Beruflich Dokumente
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Discipline Course-I
Semester-II
Paper No: Thermal Physics : Physics-IIA
Lesson: Applications of Maxwell’s Thermodynamical
Relations part1
Lesson Developer: Dr. Vinita Tuli
College/ Department: ARSD College, University of Delhi
Table of Contents
Summary
Exercise/Practice
References/Bibliography
Introduction
Out of several properties of a thermodynamic system some of these like internal energy and
entropy cannot be measured. So thermodynamic relations can relate these properties with
those that can be measured like pressure,temperature, compressibility etc. In
thermodynamic relations un-measurable properties can be written as partial derivatives
involving both intensive and extensive variables. A thermodynamical relations is a rule
which is obtained by a simple thermodynamic reasoning and applies to most of the systems.
The usefulness of the above relations lies in the fact that they relate quantities which seem
unrelated. They help us to link data obtained in various ways or replace a difficult
measurement by another one. They can also be used to obtain values of one variable from
the calculations of another variable. These relations are very general and immensely useful
as they simplify analysis of thermodynamic systems. The most convenient way to derive
these relations is to use partial differentiation.
Value Addition
Note : The first four Maxwell’s thermodynamical relation need not be memorized. These
can be easily written by remembering the word SP or TV i e (sportive). In this, SP TV
represent entropy, pressure, temperature and volume. In deriving the first two relations,
S is written in the numerator on the left hand side of the equation and the rest of the
quantities P, T and V are written (i) in the clockwise order and (ii) in the anticlockwise
order. In the clockwise direction, the right hand side expression in with a + sign and for the
anticlockwise direction, it is –ve. These equations are
S P
= …(i)
V T T V
S V
= …(ii)
P T T P
Similarly to write the other equation, S is written in the denominator of the right hand side
of the equation and the other quantities are written (i) in the anticlockwise direction and (ii)
in the clockwise direction. These equations are
T P
= …(iii)
V S S V
T V
= …(iv)
P S S P
Applications
1.
Specific Heat Equation
Q
CP =
T P
S
= T ( Q T S )
T P
Q
CV =
T V
S
= T
T V
S S
dS = dT dV
T V V T
S S T S V
=
T P T V T P V T T P
S S S V
T =T T
T P T V V T T P
S P
= ( from Maxwell’s second relation)
V T T V
S S P V
T T = T
T P T V T V T P
P V
CP CV = T …(1)
T V T P
PV = RT
P R
=
T V V
V R
=
T P P
equation (1) takes the form
R R
CP CV = T
V P
R 2T
=
PV
R 2T
=
RT
CP CV = R
a
P 2 (V b) =RT
V
a RT
P 2 =
V (V b)
P R
=
T V (V b)
2a V RT V R
0 3 = 2
V T P (V b) T P (V b)
V RT 2a R
3 =
T P (V b) V (V b)
2
R
(V b)
V
=
T P RT 2a
(v b) 2 V 3
P V
Substituting the value of and in equation (1), we have
T V T P
R R
T
CP CV =
V b V b
RT 2a
(V b) 2 V 3
R
=
2a (V b) 2
1 3
V RT
R
CP CV =
2a V 2
1 3
V RT
R
=
2a
1
VRT
1
2a
= R 1
VRT
Expanding binomially the above equation and neglecting higher powers of a as a is very
small in comparison to V, we have
2a
CP CV = R 1
VRT
2.
To Show that CP CV TE 2V
where T is the absolute temperature
E is the isothermal elasticity of the gas,
is the coefficient of volume expansion and
V is the specific volume of the gas.
S P
=
V T T V
Q
CP =
T P
S
= T
T P
Q
CV =
T V
S
= T
T V
Taking S f (T ,V ), we have
S S
dS = dT dV
T V V T
dividing the above equation by dT and then carrying out the process at constant pressure
we have
S S T S V
=
T P T V T V T T P
But from the maxwell’s relation , we have
S P
=
V T T V
S S P V
T = T T
T P T V T V T P
P V
CP = CV T …(2)
T V T P
P P
dP = dT dV
T V V T
dP P P V
=
dT T V V T T P
At constant pressure
dP = 0
P P V
=
T V V T T P
P V
2
CP CV = T …(3)
V T T P
V P
2
CP CV = T …(4)
T P V T
P
E = V
V T
1 V
=
V T P
C p CV = TE 2V …(5)
dP L
The equation was derived by Clapeyron using Carnot’s reversible cycle.
dT T (V2 V1 )
Therefore, it is also called Clapeyron’s eqauation.
Whenever there is a change of state, from a solid state to liquid state or from liquid state to
vapour state, the temperature remains constant as long as the change takes place. This
temperature (either melting point or boiling point) depends upon the pressure and is a
characteristic of each substance. The above relation tells us how melting or boiling points
vary with pressure. Later Clausius also obtained the same relation by using the Maxwell’s
thermodynamic relations.
Derivation :
S P
=
V T T V
Multiplying both sides by T, we get
S P
T = T
V T T V
We know that
T S = Q
Substituting this in the above equation, we get
Q P
= T …(6)
V T T V
Q
represents the quantity of heat absorbed or liberated per unit change in volume at
V T
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 (melting) or liquid to vapour (boiling) state when the temperature remains
constant, during the change of state.
