Thermodynamics

The law of thermodynamics deals with energy
change of macroscopic system containing large
no of molecules by measuring pressure and
temperature.
Thermodynamics state
• System – Open, Closed, Isolated
• Surrounding
• Universe
System + Surrounding = Universe

State Function\State
Variable

The quantity which describe the state (no physical
state) of system like p,t,v,n are called state
function\state variable. Its value depends on only
initial and final state but not how the change is
carried out. It is of two types extensive depend on
mass- V, E, heat. Intensive not depend on mass – T,
viscosity, surface tension.

Internal energy
• It is the total energy of the system (chemical, mechanical, electrical, other).
It is at constant volume. It cannot be measured but change in internal
energy can be measured. It change due to :- (i) Heat absorb +q or heat
evolve –q
(ii) Work done on system +w and work
by system –w
• Internal energy is state function because it depends on change in w,q
• Mathematically ∆U = q + w
• q is state function : depend on initial and final temperature of system
w is state function: work done during adiabatic process ( no transfer of
heat with system/surrounding) but only change the temperature which is
state function.
As q and w are state functions. Therefore ∆U is also state function.
First law of
thermodynamics


• Energy of isolated system is constant
• Mathematically ∆U = q + w
Calculation of work
• For mechanical work. If in a cylinder ideal gas is
compressed with a piston of area A by length l then
W =F Χ d = P.A Χ l = P(-∆v) [ negative sign v
decreases]
• W = -P∆V Since p is constant by integration W
= 2.303nRT log
vf
/
vi


Free expansion

• Expansion of gas in vaccum ( p
ex
=d is called free
expansion)
• No work is done during free expansion ∆U = qv (H.E
at constant V)
• For isothermal change T=0, W=0, q=0 ∆U=0
• Therefore for isothermal irreversible change q=-W=-
p∆v
• For reversible change q=-W=-nRT log
e
V
f
/V
i


Enthalpy
• Most of the chemical reaction carried out at constant
pressure. Heat energy change of reaction at constant
pressure is called enthalpy. It cannot be measured but
enthalpy change can be measured H = U + PV
∆H=∆U + P∆V
• For exothermic ∆H = -ve Endothermic ∆H = +ve
• For gas system = ∆H = ∆U + ∆nRT

Specific Heat (c)



• Specific heat of a substance is the heat energy
required to raise the temperature by 1 degree Celsius
or 1 Kelvin of unit mass.

Heat Capacity
• Heat energy required to raise the temperature
by 1 Kelvin of given mass denoted by capital C.
C = mc

Molar heat capacity


• Heat energy required to raise the temperature by 1
Kelvin of 1 mole substance.
Relation between Cp
and Cv

• heat energy at constant volume qv = Cv∆T = ∆U

• Heat energy at constant pressure qp = Cp∆T = ∆H
• We know ∆H = ∆U + ∆nRT or Cp∆T = Cv∆T +
∆nR∆T
• Cp – Cv = R R= 8.314 joule/mole

Enthalpy of reaction

• ∆
r
H = ΣHp - ΣH
r

• Standard enthalpy of reaction ∆
r
H
0
at 1 bar and
298K

Standard enthalpy of
formation

• Enthalpy change for the formation of 1 mole of
compound from its elements in their most stable state
is called ∆
f
H
0

• ∆
f
H for element = 0

Enthalpy of fusion

• The enthalpy changes that accompany melting of one
mole of a solid substance in standard state is called
enthalpy of fusion.

Enthalpy of
vaporisation


• Amount of heat required to vaporize one mole of a
liquid is called enthalpy of vaporization.

Enthalpy of sublimation


• Change in enthalpy when one mole of a solid
substance at constant temperature and pressure is
called enthalpy of sublimation

Thermodynamic
equation

• A balanced chemical equation in with physical state
of reactant and product and enthalpy of reaction is
called thermodynamic equation.
• C
2
H
5
OH(l) + Na(g) → C
2
H
5
COONa + H
2
(g)

r
H
0
= -3167Kj/mole

hess’s law of constant
heat summation

• If a reaction takes place in more than one step then
total enthalpy change in each step is equal to sum of
standard enthalpy in each step at same temperature

r
H = H
1
+ H
2
+ H
3
+H
4


Standard enthalpy of
combustion
• Enthalpy change during combustion of one mole
substance at specific temperature. It is denoted by
∆cH
0

• Enthalpy of atomization: ∆aH
o
Enthalpy change to
get atom is gaseous state.
• H
2
→ 2H ∆aH
o
436KJ/mole

Bond enthalpy
• Enthalpy change during the formation of bond or
dissociation of bond of one mole substance is called
bond enthalpy.
Bond enthalpy = ΣHr – ΣHp
Enthalpy of solution
• Enthalpy change when one mole of solute dissolve in
specific amount of solvent
• If more the lattice enthalpy the solute will not
dissolve CaF
2
is less soluble than CaCl
2
. Since, lattice
enthalpy of CaF
2
is high.
Lattice Enthalpy
• Enthalpy change in ionic compound when one mole of
ionic compound dissociate into its ion in gaseous
state. It cannot be measured directly. So it is
determined by Born Habber cycle.
• ∆
f
H
0
= ∆
sub
H
0
+ ∆
ion
H
0
+ ∆
diss
H
0
+ ∆
EG
H
0
+ ∆
Latti
H
0

• Na(s)
∆sub H0
Na (g)
∆IE H0
Na
+
Na
+
+ Cl
-

∆LatticeH0
NaCl
• ½ Cl
2

∆dissH0
Cl
∆egH0
Cl
-


Spontaneous Process

• The process which occur naturally i.e. no external
energy is supplied to carry spontaneous process.
Physical spontaneous
processes

• Flow of water from high level to low level, mixing of
ink in water, free expansion of ideal gas.
Chemical spontaneous
process

• They are generally exothermic.
C
8
H
18
+ O
2
→ CO
2
+ H
2
O

Endothermic
spontaneous process


• 2Na
2
O
5
→ 4NO
2
+ O
2
∆H = -1095KJ/mol
Non spontaneous
Process

• The process which needs external energy to carry out
is called non spontaneous process.
Eg- Flow of water from low level to high level
Entropy [s]
• It measures degree of randomness. ∆S = q
reversible/T
∆S = ΣSp – ΣSr
∆S
total
= ∆S
system
- ∆S
universe


gibb’s free energy
• Max available energy of system that can be converted into useful
work.
• G = H – Ts
• ∆G = ∆H – T∆S
• ∆G = ΣGp – ΣGr
• To show ∆G
system
= -T∆S
total

• ∆S
total
= ∆S
system
+ ∆S
surrounding
= ∆S
system
- ∆H
system
/T
• or, T∆S
total
= T∆S
system
- ∆H
system

• H
system
- T∆S
system
= -T∆S
total

• Therefore ∆G
system
= -T∆S
total

• If G < 0(-ve) process is spontaneous, ∆G > 0 (+ve) process in non-
spontaneous and if ∆G=0 Equilibrium

relation between ∆g
0

and Kc

• We know that ∆G = ∆ G
0
+ 2.303RTlog
e
Qc
• At equilibrium ∆G = 0, Qc = Kc
• Therefore, ∆G
0
= -2.303RTlog
e
Kc

Thermodynamical
Laws
• First law of thermodynamics :- Energy of isolated
system remains constant.
• Second law of thermodynamics :- Entropy of the
system increase during every spontaneous process
∆S > 0 and at equilibrium ∆S =0
• Third law of thermodynamics :- Entropy of perfect
crystalline system at absolute zero (0) is zero.


Formulae
• ∆U = q + w
• ∆H=∆U + P∆V
• for gas ∆H=∆U + ∆nRT
• ∆
r
H = ΣHp - ΣH
r

• ∆S = q/T
• ∆S = Sp – Sr
• ∆G = ∆H – T∆S = ΣGp – ΣGr
• ∆G = ∆ G
0
+ 2.303RTlog
e
Qc
• ∆G
0
= -2.303RTlog
e
Kc
• Cp – Cv = R C
m
= c/n
• ∆
f
H
0
= ∆
sub
H
0
+ ∆
ion
H
0
+ ∆
diss
H
0
+ ∆
EG
H
0
+ ∆
Latti
H
0