CETD-I UNIT IV

UNIT –IV
The thermodynamic properties of the fluids can be evaluated from the measurable quantities like
pressure, volume, temperature, heat capacity data and coefficients of expansions and compressibility.
Classification of Thermodynamic Properties:
i. The reference properties
ii. The energy properties
iii. The derived properties
Reference properties:
1. Also known as primary properties, these properties are the ones that are used to define the state of
the system.
2. They have absolute values, as against energy properties, which are measured relative to some
arbitrary reference state. Examples: temperature, pressure, volume, and entropy.
Energy Properties:
1. The four energy properties are internal energy (U), enthalpy (H), the Helmholtz free energy (A),
the Gibbs free energy (G).
2. Because, the changes in these thermodynamic functions indicate useful work under certain
conditions of restraint.
Derived properties:
1. These are partial derivatives of energy properties or the reference properties.
2. Examples include specific heat (C), coefficient of expansion (β), Joule Thompson coefficient (µ),
and coefficient of compressibility (Κ).
Work function (Helmholtz free energy)
1. The Helmholtz free energy (A) of a system is defined as,
A = U – TS --------- (4.1)
2. Where U, T, and S are internal energy, temperature and entropy of the system respectively. Since
they are characteristic of the system and depend only on its thermodynamic state, Helmholtz free
energy is a state function. Since U and S are both extensive property.
3. To understand the physical significance of work function, consider isothermal reversible change
occurring from state 1 to state 2. The from Eq. 4.1, the change in the work function accompanying
this process is,
ΔA = ΔU –TΔS ------- (4.2)
4. ΔA, ΔS, and ΔU denote changes in work function, the internal energy and the entropy respectively
of the system during the process. Since the process is reversible, the heat absorbed QR = TΔS, and
Eq.(4.2) can be written as,
ΔA = ΔU – QR--------- (4.3)
5. According to the first law of thermodynamics for a closed system,
ΔU = Q – W ---------- (4.4)

Substituting in (4.3) we get,

ΔA = -WR-------- (4.5)
6. The right-hand side of Eq. (4.5) is the decrease in work function. The equation therefore means
that the decrease in the work function accompanying a process at constant temperature is equal to
reversible work done by the system during the process.

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 UNIT IV
7. Since the reversible work is the maximum work obtainable from any change in state, the decrease
in the work function in an isothermal process is a measure of the maximum work available from a
given change of state.
8. In any actual isothermal process, the work done by the system would be less than the decrease in
the Helmholtz free energy , but the maximum work that can be done by the system is equal to –
ΔA in the limit of a reversible process.
Gibbs free Energy:
1. For the process in which zinc metal is allowed to react with dilute acid reversibly in a galvanic
cell, we have seen that the decrease in Helmholtz free energy determines the maximum work
which includes the electrical energy, and the work of expansion resulting from the reaction.
2. The maximum useful work, which in case is the amount of electrical energy produced, is given by
the decrease in another thermodynamic property known as the Gibbs free energy. It is denoted by
G, and like the work function, makes use of entropy in its definition.
G= H – TS ------- (4.6)
3. Like the work function A, Gibbs free energy G is a single valued function of the thermodynamic
state of the system and is an extensive property. It is widely used in the study phase equilibria and
chemical reaction equilibria. Since by definition, enthalpy H = U + PV, Eq. (4.6), can be written
as,
G= (U+PV) – TS = A + PV---------- (4.7)
4. The above equation reveals that A is related to G in the same way as U is related to H.The
physical significance of the Gibbs free energy function can be made clear if we consider a
reversible process at constant temperature and pressure. Equation (4.7) gives ΔG, the change in
free energy for a finite change in state of the system as,
ΔG = ΔA + Δ(PV) ---------(4.8)
5. We have already seen that ΔA = ̶ WR for reversible process at constant temperature. For a
constant pressure process,
Δ(PV)=P(ΔV).
Therefore, Eq. (4.8) becomes
G = ̶ WR + PΔV
-ΔG= WR ̶ PΔV-------- (4.9)
6. WR represents the total reversible work obtainable from a given change of state, which includes in
addition to work of expansion, other forms of work such as electrical and surface work.
7. Thus, we see that the decrease in Gibbs free energy in a process occurring at constant temperature
and pressure is maximum work other than the work of expansion available from the process, or
the maximum ‘net work’, WR’. Obtainable from the process.
WR’= ̶ ΔG--------- (4.10)
8. It is because of the fact that the change in Gibbs function G measures the net useful work, it is
known as ‘free energy’.
9. For the electrochemical cell that we have considered earlier, the total work obtained (WR) includes
electrical work and the work done against the constant pressure of the atmosphere (PΔV). The
latter work is always done whether the process is reversible or irreversible.
10. Thus, the maximum electrical work that could be done by the system undergoing a given change
in state is less than the total maximum work, ̶ ΔA, by the expansion work and is measured by the
decrease in the Gibbs free energy, ̶ ΔG.

