By: P.

Anggai
 Burning of coal
Chemical energy  heat energy Burning of coal
Chemical energy  mechanical energy
Thermodynamics is the study of the relations between heat, work, temperature, and energy.

Thermodynamics deals inter-conversion of heat and other forms of energy.

System, surrounding, boundary
• System  part of the universe which is under
study/observation

• Surrounding  include everything other than the

system which can interact with the system

• Universe = system + surrounding

• Boundary  separates the system and surrounding

• Boundary can be real or imaginary ; rigid or non-

rigid.

• Boundary is designed to track all movements

between the system & surrounding.

• Diathermic wall: allows heat exchange between

system and surrounding

• Adiabatic wall: does not the exchange of heat

between system & surrounding.
Types of systems based on boundary
 Types of systems based on composition

Homogeneous system Heterogeneous system

• Completely uniform throughout • Not uniform throughout

• Made of one phase only • Consists of two or more phases
• For example: mixture of two miscible liquids. • For example: mixture of insoluble solid in water.
Illustration for intensive & extensive property
 The operation done to
Thermodynamic processes
change a system from
one state to another state
e) Cyclic process
is called
When a system
thermodynamic
undergoes a number of
process.
different processes and
finally returns to its
a) Isothermal Process initial state.
The process in which ΔU =0 & ΔH =0
change in pressure and
volume takes place at a d) Isochoric
constant temperature, (b) Adiabatic (c) Isobaric
Process
is called a isothermal Process Process
The process in
change. It may be noted The process in which The process in
which changes in
that in such a change change in pressure which change in
pressure and
total amount of heat of and volume and volume and
temperature take
the system does not temperature takes temperature of a
place in such a
remain constant. place without any gas take place at a
way that the
ΔT =0 heat entering or constant pressure
volume of the
leaving the system is is called an
system remains
called adiabatic isobaric process.
constant, is called
change. ΔP =0
isochoric process.
q =0
State of the system
• The state of a system is determined with the help of some measurable quantities like
volume
temperature
density
pressure, etc.
• These quantities that can identify the state of a function are called properties.
• State and path functions both are thermodynamics terms that are used to name these properties.

State variable/function
A thermodynamic Eg:
property that depends • Density is a state function.
only on the initial • substance's density is not affected
and final state and by how the substance is obtained.
does not depend on • Consider a quantity of H2O:
the path taken to it does not matter whether that H2O
reach the final state is obtained from the tap, from a well,
or value is known as or from a bottle, because as long as
the state function or all three are in the same state, they
point function. have the same density.
Enthalpy as state function

Therefore Enthalpy is a state

function.
Examples of path function:
Heat , work
Work is a path function
Sign convention for heat and work
 Internal energy

• Internal energy is the sum of different types of energies associated with atoms and molecules
such as electronic energy (Ee), nuclear energy (En), chemical bond energy (Ec ), potential
energy (Ep), kinetic energy (Ek) which is the sum of translational energy (Et) , vibration energy
(Ev) and rotational energy (Er).

• It is represented by symbol U or E.

• U or E = Ee + En + Ec + Ep + Ek

• The energy thus stored within a substance is called its internal energy.

• Every substance is associated with a definite amount of internal energy but it is not possible to
find its absolute value because it involves certain quantities which cannot be measured.

• It is a state function.

• It is an extensive property.
Internal energy change

• If the internal energy of the system in the initial state is U1 and in the final state, U2 , then the
change of internal energy may be given by
ΔU = U2 – U1

• In a chemical reaction ,if UR is the internal energy of the reactants and Up is the internal
energy of products, then energy change accompanying the reaction would be:
ΔU = UP – UR

• Internal energy of a system changes when

(1) Heat passes in or out of the systemΔ
(2) Work is done on or by the system
(3) Matter enters or leaves the system

• There is no change in internal energy in a cyclic process.

