Unit-6

THERMODYNAMICS
Thermodyammes deals with energy in its
Therlynannics literally, means conversion of heat into workvarious forms and
and vice vcrsa.
their
B interconversion
Thermodynamics isprimarily based up on tree fundamentat
generalisations are called F'irst, Second and 'Third laws of gcneralisations. These
thermodynarnics.
Some basic concepts in
thernmodynamies
System aud surroundings:
(System imay be detfined as the part of the universe in which
observatior's are made.

Surroundings nmay be defined as the part of the universc other than

surrvndingstogether constitute the universe. But usually for practical purposesthethhesystem)System and the
regiom of space in the
neighhourhood of the system constitutes the surroundings

Che universe The system

=
t+ The
surroundings
The
systcm and surroundings
wall that separales the
are separated by some sort of wall whicl1 is real ir imaginary. The
system from the surrounding is called boundary.
tor
exannple, if we carry out a chemical rcation in a bcaker. then the beaker
reaclin inure, is the system whiie the room
where the beaker is kept
containing the
represcnts the
G y i c yvaicr icpieseií tine boundary beiweo the systeim äid the sur+ounding surroundings. The

Types of systeums: Systems can be classified into 3 types.

) Open system:
A
system which can exchange matter as well as energy with
system.
the surroundings_is called an open
E.g. The reaction taking place in an an open beaker is an example of open system.

by Closed system:
A system that can
exchange energy with the surroundings but no matter is called a closed system.
E.g. The reaution laking place in a closed vessel made of conducting material is an exampie of open
system

e) Isolated systen:
A SYslem, wlich canneither exchangematter nor energy with the surroundings is callexd isolated
system.
E.g A reactin carried out in a closed and well insulatcd vesset like thermos flask

State of the system

Stale of the system impthes the conditions of cxistence of a particular system when its nmacroscopic
properties have defite values.

For example cousiderliquid water as the system at 25°C and one atmosphere pressure. Here all the
macroscopic properties willhave definite values. Then water at 25°C is a state of the water system. Now
the temperatureis increasedto S0'C. Then the macroscopic properties will change automatically and attain
new definite values. Sowater at 50 C will constitule another state of the water system.
 The state of a thermodynamic system is described by its measurable or macroscopic pron
rop
ne state of a system is usually described by quoting its pressure (P), volume (V, temperakure
amount(n) ete. These variables like P, V, T etc are called state variables or statefunctions.

But the two important thermodynamics parameters namely heat (9) and work (W) are not

the state functions because these are path dependent.

Exténsive and intensive properties:
(a)Extensive properties:(Theproperties ofthe system which depend uponthe quantityorsize of matter
present in the systcm, are called extensive properties.
E.g. Mass, volume, internal energy, enthalpy, heat capacity ete, elro2
The of the system which independent of the quantity or size of
(b)Intensive properties: properties are

matter present in it are called intensive properties.

E.g Temperature, pressure, refractive index, viscosity, density, specific heat etc

Usually molar properties like molar volume, molar heat capacity etc are intensive properties. A |
molar property is the value of an extensive property () for 1 mole of the substance

LThereforeit isindependent of matter.

Thermodynamic processes:
in the state of the system, is called thermodynamic
The operation, which brings about the changes
process. The various types of processes are,

constant temperature. For au isoil:ei+

(1) Isothermal process:_It is a process, which is caried out at
process, AT=0.

occurs between the system and

the
(2) Adiabatie process: It is process in which no heat exchange
a
isolated from the surroundings. Here the
surroundings (Bq o). Here the system is completely
=

temperature of the system does not remain constant.

process, which is carried out at

constant pressure. (AP ==0).
(3) Isobaric process: It is a
(4) Isochoric process: It is a process, which is carried out at constant volume. (AV =0).

returns to the original state after a series c

(5) Cyclic process: It is a process in which the system
changes.
The intermal energy change (AU) and enthalpy change (AH) for a cyclic process is zero.

o
(6) Reversible and irreversible_process: Reversible process is a process, which is caried
and t
infinitesimally slowly so that all changes can be exactly reversed. Here the system
surroundings remain in a state of equilibrium. The process is conducted in infinite number of ste
and the opposing
force is infinitesimally smaller than the driving foroe.
Irreversible process is a process, which is carried out rapidly, and it cannot be revert
without the help of external agemcy. Here the system does not have chance to achieve equilibriu
Here the driving force is greater than the opposing force. All natural processes are irreversible
nature.
(a) Pressúre
Thisvolume
type ofwork:
work is significant for systems, which consist of gases and involve volume changes
against external pressure.
areas of croSS-section
Consider a gas enclosed in a cylinder fitted with a frictionless piston having
a . Let the gas expand against the external pressure 'P through a small distance ".