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 UNIT IV
11. The value of ΔG in any process is quite definite, No matter under what conditions the process is
carried out, but only when temperature and pressure are constant the free energy change would
represent the maximum net work available from net work available from the given change in state.
Relationships among Thermodynamic properties:
The method of partial derivatives is used here to develop the important thermodynamic
relationships. The major thrust of this section is to express thermodynamics properties in terms of
measurable quantities.
Exact differential equations:
1. Let z be a single valued function of two independent variables x & y.
Z=f (x, y)
2. The total differential of z can be written in terms of partial derivatives with respect to independent
variables x and y as,
 Z   Z 
dZ =   dx +   dy − − − − − − − (4.11)
 x  y  y  x
3. A differential equation of this type is termed an exact differential equation. The value of ∫ 𝑑𝑧
between the two end conditions depends only on the values of z at these conditions, i.e.
2

 dZ = Z
1
2 − Z1

4. This value is independent of the path followed in bringing about the change from the initial
condition 1 to the final condition 2. The thermodynamic properties, in general, possess these
characteristics of the function Z.
5. For eg. The work function or free energy can be regarded as the single valued function of the
thermodynamic state, and dA and dG can be treated as exact differentials. Equation (4.11) can be
written as,
dz=Mdx+ndy − − − − − −(4.12)
Where M = (z/ x) y and N = (z/ x) x
Also, we can write,
 M   N 
  =  
 y  x  y  y

 2z  2z
= − − − − − − − (4.13)
yx xy
6. A property of exact differential equation that will be using frequently is shown by Eq. (4.13)
Fundamental property relations:
1. The differential of energy properties from the basis for derivation of a large number of equations
relating thermodynamic properties. These are developed below for systems of constant mass and
composition in which the only external is the pressure and the process occurring is reversible.
2. The first law for non-flow process is provided by dU = dQ - dW. For present case, the heat and
work terms are related to the properties of the system as dQ = T dS and dW =P dV, so that first
law for non-flow process becomes
dU = T dS – P dv----------(4.14)
3. Eq. (4.14) can be treated as the combined statement of first and second laws of thermodynamics
for reversible processes.
4. Using the definition of enthalpy (i,e., H= U + PdV), the differential of H is
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 UNIT IV
dH = dU + VdP + PdV − − − − − (4.15)
5. Combining this with equation (4.14), we get
dH = TdS + VdP − − − − − −(4.16)
6. In a similar way, starting from the definition of Helmholtz free energy, Eq (4.1), and Gibbs free
energy, Eq (4.6), the following relationships can also be derived
dA = − SdT − PdV − − − − − − − −(4.17)
dG = − SdT + VdP − − − − − − − −(4.18)
7. Equations (4.14), (4.16), (4.17) and (4.18) are the fundamental differential equations which
express the energy properties in terms of the four reference properties P, V, T, and S. It can be
seen that each of the energy change properties is functionally related to a special pair of variables
.For examples, Eq.(4.18) shows that
G = f ( P, T )
8. Thus P and T are the canonical variables or special variables for Gibbs free energy G. Canonical
variables for the work function are V and T.
Maxwell Equations:
1. Maxwell’s equations are helpful in replacing immeasurable quantities appearing in
thermodynamics equation by measurable quantities.
2. Using these relations, the partial derivatives of entropy with respect to pressure and volume are
expressed as possessing easily identifiable physical meaning. Each of the four Maxwell’s equation
is derived from the exact differential equation of the four energy properties.
3. Consider the exact differential of internal energy, i.e. Eq (4.14). At constant volume, it becomes
 U 
  =T
 S V
4. Differentiating the above with respect to volume at constant S
 2U  T 
=  − − − − − − − −(4.19)
VS  V  S
5. At constant entropy, Eq. (4.14) reduces to
 U 
  = −P
 V  S
6. Differentiating this with respect to S at constant V
 2U  P 
= −  − − − − − − − −(4.20)
SV  S V
7. Comparing Eq. (4.19) with Eq. (4.20) and utilising the properties of exact differential equations
given by Eq. (4.13), we get,
 T   P 
  = −  − − − − − − − −(4.21)
 V  S  S V
8. This is the first of the four Maxwell’s equation. The remaining three equations are obtained in
similar way starting from Eqns. (4.16), (4.17) and (4.18). The results are given below.
 T   V 
  =  − − − − − − − −(4.22)
 P  S  S  P
 P   S 
  =  − − − − − − − −(4.23)
 T V  V T
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 UNIT IV
 V   S 
  = −  − − − − − − − −(4.24)
 T  P  P T
Mnemonic diagram:
1. A square drawn with the diagonal arrows pointing upwards is shown in fig.1. The sides of the
squares are labelled with the energy properties in alphabetical order (A, G, H and U) starting with
the topside.
2. The corners are labelled with the canonical variables of the energy properties in such a way that
each energy property is flanked by its canonical variables.
3. The diagram can be used as a convenient tool for writing the differential equations for the energy
properties as well as the Maxwell’s equations. The differential equations contain the differentials
of its natural variables and their coefficients.
4. The differentials are obtained from the variables adjacent to the energy property under
consideration, and the coefficients are obtained from the variables that are diametrically opposite
to these variables.
5. The sign of the coefficient is to be decided from the direction in which the arrows are pointing. If
the arrow is pointing away from the canonical variable, the coefficient is positive and if the arrow
is pointing towards the canonical variable, the coefficient is negative.
6. For example, dU is written in terms of its canonical variables dS and dV. The coefficients are
respectively T and P which are diametrically opposite to S and V. Since the arrow is pointing
away from S and towards V the sign of T is positive and that of P is negative. Therefore,
dU = TdS − PdV .

