by Pauling and Slater:
(i) The extent of overlapping is dependent on:
(a) The nature of orbitals involved,
(b) type of overlapping.
(ii) More closer the valence shell to the nucleus, higher is the extent of overlapping and higher is
the bond energy.
(iii) Out of two sub-shells of same energy level, the one which is more directionally concentrated
shows higher extent of overlapping.
(iv) s-orbital, being spherically symmetrical, shows only head-on overlapping; while p-orbitals,
being directionally concentrated, show either head-on or lateral overlapping.
(v) When a bond is formed by overlapping of two half-filled orbitals along the internuclear axis
(i.e., the line passing through the centre of nuclei of the two atoms involved), it is known as
sigma bond (denoted by ). Sigma bond is a strong bond.
(vi) When a bond is formed by the sidewise overlap of two half-filled orbitals, it is called pibond (denoted by ). A -bond is a weak bond. A -bond shortens the internuclear distance.

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Amperometric titration refers to a class of titrations in which the equivalence point is


determined through measurement of the electric current produced by the titration reaction. It is
a form of quantitative analysis. In Amperometric titration current passes through the titration
cell between a polarisable electrode and non polarisable electrode is measured as function of
volume of titrant added.
The chief advantage over direct amperometry is that the magnitude of the measured
current is of interest only as an indicator. Thus, factors that are of critical importance to
quantitative amperometry, such as the surface area of the working electrode, completely
disappear from amperometric titrations.
The chief advantage over other types of titration is the selectivity offered by the electrode
potential, as well as by the choice of titrant. For instance, lead ion is reduced at a potential of 0.60 V (relative to the saturated calomel electrode), while zinc ions are not; this allows the
determination of lead in the presence of zinc. Clearly this advantage depends entirely on the
other species present in the sample.

ELECTROMERIC EFFECT
The electromeric effect (E effect) refers to the polarity produced in a multiple bonded
compound as it is approached by a reagent. Electromeric effect refers to a temporary polarization
between atoms in a multiple bond in the presence of an attacking reagent. The effect is temporary
and it will revert when the reagent is removed. When a double bond or triple bond is exposed to
an attack by a reagent, a pair of bonding electrons involved in the bond is transferred
completely from one atom to another. This effect will remain as long as the attacking reagent is
present. As soon as the reagent is removed, the polarized molecule will come back to the original
state.
Electromeric effect can be classified into +E and -E effects based on the direction of
transfer of the electron pair. When the electron pair moves towards the attacking reagent, it is
termed as the +E effect. The addition of acids to alkenes is an example of the +E effect. When the
electron pair moves away from the attacking reagent, it is termed as the -E effect. The -E effect
can be found in reactions such as addition of cyanide ion to carbonyl compounds.

HYPERCONJUGATION
In organic chemistry, hyperconjugation is the interaction of the electrons in a sigma
bond (usually CH or CC) with an adjacent empty (or partially filled) non-bonding porbital, antibonding or orbital, or filled orbital, to give an extended molecular orbital that
increases the stability of the system. Only electrons in bonds that are to the positively charged
carbon can stabilize a carbocation by hyperconjugation.
Unlike the electromeric effect which involves the transfer of electrons, hyperconjugation
involves the displacement of both and electrons. This type of effect is mainly seen in atoms
with a hydrogen atom on the -carbon atom attached to the unsaturated carbon atom i.e. (H-CC=C). Stability of the compounds such as alkenes can best be explained with the help of
hyperconjugation.

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ELECTRONIC CONFIGURATIONS AND TYPES OF ELEMENTS:


s-, p-, d-, f- BLOCKS
An electron in an atom is characterized by a set of four quantum numbers, and the
principal quantum number (n) defines the main energy level known as shell. The filling of
electrons into different subshells, also referred to as orbitals (s, p, d, f ) in an atom. The
distribution of electrons into orbitals of an atom is called its electronic configuration. An
elements location in the Periodic Table reflects the quantum numbers of the last orbital filled.
We can classify the elements into four blocks viz., s-block, p-block, d-block and f-block
depending on the type of atomic orbitals that are being filled with electrons.
The s-Block Elements
The elements in which the last electron enters the s-orbital of their outermost energy level
are called s-block elements. The elements of Group 1 (alkali metals) and Group 2 (alkaline
earth metals) which have ns1 and ns2 outermost electronic configuration belong to the s-Block
Elements. They lose the outermost electron(s) readily to form 1+ ion (in the case of alkali metals)
or 2+ ion (in the case of alkaline earth metals).Thus, the general electronic configuration of
s-block elements may be written as: ns1-2.
The p-Block Elements
The elements in which the last electron enters the p-orbital of their outermost energy
level are called p-block elements. The p-Block Elements comprise those belonging to Group 13
(IIIA) to 18 (VIIIA) and these together with the s-Block elements are called the Main Group
Elements. The outermost electronic configuration varies from ns2np1 to ns2np6 in each period.
Thus, the general electronic configuration of p-block elements may be written as:
2
ns np1-6.
The d-Block Elements (Transition Elements)
The elements in which the last electron enters the d-orbitals of their last but one energy
level are called d-block elements. These are the elements of Group 3 to 12 in the centre of the
Periodic Table i.e. between s-block and p-block elements. These are characterized by the filling of
inner d orbitals by electrons and are therefore referred to as d-Block Elements. In these elements,
the outermost shell contains one or two electrons in their s-orbitals but the last electron enters
the last but one d-sub shell, i.e. (n-1)d . They are all metals. Thus, the general electronic
configuration of d-block elements may be written as: (n-1)d1-10 ns0-2.
The f-Block Elements (Inner-Transition Elements)
The elements in which the last electron enters the f-orbitals of their atoms are called fblock elements. These consist of two series of elements placed at the bottom of periodic table.
The first series follows lanthanum and the elements present in the series are called
Lanthanides. The second series follows actinium and the elements present in the series are
called Actinides. Thus, the general electronic configuration of f-block elements may be
written as: (n-2)f 1-14 (n-1)d0-1 ns2.

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