CONTENTS

• Introduction
• Some thermodynamic terms: system, surrounding, boundary and types of
system (open, closed and isolated)
• Thermodynamic functions: State functions and Path functions
• Properties of system: Extensive properties and Intensive properties
• Exchange of energy between system and surrounding
• Internal energy
• IUPAC sign convention of heat and work
• First law of thermodynamics
• Enthalpy
• Enthalpy change for exothermic and endothermic reaction
• Enthalpy of combustion
• Enthalpy of formation
• Enthalpy of hydration/solution
• Enthalpy of neutralization
• Bond energy
• Hess's law
 Introduction
The branch of science which deals with study
of change in energy during the physical and
chemical processes is called energetics. It
deals with thermodynamics and kinetics of
reaction.
The change in energy during chemical
reaction is called energetics of chemical
reaction.
 Some thermodynamic terms:

 System
The part of the universe under thermodynamic study is called
system.
 Surrounding
The rest part of the universe except system is called
surrounding. It is also called environment.
 Boundary
An imaginary or real line which separates system from
surrounding is called boundary.

Universe= System+Surrounding
Fig.: Flask containing liquid showing system, surrounding and real boundary
Depending upon the nature of boundary, there
are three types of systems. They are:

1. Open system
A system which can exchange both heat as well as matter with
the surrounding is called open system. For eg.:

Fig.: Open flask containing liquid

2. Closed system
A system which can exchange only heat but not the matter
with the surrounding is called closed system. For eg

Fig.: Closed flask containing liquid

3. Isolated system
A system which can neither exchange neither heat nor matter
with surrounding is called isolated system. For eg.

Insulating material

Fig.: Flask conating liquid coated with insulating material

 Thermodynamic Functions

There are two different functions in

thermodynamics. They are:
1. State functions
2. Path functions
 State Functions
 The function whose value depend only upon the initial and
final states of the system but not on the path followed by the
system is called state functions. The change is state function is
given by the differences between final and initial states of
system.
Examples of state function: Pressure(P), Volume(V),
Temperature(T), Internal energy (E), Enthalpy (H), Entropy (S),
Gibb's free energy (G), Helmholtz free energy/Work function
(A) etc.
Suppose a system have enthalpy H1, when 'q' amount of heat
is given to the system, the final enthalpy becomes H2 . Then
the change in enthalpy is given by: △H = H2-H1
 EXAMPLES OF STATE FUNCTIONS:

Fig.: Path A and path B from Fig.: Change in temperature from

initial state to final state T1 to T2 depending on initial and
final states only
 Path Functions
• Those functions that depend upon the path by which the
system has achieved a particular state but not in initial and
final states are called path functions.
Examples of path functions: Heat (q), Work (w) etc.
• The change in path functions cannot be determined by the
difference between the initial and final states of the system.
For eg:
i.e. △W≠ W2-W1
Fig.: Workdone along two paths C and D (Here WD < WC )
 Properties of system
There are two properties of system:
1. Extensive properties
2. Intensive properties
 1. Extensive properties
• The property of a system that depends upon the quantity of
matter present in it is called extensive property. These
properties donot depend upon the nature of the substance.
• Examples of extensive properties: mass, number of moles,
area, volume, enthalpy, entropy, Gibb's free energy, heat
capacity etc.
 2. Intensive properties
• The property of a system that depends upon the nature
(quality) of the substance but not on the quantity of matter
present in it is called intensive property.
• Examples of intensive properties: viscosity, specific heat
capacity, temperature (melting and boiling points etc),
pressure, density, surface tension,refractive index etc.

The ratio of two extensive properties is intensive

property.
Figurative examples of extensive and intensive
properties
Exchange of energy between system and
surrounding
System and surrounding are in communication
with each other. The energy exchange
between them takes place in two different
forms:
1. Work
2. Heat
 1. Work
• If the system and surrounding are at two different pressures, then
exchange of energy between them takes place in the form of work.
• For eg., if internal pressure of gas is more than external pressure,
expansion of gas from initial volume (V1) to final volume (V2) takes place
against constant external pressure (P) unless both of them will have the
same pressure (equillibrum). In this case energy, is transferred from
system to surrounding in the form of work i.e. work is done by the
system.
Think...
What will happen if external pressure
is higher pressure than internal
pressure?? Will the gas expand or
contract???
Energy in the form of work...

