6 Chemical Thermodynamics

Syllabus : Unit VI: Chemical Thermodynamics 14 Periods

Concepts of System and types of systems, surroundings, work, heat, energy,
extensive and intensive properties, state functions.
First law of thermodynamics -internal energy and enthalpy, measurement of U
and H, Hess's law of constant heat summation, enthalpy of bond dissociation,
combustion, formation, atomization, sublimation, phase transition, ionization,
solution and dilution. Second law of Thermodynamics (brief introduction)
Introduction of entropy as a state function, Gibb's energy change for spontaneous
and non- spontaneous processes.
Third law of thermodynamics (brief introduction).
 THERMODYNAMICS
Thermodynamics is the study of
energy relationships that
involve heat, mechanical work,
and other aspects of energy
and heat transfer.

Central Heating
System
The part of universe for study is called system
and
& Surroundings : remaining portion of the
universe (except system) is called surroundings.
The universe: The system + The surroundings
Three types of system are open, closed and isolated
system.
The wall separates the system from the surrounding is
a boundary.
 Open System

• It is a system in which exchange of energy

and matter between system and
surroundings is possible.
• E.g. Reactants in an
open beaker
 Closed System

• In a closed system, there is no exchange of

matter, but exchange of energy is possible
between system and the surroundings
• E.g. The presence
of reactants in a closed
vessel made of
conducting material
 Isolated System

• In an isolated system, there is no exchange of

energy or matter between the system and
the surroundings.
• E.g. reactants in a thermos flask or any other
closed insulated vessel
 Isolated
system

Open system Closed

system
 The State of the System

• The state of a thermodynamic system is

described by its measurable or macroscopic
(bulk) properties. We can describe the state
of a gas by quoting its pressure (p), volume
(V), temperature (T ), amount (n) etc.
Variables like p, V, T are called state
variables or state functions because their
values depend only on the state of the
system and not on how it is reached.
The Internal Energy as a State
Function: sum of all forms of energy is
called internal energy
• Internal Energy (U) represents the total energy
of the system. It may be chemical, electrical,
mechanical or any other type of energy, the
sum of all these is the energy of the system.
It changes when,
heat passes into or out of the system,
work is done on or by the system,
matter enters or leaves the system.
Adiabatic process is a process
in which there is no transfer
of heat between the system
and surroundings
 Internal energy &Work

• . Take a system containing some quantity of water in

a thermos flask or in an insulated beaker.
• Let the initial state of the system be state A and its
temperature as TA. Let the internal energy of the
system in state A be called UA. We can change the
state of the system in two different ways.
• One way: We do some
mechanical work, say 1 kJ,
by rotating a set of small
paddles and thereby
churning water.
• Let the new state be
called B state and its
temperature, as TB. It is
found that TB > TA and the
change in temperature, ΔT
= TB–TA. Let the internal
energy of the system in
state B be UB and the
change in internal energy,
ΔU =UB– UA.
• Second way: We now
do an equal amount
(i.e., 1kJ) electrical
work with the help of
an immersion rod and
note down the
temperature change.
We find that the
change in temperature
is same as in the earlier
case, say, TB – TA.
• J. P. Joule was able to show that a given
amount of work done on the system, no
matter how it was done (irrespective of path)
produced the same change of state.
• So internal energy is a state function.
 Sign convention

• wad is positive when work is done on the

system. If the work is done by the system,
wad will be negative.
 Internal energy & Heat

• A system with thermally conducting walls

transfer of heat possible between the system
and surrounding (in Cu vessel).
 Sign convention

• The q is positive, when heat is transferred

from the surroundings to the system and
q is negative when heat is transferred from
system to the surroundings.
 FIRST LAW OF
THERMODYNAMICS
• If change of state is brought about both by doing work
and by transfer of heat. We write change in internal
energy for this case as:
• ΔU = q + w
• It is first law of thermodynamics
• The energy of an isolated system is constant.
• For an isolated system , there is no transfer of heat
(q=0) and matter between system and surroundings as no
work done w=0
• ΔU = q + w
• U2-U1 =0+0
• U2 = U 1
First law of thermodynamics
• It is commonly stated as the law of
conservation of energy i.e.,
• energy can neither be created nor
be destroyed.
ΔU = q + w q=0 and w=+ve