Then
Work force x dispilacement
W Fxl
But the force, F is given by the product of pressure and area,

F=Pex Xa
W Pex Xal Piston
Since 'al' refers to the change in volume (AV) i e (Vr-V) area-

W Pox AAV
During expansion the work is done by the system. As per
V

sign conventions, a negative sings is put in the expression

Gas
for work.
W=- Pax AV
Therefore the work as obtained
the system.
process work is done Here AV is negative.
For compression on

from the above equation becomes positi ve.

The general expression for PV work can be written as

W=-Pex AV
Work donein reversibleis expansion ofideal gathe process, and changes in a number of finite steps, work
f not constant
the pressure during
done on the gas will be summed over all the steps.
W PAV
than the pressure of the gas, the
If the external pressure at each stage is infinitesimally greater
at each step. Such a process is called reversible proce.
volume decreases by an infinitesimal amount dV
Then the total work done on the gas is given by
NE
Wrev Padv
Here Pex at each stage = Pn + dp for compression.

In an expansion process, Pex Pn-dP

Therefore in general case Pex (Pm t dP)

Wev PandV

-((P dP)dV
Volum
dV d P dv
Pin
small quantities.
The product dPdV can be neglected since it is the product of two extremely

Wrev -JPdv
in of its volume through gas equation.
Now the pressure of Uhe gas can be expressed terms

PV nRT P nRT/V

nRTIn Y
Wrev nRTV Vi
-2.303 nlRTlog Yr
Vi
eroth aw of Thermiwdynamics
Wlen two objects at different temperature are brought in thernnal contact they exchange heat with
cach otler mil they reach a state of thermal equilibrium. At this point the temperature of the two objects
is the sau. These idcas are known as law ofthermal equilibrium or Zeroth law of thermodynamics.

Ihe Zeroth faw can be states as follows

(i) Two objects at different temperatures in thermal contact with euch other tend to move towards
the same termperature.
OR
X (ii) Two objects in thermal equilibriun with the tinird one are in thermal equilibrium with each
other.

Internalcnergy (U) and change in internal energy (AU;

Every substance isassociated with a definite amount of energy. This energy is called internal
energy (i) or intrinsic energy. It depends upon its chemical nature and its state of existence.

mechanical
kalernalcnergy represents the total energy of the system. It may be chpmical, electrical,
or any other type of energy associated with the system.

Internal energy depends upon the quantity of suhstance and hence it is an extensive property.
internal encrgy is a slate property.
Theinternal energy of a system can be clunged hy.
Heat passes into or out
of the +ysleui
Work is done on or by the
systemu
3. Matter enters or leaves the system

The absolute value of internal

energy ofa substance cannot be determined. However it is
to deternine the change in internal possible
energy (AU). The change in internal energy is the difference between
the internal energies of the
products (UP) and that of the rcactants (UR).
AU 2U
products 2U reactants.
-

For processes involving evolution of

energy, Up <UR, the sign of AU is negative.
lFor processes involving
absorption
For isothermal processes, AU = 0.
of energy Up> UR. the sign of AU is positive.

Modes of exchange of energy IHeat and work

Energy is mainly exchanged as heat and work between the
heut arc the important modes by wlhich the internal energy of a system and the surroundings.(Work and
system can be changed.)
Work (W: physi
The internal energy of a syslem can be changed by
doing work. The work
work, *Syure-volurne avork cleciricul vork. According to latest
or
can be
mechanical
sign conventions (IUPAC).
Work donebythespstem i negotive (ci) in cheis lerk done $ête V e
prk done the
system is positive (W>) J
on
Cr Syston io e
(The positive yalue of 'W' indicates that work done on the system causes ah
encrgy ol' the increase in the intemal
system.)The nggative value of
W indicates that work done by the system causes a decrease in
the internal energy of the system.
The iwo cummon forms of work are;

(a) Pressure volume work and (b) clectrical work

3
 A0 9,1 W.
W PpaV AU- , -P 2 / .
4U, PaV

Pay
1.For
isothermal irvevesible change: q-W+P.AV
2. For isothermal reversible change -W + 2.303 nRT log
V
3. For adiabatie change 0

herefore in such a case AU+ W

To sotheoemel
Signilicanceo[Ali
According to fist law of thermodynamics cupansion g Uo
AU +w fleat wotk C n
For pressure -volume work, W= -PAV

AU q-PAV 1, aeve
Ifthe process is carried out at constant volume, AV =0
Then AU 9 Pey
Thus Al represents the heat change-taking place whenthe progess occurs.at constant volurme and constant
emperature.

Entenseve Enthalpy and enthalpy change

Heat absorbed at constant volume is equal to the change in inlernnal energy ie AU qBut most of
chemical reactions cire carried out not al constant volume, but in flasks or test tubes under constant atmospheric
presure Therejore we need another state functton which is suitable for theee conditions

Enthalpy may be defined as the sum of the internal energy and the pressure volume energy of the
system under a particular set of conditions. It is denoted by H.
Mathematically.
umc Snd ornol enepy
Srdornol eneae HU+Py WhereH enthalpy.
is U is
internalcnergy. P is pressure and V is volume

Enthalpy isan extensive property.Itisalsoastatefunction.

dume wolk The absolute value of enthalpy cannot be determined. However the change is enthalpy (AH) can
be experimentally determined.
For a chemical process

AH Hp- H
Where H is enthalpy of the products and Hg is enthalpy of the rcactants.

Siguificance of Al
According to the first law of thermodynamics.
AU W
Or AU W
Where A is the internal energy change, 'q'is the net heat absorbed aund 'W" is the work done.
ifthe work done is only pressure-volume work, then W--P AV
AU (-PAV)
AU+PAV 1)
The ethalpy 'H' is given by
-U+ PV
The change in enthalpy AH is given by
AH AU+ A(PV)
 work
free expansion the
J Free expansion expansion. During
Expansion of a gas in vacuum (Pax =0 ) is called free
is reversible or irreversible.
done by the gas is zero whether the process Kam x lo1 3 J
(bElectuialwork: [Non-expansion work)
then electrical work,
conductor and "E' is the potential difference,
Ifg'isthe charge foilowing through a
BQ4usnh turincib
W
(2)1leat (a) heat is absorbed by the
Heat is another mode of the internal energy of the system. If
changing decreases.
system, its internal energy increases. If heat
is given out by the system, its internal energy
According to sign convention (1UPAC)

Heat absorbed by the system is pasitve (q>0)

Heat given out by the system is negative (q<0)

Units of heatand wOrks and that of heat is

The SI unit of both heat and work is Joule (J). The CGS unit of work is 'erg'
calorie. The differenl units are related as
IJ 10 ergs =INm 1Kgms*
Ical 4.1841

Firstlawafthermodynamics: Maya
0
ftem holt
The law was first stated by(Mayer and Halmhollz.Jhis law is also called law of conservation of
encrgy. The law can be stated in a number of ways.
converted
Energy can neither be created nor be destroyed although one form of energy can be
intothe otherform.
Or
In any physical or chemical process the energy of system and surroundings taken together
remains constant.
Or
Energy of an isolated system is constant.

athematical expression offirst law:

Consider a system having intemal energy U,. Let the system be supplied with 'q' amount of heat,
the system, then thee
theu the internal encrgy of the system will be U, + q. If 'W amount of work i_ done on
linal internal energy l2 will be given by,
U U tqt W Intornal

-
Intornal
U-U-q+W Iplergal eneroy
+W energy
éneroy ++W
Aq+ w .c+ Final slate
l system which involve only pressure initlal state
vulume work, W = -PAV

Then
AU=q-PAV
This is the mathematical statement of first law of thermodynamics.

q and W are path functions but (q+W) is state function.

Forisothemalireversibleor reversible expansion of ideal gas, AU=0. Therefore the eyuation

AU=qtWcan beexpressed as follows
 A0
H V
A0T
CX f o
q Cho moles
g c x mxAT
yhere 'c' is the specific heat capacity, 'm' mass and AT is the
temperature change.
Therelationship between Cp and Cv
At constant volume, the heat
denoted by Cp. For solids and
capacity, C is denoted by Cv and at constant pressure, this is
liquids there is no much difference between the values of Cv and Cp.
The equation for heat, q can be written as
At constant volume,
q. = CvaT AU
Atconstant pressure, 4pCpAT = AH
The difference between Cp and Cv can be derived for an ideal gas
For one mole of an ideal gas, AH =
AU +
A(PV)
AU+A(RT) CP-Cv R.
AU + RAT
Therefore AH AU +RAT.
On putting values of AH and AU
CpAT = CVAT+ RAT Thermometer
Fring leads
Cp Cv +R
Cp- Cv = R SUrTør ~ Oxygen
net
Measurement of AU and AHH
40
Heat changes in reactions can be
measured with the help of
calorimeters. Reactions taking place at constant volume
involving gases are carried out in a bomb colorimeter. lt is madeand
of Sanple

heavy steel. The steel vessel is coated inside with

gold or platinum
to avoid oxidation of steel during chemical reactions. The vessel is Bomb

fitted with as tight screw cap. The steel vessel

(the bomb) is Oxygen
immersed in a large volume of water. A combustible sample is under
pressure
burned in pure oxygen supplied in the steel bomb. This raises thhe
temperature of water which is recorded from the thermometer. By
knowing the heat capacity of calorimeter and also the raise in Water
temperature, the heat of combustion at constant volume can be
calculated using the equation. Bomb culortmeter

AJ- -CxAT x
C Heat capacity of calorimeter system
AT Rise in temperature.
M = molecular mass of substance.

