Course No.

Phy- 1203(B), Heat & Thermodynamics, Physics Discipline, KU

Chapter – 7
Maxwell’s Thermo dynamical Relations

Md. Shohel Parvez

Lecturer
Physics Discipline, Khulna University, Khulna
Thermodynamic Potentials
The state of a system can be completely described any two of the
five variables P, V, T, S and U. out of these, U the internal energy state
variable is determined by using the remaining four, as proved below.
According to the first law of thermodynamics,
𝜕𝑄 = 𝜕𝑈 + 𝑃𝑑𝑉
And from the second law of thermodynamics,
𝜕𝑄 = 𝑇𝑑𝑆
𝜕𝑈 + 𝑃𝑑𝑉 = 𝑇𝑑𝑆
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Thus, U can be eliminated and we are left with four state variables P, V, T
and S only. This is the reason, why only four state variables are defined.
 Taking two of the four state variables at a time there are six possible
pairs i.e. (P, V), (P, T), (P, S), (V, T), (V, S) and (T, S). The pair (P, V) is
connected with composite and in exact differential quantity 𝛿𝑊 as
𝛿𝑊 = 𝑃𝑑𝑉 and pair (T, S) with 𝛿𝑄 as 𝛿𝑄 = 𝑇𝑑𝑆. Hence these two pairs
can be eliminated. Thus we are left with four pairs of thermodynamical
variables. Corresponding to each pair, we can write a thermodynamical
relation. These four thermodynamical relations are known as Maxwell’s
thermodynamic relations.
Four relations are:
1) Internal Energy, U
2) Helmholtz free energy, F=U-TS
3) Enthalpy H=U+PV
 4) Gibbs function G=U+PV-TS

Each of Maxwell’s four thermodynamical relations can be derived

from one of these thermodynamic potentials U, F, H and G.