 Internal energy as state function
• Internal energy is a state function i.e. depends only upon the state of the system and is independent of the method by
which this state has been attained.
• Let us change the internal energy of the system by doing work called adiabatic work. This can be done in two ways:
(1) By doing mechanical work by rotating a set of small paddles.
(2) By doing electrical work with the help of an immersion rod.
Changing Internal energy using different types of work
(i) Mechanical work Let the initial state be A (i) Electrical work
(1kJ) Let the final state after work done be B (1kJ)
Rotating a small paddle Initial temperature = TA Using Immersion
Final temperature = TB rod
Initial internal energy = UA
Final internal energy = UB
In both the cases TB > TA
∆T = TB – TA

Change in internal energy

∆U = UB – UA = wad

Irrespestive of the path , the change in internal energy produced is same in both cases.
So, it is a state function.
 Changing Internal energy by exchanging heat

Let us consider bringing about the same change in temperature by transfer of heat through thermally conducting
walls instead of adiabatic wall.

Temperature of water = TA
Temperature of reservoir = TB
Heat absorbed by the system = q = TB - TA
Change in internal energy = ∆U =q (when no work is done at constant volume)
 Changing Internal energy by exchanging heat and by doing work

Let us consider the general case in which a change of state is brought

about both by doing work and by transfer of heat

Internal energy for this case as:

∆U = q + w

If there is no transfer of energy as heat or as work (isolated system)

i.e., if w = 0 and q = 0
then ∆ U = 0.
 First law of thermodynamics
“Energy can neither be created nor destroyed, but it can be changed from one form to another”
•It also known as the law of conservation of energy
•It can be represented mathematically as:
∆U = q + w
Where, Sign convention
ΔU - change in internal energy
ΔU (change in Q (heat) W (work done on
q - heat given or lost internal energy) the gas)
w - work done
is “+” if is “+” if heat enters is “+” if gas is
temperature gas compressed
increases

is “-” if temperature is “-” if heat exits is “-” if gas expands

decreases gas

is “0” if is “0” if no heat is is “0” if volume is

temperature is exchanged constant
constant
 Work

• Let us consider the mechanical work done by a system.

• Mechanical work is pressure – volume work. (PV work)
• It can be either expansion or compression.

Compression Expansion
 Derivation for pressure – volume work
Change in volume = Distance (l) x Area (A)
ΔV = l x A
ΔV = Vf - Vi ------- (1)

Pressure = Force /Area

Force on Piston (F) = Pressure x Area
F = Pex x A ----- (2)

Let us consider a cylinder which contains one Work(w) = Force (F) x Distance (l) ---(3)
mole of an ideal gas fitted with a frictionless
piston. On substituting 2 in 3,
w = Pex x A x l
Total volume of the gas = Vi w = Pex x (-ΔV) {(i.e) l x A = ΔV }
Pressure of the gas inside = P
w = -Pex x (Vf - Vi)
External pressure = Pex The negative sign of this expression is required to obtain
conventional sign for w, which will be positive.
If Pex > P, piston is moved inward till the In case of compression work is done on the system :
pressure inside becomes equal to Pex. (Vf – Vi ) = -ve
(compression) negative multiplied by negative will be positive.
Hence the sign obtained for the work will be positive.
General expression for work
 Work done if pressure is not constant
Case (i): If the pressure is not constant at every Case (ii): If the pressure is not constant but changes
stage of compression, but changes in number of during the process such that it is always
finite steps, work done on the gas will be: infinitesimally greater than the pressure of the gas,
then, at each stage of compression, the volume
decreases by an infinitesimal amount, dV.
In such a case we can calculate the work done on the
gas:
 General equation for external pressure applied
Compression: Expansion: In general case:

External pressure is greater than External pressure is less than External pressure can be less than
pressure of the system. pressure of the system. or greater than pressure of the
system in a reversible reaction.
 Reversible and Irreversible processes

Reversible process Irreversible process

•A reversible process is one that takes place infinitesimally
•Processes, which are not reversible, are
slowly and the direction of which at any point can be
reversed by an infinitesimal change in the state of the known as irreversible processes
system.

Eg: Adding grains on the top of piston

•In a reversible process the system is in equilibrium in the

initial, final and all intermediate stages.
Derivation for relationship between work and internal pressure in reversible reaction

Since dp.dv is very small, we can

------ (1)

------ (2)

Substituting (2) in (1),

 Work done in free expansion

Free Expansion:
•The expansion against vacuum
•In free expansion
If the gas expands in vacuum, external
work transfer = 0 pressure Pex being zero in the expression
•Reason: zero resistance against expansion
W =-Pex.∆V
W=0

This is known as free expansion.

No work is done during the free expansion

of an ideal gas whether the process is
reversible (or) irreversible.
In the above case, if partition is removed, the
gas expands rapidly without any resisting or
opposing force.
 Modification in the equation of first law of thermodynamics
(based on type of processes)
According to the first law of thermodynamics the internal energy is,
∆U =q + w Isothermal & free expansion of an ideal gas
On substituting the value of w in the equation, When an ideal gas is subjected to isothermal
∆U = q + (- Pex.∆V) expansion (∆T = 0) in vacuum the work done
w = 0 as pex=0.
As determined by Joule experimentally q =0,
Isochoric process: thus ∆U = 0.
If the process is carried out Isothermal irreversible change:
at constant volume (∆V = 0), q = -w
work done is also zero. = pex(Vf-Vi)
No work is done during free expansion and
change in internal energy, Isothermal reversible change:
∆U =qv, q = -w
where qv - heat supplied at constant volume. = nRT ln (Vf/Vi)
= 2.303 nRT log (Vf/Vi)

Adiabatic change:
q =0, ∆U = w
 Enthalpy

To study the heat changes in a chemical reaction at constant temperature and constant pressure, a new thermodynamic
function called enthalpy was introduced.
•Enthalpy(H) is the “sum of the internal energy( U) and the product of pressure (P) and volume (V).”
{total heat content}

H = U + PV

Where,
H = Enthalpy of the system
U = Internal energy of the system
p = Pressure of the system
V = Volume of the system

• Enthalpy is a state function.

•Enthalpy is an extensive property.
• Every substance has definite value of enthalpy.
• It is impossible to calculate absolute value of enthalpy.
• The change in enthalpy can be found using initial and final enthalpy.
Change in enthalpy = Enthalpy of products - Enthalpy of reactants
∆H = HP-HR
 Derivation of Change in Enthalpy
According to first law of thermodynamics,
q= ΔU + PΔV Under conditions of constant pressure, putting w= –P ΔV
and representing the heat absorbed by qp we get,
If the process is carried out at constant volume , ΔV=0 qp = ΔU + PΔV
qv = ΔU When the system absorbs qp joules of heat, its internal
where v indicates constant volume. energy increases from U1 to U2 and the volume increases
from V1 to V2.Then, we have,
Internal energy change is the heat absorbed or evolved at ΔU = U2 – U1
constant volume.
ΔV = V2 -V1
ΔU is a state function, therefore qv ,is also a state function.
qp = ( U2 – U1 ) + P ( V2 -V1)
qp= ( U2 + PV2 ) – ( U1 + PV1)
If the process is carried out at constant pressure, the The thermodynamic quantity U + PV is called heat
work of expansion is given by content or enthalpy of the system and is represented by
w = –P ΔV symbol H.
where ΔV is the increase in volume H= U + PV
P is the constant pressure. If H2 - enthalpy of the system in the final state
H1 - enthalpy of the system in the initial state
q=ΔU – w H2 = U2 + PV2
where q is the heat absorbed by the system, H1 = U1 + PV1
ΔU is the increase in internal energy of the system
qp =H2 -H1
w is the work done by the system.
qp =ΔH
 Relationship between Enthalpy & Internal energy
The heat of reaction is given by enthalpy change ΔH as,

Consider a reaction in which

Number of moles of gaseous reactant in initial state = n 1

Number of moles of gaseous reactant in final state = n 2.