7. To get Maxwell’s equations, fig.1 is thus used: Consider, for illustration, the topside of the square.
The partial derivative formed by the canonical variable is (T V ) . The suffix to be used is the
variable that is diametrically opposite to the first variable, i.e. S. Then one of the partial
derivatives in the desired relation is (T V )S .
8. The other derivative is obtained from the opposite side of the square in a similar way. This is
(P S )V . Since the direction of arrows being opposite, i.e. towards T and away from P, the sign
of the derivatives will be opposite. Therefore,
 T   P 
  = − 
 V  S  S V
Clapeyron Equation:
1. The Clapeyron equation predicts the dependence of equilibrium pressure on temperature when
two phases of a given substance coexist. It is given by

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 UNIT IV
dP H
= − − − − − − − (4.25)
dT TV
2. Where ΔH and ΔV are the enthalpy and volume change accompanying a phase change. It can be
derived from Maxwell’s relation Eqn. (4.23), which is applicable to any closed, homogeneous or
heterogeneous system in equilibrium, with an external pressure.
3. Clapeyron equation may be used for various purposes. It can be used to calculate the heat of
vaporisation, if the variation of vapour pressure with temperature is known. Alternatively, if the
heat of vaporisation is available, it is possible to predict the vapour pressure variation with
temperature.
Clausius – Clapeyron equation:
4. If the temperature is not too near the critical point, the volume of the liquid is small in comparison
with the volume of vapour. The volume change accompanying vaporisation V = VG − VL is
therefore approximately equal to VG, the molar volume of vapour. Equation (4.25) now becomes
dP H
= − − − − − − − (4.26)
dT TVG
5. The vapour pressures in regions well below the critical point are relatively small so that the
vapour can be assumed to behave as an ideal gas. The molar volume, VG, can now be replaced by
RT / PS so that Eqn. (4.26) becomes
dP S H
= PS
dT RT 2
or
d ln P S H
= − − − − − − − −(4.27)
dT RT 2
6. This result is known as Clausius – Clapeyron equation. Assuming that the heat of vaporisation
remains constant in the temperature range T1 to T2, Eqn (4.27) can be integrated to give the
following equation.
H  1 1 
S
P2
ln =  −  − − − − − − − −(4.28)
P1
S
R  T1 T2 
S S
P2 and P1 are the saturation pressures at tempera tures T2 and T1 respective ly.
Problem 1:
Calculate the vapour pressure of water at 363 K, if the vapour pressure at 373 K is 101.3 kPa. The
mean heat of vaporisation in this temperature range is 2275 kJ/kg.