W=0 q= - ve

q=+ve, w= -ve
 REVERSIBLE PROCESS

• A process or change is said to be reversible, if a

change is brought out in such a way that the
process could, at any moment, be reversed by
an infinitesimal change. A reversible process
proceeds infinitely slowly by a series of
equilibrium states such that system and the
surroundings are always in near equilibrium
with each other. Processes other than
reversible processes are known as irreversible
processes.
 APPLICATIONS: Work

pex

pex A
l
p
Vi
pex Vf
• A cylinder contains one mole of an ideal gas
fitted with a frictionless piston. Total volume of
the gas is Vi and pressure of the gas inside is p.
If external pressure pex is greater, piston is
moved inward till the pressure inside becomes
equal to pex. Let this change be achieved in a
single step and the final volume be Vf . During
this compression, suppose piston moves a
distance, l and is cross-sectional area of the
piston is A
 • then, volume change = l × A = ΔV = (Vf – Vi )
• Pressure = force/area
• force on the piston = pex . A
• If w is the work done on the system by
movement of the piston then
• w = force × distance = pex . A .l
= pex . (–ΔV) = – pex ΔV
= – pex (Vf – Vi)
The negative sign of this expression is required to obtain
conventional sign for w, which will be positive. It indicates
that in case of compression work is done on the system.
Here (Vf – Vi ) will be negative and negative multiplied by
negative will be positive. Hence the sign obtained for the
work will be positive.
• If the pressure is not constant at every stage of
compression, but changes in number of finite
steps, work done on the gas will be summed
over all the steps and will be equal to −Σ pΔV
• volume decreases by an infinitesimal amount,
dV. In such a case we can calculate the work
done on the gas by the relation
• Vf
• w=−∫pexdV
• Vi
• We can relate work to internal pressure of
the system under reversible conditions by
• wrev= – 2.303 nRT log(Vf/Vi)
 Free expansion

• Expansion of a gas in vacuum (pex = 0) is called

free expansion. No work is done during free
expansion of an ideal gas whether the process
is reversible or irreversible.
• ΔU = q − pex ΔV
• If a process is carried out at constant volume
• (ΔV = 0), then ΔU = qV
• the subscript V in qV denotes that heat is
supplied at constant volume.
 Isothermal and free expansion of
an ideal gas
• ΔU = q + w can be expressed for isothermal
irreversible and reversible changes as follows:
• For isothermal changes, ΔU =0
• For isothermal irreversible change
• q = – w = pex (Vf – Vi )
• For isothermal reversible change
• q = – w = 2.303 nRT log(Vf/Vi)
• For adiabatic change, q = 0,
• ΔU = wad
 Enthalpy, H

• H = U + pV
• Although q is a path dependent function, H is
a state function because it depends on U, p
and V, all of which are state functions.
Therefore, ΔH is independent of path.
• ΔH = qp, heat absorbed by the system at
constant pressure.
• qp= H2 – H1 = ΔH
 Sign convention

• ΔH is negative for exothermic reactions which

evolve heat during the reaction and ΔH is
positive for endothermic reactions which
absorb heat from the surroundings.
• ΔH = qp, heat absorbed by the system at
constant pressure.
• ΔH = ΔU = qV At constant volume
 Extensive and Intensive Properties
• An extensive property is a property whose
value depends on the quantity or size of matter
present in the system.
• Example: mass, volume, internal energy,
enthalpy, heat capacity, etc.
• Intensive properties are properties which do
not depend on the quantity or size of matter
present in the system.
• For example temperature, density, pressure
 Heat Capacity
• It is the heat required to raise the temperature
of a substance by 10C.
• q = C ΔT
• q is the quantity of heat supplied, C is the heat
capacity and ΔT is the change in temperature
• When C is large, a given amount of heat results
in only a small temperature rise. Water has a
large heat capacity i.e., a lot of energy is
needed to raise its temperature.
• Molar heat capacity is the quantity of heat
needed to raise the temperature of one mole
by one degree Celsius (or one Kelvin).
• Specific heat, also called specific heat
capacity is the quantity of heat required to
raise the temperature of unit mass of a
substance by one degree Celsius (or one
Kelvin).
The relationship between Cp and
CV
• At constant volume, the heat capacity, C is
denoted by CV and at constant pressure, this
is denoted by Cp .
• Cp-CV=R

