CH-109

APPLIED CHEMISTRY

DR. SABAHAT SARDAR

DEPARTMENT OF BASIC SCIENCES AND HUMANITIES
CEME, NUST
 THERMOCHEMISTRY

Chemical Thermodynamics
Hess’s Law
Heat of formation and reaction
Relation between H and U
Measurement of heat reaction
Bomb calorimeter
“IT IS THE BRANCH OF SCIENCE WHICH QUANTITATIVELY DEALS
WITH ENERGY CHANGES THAT ACCOMPANIED DURING CHEMICAL
& PHYSICAL PROCESS.”

1. Thermo-chemistry: It is the study of thermal changes

accompanied with chemical changes during chemical reactions.
It deals with heat of reaction & spontaneity of reaction. The
amount of energy released or absorbed in a particular chemical
reaction could be determined from the energies of other reactions
over a broad range of temperature on the basis of the first law of
thermodynamics. The second law of thermodynamics provides us
with the means of predicting the direction of chemical change.
2. Thermo-mechanics:
It do the “accounting” of energy transfers (heat flow or work flow) from one
body or substance to another body, or from one form of energy to another.
it deals with co-relation of heat & work flow with physical changes like
compression or expansion of gases, change of phases etc.
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.
1. 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 + ΔSsurronding) = 0 (equilibrium)

ΔStotal = (ΔSsystem + ΔSsurronding) < 0 (non-spontaneous process

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. So0 = 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.
Heat of Reaction:
“The quantity of heat transferred into or out of a system as it
undergoes one mole of reaction i.e. all specified number of moles of
reactants in an empirically balanced thermochemical equation, are
converted completely to the specified number of moles of products
in that empirically balanced equation, all at standard states under
standard conditions i.e. 25 oC and one atmosphere pressure”.
OR “It is enthalpy change when one mole of reaction is completed,
all at standard states under standard condition”. or “Difference in
standard enthalpies of reactants & products of empirically balanced
thermo-chemical equation”.
ΔHorxn = Hofinal - Hoinitial or ΔH = Hoproduct - Horeactant
Enthalpy is a state function so enthalpy change depends upon
enthalpies of reactants and products and not on mechanism of
reaction. Its units are energy / mol.rxn or KJ/ mol. The physical
states of all species are important when ΔHrxn is reported.
 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.
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.
 Standard Heat of formation ΔHof: The enthalpy change
takes place when one mole of a compound is formed in its standard
state from it constituents elements in their respective standard
states under standard conditions i.e. 25oC & 1atm pressure.
Fe(s) + S(s) FeS(s) ΔHof = -24 Kcal
2C(s) + H2(g) C2H2(g) ΔHof = +5314 Kcal
H2(g) + Cl2(g) 2HCl(g) ΔH = -44 Kcal ≠ Hof
½H2(g) + ½ Cl2(g) HCl(g) ΔHof = -22 Kcal
By convention the standard Heat of formation of all elements in
their most stable state is assumed zero e.g. ΔHof Pb(s) = 0 KJ/mol.
ΔHof is zero for O2 but not for O and O3, similarly ΔHof is zero for
Br2 liquid but not for Br2 gas.
Standard heat of reaction can be calculated from the values of ΔHof
of its reactants & products.
ΔHorxn = Σ ΔHof (product) - Σ ΔHof (reactant)
Heat of Combustion: “The change in enthalpy of a system
when one mole of the substance is completely burnt in excess of air
or oxygen”. It is denoted by ΔHc e.g.
CH4(g) + 2O2(g) CO2(g) + 2H2O(I) ΔHc = -21.0 kcal mole-1
Or = -87.78 KJ mole-1
C (s) + O2 (g) CO2 (g) ΔHc = -94.3 kcal mole-1
C (s) + ½ O2 (g) CO (g) ΔH = -26.0 kcal mole-1
It may be noted that -94.3 kcal and not -26.0 kcal is the heat of
combustion of carbon as the combustion is complete only in the
first reaction. In the second case, oxidation has converted carbon to
carbon monoxide and is by no means complete as carbon
monoxide can be further oxidized to carbon dioxide.
It should be noted clearly that the heat of combustion of a
substance (ΔHc) is always negative. Heat energy is evolved during
the process of combustion i.e. ΔHc = -ve.
 NUMERICAL
Calculate the standard heat of formation of propane (C3H8) if
its heat of combustion is -2220.2 kJ mole-1. The heats of
formation of CO2(g) and H2O(g) are -393.5 kJ and -285.8 kJ
mol-1 respectively.
Solution:
We are given
(i) C3H8 (g) + 5O2(g) 3CO2(g) + 4H2O(l) ΔHc = -2220.2 kJ mole-1
(ii) C (s) + O2(g) CO2(g) ΔHc = -393.5 kJ mole-1
(iii) H2(g) + ½ O2 (g) H2O(l). ΔHc = -285.8 kJ mole-1
We should manipulate these equations in a way so as to get the
required equation.
3C (s) + 4H2(g) C3H8(g) ΔH = ?
Multiplying equation (ii) by 3 and equation (iii) by 4
3C (s) + 3O2(g) 3CO2(g) ΔHc = -1180.5 kJ mole-1
4H2(g) + 2O2 (g) 4H2O(l) ΔHc =-1143.2 KJ mole-1

(iv) 3C(s) + 4H2(g) + 5O2(g) 3CO2(g) + 4H2O(l) ΔH = -2323.7 kJmole-1

Subtracting equation (i) from equation (iv) , we have

3C(s) + 4H2(g) + 5O2(g) - C3H8 (g) - 5O2(g)

3CO2(g) + 4H2O(l) - 3CO2(g) - 4H2O(l)

ΔHf = -2323.7 kJ mole-1 – (-2220.2 kJ mole-1)

3C(s) + 4H2(g) C3H8 (g) ΔHf = -103.5 kJ mole-1

The heat of formation of propane is -103.5kJ mole-1.

3(-393.5) + 4(-285.8) = -2220.2 + x
x = -103.5 KJ/mol
Bomb Calorimeter: