a series by INVISIBLE MECHANICS

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 & surrounding

SYSTEM
Open Energy and matter can exchange
Closed Only energy can exchange
Isolated Neither energy nor matter
 State function
Properties which depends only on initial & final state of system & not
on process or path.
e.g. U, H etc.
Path function
Depends on path or process .
e.g. work, heat

THERMODYNAMIC PROPERTIES
1. Extensive : Properties which are dependent of matter (size &
mass) present in system
 2.Intensive : Properties which are independent of matter (size
& mass) present in system.
Extensive Properties Intensive Properties
Molar volume
Number of moles Density
Volume Refractive index
Mass Surface tension
Viscosity
Free Energy (G)
Free energy per mole
Entropy (S) specific heat
Enthalpy (H) Pressure
Internal energy (E & U) Temperature
Heat capacity Boilling point
freezing point etc
 Process

Isothermal Isochoric Isobaric Adiabatic Cyclic

Initial &
No heat
final state
T = const. V = const. P = const. exchange
of system
dq = 0
are same
Reversible process Irreversible process

Slow process
Fast process
At any time system
No equilibrium between
and surrounding are
system and surrounding
n equilibrium
P sys = Psurr ±ΔP
P sys = Psurr ±dP
 Heat(q)
Energy exchange due to temperature difference
q = CΔT, q = nCmΔT, q = msΔT
C = heat capacity
Cm= molar heat capacity
s = specific heat capacity
m = Amount of substance
 General values of CV & CP for an ideal gas can be taken as follows.

γ = n C + n C ....
n C + n C ....
WORK (W)
Reversible Irreversible

W = -∫P dV W = – P (V –V )
Sign Convention
W W

(+)ve SYSTEM (-)ve

q q

INTERNAL ENERGY (E & U)

Every system having some quantity of matter is associated
with a definite amount of energy, called internal energy.
U = UKinetics+ U Potential + UElectronic + Unuclear+ .....

U is a state function & is an extensive property

ΔU = U final – U initial
For a given closed system
U = f(T, V)

( (
∂U
( ∂U
( dV
dU = dT +
∂T V ∂V T

FIRST LAW OF THERMODYNAMICS (FLOT)

Law of conservation of energy
ΔU = 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
ΔH = ΔU + Δ(PV) at constant pressure
ΔH = ΔU + PΔV combining with first law.
ΔH = q
p
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)

( (
∂H
( ∂H
( dP
dH = dT +
∂T P
∂V T
 RELATIONSHIP BETWEEN ΔH & ΔU
The difference between ΔH & ΔU becomes significant only
when gases are involved (insignificant in solids and liquids)
ΔH = ΔU + Δ(PV)
If substance is not undergoing chemical reaction or phase
change.
ΔH = ΔU + nR ΔT
In case of chemical reaction
ΔH = ΔU + ( Δn g )RT
 WORK DONE IN VARIOUS PROCESS

Isochoric Isobaric Free expansion ISOTHERMAL

Pext =0 dT =0
W =0
W= -Pext (V2 - V 1 ) W=0, ΔU=0,q=0 ΔU=0 (for ideal gas)
ΔU=q=nCvΔT
q =–W

ADIABATIC
γ= C
q=0 ΔU =W= nCV ΔT W = P V - P1 V P
2 2 1 CV
γ-1
C P- C V =R C P = molar heat capacity at constant P
C V= molar heat capacity at constant V
DETAIL OVERVIEW OFVARIOUS PROCESS
 SPONTANEOUS PROCESS
A process which takes place on it's own (without any external
assistance). The driving force of a spontaneous process is large
or finite
CARNOT CYCLE
AB – Isothermal reversible expansion
q = - WAB= nRT2 ln 2V
2
V1
BC – adiabatic reversible expansion
W=BC
nC (T -T
V 1 2
)
 CD – Isothermal reversible compression
V4
q = - WCD= nRT1 ln
1 V3
DA – adiabatic reversible compression
W=
DA
nC (T -T
V 2 1
)
-Wtotal = q 2 +q 1 T 2 -T1
carnot efficiency η= =
q q2 T
2 2
q 1 q2 Entropy (denoted by
+ =0 for rev. cycle
T1 T2 S) is state function
 STATEMENTS OF SECOND LAW OF THERMODYNAMICS
(i) 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 surrounding.
(ii) In an irreversible process entropy of universe increases but
it remains constant in a reversible process.
ΔSsyt + ΔSsur = 0 for rev. process
ΔSsyt +ΔSsurr > 0 for irrev. process
ΔSsyt + ΔSsurr ≥ 0 (In general)
ENTROPY CALCULATION
 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 absolute value of entropy (unlike
absolute value of enthalpy) for any pure substance can be
calculated at room temperature.
T T

∫
STK- S0K= q rev since S = 0
T
0K
STK∫
= q
T
rev

0 0
 (ΔSr) - (ΔSr) = (ΔCp)r ln T 2
T2 T1 T1
(ΔSr) - (ΔSr) = Δn g R lnT 2
P2 P1
T1
Similarly
(ΔHr) - (ΔHr) = (ΔCp)r ( T2-T1 )
T2 T1 Krichoff's equation
(ΔUr) - (ΔUr) = (ΔCv)r ( T2-T1 )
T2 T1
 GIBBS 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
ΔG = ΔH – TΔS
If (ΔG)T,K < 0 Process is irreversible (spontaneous)
(ΔG)T,K = 0 Process is reversible
(ΔG)T,K > 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).
The equation ΔG = ΔH – TΔS takes both the factors into consideration

VARIATION OF GIBB'S FUNCTION (G) WITH TEMPERATURE AND PRESSURE

G = H – TS
= U + PV – TS
dG =dU + P dV - TdS +VdP+SdT
dG = VdP – SdT
 At constant temperature At constant pressure
ΔG = VdP ΔG = –SdT

( (
∂G
( ∂G
(
OR =V OR =-S
∂P T ∂T P
Relationship between ΔG & W
dU = q + Wpv+ Wnon-pv
for reversible process at constant T & P
dU + pdV – TdS = Wnon-pv
dH – TdS = W non-pv Non-PV work done by the system =
(dGsystem ) = Wnon-pv decrease in gibbs free energy
T,P
(dGsystem ) = (Wnon-pv ) system
T,P
 SOME FACTS TO BE REMEMBERED
(a) Standard condition
* For gases/solid / liquid
P = 1 bar
* For ion / substance in solution
Concentration = 1M
(b) ΔGr = (ΔGf )product – (ΔGf ) reactant
ΔHr = (ΔHf )product – (ΔHf )reactant
ΔSr = (ΔSf ) product – (ΔSf )reactant
 Relationship between , ΔGº and equilibrium constant
ΔG =ΔGº + RTlnQ
At equilibrium ΔG = 0
ΔGº = – RT ln Keq
ΔHº – TΔSº = – RT ln Keq
ln Keq = - Δ rHº + Δ r Sº
RT R
ln K1 = Δ rSº - Δ rHº
R RT 1
ln K 2 = Δ rSº - Δ rHº
R RT 2

(
ln K 2 = ΔHº 1 - 1
( r
K1 R T2 T2