• On the other hand, if the surrounding is at higher pressure,

the gas contracts and work is done on the system.
• In expansion or contraction, work done is given by:
W = P (V2-V1)
or, W = P△V where, P = opposing pressure
 2. Heat

• If the system and surrounding are at two different

temperatures, then exchange of energy between them takes
place in the form of heat.
• For eg.: if hot water in a vessel is kept at room temperature,
flow of heat takes place from hot water (system) to
surrounding until both of them will have the same
temperature.

Q. What will happen if ice is kept at room

temperature? Direction of heat flow?? Think...
 Internal Energy
• A thermodynamic system consists of atoms, ions or molecules. These
units have different forms of energy such as kinetic energy, potential
energy, chemical (bond) energy, rotational energy, vibrational energy
etc. The sum of different forms of energy associated with a system is
called internal energy. It is denoted by 'E' and given by:
E = K.E. + P.E. + B.E. + R.E. + V.E+.............
• Internal energy is a state function. So, change in internal energy with
the change in state of system is calculated as:
△E = E2 – E1
where, E2= internal energy of final state
E1= internal energy of initial state
• Internal energy is an extensive property.
 IUPAC Sign Convention of Heat and Work

1. Heat (q)
• If q = +ve; the reaction is endothermic [@endoP]. i.e. heat flows from
surrounding to system(energy of system increases)
• If q = -ve; the reaction is exothermic [@exoN]. i.e. heat flows from
system to surrounding (energy of system decrease)
2. Work (w)
• If w = +ve; the work is done on the system (contraction) (energy of
system increses)
• If w= -ve; the work is done by the system (expansion) (energy of
system decreases)
 First Law of Thermodynamics
Introduction:
• All natural and artificial changes occur with change in energy.
• During the change, there is transformation of energy from
one form to another form.
• First law of thermodynamics deals with the transformation of
energy.
First Law of Thermodynamics...

Statement:
• It states that, "The total energy of the isolated system (or
universe) remains constant though it may change from one
form to another." This law is also called law of conservation
of energy.
• It can also be stated as, "Energy can neither be created nor
be destroyed but it can be transferred from one form to
another." It means whenever a certain quantity of some form
of energy disappears, an exactly equivalent quantity of some
other form of energy must appear.
First Law of Thermodynamics...

Explanation:
• To explain this law, let us consider a systeem to which 'q'
amount of heat energy is supplied. Then, a fraction of
supplied energy is converted into internal energy (△E) i.e.
internal energy of the system increases from E1 to E2 while
another fraction is converted into work done (w) i.e. system
performs certain work. If the work done is expansion or
contraction work, it is given by, w =P△V at constant external
pressure (P), where △V is the change in volume from V1 to V2.
So, according to first law of thermodynamics, we can write:
q = △E + w.............................(i)
• For expansion or contraction work, we get:
q = △E + P△V.........................(ii) (since, w = P△V)
Above equation (i) and (ii) are the mathematical forms of first
law of thermodynamics.
First Law of Thermodynamics...

Special cases of the first law:

1. For an isothermal process
T = constant, △T = 0, △E = 0
 q=0+w
or, q = w
It means, the supplied energy is totally utilized to do work.
2. For an isochoric process
△V = 0 i.e. there is no expansion or contraction work.
 q = △E
It means , the supplied energy is totally utilized to increase
internal energy.
Note: Internal energy can also be defined as the total content
of heat at constant volume (Ev).
First Law of Thermodynamics...
3. For an adiabatic process
q=0
 - △E = w
or, - △E = P△V
• It means, work is done on the expense of internal energy i.e.
internal energy of the system decreases. It results cooling of
the system.
• In conclusion, total energy of the universe remains constant
however it permits the interconverssion of energy. This is the
significance of the first law of thermodynamics.

The major limitations of this law:

• It does not explain the direction of heat flow.
• It doesnot explain the spontaneity of a process.
 Enthalpy
• In general, thermal changes in lab are carried out at constant
external pressure rather at constant volume (sealed tube).
• During heat change of the gas, either expansion or
contraction work takes place. This work done is not
considered by internal energy. So, in order to include this
work, a more important thermodynamic property is required,
which is enthalpy.
• The total heat content of the system at constant pressure is
called enthalpy. Mathematically, enthalpy is defined as, "The
sum of internal energy and product of pressure and
volume(mechanical work)." ." It is denoted by 'H' and given
by:
H = E + PV
where, E = internal energy, P = pressure, V = volume
Enthalpy...
It is a state function. So the change in enthalpy with the change
in state of a system can be measured. i.e.
△H = H2 – H1 ...................(i)
Where, H2 = enthalpy of final state. It is given by;
H2 = E2 + P2V2
And, H1 = enthalpy of initial state. It is given by;
H1 = E1 + P1V-1
From equation (i), △H = (E2 + P2V2) – (E1 + P1V1)
or, △H = (E2- E1) + P2V2 – P1V1.....................(ii)
Under constant lab pressure, P1 = P2 = P, then
△H = △E + P (V2 – V1)
or, △H = △E + P△V..............................(iii)
i.e. the change in enthalpy at constant pressure is equal to the
increase in internal energy plus pressure-volume workdone.
Enthalpy...
According to first law of thermodynamics,
q = △E + P△V.....................................(iv)
From equation (iii) and (iv);
△H = q or, △H = qp
i.e. the change in enthalpy is equal to the total heat content of
the system at constant pressure.
Relation between enthalpy and internal energy:
For the reactions involving gases which occur with change in
number of moles before and after the reaction at constant
pressure and temperature; ideal gas equation is given by;
PV2 = n2RT (products) and ,PV1 = n1RT (reactants)
 P(V2 – V1) = (n2 – n1) RT
or, P△V = △nRT..................................................(v)
From equation (iii) and (iv), we have
△H = △E + △nRT...............................(vi)
Relation between enthalpy and internal energy...

△H = △E + △nRT...............................(v)

Cases:
• If △n = 0 i.e. reactants and products involved in reaction are in
solid or liquid state instead of gas then, △H = △E
• If △n = +ve; then △H > △E
• If △n = -ve; then △H < △E
 Energy Profile Diagram for Exothermic
and Endothermic Reactions
• Energy profile diagram is the diagram which shows the level
of energy of the reactants and of the products.
• Heat energy is generally absorbed or released as a result of
chemical reaction. The energy changes in chemical reactions
are due to breaking of existing bonds in reactants and
formation of new bonds between atoms in products.
• The amount of energy released or absorbed in a chemical
reaction is called enthalpy (heat) of reaction. The change in
enthalpy for a chemical reaction is given as
△H = ∑ △Hproducts - ∑ △Hreactants
where, ∑ △Hproducts = total enthalpy of products
∑ △Hreactants = total enthalpy of reactants
1. When △H is negative, the total enthalpy of product is lesser
than that of reactant and the difference in enthalpy is
released in the form of heat energy. Such reaction in which
heat energy is released is called exothermic reaction. So, for
exothermic reaction; the value of △H is negative. As a result,
heat content of a system decreases.

Fig.: Enthalpy change for exothermic reaction

2. When △H is positive, the total enthalpy of products is
greater than that of reactants and the difference in enthalpy is
absorbed in the form of heat energy. Such reaction in which
heat energy is absorbed is called endothermic reaction. So, for
endothermic reaction; the value of △H is positive.
As a result, heat content of a system increases.
 Enthalpy (or Heat) of Reaction

• Enthalpy of a reaction is defined as the amount of heat

change when all the moles of reactants as represented in a
balanced chemical equation are completely reacted to form
products. It is represented by △H and is given by:
△H = ∑△Hf(products) - ∑△Hf(reactants)

• For a generalreaction: aA+bBcC+dD

• Enthalpy of reaction, △H = ∑△Hproducts - ∑△Hreactants
= (c△HC+d△HD)-(a△HA+b△HB)
 Types of Enthalpy (Heat) of Reaction
1. Enthalpy of Combustion (△Hc ):
• The amount of enthalpy change when one mole of a reactant
is completely burnt in excess of air is called enthalpy of
combustion. It is denoted by △Hc.
• Enthalpy of combustion is always exothermic prosess i.e. △H =
-ve.
• Enthalpy of combustion for a reaction is given by:
△Hc = ∑△H f (products) - ∑△H f (reactants)
where, △H f (products) = enthalpy of formation of product
△H f (reactants) = enthalpy of formation of reactant
• For a reaction; C + O2  CO2, △H = -393.5 KJ
i.e. Enthalpy of reaction for the given reaction is -393.5 Kcal
which is also the enthalpy of combustion of carbon since, one
mole of carbon is completely burnt excess of air to give CO2
gas.
• All organic compounds on complete burning in air produce
CO2 and H2O.
i.e. Hydrocarbon + O2 CO2 + H2O
Examples:
• CH4 + 2O2 CO2 + 2H2O
(methane)
• C6H12O6 + 6O2 6CO2 + 6H2O
(glucose)
• C6H6 + 15/2O2 6CO2 + 3H2O
(benzene)
• C2H5OH + 3O2 2CO2 + 3H2O
(ethanol)
• C2H6 + 7/2O2 2CO2 + 3H2O
(ethane)
• C10H8 + 12 O2 10CO2 + 4H2O
(naphthalene)
 2. Enthalpy of formation (△Hf)
• The amount of change in enthalpy when one mole of product
is formed from its constituent elements is called enthalpy of
formation. It is denoted by △Hf.
• Enthalpy of formation of all elements in standard state is
taken as zero. For eg.: standard enthalpy of formation of
oxygen (O2) is taken as zero. i.e. △Hf (o2) = 0.
• A compound having more negative value of heat of formation
is more stable than the other having less negative (or more
+ve) value of heat of formation. i.e. greater the exothermic,
higher will be the stability of compounds. For eg.: HCl [△H f
(HCl) = -22 Kcal] is more stable than HI [△Hf (HI) = +6.2 Kcal].
Standard Enthalpy of Formation:
The amount of enthalpy change when one mole of product is
formed from its constituent elements in standard state i.e. 25
C and 1 atm pressure is called standard enthapy of formation.
It is denoted by △Hf.
• Let us take an example of a reaction:
H2 + Cl2  2HCl; △H= -336 KJ
Here, -336 KJ is the enthalpy of reaction but not the enthalpy
of formation of HCl since two moles of HCl is formed (not
one). For 1 mole of HCl, the reaction should be written as:
1/2H2 + 1/2Cl2  HCl; △H = -336/2 = -168 KJ
Enthalpy of formation of HCl = -168 KJ.
Alternative method:
We have,
△H = ∑△H f (products) - ∑△H f (reactants)
-336 = 2△H f (HCl) – {△H f(H2) + △H f (Cl2)}
-336 = 2△H f (HCl) – (0+0)
△H f (HCl) = -336/2 = -168 KJ
Q. The enthalpy of reaction for the reaction
N2 + 3H2  2NH3 △H = -92.4 KJ
Calculate the enthalpy of formation of ammonia.
Solution:
The given reaction is:
N2 + 3H2  2NH3 △H = -92.4 KJ
i.e. Enthalpy of reaction is-92.4 KJ. In this reaction, two moles
of ammonia is formed. For one mole of ammonia, reaction
should be written as:
1/2N2 + 3/2H2  NH3; △H = -92.4/2 = -46.2 KJ
Enthalpy of formation of NH3 = -46.2 KJ.
 3. Enthalpy of neutralization (△Hn):