Internal Energy U: The internal energy or the intrinsic energy is the

total energy of a system. According to the first law of thermodynamics,

𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉

𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉

And from second law of thermodynamics,

𝑑𝑄 = 𝑇𝑑𝑆

Substituting for 𝑑𝑄, we get

𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
This equation gives the change in internal energy of the system in
terms of four thermodynamical variables P, V, T and S. the internal
energy (U) is called first thermodynamical potential.
(a) For an adiabatic process:
𝑑𝑄 = 0
𝑑𝑈 = −𝑃𝑑𝑉
i.e. the work done by the system in an adiabatic process is at the
expense of its internal energy
(b) For an isochoric adiabatic process:
𝑑𝑉 = 0 𝑎𝑛𝑑 𝑑𝑄 = 0
𝑑𝑈 = 0 𝑜𝑟 𝑈 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
The internal energy of system remains constant in an isochoric
adiabatic process.
Helmholtz Free Energy F
Helmholtz free energy is defined as
𝐹 = 𝑈 − 𝑇𝑆
As U, T and S are state variables. F is also a state variable.
According to the first law of thermodynamics
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑑𝑊
If the system is maintained at a constant temperature by exchanging
heat continuously with the surroundings,
𝑇𝑑𝑆 = 𝑑 𝑇𝑆
𝑑𝑈 = 𝑑 𝑇𝑆 − 𝑑𝑊
𝑜𝑟 𝑑 𝑈 − 𝑇𝑆 = −𝑑𝑊
𝑜𝑟 𝑑𝐹 = −𝑑𝑊
Where F = (U-TS) is known as Helmholtz free energy or Helmholtz
work function
Now 𝑑𝐹 = 𝑑 𝑈 − 𝑇𝑆 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝐵𝑢𝑡 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
This equation gives the change in Helmholtz free energy during an
infinitesimal reversible process.
(a) For reversible isothermal process:
𝑑𝑇 = 0
𝑑𝐹 = −𝑃𝑑𝑉 𝑜𝑟 𝑃𝑑𝑉 = −𝑑𝐹
Thus the work done in a reversible isothermal process is equal to the
decrease in Helmholtz free energy.
(b) For isothermal isochoric process:
𝑑𝑇 = 0 𝑎𝑛𝑑 𝑑𝑉 = 0
𝑑𝐹 = 0 𝑜𝑟 𝐹 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
The Helmholtz free energy remains constant during an isothermal
isochoric process.
Enthalpy H: This is known as the total heat and is given by
𝐻 = 𝑈 + 𝑃𝑉
As, U, P and V are state variables then H is also a state variables. If the
system undergoes an infinitesimal reversible process, then
Change in enthalpy 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝐵𝑢𝑡 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
(a) For reversible isobaric process:
𝑑𝑃 = 𝑜
𝑑𝐻 = 𝑇𝑑𝑆 = 𝑑𝑄
For an isobaric process, the change in enthalpy is equal to the heat
absorbed.
(b) For an isobaric adiabatic process:
𝑑𝑃 = 0 ; 𝑑𝑄 = 0
∴ 𝑑𝐻 = 0 𝑜𝑟 𝐻 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Enthalpy remains constant during a reversible isobaric adiabatic process.
Gibbs Function or Gibbs Free Energy: Gibbs function is defined b y
equation
𝐺 = 𝑈 − 𝑇𝑆 + 𝑃𝑉
As F = U-TS, therefore, we can write
𝐺 = 𝐹 + 𝑃𝑉
This is the relation between Gibbs function and Helmholtz function. An
enthalpy H = U+PV therefore becomes
𝐺 = 𝐻 − 𝑇𝑆
𝑜𝑟 𝐻 = 𝐺 + 𝑇𝑆
Enthalpy = Gibbs free energy + latent heat
For an isothermal process: 𝑇𝑑𝑆 = 𝑑(𝑇𝑆)
For an isobaric process: 𝑑𝑃 = 0
Hence, if the process is isothermal isobaric then
𝑑𝐻 = 𝑑 𝑇𝑆 dH=TdS+ VdP

𝑑 𝐻 − 𝑇𝑆 = 0
 𝑑𝐺 = 0 𝑜𝑟 𝐺 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Thus Gibbs function (G) or Gibbs free energy remains constant in an
isothermal isobaric process.
Maxwell’s Thermodynamic Relations:
From the first and second law of thermodynamics, Maxwell was
able to derive six fundamental thermodynamical relations. The state of a
system can be specified by any pair of quantities, viz. pressure (P),
Volume (V), temperature (T) and entropy (S). In solving any
thermodynamical problem, the most suitable pair is chosen and
quantities constituting the pair are taken as independent variables.
From the first law of thermodynamics,
𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊
 𝛿𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
𝑑𝑈 = 𝛿𝑄 − 𝑃𝑑𝑉
From the second law of thermodynamics,

𝛿𝑄
𝑑𝑆 =
𝑇
𝛿𝑄 = 𝑇𝑑𝑆
Substituting this value of 𝛿𝑄, we get
𝛿𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 (1)
Considering 𝑈, 𝑆 and 𝑉 to be function of two independent variables 𝑥
and 𝑦 [here, in general, 𝑥 and 𝑦 can be any two variables out of
𝑃, 𝑉, 𝑇 and 𝑆]
𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦
 𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦

𝜕𝑉 𝜕𝑉
and dV = ( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦
Substituting these values in equation (1), we get

𝜕𝑈 𝜕𝑈
( )𝑦 𝑑𝑥 + ( )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦

𝜕𝑆 𝜕𝑆 𝜕𝑉 𝜕𝑉
= 𝑇[( )𝑦 𝑑𝑥 + )𝑥 𝑑𝑦 − 𝑃[( )𝑦 𝑑𝑥 + )𝑥 𝑑𝑦
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦

𝜕𝑆 𝜕𝑉 𝜕𝑆 𝜕𝑉
=[𝑇( )𝑦 − 𝑃 ) 𝑑𝑥 + [𝑇( )𝑥 − 𝑃 ) 𝑑𝑦
𝜕𝑥 𝜕𝑥 𝑦 𝑑𝑦 𝜕𝑦 𝑥
Comparing the co efficient of 𝑑𝑥 and 𝑑𝑦, we get

𝜕𝑈 𝜕𝑆 𝜕𝑉
( )𝑦 = 𝑇( )𝑦 − 𝑃( )𝑦 … … … … … … … (2)
𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕𝑈 𝜕𝑆 𝜕𝑉
( )𝑥 = 𝑇( )𝑥 − 𝑃( )𝑥 … … … … … … … … (3)
𝜕𝑦 𝜕𝑦 𝜕𝑦
Differentiating equation (2) with respect to y and equation (3) with
respect to x.

𝜕2𝑈 𝜕𝑇 𝜕𝑆 𝜕2𝑆 𝜕𝑃 𝜕𝑉 𝜕2𝑉

= ( )𝑥 ( )𝑦 + 𝑇 − ( )𝑥 ( )𝑦 − 𝑃
𝜕𝑦. 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥

𝜕2𝑈 𝜕𝑇 𝜕𝑆 𝜕2𝑆 𝜕𝑃 𝜕𝑉 𝜕2𝑉

𝑎𝑛𝑑 = ( )𝑦 ( )𝑥 + 𝑇 − ( )𝑦 ( )𝑥 − 𝑃
𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦
 The change in internal energy brought about by changing 𝑉 and 𝑇,
whether 𝑉 is changed 𝑑𝑉 first and 𝑇 by 𝑑𝑇 later or vice versa is the
same. It means 𝑑𝑈 is a perfect differential

𝜕2𝑈 𝜕2𝑈
=
𝜕𝑦. 𝜕𝑥 𝜕𝑥. 𝜕𝑦

𝜕𝑇 𝜕𝑆 𝜕2 𝑆 𝜕𝑃 𝜕𝑉 𝜕2 𝑉
( )𝑥 ( )𝑦 + 𝑇 − ( )𝑥 ( )𝑦 −𝑃
𝜕𝑦 𝜕𝑥 𝜕𝑦.𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝜕𝑥

𝜕𝑇 𝜕𝑆 𝜕2𝑆 𝜕𝑃 𝜕𝑉 𝜕2𝑉
= ( )𝑦 ( )𝑥 + 𝑇 − ( )𝑦 ( )𝑥 − 𝑃 (4)
𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥𝜕𝑦
Since 𝑑𝑆 and 𝑑𝑉 are also perfect differentials, we have

𝜕2𝑆 𝜕2𝑆 𝜕2𝑉 𝜕2𝑉

= 𝑎𝑛𝑑 =
𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥 𝜕𝑥𝜕𝑦 𝜕𝑦𝜕𝑥
Equation (4), therefore reduces to

𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉 𝜕𝑇 𝜕𝑆 𝜕𝑃 𝜕𝑉
( )𝑥 ( )𝑦 − ( )𝑥 ( )𝑦 = ( )𝑦 ( )𝑥 − ( )𝑦 ( )𝑥 … … . (5)
𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦

This is the general expression for Maxwell’s thermodynamical relations.

In place of the independent variables 𝑥 and 𝑦, any two of the four
variables 𝑆, 𝑇, 𝑃 and 𝑉 can be substituted so that there may be one
mechanical variable (𝑃 𝑜𝑟 𝑉) and one thermal variable (𝑆 𝑜𝑟 𝑇). Thus,
there may be four sets of possible substitutions (𝑆, 𝑉), (𝑇, 𝑉), (𝑆, 𝑃) and
(𝑇, 𝑃) providing the four Maxwell’s thermodynamical relations.

First Relation:
Put 𝑥 = 𝑆 and 𝑦 = 𝑉 in equation (5), we get
 𝜕𝑆 𝜕𝑉
= 1, =1
𝜕𝑥 𝜕𝑦
Since S and V is
𝜕𝑆 𝜕𝑉
𝑎𝑛𝑑 =0, =0 independent, s doesn'ｔ
𝜕𝑦 𝜕𝑥 depends on v and vice versa

Substituting in equation (5), we get

𝜕𝑇 𝜕𝑃
( )𝑥 = −( )𝑦
𝜕𝑦 𝜕𝑥

𝜕𝑦
𝐵𝑢𝑡 𝜕𝑉 𝑎𝑠 𝑦 = 𝑉 𝑎𝑛𝑑 𝜕𝑠 = 𝜕𝑆 𝑎𝑠 𝑥 = 𝑆 . 𝐻𝑒𝑛𝑐𝑒

𝜕𝑇 𝜕𝑃
( )𝑠 = −( )𝑉
𝜕𝑉 𝜕𝑆
This is Maxwell’s first thermodynamical relation.
Second Relation:
Put 𝑥 = 𝑇 and y=V in equation (5), so
𝜕𝑇 𝜕𝑉 𝜕𝑇 𝜕𝑉
= 1, =1 𝑎𝑛𝑑 = 0, =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥

Substituting these in equation (5) we get

𝜕𝑆 𝜕𝑃
( ) 𝑇 = ( )𝑉
𝜕𝑉 𝜕𝑇
This is Maxwell’s second thermodynamical relation.
Third Relation:
Put x = S and y = P, in equation (5)

𝜕𝑆 𝜕𝑃 𝜕𝑆 𝜕𝑃
= 1, = 1, = 0, 𝑎𝑛𝑑 =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑥
 Substituting these in equation (5), we get

𝜕𝑇 𝜕𝑉
( )𝑠 = ( )𝑃
𝜕𝑃 𝜕𝑆
This is Maxwell’s third thermodynamical relation.
Fourth Relation:
Put x = P and y=V

𝜕𝑃 𝜕𝑉 𝜕𝑃 𝜕𝑉
= 1, = 1, = 0 𝑎𝑛𝑑 =0
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝑥
Substituting these values in equation (5), we get

𝜕𝑆 𝜕𝑉
( ) 𝑇 = −( )𝑃
𝜕𝑃 𝜕𝑇
This is Maxwell’s fourth thermodynamical relation. These are the four
Maxwell’s fundamental thermodynamical relations.
Joule-Thomson Effect
According to Joule-Thomson porous plug experiment, if a gas at
constant high pressure is forced through a porous plug to a region of
constant low pressure, the temperature of escaping gas changes. This is
called Joule-Thomson effect.
Due to throttling, the gas suffers expansion. Although there is a
pressure difference on two sides of the porous plug, the enthalpy H of the
gas remains constant. This is the necessary condition i.e.
𝐻 = 𝑈 + 𝑃𝑉 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
∴ 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0
𝐵𝑢𝑡 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 ∴ 𝐹𝑖𝑟𝑠𝑡 𝑙𝑎𝑤 𝑜𝑓 𝑡𝑕𝑒𝑟𝑚𝑜𝑑𝑦𝑛𝑎𝑚𝑖𝑐𝑠
𝐴𝑙𝑠𝑜 𝑑𝑄 = 𝑇𝑑𝑆 (∴ 𝑆𝑒𝑐𝑜𝑛𝑑 𝑙𝑎𝑤 𝑜𝑓 𝑡𝑕𝑒𝑟𝑚𝑜𝑑𝑦𝑛𝑎𝑚𝑖𝑐𝑠)
 ∴ 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 = 0 1
Now 𝑑𝑆 being a perfect differential and 𝑆 is a function of 𝑃 and 𝑇
i.e. 𝑆 = 𝑓 𝑃, 𝑇 , we have

𝜕𝑆 𝜕𝑆
𝑑𝑆 = ( )𝑃 𝑑𝑇 + ( ) 𝑇 𝑑𝑃
𝜕𝑇 𝜕𝑃
Substituting in equation (1),

𝜕𝑆 𝜕𝑆
𝑇( )𝑃 𝑑𝑇 + [𝑇 ) 𝑇 + 𝑉 𝑑𝑃 = 0
𝜕𝑇 𝜕𝑃

𝜕𝑄 𝜕𝑆
𝑁𝑜𝑤 𝐶𝑃 = ( )𝑃 = 𝑇( )𝑃
𝜕𝑇 𝜕𝑇
Where 𝐶𝑃 is specific heat at constant pressure.
 𝜕𝑆
𝐶𝑃 𝑑𝑇 = −[𝑇 ) 𝑇 + 𝑉 𝑑𝑃 … … … … … . (2)
𝜕𝑃

According to Maxwell’s fourth thermodynamical relation

𝜕𝑆 𝜕𝑉
( ) 𝑇 = −( )𝑃
𝜕𝑃 𝜕𝑇
𝜕𝑉
∴ 𝐶𝑃 𝑑𝑇 = [𝑇 ) − 𝑉 𝑑𝑃
𝜕𝑇 𝑃

1 𝜕𝑉
Or, 𝑑𝑇 = [𝑇 ) − 𝑉 dP … … … . . (3)
𝐶𝑃 𝜕𝑇 𝑃

Joule-Thomson Co-efficient(μ):
The Joule-Thomson co-efficinet is given by

𝜕𝑇 1 𝜕𝑉
𝜇 = ( )𝐻 = [𝑇( )𝑃 − 𝑉]
𝜕𝑃 𝐶𝑃 𝜕𝑇
 𝜕𝑉
Now ( )𝑃 = 𝛼𝑉, where α is the co − efficient of increase of volume
𝜕𝑇

1 𝜕𝑉
at constant pressure, because α = ( )𝑃 .
𝑉 𝜕𝑇
∴ From equation (3), we have

𝑉
𝑑𝑇 = 𝛼𝑇 − 1 𝑑𝑃 …………………. 4
𝐶𝑃
Equation (4) gives the change in temperature due to Joule-Thomson
effect.

Here 𝑑𝑃 represents a fall in pressure in porous plug experiment and it is

always a negative quantity. All other quantities in equation (4) are +𝑣𝑒.
Hence,
i. There is cooling effect i.e. dT is negative if (αT-1) is +𝑣𝑒 or αT>1
ii. There is neither a cooling nor a heating effect i.e. dT=0 when (αT-
1)=0 or αT=1
iii. There is a heating effect i.e. dT is positive if (αT-1) is negative or
αT<1.
Let us apply the thermodynamical treatment of heating and cooling effect
to a perfect gas.
For a perfect gas:
According to the gas equation
𝑃𝑉 = 𝑅𝑇 𝑓𝑜𝑟 𝑝𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠
At constant pressure,
 𝑃𝜕𝑉 = 𝑅𝜕𝑇
𝜕𝑉 𝑅
∴ ( )𝑃 =
𝜕𝑇 𝑃

𝜕𝑉 𝑅𝑇
Or T( )𝑃 = =𝑉
𝜕𝑇 𝑃

𝜕𝑉
Hence [T( )𝑃 − 𝑉] = 0
𝜕𝑇

Using equation (3), we have For a perfect gas dT=0

In other words, there is no Joule-Thompson effect for a perfect gas.
Hence, the porous plug experiment provides us a method to decide
whether the given gas is perfect or not. For a perfect gas, the Joule-
Thompson co-efficient (μ) is zero
𝜕𝑇 1 𝜕𝑉
∴ 𝜇 = ( )𝐻 = [𝑇 ) −𝑉 =0
𝜕𝑃 𝐶𝑃 𝜕𝑇 𝑃
Clausius - Clapeyron’s Equation

𝑑𝑃 𝐿
The equation = was first derived by Clapeyron using
𝑑𝑇 𝑇(𝑉2 −𝑉1)

Carnot’s reversible cycle. Therefore it is some times called Clapeyron's

equation.
Whenever there is a change of state, either from a solid to liquid or from
liquid state to vapour state, the temperature remains constant; as far as
the change takes place.
This temperature (either melting or boiling) depends upon the pressure
and is a characteristics of each substance. The above relation shows how
melting or boiling points vary with pressure and was derived by
Clapeyron by applying law of thermodynamics. Later Clausius obtained
the same relation by using Maxwell’s thermodynamic relations as under;
From Maxwell’s second thermodynamical relation

𝜕𝑆 𝜕𝑃
( ) 𝑇 = ( )𝑉
𝜕𝑉 𝜕𝑇
Multiplying both sides by T, we have

𝜕𝑆 𝜕𝑃
𝑇( ) 𝑇 = 𝑇( )𝑉
𝜕𝑉 𝜕𝑇
But T𝜕𝑆 = 𝜕𝑄

𝜕𝑄 𝜕𝑃
∴ ( ) 𝑇 = 𝑇( )𝑉
𝜕𝑉 𝜕𝑇
𝜕𝑄
The quantity ( ) 𝑇 represents the quantity of heat absorbed or liberated
𝜕𝑉

per unit change in volume at constant temperature. As there is a change

in volume due to the heat absorbed at constant temperature, the heat
represents the latent heat used when a substance changes from solid to
liquid or liquid to vapour state when the temperature remains constant,
during the change of state.
If 𝐿 is the quantity of heat required to change the state of a unit mass of the
substances 𝑉2 𝑎𝑛𝑑 𝑉1 the corresponding specific volumes then
𝜕𝑄 = 𝐿 and 𝜕𝑉 = 𝑉2 − 𝑉1
𝜕𝑄 𝐿
Hence, ( ) 𝑇 =
𝜕𝑉 𝑉2 −𝑉1

𝐿 𝜕𝑃
Therefore = 𝑇( )𝑣
𝑉2 −𝑉1 𝜕𝑇

𝑑𝑃 𝐿
Or, =
𝑑𝑇 𝑇(𝑉2 −𝑉1 )

Where 𝑑𝑇 is the change in melting point or boiling point due to change in

pressure 𝑑𝑃. This is Clausius-Clapeyron latent heat equation.
 Triple point
(i) The melting point of ice decreases with increase in pressure. It
means that ice melts at a temperature lower than 0° 𝐶 at a pressure higher
than the normal pressure.

The curve AB (Fig.) represents the

relation between pressure and the
temperature. The curve AB is called
the ice line. The substance will exist in
the solid state (ice) to the left of the
curve AB and in the liquid state to the
right of the curve AB.
The curve AB represents the equilibrium between the liquid and solid states
 (ii) The boiling point of water increases with increase in pressure.
The curve CD represents the relation between pressure and temperature
and it is called the steam line. Above the curve CD the substance is in the
liquid state and below the curve CD it is in the vapour state. The curve
CD represents the equilibrium between the liquid and the vapour states.
(iii) The curve EF represents equilibrium between the solid and the
vapour states of a substance and is called the Hoar Frost line. Above the
curve EF the substance is in the solid state and below the curve EF it is
in the vapour state.
These three curves should meet at a point O (fig.). Suppose these
curves do not meet at a point as shown fig.
 And they enclose an area ACF. It means, according to the ice line, the
substance must be only in the solid in the shaded portion. According to
the steam line, the substance must be only in the liquid state and
according to the hoar frost line the substance must be only in the vapour
state. Thus in the shaded portion, the substance must exist
simultaneously in the solid, liquid and vapour states. It is not possible.
Therefore, the three curves must meet at a single point O, called the
triple point