Solution:

From eqn (4.28),

T1 = 363 K; T2 = 373K; P2 = 101.3kPa; H = 2275 * 18kJ / kmol; R = 8.314kJ / kmol.K .
S

Substituting the values in Eqn (4.28), we get

101.3 2275 *18  1 1  101.3

=  −   ln = 0.3638  P1 = 70.41kPa
S
ln
P1
S
8.314  363 373  P1
S

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 UNIT IV
Entropy-Heat Capacity Relationships:
1. Maxwell’s equations provide the partial derivatives of entropy with pressure or volume. The
partial derivatives of entropy with temperature are provided by the entropy-heat capacity
relationships.
2. The specific heats at constant pressure (CP) and constant volume (CV) are discussed in section.
These are defines as under,
 Q 
CP =   - - - - - - - - - (4.29)
 T  P
 Q 
CV =   - - - - - - - - - (4.30)
 T V
Since dQ = T dS for reversible process Eqs (4.29) and (4.30) can be written as
3.
 S   S 
CP = T   , CV = T  
 T  P  T V
which on arrangement give the following relationships,
 S  C
  = P - - - - - - - - - (4.31)
 T  P T
 S  CV
  = - - - - - - - - - (4.32)
 T V T
4. An important use of Eqs (4.31) and (4.32) is in the determination of entropy change of a system at
constant pressure or at constant volume respectively, for a specified change in temperature.
Equation (4.31) on integration gives
dT
S =  C P
T
5. If CP is independent of temperature, the above equation can be written as
T2
S = C P ln - - - - - - - - - - - (4.33)
T1
6. If CP varies with temperature, the required integration can be performed analytically provided CP
is expressed as a function of temperature. In the absence of such a relationship, graphical
integration will give the desired result. In the graphical method, the values of CP / T are plotted
against T (or, CP against ln T ) and the area under the curve between T1 and T2 ( or, between ln T1
and ln T2 ) will give S .
Problem 2: Determine the increase in entropy of solid magnesium when the temperature is increased from
300K to 800K at atmospheric pressure. The heat capacity is given by the following relation
CP = 26.04+5.586 * 10-3 T + 280746 * 104 T-2
Where CP is in J/mol K and temperature in K.
Solution: Equation (6.31) on integration gives
 26.04 
800
dT
S =  C P =  + 5.586 *10 −3 + 28.476 *10 4 T −3 dT
300  
T T
= 25.55 + 2.793+ 1.360 = 29.693 J/mol K

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 UNIT IV
Differential equations for entropy:
1. The state of a pure homogeneous fluid is uniquely determined by specifying any two
thermodynamic properties. Choosing temperature and pressure as variables, other properties like
entropy are related to them as S = f (P, T). The total differential of S is
 S   S 
dS =   dP +   dT - - - - - -(4.34)
 P T  T  P
2. Substituting Eqs (4.24) and (4.31) into the above
CP  V 
dS = dT −   dP - - - - - -(4.35)
T  T  P
3. If entropy were as function of temperature and volume, then S = f (V, T) and
 S   S 
dS =   dV +   dT - - - - - -(4.36)
 V T  T V
4. Substituting Eqs (4.23) and (4.32) into Eqs (4.36), we get
CV  P 
dS = dT +   dV - - - - - -(4.37)
T  T V
5. The partial derivatives (P T )V appearing in Eqs (4.37) can be expressed in terms of (V T )P
and (V P )T which, in turn, are related to the coefficient of volume expansion and
compressibility of the substance respectively. This is done as below.
6. Let the volume V be expressed as a function of P and T. V = f (P, T). Then the total differential of
V can be written as
 V   V 
dV =   dP +   dT
 P T  T  P
7. At constant volume, dV = 0 so that the above equation becomes
 V   V 
  dP = −  dT (at constant volume)
 P  T  T  P
8. This on rearrangement gives
 P  (V T )P  V   P 
 =− = −    − − − − − −(4.38)
 T  (V P )T  T  P  V T
9. When Eqs (4.38) is substituted into Eqs. (4.37), we get the differential equation for entropy as
below.
CV (V T )P
dS = dT − dV − − − − − −(4.39)
T (V P)T
Modified Equations for U and H
1. Changes in the internal energy and enthalpy can now be expressed in terms of changes in
measurable quantities like pressure, volume, temperature and specific heat of the fluid. Equations
(4.14) and (4.16) give the differentials of internal energy and enthalpy respectively.
2. Modified equations for U and H would result when Eq.(4.35) or Eq. (4.39) is substituted into
Eq.(4.14) and (4.16). Rewriting Eqs.(4.14) using Eq.(4.39), we get