• Heat capacity is an extensive property

• Molar heat capacity is an intensive property
• Specific heat capacity is an intensive property
 MEASUREMENT OF ΔU AND
ΔH: CALORIMETRY
Measurements are made under two different
conditions:
1. at constant volume, qV
2. at constant pressure, qp
ΔU measurements
• A steel vessel is immersed in water bath to
ensure that no heat is lost to the surroundings.
A combustible substance is burnt in pure
dioxygen supplied in the steel bomb. Heat
evolved during the reaction is transferred to
the water around the bomb and its
temperature is monitored. Since the bomb
calorimeter is sealed, its volume does not
change i.e., the energy changes associated with
reactions are measured at constant volume.
• Under these conditions, no work is done as
the reaction is carried out at constant volume
in the bomb calorimeter. Temperature
change of the calorimeter produced by the
completed reaction is then converted to qV ,
by using the known heat capacity of the
calorimeter with the help of equation
• q = c.m.ΔT
ΔH measurements
• Δ H = qp (at constant p) and, therefore, heat
absorbed or evolved, qp at constant pressure is
also called the heat of reaction or enthalpy of
reaction, ΔrH. In an exothermic reaction, heat is
evolved, and system loses heat to the
surroundings. Therefore, qp will be negative
and ΔrH will also be negative. Similarly in an
endothermic reaction, heat is absorbed, qp is
positive and ΔrH will be positive.
Reactants → Products
The enthalpy change accompanying a reaction is called the
reaction enthalpy
ENTHALPY CHANGE, ΔrH OF A
REACTION – REACTION
ENTHALPY
• The enthalpy change accompanying a
reaction is called the reaction enthalpy (ΔrH).
• Reactants → Products
• ΔrH = (sum of enthalpies of products) – (sum
of enthalpies of reactants)
 Standard enthalpy of reactions
• The standard enthalpy of reaction is the
enthalpy change for a reaction when all the
participating substances are in their standard
states. (The standard state of a substance at a
specified temperature is its pure form at 1
bar.)
Thestandard enthalpy of reaction is the enthalpy change
for a reaction when all the participating substances are in
their
standard states.
The standard state of a substance at a specified
temperature is its pure form at 1 bar. For example, the
standard state of liquid ethanol at 298 K is pure liquid ethanol
at 1 bar; standard state of solid iron at 500 K is pure iron at 1
Enthalpy changes during phase
transformations
• The enthalpy change that accompanies melting of one
mole of a solid substance in standard state is called
standard enthalpy of fusion or molar enthalpy
of fusion, ΔfusH0.
• Solid liquid
• Amount of heat required to vaporize one mole of a
liquid at constant temperature and under standard
pressure (1bar) is called its standard enthalpy of
vaporization or molar enthalpy of
vaporization, ΔvapH0.
• Liquid vapour or gas
• Standard enthalpy of sublimation,
ΔsubH0 is the change in enthalpy when one
mole of a solid substance sublimes at a
constant temperature and under standard
pressure (1bar).
• Solid gas
Standard enthalpy of formation
• The standard enthalpy change for the
formation of one mole of a compound from
its elements in their most stable states of
aggregation is called Standard Molar
Enthalpy of Formation. Its symbol is ΔfH0
Is not the enthalpy of formation of calcium carbonate as it
is not formed from elements in their standard state
Consider the following reaction
Thermochemical equations

• A balanced chemical equation together with

the value of its ΔrH is called a
thermochemical equation.
C(graphite, s) + 2 S(l) → CS2(l); ΔrH0 = +128.5 kJ mol–1
Conventions regarding thermochemical
equations.
• The coefficients in a balanced thermochemical
equation refer to the number of moles (never
molecules) of reactants and products involved
in the reaction.
• The numerical value of ΔrH0 refers to the
number of moles of substances specified by an
equation. Standard enthalpy change ΔrH0 will
have units as kJ mol–1.
 Hess’s Law of
Constant Heat Summation
• If a reaction takes place in several steps then
its standard reaction enthalpy is the sum of
the standard enthalpies of the intermediate
reactions into which the overall reaction are
divided at the same temperature.
 ENTHALPIES FOR DIFFERENT
TYPES OF REACTIONS
• Standard enthalpy of combustion (ΔcH0)
• Standard enthalpy of combustion is defined as the
enthalpy change per mole (or per unit amount) of a
substance, when it undergoes combustion and all the
reactants and products being in their standard states at
the specified temperature.
• Cooking gas in cylinders contains mostly
butane (C4H10). During complete combustion
of one mole of butane, 2658 kJ of heat is
released.
• Combustion of glucose gives out 2802.0
kJ/mol of heat. Our body also generates
energy from food by the same overall process
as combustion.
Enthalpy of atomization
(ΔaH )
0

• Enthalpy of atomization is the enthalpy

change on breaking one mole of bonds
completely to obtain atoms in the gas phase.
• H2(g) → 2H(g); ΔaH0 = 435.0 kJ mol–1
• In case of diatomic molecules, the enthalpy of
atomization is also the bond dissociation enthalpy.
• Na(s) → Na(g) ; ΔaH0 = 108.4 kJ mol–1
• In this case, the enthalpy of atomization is same as
the enthalpy of sublimation.
 Bond Enthalpy (ΔbondH0)

It can be of two types

• Bond dissociation enthalpy
• Mean bond enthalpy
Bond dissociation enthalpy
• The bond dissociation enthalpy is the change
in enthalpy when one mole of covalent bonds
of a gaseous covalent compound is broken to
form products in the gas phase.
• H2(g) → 2H(g) ; ΔH–HH0 = 435.0 kJ mol–1
• It is same as the enthalpy of atomization for
all diatomic molecules.
 Mean Bond Enthalpy
• In methane, all the four C – H bonds are
identical in bond length and energy. However,
the energies required to break the individual
C–H bonds in each successive step differ
Bond enthalpies of H2 and Cl2 , H-Cl are are 436 ,243, 431 kj/mol
respectively. Find the ∆H0 of a reaction .
H2 + Cl2 → 2H-Cl
∆H0r = bond enthalpy of H2 + bond enthalpy of Cl2 - 2x bond enthalpy of HCl

= 436 + 243 – 2 x 431

= -183kj/mol
Enthalpy of solution
for ionic compounds
• When an ionic compound dissolves in a
solvent, the ions leave their ordered
positions on the crystal lattice. These are now
more free in solution. But solvation of these
ions (hydration in case solvent is water) also
occurs at the same time.
• ΔsolH0 =ΔlatticeH0 + ΔhydH0
 Lattice Enthalpy

• The lattice enthalpy of an ionic compound is

the enthalpy change which occurs when one
mole of an ionic compound dissociates into
its ions in gaseous state.
• Since it is impossible to determine lattice
enthalpies directly by experiment, we use an
indirect method where we construct an
enthalpy diagram called a Born-Haber Cycle
• Step 1: Sublimation of sodium metal,
• Na(s)→ Na(g) , ΔsubHV =108.4 kJ mol–1
• Step 2: The ionization of sodium atoms,
• Na(g)→ Na+(g), ionization enthalpy ΔiH0 = 496 kJ mol–1
• Step 3: The dissociation of chlorine molecule to
form chlorine atom, the reaction enthalpy is half
the bond dissociation enthalpy.
• 1/2Cl2 (g) → 2Cl(g) ,1/2 ΔbondH0=121 kJ mol–1
• Step 4: Formation of Cl- ion
• Cl(g)+ e−(g) → Cl −(g); ΔegH 0 = –348.6 kJ mol–1.
 • Step 5: formation of crystal lattice of NaCl
• Na+ (g) + Cl− (g) → NaCl (s); ΔlatticeH0
• over all reaction
• Na(S)+ ½ Cl2(g) → NaCl (S) ΔrH 0 = -411.2

As per Hess’s law enthalpy change is same whether the reaction

takesplace in one step or in several step
ΔrH 0 = ΔsubH0 + ΔiH0 + 1/2 ΔbondH0 + ΔegH 0 + ΔlatticeH0

-411.2 = 108.4 +496+121+(-348.6) + ΔlatticeH0

ΔlatticeH0 = -411.2 - 108.4 -496-121+348.6 = -788kj/mol
Na+ (g) + Cl− (g) → NaCl (s); ΔlatticeH0 = -788j/mol

For dissociation
 Enthalpy of Solution (ΔsolH0 )

• Enthalpy of solution of a substance is the

enthalpy change when one mole of it
dissolves in a specified amount of solvent.
•.
 SPONTANEITY

• A spontaneous process is a process having

the potential to proceed without the
assistance of external agency.
• A spontaneous process is an irreversible
process and may only be reversed by some
external agency.
Is decrease in enthalpy a criterion
for
spontaneity ?
• A chemical reaction is expected to be
spontaneous if there is decrease in energy, as
in the case of exothermic reactions.
• But many endothermic reactions are
spontaneous. Therefore, it becomes obvious
that while decrease in enthalpy may be a
contributory factor for spontaneity, but it is
not true for all cases.
Entropy
Randomness or disorder decreases
•  Entropy
For a spontaneous process ΔS total
>0
when the system is in equilibrium ΔS = 0
At 0 K, the constituent particles arestatic and entropy is minimum. If temperature is
raised to 115 K, these begin to move and oscillate about their equilibrium positions in
the lattice and system becomes more disordered, therefore entropy increases.
(iii) Reactant, NaHCO3 is a solid and it has low entropy. Among products there are
one solid and two gases. Therefore, the products represent a condition of higher
entropy.
(iv) Here one molecule gives two atoms i.e., number of particles increases leading to
more disordered state. Two moles of H atoms have higher entropy than one mole of
dihydrogen molecule.
 Entropy and spontaneity

• Neither decrease in enthalpy nor increase in

entropy alone can determine the direction of
spontaneous change for open and closed
systems.
Second law of thermodynamics : The entropy of
universe increases for spontaneous process.
Third law of thermodynamics : Entropy of a perfectly
crystalline substance is zero at absolute zero
 Gibbs energy and spontaneity

• Gibbs energy or Gibbs function, G is given by

G = H – TS
• Gibbs function, G is an extensive property
and a state function.
• The change in Gibbs energy for the system
can be written as
• ΔG = ΔH − T ΔS
 ‘Free Energy’
• ΔH is the enthalpy change of a reaction, TΔS
is the energy which is not available to do
useful work. So ΔG is the net energy available
to do useful work and is thus a measure of
the ‘free energy’. For this reason, it is also
known as the free energy of the reaction.
ΔG gives a criteria for spontaneity at constant
pressure and temperature.
• If ΔG is negative (< 0), the process is
spontaneous.
• If ΔG is positive (> 0), the process is non
spontaneous.
• ( G = 0, EQUILIBRIUM )
• 
ΔrH0 ΔrS0 ΔrG0 Description

•– + – Reaction spontaneous

• – – – (at low T ) Reaction spontaneous

• – – + (at high T ) Reaction nonspontaneous

• + + + (at low T ) Reaction nonspontaneous

•+ + – (at high T) Reaction spontaneous

• + – + (at all T ) Reaction nonspontaneous

A knowledge of the sign and magnitude of the
free energy change of a chemical reaction
allows:
• Prediction of the spontaneity of the chemical
reaction.
• Prediction of the useful work that could be
extracted from it.
GIBBS ENERGY CHANGE AND
EQUILIBRIUM
• ‘Reversible’ under strict thermodynamic
sense is a special way of carrying out a
process such that system is at all times in
perfect equilibrium with its surroundings. It is
possible only if at equilibrium the free energy
of the system is minimum. It is because the
reactions in both the directions should
proceed with a decrease in free energy,
which seems impossible.
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