If L is the quantity of heat required to change the sate of a unit mass of the substance,
V2 and V1 the corresponding specific volumes (Volume per unit mass) then
Q = L
V = V2 V1
Dividing the above equations we get
Q L
=
V T V2 V1
L P
Therefore we have =T
V2 V1 T V
dP L
= …(7)
dT T (V2 V1 )
Where dT is the change in melting point or boiling point due to a change in pressure dP.
When a liquid converts into vapour state, we know that there is always an increase in
P
volume. Implies that V2 V1 ; T and L are always positive quantities, therefore is
T V
+ve. This shows that boiling point of the liquid is raised by increasing the pressure. This is
known as
When a solid melts, there may be an increase in volume, as in case of wax (such substances
are called wax type substances) or there may be a decrease in volume, as in the case of
(V2 V1 ) = +ve
Which implies
dP
= +ve
dT
Hence the melting point of the substance is raised with the increase in pressure.
In case of ice
(V2 V1 ) = – ve
hence melting point of such substances is lowered with increase in pressure. This is known
as depression in melting point. Substances which expands on melting, have their melting
points raised with the increase of pressure and the substance which contract on melting
have their melting points lowered with the increase of pressure.
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dL L
C2 C1 =
dT T
where C1 and C2 are the specific heat of a liquid and its vapour and
L is the latent heat of the vapour.
Where S1 and S2 are the entropies of the liquid and vapour states
Differentiating equation (8) with respect to T, we have
dS2 dS1 1 1 dL
= L 2
dT dT T T dT
dS dS L dL
T 2 T 1 =
dT dT T dT
dL L
C2 C1 = …(9)
dT T
This is known as Clausius second latent heat equation.
i. Calculate the specific heat of saturated steam given that the specific heat of water at
100°C = 1.01 and latent heat of vaporization decreases with increase in temperature at
the rate of 0.64 cal/K. Latent heat of vaporization of steam is 540 cal.
C2 = ?
T = 373 K
dL
= – 0.64 cal/K
dT
dL L
C2 C1 =
dT T
dL L
C2 = C1
dT T
540
= 1.01 (0.64)
373
= – 1.077 cal/g
ii. If L = 800 – 0.705 T, show that the specific heat of steam is negative.
dL
= – 0.705
dT
At normal boiling point of water i.e., at 100°C = 373 K, the value of L would be
= – 1.14467
5. To prove that for any substance, the ratio of the adiabatic and isothermal elasticities is
equal to the ratio of the two specific heats.
P
V
ES V S
=
ET P
V
V T
P
V S
=
P
V T
P T
T S V S
=
P S
S T V T
Taking the first term of the numerator to the denominator and the first term of the
S T
ES P T V S
= …(i)
ET T S
P S V T
from the first four Maxwell’s equations we have
S V
=
P T T P
T P
=
V S S V
T V
=
P S S P
S P
=
V T T V
V P
ES T P S V
=
ET V P
S P T V
Taking the first term of the denominator to the numerator and the second term of the
S V
ES V P T P
=
ET S P
P V T V
S
T
T P
=
S
T
T V
Q
T P
=
Q
T V
We know
Q
= CP
T P
Q
and = CV
T V
ES CP
= = …(ii)
ET CV
6. Using Maxwell’s thermodynamical relations, to prove that the ratio of the adiabatic to
the isobaric coefficient of volume expansion is
1
(1 )
1 V
S = ...(i)
V T S
1 V
P = …(ii)
V T P
V
T S
=
V
T P
1
=
T V
V S T P
T P
=
V S S V
1
=
P T V
T V S V T P
Taking the second term of the denominator to the numerator and multiplying by T
S
T
T V
=
P V
T
T V T P
We know that
P V
CP CV = T
T V T P
and
S
CV = T
T V
Substituting these values in the above equation we get
S CV
=
P (CP CV )
S 1
=
P C
1 P
CV
CV
S 1
= …(iv)
P 1
7. Using Maxwell’s thermodynamical relations prove that the ratio of the adiabatic to the
isobaric pressure coefficient of expansion is
( 1)
1 P
S = ...(i)
P T S
Isochoric pressure coefficient of expansion is
1 P
V = …(ii)
P T V
P
T S
=
P
T V
1
=
T P
P S T V
T V
= …(iv)
P S S P
S 1
= …(v)
V V P
S P T V
1
=
V T P
T P S P T V
using
P V
CP CV = T
T V T P
And we get
S CP
=
V CP CV
CP
S CV
=
V CP
1
CP
= …(vi)
1
Summary
Exercise
1. Derive Maxwell’s thermodynamical relations connecting the thermodynamic
quantities.
2. Show that
P V
CP CV = T
T V T P
where symbols have their usual meaning.
2. Use Maxwell’s relations to obtain CP CV R for an ideal gas where CP and CV are
specific heats at constant pressure and constant volume.
dP L
=
dT T (V2 V1 )
and explain the effect of pressure on
S P
=
P T T P
OBJECTIVE QUESTIONS
ES
3. From Maxwell’s thermodynamic relations ?
ET
(a) 1
1
(b)
(c)
(d) 2
References: