Class XI Chemistry

Unit 6
THERMODYNAMICS
Topic:-THERMODYNAMIC TERMS
• Sub topics:-
• The System and the Surroundings
• Types of the System
• State of the System
• State Functions
• Adiabatic System
By Vinod Kumar
Thermodynamics
• The branch of science which deals with the quantitative relationship
between heat and other forms of energies is called thermodynamics
• For example,
• Chemical energy stored by molecules can be released as heat during
chemical reactions when a fuel like methane, cooking gas or coal burns
in air.
• The chemical energy used to do mechanical work when a fuel burns in an
engine
• The chemical energy used to provide electrical energy through a
galvanic cell like dry cell.
• The study of these energy transformations forms the subject matter of
thermodynamics
 The System and the Surroundings

• The part of universe in which observations are made or which is under

investigation is called system
• Surroundings is the part of universe other than system . The
surroundings include everything other than the system.
• System and the surroundings together constitute the universe .
• The universe = The system + The surroundings
 Continue…
The System and the Surroundings

• For example, if we are studying the

reaction between two substances A and B
kept in a beaker, the beaker containing the
reaction mixture is the system and the
room where the beaker is kept is the
surroundings
• System and surroundings are separated by
a boundary.
• This boundary may be real or imaginary.
 Types of the System
Open System
• There is exchange of energy and matter between system and surroundings.
• For example. the presence of reactants in an open beaker.
• Here the boundary is an imaginary
Closed System
• There is no exchange of matter, but exchange of energy is possible between
system and the surroundings.
• For example, the presence of reactants in a closed vessel made of conducting
material.
Isolated System
• There is no exchange of energy and matter between the system and the
surroundings
• For example, the presence of reactants in a thermos flask or any other closed
insulated vessel
Continue…
Types of the 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.
State Functions
• The macroscopic properties whose values depend only on the state of the
system(initial and final) and not on how it is reached are called state
functions.
• For example, P, T, V, Internal energy, Enthalpy, Entropy

• Path functions depend on

the path taken to reach one
state from another.
Adiabatic System
• The system which will not allow exchange of
heat between the system and surroundings
through its boundary but energy of the
system may change by work.
• Adiabatic process is a process in which there
is no transfer of heat between the system and
surroundings.
• Bursting
The wall separating
of tyre the of
is an example system and
adiabatic the
process.
surroundings
• it isthere
happens so fast, called theenough
is not adiabatic wall.
time to
exchange heat with surroundings
 Adiabatic System Isolated System

It has no exchange of energy and matter It has no transfer of energy and matter
with the surrounding environment through its boundaries .
It has a surrounding environment It doesn’t have a surrounding
environment
It does not gain or loss energy but Energy is conserved
internal energy can be changed due to
work done by the system
Internal energy can be changed Internal energy can not be changed
 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
• Internal Energy (U)
• Mathematical statement of the first law of
thermodynamics

By Vinod Kumar
Internal Energy (U)
• Total energy of the system is called internal energy of the system.

• It is the sum of kinetic(translational , vibrational and rotational)

potential , chemical, electrical, mechanical energies etc.
• Internal energy is a state function-depends on initial and final states of
the system
• Absolute value of U can not be determined.
• Change in internal energy (ΔU) is determined. ΔU = U2-U1
• It may change, when
• heat passes into or out of the system,
• work is done on or by the system,
• matter enters or leaves the system.
 Ways of Changing Internal Energy

Work: Consider an adiabatic system

• Initial state of the system = A and its temperature =TA.

• Internal energy of the system in state A = UA.

• We can change the state of the system in two different
ways.
One way: By mechanical work (1 kJ):- by rotating a set of
small paddles
• Final State =B state and its temperature=TB.

• if TB > TA and the change in temperature, DT = TB–TA.

• The internal energy of the system in state B = UB and

• The change in internal energy, DU =UB– UA =Wad.

 Continue…
Ways of Changing Internal Energy
Work
• 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,
TB – TA

• The change in internal energy, DU =UB– UA =Wad.