W mass of substance taken. hemometer

At constant volume heat absorbed gives the increase in internal cnergy

Measurement of AFH Foamed polystyrene

CUp
Measurement of heat change of constant pressure can be done in
calorimeter kept open to the atmosphere. The calorimeter is immersed
in an insulated water bath fitted with stirrer and thermometer. The initial
temperatureis noted. At the end of the reaction the change in temperature
is caleulated. Knowing the heat capacity, heat absorbed or evolved in the Reaction mixture

reactioncan be calculated. At constant pressure, heat absorbed is equal to

increases in enthalpy.

8
 A V I VAP
Wlun prme i . kept constant, AP =0
AV . - (2)

T
tl nthalpy change represcnts the heat change-taking place
t lqi.adu and constant preSsure. during the process occurring at

Relaunhp betwecn AH and AU:

da a reaction involving gases,
') Tet be tne total volume
which is carvicd out at constant temperature and constant
of the gaseous reactants and V, be the total volume of
\ n, be the number
of moles of gaseous rcactants and nu the number the gaseous
of moles of gaseous
RT

y R
s PV ng RT- na RT
ItNV (g-na) RT
PAV AnRT
ihnye in enthalny duriny tlhe process is given hy

i i n g ti valie ol t.\
AHAH AU +(A)RT Or P +ART
Hete n represcnts the chungein the number of moles of
gaseous spccies during the process.
i An is 0 AH AU
i y if An is -ve AHAU
(tO!f An is tve AH>AU
or reaction
involving ny change in volume or those having
pnducts or those ivulving no gaseous reactants or products. same number of moles of reactants and
.94 (v) or AH= AU

lea apacity and speeific heat capacity

The lieat capacity of a substance is the quantity af heat neededto raise ils lemperature by one
le elsius (or oIe Kelvin))
ileal capacity (") C
AT
(*lee q is the quantity »f heat given to the system to raise fie temp irom P, to T,
leat capauily is dircctly proportional to the amount of a substance. Hence the terms
pr fir heut capacity atd molar heut cupucity are used

The molar heat cujpacity is the quantity of heat needed to raise the temperature of one mole
l I m e e by one degree celsius.

he speeifie heut capnclty is tue quantity of heat required to raise the teinperature of unit Cq
masn ofa substance by one degree Celsius ( or one Kelvin).

Iorlinding the heat,q required to raise the temperature of a sample,

 The important conventions of thermochemical equations
.The coellicients in a balanced thermochemical equation refer to the number ofmoles of reactants
and products involved in the reaction.
2. The numerical value of AH refer to the number ofmoles of substances specified by an equation.
3. When a chemical equati on is reversed, the value of AH is also reversed.
Na + 3H2 - 2NH Al1 = -91.8 kJ/mol

2NH3 N2 + 3H AM = +91.8 kJ/mol

4. -When the coeflicients in the chemical equation are multiplied or divided by some intiger, the AH
value must also be multiplied.
H28) Oztg) HOm AH=-286kJ
212) O2g)t
2H,0) AH=-572kJ
S. The physical state of all species must be specified in a thermochemical equation.
. 7he value of AlI shows small change with increase oftemperature.

A1Standard Enthalpy of Formation 1AH'L(Standard Heat offormation)

Che standard enthalny of formation_is the enthalpy change accompanying the formation of one
The standard state
mole of a compound-from its elementsin their standard states.It is denoted by A H.
refers to 298K and 1 bar pressure.

For example
H2(6)+% Og) H,O AH°= -285.8kJJ
This means that when one mole of HO is formed, 286 kJ of heat energy is liberated.

Eg: It may be noted that

I. The standard enthalpy of formation ofsubstance is also called its standard enthalpy. (H)
2. Byconvention the standard enthalpies of free elements are taken to be zero,
element in its most stable form at 298K and one
3. Standard state of element refer to the pure
sulphur, bromine and iodine are C
atmosphere pressure. Eg The standard states of carbon, oxygen,
(graphitc), O(g), Ss(rhombic), Bra(1) and l(s) respectively.
different reactants and products, the standard
4. Knowing the standard enthalpies of formation of the
calculated.
enthalpy change of the particular reaction can be
XAH (Products) AH (Reactants)
A
2YStandard Enthalpyofcombu_tion A,H chongt acccmany ir th
Standard enthalpy of combustion is defined as the enthalpylper mole of a substance when it
standard states (at 298K andi bar
undergoes combustion and all the reactants and products are in their
pressure)
ecem Hr elcwar v Complete cmbrutin
Eg: For example the combustion of I mole of butane, 2658 KJ of heat
is liberated6 T moC o
CaH1o (g) +during
13/2 Ora) 4COg)5H2Oo AH = 2658 kJ/mol dubs tance*inenczod
or