Initial enthalpy = H1
Initial internal energy = U1
Initial pressure = P1
Initial volume =V1

Final enthalpy = H2
Final internal energy = U2 If qP and qV are the heats involved in the reaction at constant
Final pressure = P2 pressure and constant volume respectively, then since
Final volume =V2 qp = ΔH and qv = ΔU.
∴ qp = qv +ΔnRT
 Heat capacity

• Thermal capacity, also known as heat capacity, is defined as “the amount of heat required to raise the
temperature of the whole body (mass m) through 1°C or 1 K.”

• It is represented by C.

• When some of heat is supplied to a body of mass m, its temperature rises.

• Let the change in temperature of the body be ΔT and the heat energy supplied be q.

• Then the relation between the heat capacity (C) of the body, the change in temperature (ΔT) of the body and the
supplied heat Q is given as
q=C ΔT
• Therefore,
C=q /ΔT
 Characteristics of Heat capacity
• The value of thermal capacity of a body depends upon the nature of the body and its mass.

• 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.

• C is directly proportional to amount of substance.

Molar Heat capacity

“The amount of heat required to raise the temperature of 1 mole of a substance through 1° C.”
Cm = C/n

Specific Heat capacity

“The amount of heat required to raise the temperature of 1 gram of a substance through 1°C.”

The amount of heat , q , required to raise the temperature from T 1 to T2 of mass m grams of a sample and having specific
heat capacity, c, can be calculated as:
q= m × c × ΔT
q = C × ΔT

Specific heat capacity of water is 1 cal g-1 K-1 or 4.18 J g-1 K-1.
Relationship between Cp and Cv for an ideal gas

Where
Cv – heat capacity at constant
volume

Cp – heat capacity at constant

pressure
 Measurement of ΔU and ΔH using CALORIMETRY
The change in energy associated with chemical or physical processes can be measured by an experimental technique
called calorimetry.

• In calorimetry, the process is carried out in a vessel called calorimeter, which is

immersed in a known volume of a liquid.

• Knowing the heat capacity of the liquid in which calorimeter is immersed and the heat
capacity of calorimeter, it is possible to determine the heat evolved in the process by
measuring temperature changes.

• Measurements are made under two different conditions:

i) at constant volume, qv
ii) at constant pressure, qp
 (a) Measurement of ΔU
Internal energy change is measured experimentally using an apparatus called Bomb calorimeter.

It consists of a strong steel vessel which can stand high

pressure.
It is surrounded by a bigger vessel which contains water
and is insulated.
A thermometer and a stirrer are suspended in it.

Procedure
• A known mass of compound is taken in the platinum
cup.
• Oxygen under high pressure is introduced into the bomb.
• A current is passed through the filament immersed in the
compound.
• Combustion of the compound takes place. The value of ΔU can be calculated using the formula:
• The increase in the temperature of water is noted. ΔU = (Q × Δt × M ) / m
• From this, the heat capacity of the apparatus can be where
calculated. Q =heat capacity of the calorimeter
• The experiment is repeated as in step 1. Δt = rise in temperature
• As the reaction is carried out in a closed vessel, therefore, m= mass of the substance taken
heat evolved is the heat of combustion at constant M =molecular mass of the substance
volume and hence is equal to internal energy change.
 (b) Measurement of ΔH
Heat change at constant pressure (at atmospheric pressure) can be measured using a coffee cup calorimeter.

Instead of bomb, a styrofoam cup is used in this calorimeter.

It acts as good adiabatic wall and doesn't allow transfer of heat produced during the
reaction to its surrounding.
This entire heat energy is absorbed by the content inside the cup.
This method can be used for the reactions where there is no appreciable change in
volume. The change in the temperature of water is measured and used to change in heat
energy.
The chemical reaction of heat of neutralisation between an acid (HCl) and a base (NaOH)
can be used to demonstrate the calculation of ΔH.

Procedure
• Take a known volume and a known concentration of HCl in a beaker.
• Take the same volume and a concentration of NaOH in another beaker.
• Keep both the beakers in a water bath to bring them to the same temperature. A Coffee-Cup Calorimeter.
This simplified version of a
• Note the initial temperature of both the acid and the base. constant-pressure calorimeter
• Pour both the acid and the base into the bottle of the calorimeter. consists of two Styrofoam cups
• Stir them together. nested and sealed with an
insulated stopper to thermally
• Note the highest temperature attained by the solution.
isolate the system (the solution
• Note the total mass of the solution. being studied) from the
Heat produced = mass x specific heat x rise in temperature surroundings (the air and the
ΔH= qp = m × cp × ΔT laboratory bench).
 Enthalpy of reaction
In any general chemical reaction, the reactants undergo chemical changes and combine to give products.
It can be represented by the following equation:

For any such reaction, the change in enthalpy is represented as ΔrH and is termed the reaction enthalpy.
The reaction enthalpy is calculated by subtracting the sum of enthalpies of all the reactants from that of the
Mathematically,
products.
ΔtH = Sum of enthalpies of the product – sum of the enthalpies of the reactants.

Where,
constants ai and bi - stoichiometric coefficients of the products and the reactants respectively

Standard Enthalpy of reaction

The standard enthalpy of reaction is the enthalpy change for a reaction when all the participating substances are in their
standard states.
Standard conditions are denoted by adding the superscript ° or a Plimsoll (⦵) character to the symbol ∆H, e.g., ∆H º
The standard state of a substance at a specified temperature is its pure form at 1 bar.
Example:
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.
Enthalpy changes during phase transformation
 Standard Enthalpy of formation
Standard enthalpy of formation is defined as the enthalpy change when one mole of a compound is formed from its elements
in their most stable state of aggregation (stable state of aggregation at temperature: 298.15 K, pressure: 1 atm).

Example: formation of methane from carbon and hydrogen

Enthalpy of formation is basically a special case of standard enthalpy of reaction where two or more reactants combine to
form one mole of the product.
Let us take an example of the formation of hydrogen bromide from hydrogen and bromine.

As we can see in this case two moles of hydrogen bromide are produced.
Hence, enthalpy of reaction cannot be taken as enthalpy of formation of hydrogen bromide rather we can say:

All elements in their standard states (oxygen gas, solid carbon in the form of graphite, etc.) have a standard enthalpy of
formation of zero.
 Application of Standard Enthalpy of formation

Suppose, you are a chemical engineer and want to know how much heat is required to decompose calcium carbonate to
lime and carbon dioxide, with all the substances in their standard state.

Here, we can make use of standard enthalpy of formation and calculate the enthalpy change for the reaction.
The following general equation can be used for the enthalpy change calculation.

where a and b represent the coefficients of the products and reactants in the balanced equation.
Let us apply the above equation for decomposition of calcium carbonate.
Here, coefficients ‘a’ and ‘b’ are 1 each

Thus, the decomposition of CaCO3 (s) is an endothermic

process and you have to heat it for getting the desired products
 Thermochemical Equations

A balanced chemical equation together with the value of ∆rH and the physical state of reactants and products is known
as thermochemical equation.

Fractional coefficients may be used in writing a thermochemical equation.

H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) +285.8 KJ mol-1

H2 ( g ) + ½ O2 ( g ) ———> H2O ( l ) ΔH = – 285.8 KJ mol-1
285.8 KJ mol-1 of heat is produced when 1 mole of hydrogen reacts with 0.5 mole of Oxygen.
If the quantities of reactants are doubled, the heat produced will also be doubled.

2H2 ( g ) + O2 ( g ) ———> 2 H2O ( l ) + 571.6 KJ mol-1

2H2 ( g ) + O2 ( g ) ———> 2H2O ( l ) ,ΔH = – 571.6 KJ mol-1
 Conventions about thermochemical
1)equation
For exothermic reaction, ΔH is negative whereas for endothermic reaction, ΔH is positive.

2) ΔH values are for the standard state of the substance ( 298 K and 1 bar pressure )

3) The coefficients of different substances represents the number of moles of reactants and products.

4) The physical state of the different substances must be mentioned as the heat evolved or absorbed depends upon the
physical state.