• Therefore, internal energy, U, of the system is a state function.
• J. P. Joule showed 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, as measured by the change in the temperature of the
system. By conventions:-
• Work done on the system = positive work (+W) internal energy of
system increases.
 Continue…
Ways of Changing Internal Energy
Heat(q) :
• If system and surroundings are at different temperatures , internal energy of the
system is changed by transfer of heat through thermally conducting walls

• If temperature of System = TA and Temperature of surroundings = TB

• TB < TA heat is transferred from system to surroundings till TB=TA

• TB > TA heat is transferred from surroundings to system till TB=TA

• In this case change in internal energy, DU= q, when no
work is done at constant volume.
 Continue…
Ways of Changing Internal Energy

Heat(q) :
• By conventions
• The q is positive (+q)= heat is transferred from the
surroundings to the system and the internal energy of the
system increases and
• q is negative (-q) = heat is transferred from system to the
surroundings resulting in decrease of the internal energy of the
system..
 Mathematical statement of the first law of
thermodynamics

• DU = U2 – U1 = q + w
• DU = q + w mathematical statement of the first law of thermodynamics,
• which states that The energy of an isolated system is constant.
• It is commonly stated as the law of conservation of energy i.e., energy can
neither be created nor be destroyed.
Continue…
Mathematical statement of the first law of
thermodynamics
• q and w are path functions but q +w = DU will depend
only on initial and final state therefore (q + w) is state
function
• It will be independent of the way the change is carried
out.
• If there is no transfer of energy as heat or as work
(isolated system) i.e., if w = 0 and q = 0, then D U = 0.
Problem 6.1
Express the change in internal energy of a system when
(i) No heat is absorbed by the system from the surroundings, but work
(w) is done on the system. What type of wall does the system have ?
Solution:- D U = wad, wall is adiabatic
(ii) No work is done on the system, but q amount of heat is taken out from
the system and given to the surroundings. What type of wall does the
system have?
Solution:- D U = – q, thermally conducting walls
(iii) w amount of work is done by the system and q amount of heat is
supplied to the system. What type of system would it be?
Solution:- D U = q – w, closed system.
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
• Pressure-Volume Work
• Reversible and Irreversible process

By Vinod Kumar
 Pressure-Volume Work

• A cylinder contains one mole of an ideal gas

fitted with a frictionless piston.
• Initial volume the gas is Vi and pressure of
the gas inside is p.
• pex = external pressure , pex > p

• piston is moved inward till pex= p

• Final volume = Vf .
• During this compression, piston moves a
distance, l and is cross-sectional area of the
piston is A
 Pressure-Volume Work

then, volume change = l × A = DV = (Vf – Vi)

Therefore, force on the piston = pex . A

If w is the work done on the system by movement of the piston then
w = force x distance = pex . A .l w = pex . (Vf – Vi )= – pex DV
w = – pDV
• The negative sign of this expression is required •
This formula is also applicable for
to obtain conventional sign for w, which will be expansion work which is done by the
positive. system so it will be negative.
• compression work is done on the system.
• In expansion (Vf – Vi ) will be
• (Vf – Vi ) will be negative and negative
positive
multiplied by negative will be positive.
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 (‌ˈटे᠎̮‌extremely small )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.

Irreversible processes
• Processes other than reversible processes are known as irreversible
processes.
• All natural processes are irreversible.
 Differences between Reversible and Irreversible process

Reversible process Irreversible process

The process is carried out infinitesimally It is carried out rapidly

slowly.
At any stage, the equilibrium is not Equilibrium may exit only after the
disturbed completion of the process.
It takes infinite time for completion. It takes a finite time for completion.
Work obtained in this process is Work obtained in this process is not
maximum maximum`
It is an imaginary process. It is a natural process
 Continue…
Pressure-Volume Work
• If the compression of gas is carried out in number of finite steps,
work done on the gas will be summed over all the steps and will
be equal to Ʃ pDV
Fig :-
• pV-plot when pressure is not constant and
changes in finite steps during compression
from initial volume, Vi to final volume, Vf
• Work done on the gas is represented by
the shaded area.
 Continue…
Pressure-Volume Work in Reversible
process
• If the compression of gas is carried out in infinite steps through reversible
process, at each stage of compression, the volume decreases by an
infinitesimal amount, dV.
• In this case, the work done on the gas is calculated by the following
• Here, pex at each stage is equal to (pin + dp) in case of
relation
compression.
• In an expansion process, pex = (pin– dp).

• In general, pex = (pin ± dp).

 Continue…
Pressure-Volume Work in Reversible
pV =nRT
process

Fig. pV-plot when pressure is not constant and

changes in infinite steps (reversible conditions)
during compression from initial volume, Vi to final
volume, Vf .
• Work done on the gas is represented by the
shaded area.
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
• Free expansion
• Problem 6.2, 6.3, 6.4

By Vinod Kumar
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.

w = – pex DV if pex =0 w=0

• mathematical statement of the first law of thermodynamics
DU = q + w
DU = q – pex DV
• If a process is carried out at constant volume (DV = 0), then
DU = qv
• Change in internal energy is the heat supplied at constant
volume.
 Isothermal and free expansion of an
ideal gas
• For isothermal (T = constant) expansion of an ideal gas
into vacuum ; w = 0 since pex = 0.
• Also, Joule determined experimentally that q = 0;

DU = q +therefore,
w can beDU =0
expressed for isothermal irreversible and reversible
changes as follows:
1. For isothermal irreversible change
2. For isothermal reversible change

3. For adiabatic change, q = 0

Problem 6.2
Two litres of an ideal gas at a pressure of 10 atm expands isothermally at 25 °C
into a vacuum until its total volume is 10 litres. How much heat is absorbed
and how much work is done in the expansion ?
Solution
For isothermal process
w = -pex (Vf- Vi) = 0(10 – 2) = 0(8) = 0 No work is done; no heat is absorbed.
Problem 6.3
Consider the same expansion, but this time against a constant external
pressure of 1 atm.
Solution

We have q = – w = pex (8) = 8 litre-atm

Problem 6.4
Consider the expansion given in problem 6.2, for 1 mol of an ideal gas
conducted reversibly.
Solution
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
• Enthalpy
• Relation between DU And DH
By vinod kumar
 Enthalpy, H

• The heat absorbed at constant volume is equal to change in the Internal

Energy i.e., DU = qv
• But most of chemical reactions are carried out not at constant volume, but
in flasks or test tubes under constant atmospheric pressure.
• Another thermodynamic function, the enthalpy H [Greek word enthalpien,
to warm or heat content] as : H = U + pV
• Enthalpy is the sum of internal energy and product of pressure-volume.
• Enthalpy is a state function-depends on initial and final states of the
system
• Absolute value of H can not be determined.
• Change in enthalpy (ΔH) is determined. ΔH = H2-H1
 Continue… Enthalpy, H
mathematical statement of the first law of thermodynamics DU = q + w,
w = – pDV
At constant pressure, DU = qp – pDV,
where qp is heat absorbed by the system and –pDV = expansion work done by
the system.
Let us consider two state state 1 state 2
Internal energy U1 U2

Volume V1 V2

Change in internal energy U2–U1 = qp – p (V2 – V1)

On rearranging, qp = (U2 + pV2) – (U1 + pV1)

From H = U + pV H2=U2 + pV2

H1=U1 + pV1
 Continue… Enthalpy, H
• For finite changes at constant pressure the equation H = U + pV can be
written as
• DH = DU + DpV Since p is constant, we can write
• DH = DU + pDV
• DH = qp, heat absorbed by the system at constant pressure
• DH is negative for exothermic reactions which evolve heat during the reaction
and
• DH is positive for endothermic reactions which absorb heat from the
surroundings.
• At constant volume (DV = 0), DU = qV,

• DH = DU + pDV DH = qp = DU = qV
• The difference between DH and DU is not usually significant for systems
Relation between ΔH and ΔU for the system having Gases
• Let us consider a reaction involving gases.
• If VA = total volume of the gaseous reactants, VB = total volume of the
gaseous products,
• nA = No. of moles of gaseous reactants , and nB = No. of moles of
gaseous products,
• At constant T and P, pVA = nART and pVB = nBRT
Dng refers to the number of moles of
• Thus, pVB – pVA = nBRT – nART = (nB–nA)RT
gaseous products minus the number of
p (VB – VA) = (nB – nAmoles
) RT of gaseous reactants.

or p DV = DngRT
DH = DU + pDV
DH = DU + DngRT
Problem 6.5
If water vapour is assumed to be a perfect gas, molar enthalpy change for
vapourisation of 1 mol of water at 1bar and 100°C is 41kJ mol–1. Calculate the
internal energy change, when 1 mol of water is vapourised at 1 bar pressure and
100°C.
Solution
The change DH = DU + DngRT

or DU = DH – DngRT ,

DH = 41 kJ mol–1 Dng = 1 R = 8.3 JK-1mol-1 = 8.3 x 10-3 kJK-1mol-1

T = 100°C = 373 K
DU = 41 kJ mol–1 – 1 x 8.3 x 10-3kJK-1mol-1 x 373 K = 41 kJ mol-1 – 3.096 kJ mol-1
DU = 37.904 kJ mol–1
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
• Extensive and Intensive Properties
• Measurement Of DU And DH
By vinod kumar
 Extensive and Intensive Properties

• An extensive property is a property whose value depends on the

quantity or size of matter present in the system.
• For example, mass, volume, internal energy, enthalpy, heat
capacity, etc. are extensive properties.
• Those properties which do not depend on the quantity or size of
matter present are known as intensive properties.
• For example temperature, density, pressure, molar heat capacity
etc. are intensive properties.
 Continue…
Extensive and Intensive Properties

• considering a gas enclosed in a container of

volume V and at temperature T .
• Let us make a partition such that volume is
halved, each part now has one half of the
original volume,V/2 , but the temperature
will still remain the same i.e., T.
• It is clear that volume is an extensive
property and temperature is an intensive
property.
 MEASUREMENT OF DU AND DH:

CALORIMETRY:-
• Experimental technique used to measure energy changes associated with
chemical or physical processes is called calorimetry
• A calorimeter is a device used to measure the amount of heat changed in
a chemical or physical process by measuring temperature changes.
• Measurements are made under two different conditions:
• i) at constant volume, qV

• ii) at constant pressure, qp

 DU Measurements
• For chemical reactions, heat absorbed at
constant volume, is measured in a bomb
calorimeter .
• Here, a steel vessel (the bomb) is
immersed in a water bath. The whole
device is called calorimeter.
• The 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
 Continue…
DU Measurements

• 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
 DH Measurements
• Measurement of heat change at constant pressure
(generally under atmospheric pressure) can be
done in a simple calorimeter. DH = qp (at
constant p)
• Heat absorbed or evolved, qp at constant pressure
is also called the heat of reaction or enthalpy of
reaction, DrH.
• In an exothermic reaction, heat is evolved, and
system loses heat to the surroundings. Therefore,
qp will be negative and DrH will also be negative.
• Similarly in an endothermic reaction, heat is
absorbed, qp is positive and DrH will be positive.
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
• Standard Enthalpy of Reactions
• Enthalpy Changes during Phase
Transformations
• Standard Enthalpy of Formation

By vinod kumar
 Enthalpy Change, DrH Of A Reaction – Reaction
Enthalpy
• The enthalpy change accompanying a reaction is called the reaction
enthalpy (DrH) or Enthalpy of a Reaction.
Standard Enthalpy of Reactions, DrHƟ
• 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. 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 bar. Usually data are taken at 298 K.
• Standard conditions are denoted by adding the superscript Ɵ to the
symbol DH, e.g., DHƟ
 Enthalpy Changes during Phase
Transformations
Standard enthalpy of fusion
• 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, DfusHƟ.
• Melting of a solid is endothermic, so all enthalpies of fusion are positive

Standard enthalpy of vaporization

• 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, DvapHƟ.
 Continue…
Enthalpy Changes during Phase
Transformations
Standard enthalpy of sublimation
• Sublimation is direct conversion of a solid into its vapour.
• DsubHƟ is the change in enthalpy when one mole of a solid substance
sublimes at a constant temperature and under standard pressure
(1bar).
• Solid CO2 or ‘dry ice’ sublimes at 195K with DsubHƟ=25.2 kJ mol–1;