Combustion reactions are generally accompanied by liberation of heat. Therefore the enthalpy cu
combustion (AH) is always negative.
Oygen
S: C+ vOt Cot toH,-8q0.3 *S]nul
Calorific value of foods and fuels. food fuel is usually compared terms ot tneir
in
released by the combustion of or
The energy
calorific values. The calorific value of food or fuel is defined as the amount of heat energy proulceu w
one gram of the substance (food or fuel) is completely burnt or oxidised.
Eg. When methane burns 890.3 kJ/mol of energy is released.
CHA + 20 CO2)+2H,O AH =890.3 kJ

10
 A

cod.mt pressure is also

called the heat of reuction.
at
In endothermic reaction heat is
heat is evolved. Therefore q. will be ncagative.
an
In esth eatin

bwll hen q, s poositive and AH will be positive.

ithernmiç nnd Eudothermic reactions

exothermic rcactions.
liberation of heat energy are called
R a t i m s which are accompanied by the endothermic reactions.
oms which are accompanied by absorption of energy are called
heal
Te c
eohermie reactions - AH is negative and ALLisalso-negative-
Io endothermic reactions AH is positive and Allis also positive.

C O g ) AI =-393.5KJ The reaction is exothermic

AH = + 180.5 KJ The reaction is endothermic.
N . 2 NOs),

Fprhaly ofa reaction (Heat ofa reaction)

Ina chemical reaction reactants are converted into products.
Reactants - Products
lt is denoted by the
nth.alpy change accompanying a reaction is called lhe enthalpy of a reaction.
sy i.AR
of enthalpies of products] I sum of enthalpies of reactants] kirchb
CAt
Isum
-

A,
- a Hpraducs2b Hrauctants the balanced chemical equation
e a' and 'b' are stoichiometric coefficients in
xaniple
Eg: CHa() + 20%8) CO6) +2H20
kirch
AH 2a Hproducs b Heactants
= [Hn (CO+ 2 H,, (H2O) )) - [1. (CHa ) + 2 H,, (O)

where Hnm is the molar enthalp

-

StundurdThe
enthalpy ofareuction the conditions under which the reaction is
carried out. For
reaction
enthalpy a depends on
ofAH for different reactions are expressed at a particular temperature and pressure
k e of comparison,
most Standard (pure form) of the
is the stable state
al he standard state of Ihe substance. state

u c e at I bar pressure anud 298K.

reaction and
reaction the standard state is called the standard enthalpy of the
The enthalpy of a al

1pesented by AH°
upon the type of the
reaction.
lnthalpy of a reaction is given different names depending

heruochemical equations
chemical equation together with a designation of its value of
AH is called a
Abalanced
Ochemical eguation.
fr Caanple
C2H,OHy +
30 2 C 0 2 + 3H,O AH° = -1367kJ/mol

9
 Illuili viale of methane =890 =
55.64 kJ/g
16

ntlpy ol alomization: A,H

Eq: CH g) 4 H9,
thalpy change accompanying the breaking of one mole of a substance into its atoms in 1665 k
2H AH" =435 kJ/mol
( dialomie molecules it is same bond dissociation energy. But in the case of metais the enthalpy
l
lni:l is sane as the sublimation energy)
N AI= 108.4 kmol
Nag
(4nthalpy of Neutralisation

J delined as the enthalpy change accompanying the neutralisation of one gram equivalent of an
t d pran
equivalent of a base in dilute solutions.
NaOHe) - NaCi (ag) + H,O) AH -"57 kJ.

i tKOH()KNOe tHO AH 57 k

yriments revealthat theheat ofneutralization of all strong acids

and bases is almost a constant
JInd a t i to K i e a t ofneutralization is the heat of lonnation of one mole of water from H and

ve ver, if the acid or base is weak. then the heat liberated is less than 57 kJ This is because a
C y liber.atad dluring tle combination of l ' and OUr ions is utilized for the ionizalion of the
we.t letulyte.

Xka tNaOHan) CH-coONa (aq) +H,O» AH-55.5 kJ

51uthatpy ofsolution(Heatof solution)A
nthalpy of solution isdefined as the change in enithalpy when 1mol ofa substanceis dissolvedin
pecled amount ofsolvent. ):
Eg: HCl+50 HOg HCI (50HO) AH = 72 kJ.
i.
mcans that whenI mol of HICI is dissolved in 50 moles of water, 72 kJ of heat energy is liberated.

I thfiual solution is very dilute tihe equation is representcd as

HCh +(aq)
->
HCI ()
AH =Qkl.

of water. The corresponding AH is called the heat of solution

Where 'a represents large exCCsS

. t sliniie dilution.

d enthalny,AMa
terms are
With refercnce to the enthalpy changes associaled with chenical bonds, two ditlerent
r l m tiermodynamics
Bond dissociation enthalpy
Mcan bord enthalpy
when one mole of covalent bonds
Bond dissoclution enthalpy is defined as the change in enthalpy in k/moi.
compound is broken to form products in the gas phase. lt is expressed
f A pacus covalent

H-H 2 Al -435 kJ/mol

Bond cnthalpy is t h
aveuaj arkeeunt enegt qwcl
bak o poutiaulau tpe ah bund. in I mou omettay on t
gatous aale. Lg: H, H sH: 435 k
 However in polyatomic molecules, the bond dissociation enthalpy is ol the same for
bonds although they may be of the same type. succe
SuccesSIve
For example: the bond dissociation
energy of the two 0-H bonds of water are dilferent.
H-O-H H +0-H AH=498 kJ/mol
O-H O+Hd AH 430 kJ/mol.
Thus when a molecule contains more than one bond of the
dissociation
same kind, thec mean value of the bond
enthalpy is calculated. The average amount of bond dissociation enthalpy required to break 1
mol of a particular bond is called the mean bond enthalpy
Thus the mean bond enthalpy of0-H bond in water =
498+ 430 464 KJ/mol

Bond enthalpy can be used to calculate the enthalpies of chemical reactions

A,H°= Sum of the bond enthalpies of the reactants Sum of the bond
enthulpies of the products
A,H° Bond enthalpies Reactani
=

Bond enthalpies Pradue

Enthapy changes during Phase transformations
(1) Enthalpy of Fusion (Heat of fusion) or Molar enthalpy of fusion
It is the
the solid the
enthalpy change accompanying the conversion of 1 mol of a substance from
to liquid state at its melting
point.
HO H,O AH As6 kJ.
le when one mole of ice changes into water at its m.p. 6 kJ of heat
ener8y is absorbed.
(2)Enthalpy of vapourisation (Heat of vapourisation)
It is defined as the
change in enthalpy when 1 mol of a
substance is converted from liquid to the
gaseous state at its boiling point.

H,O H20 AHnp40.6 KJ S6ihs elwn)

3) Enthalpy of sublimation. TouY bns
It is the change in
enthalpy when 1 mol of a solid substance is converted directly to the vapour.
state at a temperature below its
melting point.
For example, when 1 mol of solid
I2 sublimes, the enthalpy ange is t62.39 kJ.
AHub 62.39 KJ.
Enthalpy of sublimation is equal to the sum of the enthalpy of fusion and enthalpy of vapourisation.
AHsub AH fus +AH vap
Hess's law
One of the important applications of first law of thermodymamics is Hess's law. The law states
thalthecnthalpy change in a chemical or physical process is same wlhether the process is carried out in
oncstep or in several steps."
Consider
a process in
in one step. Let the enthalpy
a substance 'A" is changed into B
which
change of the process is represented by
AH. Now let the process is carried out in two
steps involving change
from A to C and then from C to B. Let AHi, and Al, be the enthalpy
changes. Then according to Hess's law
AHAH, +AH2

12
 4. Conversion of gascous clhlorine atom into
gaseous anion.
Clte CT (
This step involves the release
of energy and is called electron gain
5. Combination of oppositely charged gascous ions to form enthalpy A,
solid crystal.
This
Na (g+ Cl NaCl)
step involves the release of energy and is called luttice
energy Alaliel
Applying Hess's law

AH Aub+ AnH"+ % abonaH + AH +

AuticeH
Thus by using Born Haber
the values of other
cycle we can calculate the lattice energy of an ionic solid by
thermodynamic parameters. knowing
Limitatioa of the first law
The
major limitation of the first law of
he spontaneity or feasibility of a process. That is thermodynamics
is that
iprovides nu inturnation about
it provides no information about
or reaction takes why a patticular change
place while the other does not.
Spontaneous and non-spontaneous processes:
A process which has a natural tendency to occur of its own or after proper
spontaneousprocess. initiation is known as
A spontaneous process is an
irreversible process. and may only be reversed by semie external
gency
Examples:E
Spontaneous process that need no initiation
(1) Eyaporation ofwater H,OpH0 cot

(2) Dissolution of sugar in water to form a solution

CiatyOi o taq CaH2011 (ao
(3) Neutralization reaction between HCl and NaOH
HCI +NaOH> NaCl + H,0
(4) Spreading of a drop of ink in water.
(5) Mixing of two gases.
Spontuneous process that need initiation:
0) Coal burns to give CO2 when ignited
C+O2 CO2
() Hydrogen reacts with oxygen to produce water. This reaction is initiated by passing an electric
discharge.
2H2(g)+9% (8) > 2H,(0)
All spontaneous changes proceed till equilibrium is achieved.
A process which has no natural tendency to occur is called a non-spontaneous process. Many

nofn-spontaneous processes may be made to occur wlier energy from some extermal source is supplicd.
Eg Electrolysis of water. Electrolysis takes placs only when electrical energy is supplied to waler. When
electric current is stopped,
the electrolysis also stops.
HO(1) H2 (s) + 4 02 (s)
non spontane us)

Energy and spontaneity:

Some kind of driving force is rosponsible for a sp»ntaneous process. Common experience shows
that spontaneous processes proceed towards the state of lower energy. Therefore processes which are

14
 D
B 5 0 , 0,
Bas
Dec4

Applicatiwy »f less's law

)Determimatiom of enthalpy of formation

w ae a large number of compounds such as CgH, CO0, ete whose AH values cannot be
liieetly letemind But their AH values can be determined by Hess's law.