5) If the coefficient of the substances are multiplied or divided by some number , then the value of ΔH should be
multiplied or divide by the same number.
6) If the reaction is reversed ,the sign of ΔH changes but the magnitude remains the same.
Hess law of
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 may be divided at the same temperature.

Consider the enthalpy change for the reaction

Although CO(g) is the major product, some CO2 gas is always produced in this reaction.
Therefore, we cannot measure enthalpy change for the above reaction directly.
However, if we can find some other reactions involving related species, it is possible to calculate the enthalpy change for the
above reaction.
Adding equation (i) and (iii), we get the desired equation,
 Enthalpies of different types of reactions
Standard Enthalpy of combustion
(Δ𝐻⦵
c) standard enthalpy of combustion is the “ enthalpy change when one mole of substance burns completely in oxygen
• The
under standard conditions and standard states.”

• Combustion reactions are exothermic.

• Standard enthalpies of combustion are used to compare the amount of energy that can be obtained from different
types of combustible fuels.

• Eg:
standard enthalpy of combustion for ethane:

standard enthalpy of combustion for propane:

standard enthalpy of combustion for glucose:

Problem:
Standard Enthalpy of atomization
(Δ𝐻⦵a)
• Change in enthalpy when one mole of bonds is completely broken to obtain atoms in the gas phase
(or)
• Enthalpy change accompanying the dissociation of all the molecules in one mole of gas phase substance into gaseous
atoms

• Enthalpy of atomization is always positive ( Endothermic).

For diatomic molecules, enthalpy of atomization = enthalpy of bond

dissociation.
Eg:

• In the below case, the enthalpy of atomization is same as the enthalpy of sublimation.
Bond Enthalpy
(Δ𝐻⦵bond)
• Energy is required to break a bond (endothermic) ; energy is released when a bond is formed (exothermic).

• With reference to the enthalpy changes associated with chemical bonds, two different terms are used in
thermodynamics.
(i) Bond dissociation enthalpy ( used in case of diatomic molecules)
(ii) Mean bond enthalpy ( used in case of polyatomic molecules)

• Both are represented by Δ b H or Δbond H.

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.”
Example: Hydrogen gas dissociates to give hydrogen atoms.
The bond dissociation energy of Hydrogen molecule is equal to enthalpy of atomisation of hydrogen.
Mean Bond Enthalpy
The bond enthalpy for polyatomic molecules is the average value of bond dissociation enthalpies.

Example: Methane

When methane bonds dissociates it requires 1665 kJ/mol energy

In methane all C-H bonds are equal in bond length and bond energy.

But energy required to break the bonds in successive steps are differ.
Bond enthalpy is mainly used to calculate enthalpy changes in reaction.

Enthalpy of reaction = Sum of enthalpies of reactants - Sum of bond enthalpies of products.

Example: Combustion of propane

CH3 CH2 CH3 +5O2 → 3CO2 +4H2O
Bond enthalpies:
C-C =347 kJ/mol
C-H = 414 kJ/mol
C=O = 741 kJ/mol
O=O = 498 kJ/mol
O-H = 464 kJ/mol

Number of bonds broken on reactants 8 C-H bonds, 2 C-C bonds and 5 O=O are present. Number of bonds formed in
products 6 C=O & 8O-H bonds.

Enthalpy of combustion of propane = Sum of enthalpies of reactants - Sum of bond enthalpies of products.
∆rH= [(8*414)+(2*347)+(5*498)-(6*741)+(8*464)]
= -1662 kJ/mol
Lattice
Enthalpy
• Ionic compounds are generally in the form of a solid and their molecular force is very strong.
• The molecules in these ionic solids are arranged in a three-dimensional grid like structure also called the
lattice structure.
• The energy needed in order to separate one mole of a solid ionic compound into constituent gaseous
ions is called lattice enthalpy.
• It is the measurement of the strength of an ionic compound.
Eg:
lattice enthalpy of sodium chloride ( NaCl) is 788 kJ mol -1 which means it requires 788 energy to separate 1
mole if Na+ (gaseous) and cl-(gaseous) to infinite distance

• 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 to
calculate lattice enthalpy.
 Lattice Enthalpy VS standard enthalpy of formation.

