THERMODYNAMICS

DEFINITION
Deals with interaction of one body with
another in terms of energy.
System: Part of universe under investigation
Surrounding : Rest part of universe except system.
Boundary: Devide system & surounding

SYSTEM1
Open Closed isolated
Energy and matter| Only energy Neither energy
can exchange can exchange normatter

State function Path function

Properties which depends only Depends on
on initial & final state of system path or process.
& not on process or path.
e.g. U, H etc. e.g. work, heat
ttttuttttt

THERMODYNAMIC PROPERTIES
Extensivee Intensive
Properties which are dependent Properties which are
of matter (size & mass) independent of matter
present in system (size & mass) present in system.

Extensive Properties
Intensive Properties
Volume Molar volume
Number of moles Density
Mass Refractive index
Free Energy (G) Surface tension
Entropy (S) Viscosity
Enthalpy (H) Free energy per mole
Internal energy (E & U) specific heat
Heat capacity Pressure
Temperature
Boilling point, freezing point etc
 PROCESSES

Isothermal Isochoric Isobaric Adiabatic Cyclic

T const. V= const. P= const. No heat Initial &
exchange final state
dq = 0 of systemn

are same

Reversible process Irreversible process

Slow process Fast process
At any time system No equilibrium between
and surrounding are system and surrounding
in equilibrium.

P=PudP P=P
Sur
tAP

HEAT (q)
Energy exchange due to temperature difference:

CAT =nC AT, msAT

C heat capacity
Cm = molar heat capacity
Sspecific heat capacity
m = Amount of substance

General values of C, & C, for an ideal gas can be taken as follows.

Atomicity n nya
Incl. Vib Excl. Vib Incl. Vib Excl. Vib Incl. Vib

Mono
|
Di
R R
Linear 3
Tri
Non SR bR 4R TR
|Linear

Y
mix
n,C+nCB
n,Cy+nCy,...
 WORK (W

Reversible Irreversible

W-Pa dV W-PV-V)

SIGN CONVENTION

w (+ve

system

w ve 9

INTERNAL ENERGY (E & U)

Every system having some quantity of matter is associated with a definite amount of energy, called
internal energy.
U=
UKinetics +pouenial+Eesronk ucksrt
U is a state function & is an extensive property.
AU = URaadlnatial

For a given closed system

U f(T, V)

dt-T OU
T-l

FIRST LAW OF THERMODYNAMICS (FLOT)

Law of conservation of energy

AU=q+W

ENTHALPY
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has
been found useful to define a new state function Enthalpy (H) as.
H = U+ PV

AH = AU + A(PV)

at constant pressure AH = AU + PAV

combining with first law. AH = 9,

Hence transfer of heat at constant volume brings about a change in the internal energy of the system
whereas that at constant pressure brings about a change in the enthalpy of the system.

For a given closed system H = f(P, T) an =|

RELATIONSHIP BETWEEN AH & AU

The difference between AH & AU becomes significant only when gases are involved (insignificant
in solids and iquids) AH = AU + A(PV)

If substance is not undergoing chemical reaction or phase change. AH = AU + nRAT

In case of chemical reaction AH = AU + (An,)RT

WORK DONE IN VARIOUS PROCESS

Isochoric Isobaric Free expansion

W=0 W-P(V-V) eu0

AU=q=nCAT W=0, AU=0.q=0

ISOTHERMAL
dT =0; AU=0 (for ideal gas); q =-W

Reversible Isothermal Irreversible Isothermal

Wev iso-nRT(
-Pa

-nRTn
ADIABATIC:
9=0AU =W=nC,AT W=2-RV
Y-1
7 C = molar heat capacity at constant P.

C-C=RCy = molar heat capacity at constant V.

For Reversible adiabatic:

PV= constant (Ideal gas)
TVr'= constant (ldeal gas)
For irrversible adiabatic process:
aU=-PV-V)
nCyT-T)-P. nR
 Expression Expression AU AH Work on
Process
for W for PV-graph
Reversible W-nRTln2 9=nRTIn 0
process
isothermal
=-aRTIn qnRTI
Irreversiblew-P(V,-V,)=Pe(V-V)
isothermal nRT nRT
-PP P

Isobaric w--P (V-V,)|q=AlH=nCpAT |aU =nCyAT| AH=nC,AT|

= - nRAT
process

Isochoric W = 0 AU =nCyAT |AU=nCyAT| AH =nC,AT|

process

Reversible w=nCy(T-10 =0
AU=nCyAT| AH =nCpAT| Isotherm
Adabatic
adiabatic PV=constant
-1
process TV=constant V,
TP=constant
Irreversible w=nCy(T2-1) q=0 AU=nCyAT| AH =nCpAT Rev

sotherm
adiabatic PV-
Y-1
nC(T-T) AdiabatiC

process V. V.