I p l e the AH° of CO cannot be directly Ceaput) + O2()

delerminrl Ihis is because when graphite is burmed in
liteal ply f oxygen some
CO2 is always produced.
lee Al"l Og) can be calculated by using Hess's
law
Nw rurding to Hess's law COp) t %O2
All2 AH1 +AH H=33s
Ali = AH2 - AH k
=

-393.5(-283)= -110.5 KJ
i) e ulation of standard enthalpies of reactions
le oractical
application of Hess's law is that thermochemical equations can be added, subtracted,
mltlivd or divided like algebraic cquations. Thus it is possible to calculate heat of reaction which cannot
be detemined by direct
experiments.
iii 4tite ¥athalpy:
The lattice enthalpy of an ionic compound is the eithaipy change oecurs wher onc mole of an
vie counpound dissociales into its ions in gaseous
state.
Na Na ) + Cl AlaticoH= +788 KJ/mol
It is impossible to determine the.lattice enthalpy directly by experiment. It can be calculated
iiretly hy using Born-Haber Cycle.
Hon aber Cycle
hn Haber developed a simplified method to correlate lattice energies of ionic crystals to other
u dynamic data. This procedure is based on the Hess's law. This can be explained by considering the
I i n i n of NaCl. The net energy change during the process is represented as Agh

Nagy + % C l ) > NaCle +AH Na @+CIg)_

le veall process takes place in following intermediate steps.
H
Sublimation of sodium metal Na'l+1/2c1l
Na) Natg)
l renergy required for this process is AibH
lnization of sodium atoms Nalg +C @_

Na ( Na ()te (e)
Ihe energy required for this process is Nalg)+1/2C\e}
ionization enthalpy

snciations of chlorine molecule into chlorine atoms. Nalo)+L/2C,8

% Catg) Cg)
a,H
Ihe energy required for this process is half the
dissociation enthalpy %AbandH
laCls)

13
 94v thr envqy availoble in a
ALueul uwels. dystem
ayst em to
do cdo
do

Physical neaning of entropy:

degree of of disorder or randomness of the system. The greater the
Entropy provides a measure
randomness, the higher will be its entropy

For a given substance, solid state has the state of lowest entropy, and he giseus state has the

highest entropy. The liquid

state has intermediateentropy.
state,he value olfentropy change
Ifa system changes from less random state to more random
AS) will be positive.
Gibbs energY (G)and spontaneity
from a system at particular set of
amount of energy available
Free energy is defined as the of the system to do
work. That is free energy refers to the capacitics
conditions that can be put into useful
the useful work.

Mathematically
G H-TS
T= Temperature.
HEnthalpy ofthe system, S Entropy ofsystem, J/mol kJ/mol
extensive property. Its units are
or
It is a state function. It is an

But H U+ PPV

G U+PV -TS
The change in free energy AG is given by
AG = AU +A(PV) - A(TS) TAS
PAV and A(TS)
=

constant temperature, A(PV) =

constant pressure and

If the process is carried out at

AGm)
=
AU + PAV-TAS

4GTn=AH-TAS (since AU +PAV AH)

Gibb's Helmholtz equation.

This equation is known as

Erce energy changeand spontaneity: decides the spontaneity, of

the
t change (AS lotal)
For a non-isolated system, the total entropy

process.
+AS surrounding
AS total= AS system
and T.
of AH surroundings
AS surrounding can be calculated from the knowledge

AS Surrounding= AH surrounding - AH System

T
T
Therefore
AS total AS system-AH system
T
Multiplying throughout by
TASsystenm AlHsystem
-
=
TAStotal

-TAStotal =
AHsystem -T ASsystem

TAStotal= AGsystem.

16
 that negative value of AH may be
to the conclusion
exothermir in nature must be spontancous. This leads
the crilenn of spontaneity.

AH -286KJ (spontanecous)

( CO2 AH-394 KJ (spontaneous)

But mny reactions in which AH is tve or even zero are spontancous.