• Naphthalene sublimes slowly and for this DsubHƟ = 73.0 kJ mol–1

• The magnitude of the enthalpy change depends on the strength of
the intermolecular interactions in the substance undergoing the
phase transformations.
Problem 6.7
A swimmer coming out from a pool is covered with a film of water weighing
about 18g. How much heat must be supplied to evaporate this water at 298 K ?
Calculate the internal energy of vaporisation at 298K. Dvap HƟfor water at 298K=
44.01kJ mol–1
Solution:- process of evaporation 18 g of water = 1 mole of water
Heat supplied to evaporate18g water at 298 K = n × DvapHƟ = (1 mol) × (44.01 kJ
mol–1) = 44.01 kJ
DH = DU + DngRT

or DU = DH – DngRT ,

DH = 44.01 kJ mol–1 Dng = 1 R = 8.314 JK-1mol-1 = 8.314 x 10-3kJK-1mol-

1
T = 298K
DU = 44.01 kJ mol–1 – 1 x 8.314 x 10-3kJK-1mol-1 x 298 K = 44.01kJ mol-1 – 2.48 kJ
 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 (also known as reference states) is called Standard
Molar Enthalpy of Formation. Its symbol is DfHƟ
• The reference state of an element is its most stable state of
aggregation at 25°C and 1 bar pressure.
• For example, the reference state of dihydrogen is H2 gas and those

of dioxygen, carbon and sulphur are O2 gas, Cgraphite and Srhombic

respectively.
 Continue…
Standard Enthalpy of Formation

• standard molar enthalpy of formation, DfHƟ, is just a special case of

DrHƟ, where one mole of a compound is formed from its constituent

elements.
• It is not an enthalpy of formation of calcium carbonate, since calcium
carbonate has been formed from other compounds, and not from its
constituent elements.
 Continue…
Standard Enthalpy of Formation
• for the reaction given below, enthalpy change is not standard
enthalpy of formation, DfHƟfor HBr(g)

• Here two moles, instead of one mole of the product is formed from the
elements, i.e., .
Dr HƟ = 2Df HƟ
• expression for enthalpy of formation of HBr (g) is written as
 Continue…
Standard Enthalpy of Formation

• By convention, standard enthalpy for formation, DfHƟ, of an

element in reference state, i.e., its most stable state of
aggregation is taken as zero.
• How much heat is required to decompose calcium carbonate?

decomposition of CaCO3 (s) is an endothermic

process
 Class XI Chemistry
Unit 6
THERMODYNAMICS

• Topic:-
 Thermochemical Equations
 Hess’s Law of Constant Heat Summation

By vinod kumar
 Thermochemical Equations
• A balanced chemical equation together with the value of its DrH is
called a thermochemical equation.
• We specify the physical state (along with allotropic state) of the
substance in an equation.

• The above equation describes the combustion of liquid ethanol at

constant temperature and pressure.
• The negative sign of enthalpy change indicates that this is an
exothermic reaction.
 Continue…
Thermochemical Equations

remember the following conventions regarding thermochemical

equations.
1) The coefficients in a balanced thermochemical equation refer to the
number of moles (never molecules) of reactants and products
involved in the reaction.
2) The numerical value of DrHƟ refers to the number of moles of
The unit for
•substances D r H Ɵ
is kJ mol –1
, which means
specified by an equation. per enthalpy
Standard mole of change D HƟ
r

willreaction.
have units as kJ mol–1.
• Once we balance the chemical equation in a particular way,
this defines the mole of reaction.
Continue…
Thermochemical Equations
Continue…
Thermochemical Equations
 Continue…
Thermochemical Equations