n=

Polytropic
PV,-PV
n-1 -f AU=nCyAT AH=nCpAT
w R(T-2
n-1)_ w R(T-T)
n-1) V,
Cyclic Area encolsed in I5-W

Process PV-diagram
For clockwise
it is -ive
it is +ive
A process whichtakes place onit's own (without any externalassistance). The driving force of
aspontaneous processis large or finite.
 STATEMENTS OF SECOND LAW OF THERMODYNAMICS
) No cyclic engine is possible which take heat from one single source and in a cycle completely
convert it into work without producing any change in surounding.

Source
W

Sink

(i) In an irreversible process entropy of universe increases but it remains constant in a reversible process.

AS+AS =0 Sur
for rev. process
AS+ASu0 for irrev. process
AS+AS20 (In general)

PHYSICAL SIGNIFICANCE OF ENTROPY

One can think entropy as a measure of the degree of randomness or disorder in a system. The
greater the disorder in a system, the higher is the entropy.
(i) The entropies of substance follow the order,
S(g) > S()> S(s)
(ii) If more no. of gaseous moles are present on product side, AS will be +ive (since gas is more
disordered than solid or liquid).
ii) Entropy rises with increasing mass, other thing being same e.g. atomicity in gas phase.
e.g. F,g) S° 203 J/K-mole

CLg) s° 223 J/K-mole

Br,(g) s° 245 J/K-mole

(iv) Entropy increases with chemical complexity
For CuSOnH,O
n =0 n =l n = 3 n 5
s 113 150 225 305

CALCULATION OF ENTROPY CHANGE FOR AN IDEAL GAS

General Expression

AS = nC, In T n R In

=nc,innln
Reversible & irreversible isothermal expansion or contraction of an ideal gas

AS nR In
=
y
13
 Isobaric heating or cooling:
AS =

Isochoric heating or cooling:

AS nC, In

Adiabatic process:
aS =nC, In+ nR In for ireversible process

AS = 0 for reversible adiabatic compression and expansion.

ENTROPY CALCULATION

Process ASarr.
- Asys
Isothermal AS= nR(n2
reversible

Isothermal AS =nRn2 su 9sys.Wsys-PV,-V2

T T
irreversible

Adiabatic AS 0 ASu 0
Sut.

reversible

Adiabatic SnCnnR(n ASSu=0

irreversible

Isochoric - sys
ASgynCyn Asum
reversible

-sys-nCyAT
Isochoric AS=nCyn ASsur r.T
irreversible
 THIRD LAW OF THERMODYNAMICS
"At absolute zero, the entropy of a perfectly crytalline substannce is zero", which means that
at absolute zero every crystalline solid is in a state of perfect order and its entropy should be zero
By virtue of the third law, the absoBlute value of entropy (unlike absolute value of enthalpy) for
any pure substance can be calculated at room temperature.

S-SOK
Since Sox = 0

S,
Absolute entropies of various substances have been tabulated and these value are used to calculate
entropy changes for the reactions by the formula;

AS S (products) S (reactants)

VARIATION OF AS, WITH TEMPERATURE & PRESSURE:

(As,)-(AS,), =(ac,), In
(AS-(AS,) =An,R ln
P2
Similarly

(AH,,-(aH,), =(ac),(T,-T) (Krichoffs equation)

(Au,), -(au,), (ac.),(T, -T)

=

OGIBBS FREE ENERGY (G) AND SPONTANEITY:

A new thermodynamic state function G, the Gibbs free energy is defined as
G H TS
at constant temperature and pressure
AG AH -T AS
f
(AG<0 Process is ireversible (spontaneous)
(AG) 0 Process is reversible
(AG) 0 process is impossible (non spontaneous)
The use of Gibbs free energy has the advantage that it refers to the system only (and not
surroundings).
To summaries, the spontaneity of a chemical reaction is decided by two factors taken together
The enthalpy factor
(ii) The entropy factor
 The equation AG = AH - T AS takes both the factors into consideration.