Example:

(Lattice enthalpy)

(Standard enthalpy of formation)

 Born Haber cycle for NaCl

PATH -2

Applying Hess’s law, we get,

PATH -1
Enthalpy of solution (Δ𝐻⦵sol)

• Enthalpy of solution of a substance is the enthalpy change when one mole of it dissolves in a specified
amount of solvent.

• There are three steps to solvation:

(i)breaking bonds between solute molecules  Endothermic
(ii)breaking intermolecular bonds between solvent molecules  Endothermic
(iii)making new bonds between solute and solvent  Exothermic

• Enthalpy of solution can be endothermic or exothermic.

( Endothermic ) ( Exothermic )
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.
This is shown diagrammatically, for an ionic compound,
AB (s)

The enthalpy of solution of AB(s),, in water is, therefore,

determined by the selective values of the lattice
enthalpy, and enthalpy of hydration of ions, as
• For most of the ionic compounds, enthalpy of solution is positive and the dissociation
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.

• The solubility of fluorides is much less than corresponding chlorides because

of high lattice enthalpy.
Enthalpy of dilution (Δ𝐻⦵dil)

• The standard enthalpy of dilution is the enthalpy change when a solution of a substance is diluted
infinitely per mole of substance.

Eg: Enthalpy change for dissolving one mole of gaseous hydrogen chloride in different volume of water can
be represented by the following equations.
For convenience we will use the symbol aq. for water

• This value (–0.76kJ/mol) of ∆H is enthalpy

of dilution.

• It is the heat withdrawn from the

surroundings when additional solvent is
added to the solution.

• The enthalpy of dilution of a solution is

S2 – S1 : dependent on the original concentration
HCl.25 aq. + 15 aq. → HCl.40 aq. of the solution and the amount of solvent
∆H = [ –72.79 – (–72.03)] kJ / mol added.
= – 0.76 kJ / mol
 First law of thermodynamics
“Energy can neither be created nor destroyed, but it can be changed from one form to another”

∆U = q + w

The first law of thermodynamics tells us about the relationship between the heat absorbed and the work
performed on or by a system.

It puts no restrictions on the direction of heat flow.

Spontaneit
y

• Flow of heat is unidirectional.

• Heat flow from higher temperature to lower
temperature.
• Heat will not flow from colder body to warmer body on
its own
 Spontaneous
reaction
What is spontaneous reaction?

Guess (1):

Spontaneous reaction is one which occurs immediately when contact is made between the reactants.

Let us consider an example:

• Combination of hydrogen and oxygen
• These gases may be mixed at room temperature and left for many years without observing any perceptible change.
• Although the reaction is taking place between them, it is at an extremely slow rate.
• It is still called spontaneous reaction.

So, guess (1) is wrong.

“ Spontaneous reactions are the one 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.”

• Spontaneous reaction cannot reverse their direction on their own.

• It is unidirectional.
 Criteria for
spontaneity
Guess (1) : Is Decrease in Enthalpy a Criterion for But even some endothermic reactions are also
Spontaneity ? spontaneous.
We may be tempted to state that exothermic
reactions are spontaneous.
Then, what drives the spontaneous process in a given direction ?
Let us examine such a case in which ∆H = 0 i.e., there is no change in enthalpy, but still the process is spontaneous.

After removing partition

 Entropy
• 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
• Entropy : It is a measure of the degree of randomness or disorder in the system.
• It is a state function and extensive property.
• The greater the disorder in an isolated system, the higher is the entropy.
• In a reaction, entropy change can be attributed to rearrangement of atoms or ions from one pattern in the reactants to
another.
• If the structure of the products is very much disordered than that of the reactants, there will be a resultant increase in
entropy.
• Decrease of regularity in structure would mean increase in entropy.
• The crystalline solid state is the state of lowest entropy (most ordered).
• The gaseous state is state of highest entropy.

• 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.
• Entropy change is inversely proportional to the temperature.
• The total entropy change ( ∆Stotal) 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 is zero, ∆S = 0.