( vaporation of water
AH- 40.6KJ
H,O() H,O(g)
CDisolution of NH,Cl in water
1SKI
NILCKS)+water NH" (ag) +Cl(aq) Al

(ecnpositionofN,Os
2N,0s(g) 4NO, (g) +O2 (g) AH=+219 Ki/mod
( ntemis 1g of non reacting gases AH=0

careful study of the above processes reveals that all those processes proceed towards a more
diubrl or more random state. Therefore another criterion of' spontaneity is disorder or randomness of

th tem.

AS: V
Entopy the
It is denoted by
Calropy is a nieasire of the degrec of randomness or disorder of a system,
syabS isastatefunctiu and dependsuponthestaieofasysten.Itisalsoan extensive property
T change in enuopy
Change i n entropy (4S) =
during provess is represented by As
a
Snal
Diniial
Dproducts Dreactarnts
When heat is added to a system, it increases molecular motions causing increased randpmness in

system. Entropy also depends the temperature at vhich heat is absorbed. Heat added to a system at
tilower temperature causes greater
on
randomness than when same quantity of heat is added to it at higher

t nperature. Thus AS is related wih 'q and T for a reversible process as

AS9 iuevT
Thus change in entropy 'AS' is defined as the ratio of heat absorbed by the system isothermally
ad revers1bly to the temperature at which it is absorbed.

J/K
joule (J) and temperature in Kelvin (K), then entropy change given by
is or
Ifq is expressed in
JK
he total entropy change [AS total }for the system and surroundings is given by

AS otal- AS sysuem +AS surroundings.

or the process to be spontaneous, AS total must be positive.

AStotal AS systm i AS surroundings 0

the change in entrpy

isolated system is in equilibrium, tlhe entiopy is maximum and
When an
(1S) is zero.

AS 50 (at equilibriumm).

AS total >0: process is spontaneous.

state.
AS total =0: equilibriun
AS total <0: process is non-spolntaneous.

15
This cIatn forns the basis for thie criterion of
e nlaneous AStuta should spontaneity in ternis of free energy
to change. For a process
be positive. So it follows that AGautean should be negative
Alo .it femperatui and pressure,
ti) If AGsystem is negative (<0), the process is
(ii) If AGsystem is spontancous.
positive (0), the process
(iii) Tf aG 0, the system is in equilibrium.
is
non- spontaneous. n fonuOAol auAechre-
Conditiyn for AG to be negative:
According to Gibb's Helmholtz equation
AS- + ve
A H - v e

AG AH TaS
(1 h the energy factor as well as entropy factor are lavorable. ie AH is
negative and aS is positive.
len AG. would be definitely and the process would be
negative spontaneous
-ve
A n y actor favors but entropy factor opposes. ie, All is negative and AS is also negative. Under these t?
ditions AG would be negative if AH is
greater than TAS in magnitude. AS Ve
factor opposes but entropy factor favors. ie Ail is posiive and aS is also positive. Under these
litions AG would be negative if TAS is greater than All in nmagnitude.
Erlee of temperature on spontaneity
Aprocess, which is spontaneous at a particular temperature may be non-spontaneous at somne 3HCTASs-
oflw
WI
Ie1erature. Temperature effects feasibility of endothermie and exothermic reactions in different atn temp
o r endoihermic reartions:
mus
Snmust
iivrcess Atis nusitive
be posiluVe and 8eate
(otposing). Then for the process to be spontanequs
than ak.(v. ith incrcase in Lemperature l ' S wilt inereas
whereas AH does not change\much. So for al endothemic process higher ten1perature favors
the spontaneity or feasibility of the
process.

(2) For exothermie process:

For an exothermic process AH is negative (favorable) and TAS would be generaly negative
opposing). Then for the process to be spontaneous the magnitude of AH must be greater Tas.
With increase in temperature, the opposing factor TAS increases whereas favorable factor AH
remain almost constant. So for an exothermic process low temperature favor the spontaneity of
the process.
'se of Gibb's energy change O G+RTnk
The knowiedge of the sign and magnitude of free energy change allows
Prediction of spontaneity of the chemical reaction.
2 Prediction of the useful work that could be extracted from it.

Gibbs energy and equilibrium constant:

46
R i RT
Consider a
+BC+D.
reversible reaction, A
For a reversible reaction at equilibrium the free energy of the system is minimum but free energy change is
zero (AG=0 ). At equilibrium, the relationship between standard free energy (AG) and equilibrium
constant is given byy

0 =
AG° + RT In Keq
Where R = U n i v e r s a l gas constant, T = temperature

AG = -RT In Keq

AG-2.303 RT log K

AG1 303 RT Aog Kea 17

 Themody namitj
W= P v ,

40 Ay+w
AU q - PAV

4H 4 U t4PV)
OR AH AU
C Cy- R +AnRTa9 9,t4nRT
AG 4H- TAs bb's elmhalla Equalicn
AH:-Ve
AS tVe SPONNTA NLEO US
H -Ue