3) When a chemical equation is reversed, the value of DrHƟ is

reversed in sign. For example
 Hess’s Law of Constant Heat
Summation
• Enthalpy is a state function
• Enthalpy change for a reaction is the same whether it occurs in one step or
in a series of steps.
• Statement:
• 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 may be divided at the same
temperature.
Continue…
Hess’s Law of Constant Heat
Summation
 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
 Standard Enthalpy of Combustion
 Enthalpy of Atomization
 Bond Enthalpy

By vinod kumar
 Standard Enthalpy of Combustion (symbol :
DCHƟ)
• Combustion reactions are exothermic in nature.
• 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 (C4H10).
Problem 6.9
The combustion of one mole of benzene takes place at 298 K and 1 atm. After
combustion, CO2(g) and H2O (l) are produced and 3267.0 kJ of heat is

liberated. Calculate the standard enthalpy of formation, Df HƟ of benzene.

Standard enthalpies of formation of CO2(g) and are –393.5 kJ mol–1 and –

285.83 kJ mol–1 respectively.
Solution
The formation reaction of benzene is given by :
Continue.. Solution of Problem 6.9
The enthalpy of combustion of 1 mol of benzene is

The enthalpy of formation of 1 mol of CO2(g) :

The enthalpy of formation of 1 mol of H2O(l) is :

Using equation (ii), (iii) and (iv) we have to bring the following equation (i)

So multiply equation (iii) by 6 and (iv) by 3 and reverse equation (ii)

Continue.. Solution of Problem 6.9

Now add equation (v), (vi) and (vii)

 Continue.. Solution of Problem 6.9
Alternate method

Given DfHƟ CO2(g) = –393.5 kJ mol–1 and DfHƟ = – 285.83 kJ mol–1 , D fH Ɵ

 Enthalpy of Atomization (symbol: DaHƟ)

• It is the enthalpy change on breaking one mole of bonds completely to

obtain atoms in the gas phase.

• In case of diatomic molecules, like dihydrogen , the enthalpy of atomization

is also the bond dissociation enthalpy.
• Other examples

In this case, the enthalpy of

atomization is
same as the enthalpy of sublimation
 Bond Enthalpy (symbol: DbondHƟ)
(i) Bond dissociation enthalpy
(ii) Mean bond enthalpy
(i) Bond dissociation enthalpy
• For diatomic molecules 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.

it is the same as the

enthalpy of
atomization
(ii) Mean bond enthalpy
• Used for Polyatomic Molecules
• 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 :

 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
 Lattice Enthalpy
 Born-Haber Cycle
 Enthalpy of Solution
 Enthalpy of Dilution

By vinod kumar
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
The importance of the cycle is that,
the sum of the enthalpy changes
round a cycle is zero.
 Enthalpy of Solution (symbol : DsolHƟ )
• Enthalpy of solution of a substance is the enthalpy change when
one mole of it dissolves in a specified amount of solvent.
• The enthalpy of solution at infinite dilution is the enthalpy change
observed on dissolving the substance in an infinite amount of
solvent when the interactions between the ions (or solute
molecules) are negligible.
 Continue…
Enthalpy of Solution (symbol : DsolHƟ )
• For most of the ionic compounds, Dsol HƟ is positive and the
dissolution process is endothermic.
• Therefore the solubility of most salts in water increases with
rise of temperature.
• If the lattice enthalpy is very high, the dissolution of the
compound may not take place at all.
 Enthalpy of Dilution
• It is the heat change when additional solvent is added to the
solution.
• The enthalpy of dilution of a solution is dependent on the original
concentration of the solution and the amount of solvent added.
• Enthalpy change for dissolving one mole of gaseous hydrogen
chloride in 10 mol of water (10 aq.)

• The values of enthalpy of solution depend on amount of solvent.

• Enthalpy of solution approaches a limiting value, i.e, the value in infinitely
dilute solution(S-3)
 Continue…
Enthalpy of Dilution

Subtract equation S-1 from the equation S-2

we obtain–

• This value (–0.76kJ/mol) of DH is enthalpy of dilution.