For water, the temperature and pressure

corresponding to the triple point are
0.0075℃ and 4.58𝑚𝑚 of Hg
respectively.
Heat of Reaction
The heat of reaction (also known and Enthalpy of Reaction) is the
change in the enthalpy of a chemical reaction that occurs at a constant
pressure. It is a thermodynamic unit of measurement useful for
calculating the amount of energy per mole either released or produced in
a reaction. Since enthalpy is derived from pressure, volume, and internal
energy, all of which are state functions, enthalpy is also a state function.
°
It is denoted by ΔH and ∆𝐻𝑟𝑥𝑛
• Δ = represents the change in the enthalpy; (∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 )
 a positive value indicates the products have greater enthalpy, or
that it is an endothermic reaction (heat is required)
  a negative value indicates the reactants have greater enthalpy, or
that it is an exothermic reaction (heat is produced)
• º = signifies that the reaction is a standard enthalpy change, and occurs
at a preset pressure/temperature
• rxn = denotes that this change is the enthalpy of reaction
Heat of combustion
The heating value (or energy value or calorific value) of a substance,
usually a fuel or food (see food energy), is the amount of heat released
during the combustion of a specified amount of it.
The calorific value is the total energy released as heat when a
substance undergoes complete combustion with oxygen under standard
conditions.
 The chemical reaction is typically a hydrocarbon or other organic
molecule reacting with oxygen to form carbon dioxide and water and
release heat.
It is the amount of heat evolved when 1 g molecule of it is
completely oxidised. That is the amount of energy released when a given
compound undergoes complete combustion with oxygen under standard
conditions. The chemical reaction is hydrocarbons reacting with oxygen
to form 𝐶𝑂2 , 𝐻2 𝑂 and heat.
There are two kinds of heat of combustion, called higher and lower
heating value, depending on how much the products are allowed to cool
and whether compounds like 𝐻2 𝑂 are allowed to condense.
Heat of Neutralization
The heat of reaction resulting from the neutralization of an acid or
base; especially : the quantity produced when a gram equivalent of a base
or acid is neutralized with a gram equivalent of an acid or base in dilute
solution.
The heat of neutralisation of an acid is defined as the amount of heat
evolved when one equivalent of an acid and one equivalent of a base
undergo a neutralisation reaction to form water and a salt. Similarly the
heat of neutralisation of a base is the amount of heat evolved when 1 g
equivalent of the base is completely neutralised by a strong acid in a
dilute solution.
𝐻𝐴 + 𝐵𝑂𝐻 ⇋ 𝐴𝐵 + 𝐻2 𝑂 + 57.3 𝐾𝐽
 𝐻 + + 𝐴− + 𝐵 + + 𝑂𝐻 − ⇋ 𝐴− + 𝐵+ + 𝐻2 0 + 57.3𝐾𝐽
𝐻𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙) + 𝑕𝑒𝑎𝑡
Heat of vaporization
The (latent) heat of vaporization (∆𝐻𝑣𝑎𝑝 ) also known as the enthalpy
of vaporization or evaporation, is the amount of energy (enthalpy) that
must be added to a liquid substance, to transform a given quantity of the
substance into a gas.
Because the molecules of a liquid are in constant motion and possess
a wide range of kinetic energies, at any moment some fraction of them
has enough energy to escape from the surface of the liquid to enter the
gas or vapor phase. This process, called vaporization or evaporation,
generates a vapor pressure above the liquid.
 The Heat of Vaporization (also called the Enthalpy of Vaporization)
is the heat required to induce this phase change.
Hess's law
Hess‘s law of constant heat summation, also known as Hess‘s law (or
Hess's law), is a relationship in physical chemistry named after Germain
Hess, a Swiss-born Russian chemist and physician who published it in
1840. The law states that the total enthalpy change during the complete
course of a chemical reaction is the same whether the reaction is made in
one step or in several steps.
Hess‘s law is now understood as an expression of the principle of
conservation of energy, also expressed in the first law of
thermodynamics, and the fact that the enthalpy of a chemical process is
 independent of the path taken from the initial to the final state (i.e.
enthalpy is a state function).