• Entropy for a spontaneous process increases till it reaches maximum and at equilibrium the change
in entropy is zero.

• Change in entropy of a reversible process:

• Both for reversible and irreversible expansion for an ideal gas, under isothermal conditions, ∆U = 0
(but)
• ∆Stotal not zero for irreversible process.

• ∆U does not discriminate between reversible and irreversible process, whereas ∆S does.
 Gibbs
Energy
• Neither decrease in enthalpy nor increase in entropy alone can determine the direction of spontaneous change for
open and closed systems.

• We define a new thermodynamic function the Gibbs energy or Gibbs function, G.

• Gibbs free energy is used to measure the amount of energy that can be converted into useful work.

• G is an extensive property and a state function.

• Change in Gibbs energy for the system:

• At constant temperature, ∆ T = 0,
 How ∆G is related to reaction spontaneity?

We know

If the system is in thermal equilibrium with the surrounding,

then temperature of the surrounding = temperature of the
system.

Increase in enthalpy of the surrounding = decrease in the

enthalpy of the system. ∆Hsys is the enthalpy change of a reaction

Therefore, entropy change of surroundings T∆Ssys is the energy which is not available to do
useful work.

∆G 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

Rearranging the above equation:
of the reaction.

For spontaneous process, ∆Stotal > 0

∆G gives a criteria for spontaneity at constant pressure and
temperature.
If a reaction has a positive enthalpy change and positive entropy change, it can be spontaneous when T∆S is large enough
to outweigh ∆H.
This can happen in two ways:
(a) The positive entropy change of the system can be ‘small’ in which case T must be large.
(b) The positive entropy change of the system can be ’large’, in which case T may be small.
The former is one of the reasons why reactions are often carried out at high temperature.
 Second law of thermodynamics

The second law of thermodynamics states that any spontaneously occurring process will
always lead to an escalation in the entropy (S) of the universe.
 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.

• When temperature of the system rises, these motions become more vigorous and entropy increases.
• On the other hand when temperature is lowered, the entropy decreases.
• The statement is confined to pure crystalline solids because theoretical arguments and practical evidences have
shown that entropy of solutions and super cooled liquids is not zero at 0 K.
 GIBBS ENERGY CHANGE AND EQUILIBRIUM

Sign and magnitude of the free energy change of a chemical reaction allows:
(i) Prediction of the spontaneity of the chemical reaction.
(ii) Prediction of the useful work that could be extracted from it.

FREE ENERGY CHANGES IN REVERSIBLE REACTIONS.

• The term ‘reversible’ indicates that a given reaction can proceed in either direction simultaneously.
• 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.
• If it is not, the system would spontaneously change to configuration of lower free energy.
• So, the criterion for equilibrium
A + B ⇌ C + D ; ∆r G = 0
Standard Gibbs energy (∆r G°) :
Gibbs energy for a reaction in which all reactants and products are in standard state, ∆r G°
Relationship between Standard Gibbs energy (∆r G°) and equilibrium constant (K) :
∆r G° is related to the equilibrium constant of the reaction as follows:
ΔG = ΔG° + RT In Q
{ At equilibrium Q = K ; ΔG = 0 }

We also know that

For strongly endothermic reactions, the value of ∆r H° may be large and positive.
In such a case, value of K will be much smaller than 1 and the reaction is unlikely to form much product.
In case of exothermic reactions, ∆r H° is large and negative, and ∆r G° is likely to be large and negative too.
In such cases, K will be much larger than 1.
We may expect strongly exothermic reactions to have a large K, and hence can go to near completion.
∆r G° also depends upon ∆r S° , if the changes in the entropy of reaction is also taken into account, the value of K or extent
of chemical reaction will also be affected, depending upon whether ∆r S° is positive or negative

Using,
(i) It is possible to obtain an estimate of ∆G° from the measurement of ∆H° and ∆S°, and then calculate K at any
temperature for economic yields of the products.
(ii) If K is measured directly in the laboratory, value of ∆G° at any other temperature can be calculated.