 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
 Spontaneous Process
 Criterion for Spontaneity-Driving force for
spontaneous process
 Entropy
By vinod kumar
Spontaneous Process
• A spontaneous process is one that occurs on its own or once
started proceeds, without the external input of energy.
• It cannot be reversed on its own. It is unidirectional
• All natural processes are spontaneous.
• For example,
• a gas expanding to fill the available volume,
• burning carbon in dioxygen giving carbon dioxide
• Rolling of ball downhill
• Rusting of iron
• Freezing of water at temperatures below 0oC
• Melting of ice
 Criterion for Spontaneity-Driving force for
spontaneous
Decrease process
in Enthalpy
• Spontaneous physical process
• flow of water down hill
• fall of a stone on to the ground
• there is a net decrease in potential energy in the
direction of change.
• Exothermic chemical reactions are
spontaneous because decrease in
energy has taken place
• Driving force for a spontaneous
process is ‘decrease in energy
(enthalpy)’ i.e. - ΔH
 Continue…
Criterion for Spontaneity-Driving force for
spontaneous process
• Decrease in the
Now examine Enthalpy
following reactions:
• The reaction between solid barium hydroxide octahydrate and solid
ammonium thiocyanate is endothermic and spontaneous.
• While most acid-base reactions are exothermic, the reaction of baking
soda with vinegar is endothermic.
• Dissolution of Common salt into water is endothermic and
• These
spontaneous
reactions though endothermic (ΔH is positive), are spontaneous.
• Therefore, it is concluded that decrease in enthalpy may be a contributory
factor for spontaneity, but it is not true for all cases.
Continue…
Criterion for Spontaneity-Driving force for spontaneous process
Another criteria
• examine such a case in which DH = 0 i.e., there is no change in
enthalpy, but still the process is spontaneous.
• Consider diffusion of two gases into each other in a closed container
which is isolated from the surroundings
Continue…
Criterion for Spontaneity-Driving force for spontaneous process
Another criteria
• We may now formulate another postulate:
• in an isolated system, there is always a tendency for the systems’
energy to become more disordered or chaotic and this could be a
criterion for spontaneous change !
• To express this disorder of system, another thermodynamic term is
used which is called Entropy
 Entropy (S)
• Entropy is a measure of the degree of randomness or disorder in the system.
• The greater the disorder in an isolated system, the higher is the entropy.
• Qualitatively, Order of entropy :-Solid(lowest entropy) < Liquid < gas (highest
entropy)
• Entropy is a state function and DS is independent of path.
• Whenever heat is added to the system, it increases molecular motions causing
increased randomness in the system.
• A system at higher temperature has greater randomness in it than one at lower
temperature.
• Heat added to a system at lower temperature causes greater randomness than
when the same quantity of heat is added to it at higher temperature.
• This suggests that the entropy change is inversely proportional to the
temperature.
 Continue…
Entropy (S)
• DS is related with q and T for a reversible reaction as
• The total entropy change ( DStotal) for the system and surroundings of a
spontaneous process is given by

• When a system is in equilibrium, the entropy is maximum, and the change in

entropy, DS = 0.
• Entropy for a spontaneous process increases till it reaches maximum and at
equilibrium the change in entropy is zero.
• Since entropy is a state property, we can calculate the change in entropy of
a reversible process by
 Continue…
Entropy (S)
• Both for reversible and irreversible expansion for an ideal gas, under
isothermal conditions, DU = 0, but DStotal i.e., DSsys + DSsurr is not zero for
irreversible process.
• Thus, DU does not discriminate between reversible and irreversible process,
whereas DS does.
• DStotal > 0 Process is spontaneous

• DStotal < 0 Process is Non-spontaneous

•• DS total = 0 System
Conclusion:-neither is in equilibrium
decrease in enthalpy nor increase in entropy of the
system
• DS alone
sys alone cancan
notdetermine
decide thethe direction of
spontaneity of spontaneous change
the process for for
closed closed
and open
and open systems
system.
 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
 Gibbs Energy
 Gibbs Energy and Spontaneity
 Effect of Temperature on Spontaneity of
Reactions

By vinod kumar
 Gibbs Energy or Gibbs Function, G
• G = H – TS Gibbs function, G is an extensive property and a state
function.
• Its absolute value also can not be determined.
• The change in Gibbs energy for the system, DGsys can be written as

