CH-102
Fundamentals of CHEMISTRY
DR. SABAHAT SARDAR
DEPARTMENT OF BASIC SCIENCES AND HUMANITIES
CEME, NUST
PHYSICAL CHEMISTRY
Chemical Equilibrium
Kinetics
Thermodynamics
Reversible Vs Irreversible
1. Exothermic reactions:
“Those reactions which are accompanied by the evolution of heat
energy are called exothermic reaction”.
In exothermic reaction enthalpy of chemical system decreases i.e.
product’s enthalpy is less than reactant’s enthalpy so ΔH < 0 or - ΔH
H2(g) + ½ O2(g) H2O (l) ΔHo298 = -285.83 KJ
C(s) + O2(g) CO2(g) ΔHo298 = -393.5 KJ
2. Endothermic reactions:
“Those reactions which are accompanied by the absorption of heat
energy are called endothermic reactions”.
In endothermic reaction enthalpy of chemical system increases i.e.
product’s enthalpy is more than reactant’s enthalpy (ΔH > 0 or + ΔH)
½ Br2(l) + ½ Cl2(g) BrCl(g) ΔHo298 = 14.64 KJ
Activation Energy: “Minimum amount of energy, which is required
by reactant/s to undergo a chemical reaction i.e. to convert into product/s.”
According to transition state theory. In a chemical reaction, during collision,
the reactant molecules form a transition state or activated complex which
then decompose to give products.”
A + B C [ A B C] A B + C
Reactants Activated Complex Products
When potential energy of a system undergoing reaction is plotted against
the reaction progress coordinate then difference in the potential energy
between the reactants & activated complex is called activation energy.
Kinetics of a chemical reaction
The catalyst functions by providing another pathway with lower
energy barrier, so a large proportion of collisions become effective
thus reactions go faster. Although catalyst lowers the activation
energy but the energy difference between products and reactants
(ΔE) remain the same.
“ Thermodynamics is the study of heat & its transformation.
IT IS THE BRANCH OF SCIENCE WHICH QUANTITATIVELY
DEALS WITH ENERGY CHANGES THAT ACCOMPANIED
DURING CHEMICAL & PHYSICAL PROCESS.”
Thermo-chemistry: branch of thermodynamics, deals with heat
involved in chemical reaction.
All changes in matter - accompany by changes in the energy/heat
content of the matter.
1. Snow melts - energy is absorbed
2. H2O vapor condenses to rain -
energy is release
First law of thermodynamics/ law of conservation of energy
”The total amount of energy in the universe (system & its surrounding) is
constant.” or
“Energy is neither created nor destroyed in ordinary chemical reactions and
physical changes” or
A mathematical statement of the first law is that
“The change in the internal energy of a system (ΔE) is equal to the sum of
the work done on / by the system (w) and the heat flowing out / into the
System (q).
ΔE = E2 – E1 = q + w
ΔE is a state function and q & w are not state functions. ΔE is independent
of the path, while the manner in which it is apportioned between q & w
depends on the particular path. When energy is transferred to a system
from it surroundings then ΔE & q + w are positive quantities. While when
energy is transferred from the system to the surroundings; ΔE & q + w are
negative. When the system is isolated i.e. no q + w flow between system &
surrounding then ΔE & q + w are zero.
Entropy: “Entropy is a thermodynamic state function quantity
which is measure of the randomness or disorder of the molecules of the
system at particular temperature”.
The symbol of entropy is S, while usually change in entropy accompanying
a process from start to completion is reported which represented by ΔS.
ΔS = Sfinal - Sinitial
ΔS = q T = Temperature in Kelvin
T
Its units are cal mol-1 K-1 or J mol-1 K-1
If heat is absorbed (+q) then ΔS is positive and entropy will be
increased as energetic particles vibrate more vigorously cause more
disorderness & vice versa. For any substance, the particles are more
highly ordered in the solid state than in liquid state and more in liquid
state than in gaseous state. So Entropy increased as degree of freedom
or roaming is increased.
Gas > Liquid > Solid , Amorphous solid > Crystalline solid
Same heat amount input will cause more disorderness (ΔS) at low
temperature & less at higher temperature.
Second law of thermodynamics:
“In a spontaneous process, the total entropy of a system plus its surroundings
increases” or
“In spontaneous process, universe tends towards a state of greater disorder”
ΔStotal = (ΔSsystem + ΔSsurronding) > 0 (spontaneous process)
ΔStotal = (ΔSsystem + ΔS = 0 (equilibrium)
surronding)
ΔStotal = (ΔSsystem + ΔS < 0 (non-spontaneous process
surronding)
but reverse is spontaneous)
The idea of entropy, order and
disorder are related to probability.
The more ways an event can
happen, the more probable that event
is. As orderly arrangement has only
one way so it has less probability but
disorder can occur in a number of
ways so more probability i.e. disorder
in universe is increasing.
Applications:
When a liquid substance is placed in
surrounding temperature below than
its freezing point then it spontaneously
solidified although ΔS system is
negative b/c heat released and solid
forms from its liquid but ΔS
surrounding is positive b/c heat add
into surrounding. Although same
amount of heat transfer involved b/w
system & surrounding but it caused
more disorder in surrounding than
extent of order bring into system b/c
surrounding is at lower temperature
than system.
The situation is reversed when a solid
substance is placed in surrounding at
temperature higher than it M.P. Now
melting is spontaneous as ΔSsystem is
more positive than ΔSsurrounding is
negative.
Third law of thermodynamics:
“The entropy of a pure, perfect
crystalline substance (perfectly ordered)
is zero at absolute zero (0K)
temperature”.
Third law of thermodynamics establishes a
reference state for absolute entropy by
specifying zero of entropy scale. At
absolute zero temperature, all thermal
disorder has been quenched off from a
substance and, in the case of perfect
crystal i.e. crystal with no imperfections, the
atoms or molecules are in a completely
ordered state. So it is believed that all
elements and compounds which form
perfect crystals possess the same entropy
at 0K thus it is convenient to set the value
to zero i.e. So 0 = 0.
Hess’s law of heat summation:
The enthalpy change for a reaction is the same whether it
occurs by one step or by any series of steps. Enthalpy is a
state function. Its change is therefore independent of the
pathway by which a reaction occurs.
This law is an application of first law of thermodynamics to
chemical reactions e.g. enthalpy of combustion for graphite to form
CO2 is same whether it occurs by complete oxidation in a single
step or by partial oxidation in two steps.