• The amount of change in enthalpy when one gram equivalent

of acid is completely neutralized by one gram equivalent of
base or vice versa is called enthalpy of neutralization. It is
denoted by △Hn.
For a reaction:
HCl + NaOH  NaCl + H2O,△Hn = -57.3 KJ
i.e. enthalpy of neutralization of this reaction is -57.36 KJ.
 4. Enthalpy of Solution (△Hs):
• The amount of change in enthapy when one mole of solute is
completely dissolved in excess of solvent at a given
temperature is called enthalpy of solution. Is is denoted by
△Hs. For eg:
CuSO4.5H2O + aqueous  CuSO4 (aq.), △Hs = +11.7 KJ mol-1
i.e. enthalpy of solution of blue vitriol is +11.7 KJ mol-1.
Numericals
Q. The enthalpy of formation of CO2 and H2O is -395 KJ mol-1 and -210
KJ mol-1 respectively. The enthalpy of combustion of ethyl alcohol is -
1250 KJ mol-1. Find the enthalpy of formation of ethyl alcohol.
Solution: Given,
Enthalpy of formation of CO2 (△Hf (CO2)) = -395 KJ mol-1
Enthalpy of formation of H2O (△Hf (H2O)) = -210 KJ mol-1
Enthalpy of combustion of C2H-5OH (△HC (C2H5OH)) = -1250 KJ mol-1
The balanced chemical equation for the combustion of ethyl alcohol is
given as:
C2H5OH + 3O2  2CO2 + 3H2O
We have, enthalpy of combustion is given as:
△Hc = ∑△Hf (product) - ∑△Hf (reactant)
△Hc (C2H5OH) = {2△Hf (CO2) + 3△Hf (H2O)} – {△Hf (C2H5OH) + 3 △Hf (O2)}
-1250 = {2  (-395) +3  (-210)} – {△Hf (C2H5OH) + 3  0}
△Hf (C2H5OH) = -790 -630 +1250
= -170 KJ mol-1
Enthalpy of formation of ethyl alcohol is -170 KJ mol-1.
Q. The enthalpy of combustion of C, H and CH4 are -5, -6 and -11 KJ
mol-1 respectively. Find the enthalpy of formation of methane.
Solution:
Given,
The chemical equation for the enthalpy of combustion of C is given as
C + O2  CO2 , Here, △Hc (C) = △Hf (CO2) = -5 KJ mol-1
Therefore, enthalpy of formation of CO2 is -5 KJ mol-1
Again,
The chemical equation for enthalpy of combustion of hydrogen is
given as
H2 + ½ O2  H2O, △Hc (H2) = △Hf (H2O) = -6 KJ mol-1
 Enthalpy of formation of H2O is -6 KJ mol-1.
And, Enthalpy of combustion of methane (△Hc (CH4)) =-11 KJ mol-1
The balanced chemical equation for the combustion of methane is
given as:
CH4 + 2O2  CO2 + 2H2O
We have, enthalpy of combustion is given as:
△HC = ∑△Hf (product) - ∑△Hf (reactant)
△Hc (CH4) = {△Hf (CO2) + 2△Hf (H2O)} – {△Hf (CH4) + 2 △Hf (O2)}
-11 = {-5 +2  (-6)} – {△Hf (CH4) + 2  0}
△Hf (CH4) = -17 + 11
= -6 KJ mol-1
Enthalpy of formation of methane is -6 KJ mol-1.
 Questions for Practice:
1. Calculate the standard heat of formation of CH4 from the following
data:
CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l); △H = -890.3 KJ
C (graphite) + O2 (g)  CO2 (g); △H = -393.5 KJ
2H2 (g) + O2 (g)  2H2O (l); △H = -571.7 KJ (Ans: -74.9 KJ)
2. Enthalpy of formation of benzene is 55 KJ. Enthalpy of formation of
water and carbon dioxide are -395 KJ and -285 KJ respectively.
Calculate the enthalpy of combustion of benzene.(Ans: -2950 KJ)
3. Calculate the heat of formation of naphthalene from the following
data:
C (s) + O2 (g)  CO2 (g); △H = -94.405 Kcal
H2 (g) + ½ O2 (g)  H2O (l); △H = -68.3 Kcal
C10H8 (s) + 12 O2 (g)  10CO2 (g) + 4H2O (l); △H = -1231.5 K cal
(Ans: +14.35 Kcal)
4. Calculate the enthalpy of formation of ethane at 298 K, if the
enthalpies of combustion of carbon, hydrogen and ethane are -
94.14, -68.47 and -373.3 Kcal respectively. (Ans: -20.39 Kcal)
5. The standard heat of formation of SO2 (g) and SO3 (g) are -296.6 KJ
and -396 KJ respectively. Calculate enthalpy of reaction for the
reaction:
SO2 (g) + ½ O2 (g)  SO3 (g) (Ans: -99.4 Kcal)
6. Calculate the enthalpy of formation of NH3 from the following
equation:
N2 (g) + 3H2 (g)  2NH3 (g); △H = -186 KJ (Ans: -93 KJ)
 Bond Energy
• The amount of energy required to break the bond existing between
two atoms in a covalent compound in gaseous state is called bond
energy.
• Bond breaking is endothermic process while bond formation is
exothermic process.
• The enthalpy (or heat) is changed when all the bonds existing in
reactants gets broken down and formation of new bonds between
atoms in products take place in a balanced chemical equation in
gaseous state.
• Mathematical expression for the enthalpy of reaction in terms
of bond energy is given by:
△H = ∑ B.E. (reactant) - ∑ B.E. (product)
where, ∑ B.E. (reactant) = total bond energy of reactant
∑ B.E. (product) = total bond energy of product
For eg.:
2H2(g) + O2(g)  2H2O(g)
2 H-H + O=O  2 H-O-H
 △H = {2  B.E.(H-H) +B.E.(O=O)} – 22 B.E.(O-H)
Q. Calculate the change in enthalpy for the following reaction if:
B.E.(C-H) = 18 Kcal
B.E.(O=O) = 20 Kcal
B.E.(C=O) = 14 Kcal
B.E.(H-O) = 12 Kcal for the following reaction:
CH4 + 2O2  CO2 + 2H2O
Solution:
C

The change in enthalpy is given by:

△H = ∑ B.E. (reactant) - ∑ B.E. (product)
= {4B.E.(C-H) + 2B.E.(O=O)} – {2  B.E.(C=O) + 22  B.E.(H-O)}
= {418 + 220} – {214+412}
= 72+40-28-48
= 36 Kcal
Q. Estimate the enthalpy change for the reaction:
H2(g) + Cl2(g)  2HCl
Given; bond energy of H-H = 435 KJ/mole
bond energy of Cl-Cl = 243 KJ/mole
bond energy of H-Cl = 430 KJ/mole
[Ans: -182 KJ]
Q. The bond enthalpies of gaseous H2, Cl2 and HCl
are 104 Kcal mol-1, 58 Kcal mol-1 and 103 Kcal
mol-1. Calculate the enthalpy of formation of
HCl(g). [Ans: -22 Kcal/mol]
 Hess's Law of Constant Heat
Summation
Statement:
" The total amount of change in enthalpy in a
chemical reaction is always same, no matter
wheather the reaction is carried out in a single
step or through multiple steps."
Explanation:
Let us suppose a reactant 'A' is converted into 'D' directly. i.e.
A  D, △H = Q KJ
Suppose, the same change is carried out in different steps. i.e.
A  B, △H1 = q1 KJ
B  C, △H2 = q2 KJ
C  D, △H3 = q3 KJ
According to Hess's law:
△H = △H1 + △H2 + △H3
Q = q1 + q2 + q3
Thus, Hess's law implies that change in enthalpy of a chemical
reaction depends upon the initial and final state of a chemical
reaction irrespective of the number of steps involved in the chemical
reaction.
Illustration:
The change in enthalpy of formation of carbondioxide can be
determied in two ways:
Single step preparation:
Carbon is burnt in excess of air to form CO2. i.e.
C + O2 CO2, △H = -395 KJ
Multiple step preparation:
Step 1: Carbon is burnt in air in limited supply of oxygen to
form CO.
i.e. C + O2 CO, △H1 = -111 KJ
Step 2: CO is then burnt in excess of oxygen to form CO2.
i.e. CO + O2 CO2 , △H2 = -284 KJ
According to Hess's law:
△H1 + △H2 = -111-284 = -395 KJ = △H
i.e. The total amount of enthalpy change during the formation
of CO2 in single step and multiple steps is same which
illustrates the Hess's law.

Applications of Hess's law:

• Thermochemical equations can be added or multiplied like
ordinary algebric equation.
• It is useful to calculate heat of many reactions which donot
take place directly.
• It is useful to find out the heat of formation, heat of
neutralization etc.