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