DG has units of energy

i.e J
• DH is the enthalpy change of a reaction, TDS is the energy which is not available
to do useful work.
• So DG 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.
 Gibbs Energy and Spontaneity

• If the system is in thermal equilibrium with the surrounding, then the

temperature of the surrounding is same as that of the system.
• Also, increase in enthalpy of the surrounding is equal to decrease in the
enthalpy of the system.
• Therefore, entropy change of surroundings,
 Continue…
Gibbs Energy and Spontaneity

• DStotal > 0 Process is spontaneous DG < 0

(Negative)
• DStotal < 0 Process is Non-spontaneous DG > 0
(Positive)
• DStotal = 0 System is in equilibrium DG =
0 (Equilibrium)
Effect of Temperature on Spontaneity of
Reactions
 Class XI Chemistry
Unit 6
THERMODYNAMICS
• Topic:-
 Second Law of Thermodynamics
 Third Law of Thermodynamics
 Gibbs Energy Change And Equilibrium

By vinod kumar
 Entropy and Second Law of
Thermodynamics
• Entropy is the loss of energy available to do work.
• Another form of the second law of thermodynamics states that the
total entropy of a system either increases or remains constant; it never decreases.
• Entropy is zero in a reversible process; it increases in an irreversible process .
• Entropy of any isolated system always increases.
• In exothermic reactions heat released by the reaction increases the disorder of the
surroundings and overall entropy change is positive which makes the reaction
spontaneous.
 Absolute Entropy and Third Law of
Thermodynamics
• The entropy of any pure crystalline substance approaches zero as
the temperature approaches absolute zero. This is called third law
of thermodynamics.
• The importance of the third law is that absolute values of entropy of
pure substance can be determined.
 GIBBS ENERGY CHANGE AND
EQUILIBRIUM
• Reversible chemical reaction is the reaction which can proceed in
either direction simultaneously that is reactants convert into products
and products convert in to reactants at the same rate, so that a
dynamic equilibrium is set up.
• This means that the reactions in both the directions should proceed
with a decrease in free energy, which seems impossible.
• It is possible only if at equilibrium the free energy of the system is
minimum.
• So, the criterion for equilibrium
A + B C + D ; is DrG = 0
 Continue…
GIBBS ENERGY CHANGE AND
EQUILIBRIUM
• Gibbs energy change for a reaction in which all reactants and products are in
standard state, is known as Standard Gibbs energy change DrGƟ
• It is related to the equilibrium constant of the reaction as follows:
DrG = DrGƟ + RT ln K at equilibrium DrG =0 so, DrGƟ= –
RT ln K
or DrGƟ = – 2.303 RT log K where K = equilibrium constant

DrGƟ = DrHƟ - T DrSƟ = – 2.303 RT log K

• For strongly endothermic reactions, the DrHƟ large and positive, value of K <<
1 and the reaction is unlikely to form much product.
• In case of exothermic reactions, DrHƟ large and negative, and DrGƟ large and
negative, K >> 1 hence can go to near completion.
Problem 6.12
Calculate DrGƟ for conversion of oxygen to ozone, 3/2 O2(g) ® O3(g)

at 298 K. if Kpfor this conversion is .

Solution
We know DrGƟ = – 2.303 RT log Kp and R =

Therefore, DrGƟ = – 2.303 ()× (298 K) (log )

= =
Problem 6.13
Find out the value of equilibrium constant for the following reaction
at 298 K.

Standard Gibbs energy change, DrGƟ at the given temperature is –

13.6 .
Solution
DrGƟ = – 2.303 RT log K

K = antilog 2.38 = 2.4 × 102

 How to By vinod
Solve log
and antilog
kumar
log 2467= 3.3909 +0.0012=3.3921
log 382.4 = 2.5821 + 0.0005=2.5826
log 55.2 =1.7419
log 2.03=0.3075
log 0.02453=log(2.453

log 5 = log 5.000 = 0.6990

log 0.2 = log (2
Anti-log table

antilog 5.2345 =1.716

antilog 15.5933 =
antilog 15 =antilog 15.000=1.000