(AH)AS) (AG) Remarks

ve +ve Always ve Reaction is spontaneous
ve e Always +ve Reaction non spontaneous
ve + ve At low temperature, AG = + ve Non spontaneous
At high temperature, AG = - ve Spontaneous

At low temperature, -
ve ve ve
Spontaneous
Ve e At high temperature, + ve Non spontaneous
VARIATION OF GIBB'S FUNCTION (G) WITH TEMPERATURE AND PRESSURE
G H Ts
= U + PV T S

dG =+ PW -TAS+VdP-SdT
dG VdP - SdT
At constant temperature
AG VäP

orFV
At constant pressure
AG = -SdT

Relationship between AG & non-PV

dU =
q+ Wy +
W -PV

for reversible process at constant T & P

dU+ pdV - TdS Wwnon- =
PV

dH TdS =Wn-PV
(dystemTP
system non-PV
(dystemTP=non-PVsystem
Non-PV work done by the system = decrease in gibbs free energy

SOME FACTS TO BE REMEMBERED:

(a) Standard condition
For gases/solid / liquid
P 1 bar
*
For ion / substance in solution
Concentration = IM

(b) AG, =(AG)productareactant

AH, = (AH)proxduct(Aeactant
AS, = (ASPproduct
(ASPactant
(All above equation will be derived in thermochemistry)
16
Relationship between , AG° and equilibrium constant

AG AG°+ RT/nQ
At equilibrium AG = 0

AG= -

RT /n Keq
AH° TAS° = -

RT In Keq

In K + For Exothermic reaction

In K, =
A,S A,H°
R RT In K

In 4H°
K, =

RT 1/T

In -
 THERMOCHEMISTRY

ENTHALPY OF REACTION (AH, BOND ENTHALPY

Amount of heat evolved or absorbed during a
reaction at constant pressure. Average amount of enthalpy required to dissociate
one mole gaseous bond into separate gaseous

ENTHALPY OF FORMATION (AH atoms.

Sum of bond enthalpy)_Sum of bond enthalpy
(May be endothermic o r exotherm ic)
Change in enthalpy when one mole of a substance
ArH=of gaseous reactant lof gaseous product
is formed from its constituent elements present in
RESONANCE ENERGY
standard state.
For elements aH° =0 (for standard state) AHesonance = AH° (experimental)- AH°(calculated)

AH° hombic) =
Ex. AH° [O,(E)]=0, 0 =

AcH°(cakuated)- AcH° (experimental)

AH°P(vhie0 AH°=aphito)
ENTHALPY OF COMBUSTION (A H) :
ENTHALPY OF NEUTRALIZATION (AH
(always exothermic)D (Always exothermic)
Change in enthalpy when I mole of a substance Change in enthalpy when one gram equivalent of;
is completely burmt in oxygen. an acid is completely neutralized by one g-
equivalent of a base in dilute solution.
CH(g)+O2(9)>2002(g)+3,0(O:ac tGHls]SA +SB salt +water; AH,eu
a,H° AcH°(react)-AcH°(prod.) H O i KCal eq =57.3 kJ eq"
AHecmbwt :In case of weak acid /base or both JaHg|< 13.7
Calorific valuemolecular and the difference is enthalpy of ionisation of
eq

ionisation of weak species except in case of HF;

ENTHALPY OF TRANSITION when laHl> 13.7 due to hydration of F.
Enthalpy change when one mole of one allotropic ENTHALPY OF ATOMISATION (AH atom
form changes to another. (always endothermic)
lgraphite) ldamond) Atran=1.9 kJ mol Change in enthalpy when one mole of
gaseous molecules converts into gaseous atoms.
HOH0 AH(H,O)
HO,HO; AH° (H,O) ENTHALPY OF SOLUTION (AH
HLOs,H,O A (H,0) (may be endo or exothermic)
Change in enthalpy when 1 mol of a substance is
LAWS OF THERMOCHEMISTRY dissolved in excess of water so that further dilution}
does not involve any heat change.
AB mol Lavoisier & Laplace laww
A,H=x kl
B A a,H= -x kJ mol" asO AQSO49):Ad
(i) Hess Law of Constant Heat summation ENTHALPY OF HYDRATION (AH
hydra
(always exothermic)
AH CaH, AH=sH,+AH,
Enthalpy change when 1 mole of anhydrous salt
AH or AH=AH, +AH+AH
combine with requisite amount of water to form
hydrated salt.
or aH=aH, +AH,=aH,+AH, +AH,
AH, AH
CuSO+5H,O CuS0.5H,0aHnyd
(anhy. salt) (hydra.salt)

18
ENTHALPY OF HYDROGENATION hydro
NOTE:
(Alwaysexothermic)
If in a reaction heat of reactant & products are
Enthalpy change during the complete given then heat of that reaction can be measured
hydrogenation of one mole unsaturated as follows:
organic compound into its saturated (a) For heat of combustion &for bond
compound. enthalpy
unsaturated organic compound A
saturated organic compound a,H (aHc)ntAHC),rod
or =bond) (-bond)
(b) For heat of formation
CH,+2H, CH; AH,bo A,H=(AH,)pod2AH,)ent