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 UNIT IV
C (V T )P 
dU = T  V dT − dV − PdV
T (V P )T 
3. This can be rearranged as
 (V T )P 
dU = CV dT −  P + T dV − − − − − − − (4.40)
 (V P )T 
4. Rewriting eq (4.16) using eq. (4.35) the following modified equation results:
  V  
dH = C P dT + V − T    dP − − − − − − − (4.41)
  T  P 

5. It is also possible to write dU in terms of dP and dT by substituting Eq. (4.35) into Eq.(4.14) and
dH in terms of dV and dT by substituting Eq.(4.39) into Eq.(4.16). The results are as follows:
  V  
dU = C P dT −  PdV + T   dP − − − − − − − (4.42)
  T  P 
 (V T )P 
dH = CV dT + VdP − T dV − − − − − − − (4.43)
 (V P )T 
Problem 3: Develop equations for evaluating the change in internal energy and change in enthalpy for
process involving ideal gases.
Solution:
Equations (4.40) and (4.41) are used for evaluating dU and dH.
 (V T )P 
dU = CV dT −  P + T
(V P )T 
dV

  V  
dH = C P dT + V − T    dP
  T  P 
For one mole of an ideal gas, PV = RT, and therefore,
 V  R  V  RT
  = ,   =− 2
 T  P P  P T P
Substituting these into Eqs. (4.40) and (4.41), we get
 R P 
dU = CV dT −  P − T  dV = CV dT
 (
RT P 2  )
  R 
dH = C P dT + V − T   dP = C P dT
  P 

The preceding two equations indicate that the internal energy and enthalpy of an ideal gas are
functions of temperature alone, and for isothermal process there would be no change in these properties.
Problem 4: The equation of state of a certain substance is given by the expression V = RT / P − C / T 3 ,
and the specific heat is given by the relation CP = A + BT where A, B and C are constants. Derive
expressions for changes in internal energy, enthalpy and entropy for an (a) An isothermal process (b) An
isobaric process.
Solution:

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 UNIT IV
Since, V = RT / P − C / T 3

 V  R 3C  V  RT
  = + 4,   =− 2
 T  P P T  P T P

(a) Isothermal process: dT = 0. Equation (4.42) reduces to

  V     RT C   R 3C   3C
dU = − PdV + T   dP = − Pd  − 3  + T  + 4  dP = − 3 dP
  T  P    P T   P T P  T
This is the change in internal energy.
Equation (4.41) gives the change in enthalpy
  V    RT C  R 3C  4C
dH = V − T    dP =  − 3 − T  + 4  dP = − 3 dP
  T  P   P T  P T  T
Using Eq.(4.35), we have the change in the entropy
 R 3C 
dS = − + 4 dP
P T 
(b) Isobaric process: dP = 0. Equation (4.42) reduces to
dU = CP dT − PdV
a.
Since
 V   V 
dV =   dP +   dT
 P T  T  P
we get the change in the internal energy as
 V    R 3C 
dU = ( A + BT )dT − P (
 dT = ( A + BT ) − P + 4  dT = A − R + BT − 3PCT dT
−4
)
 T  P   P T 
From Eq. (4.41), change in the enthalpy is
dH = CP dT = ( A + BT )dT
From Eq. (4.35), change in the entropy is
C A 
dS = P dT =  + B dT
T T 
Relationship between CP and CV :
1. We have seen that the partial derivatives of entropy with respect to temperature are related to the
specific heats as given by eqs.(4.31) and (4.32)
 S  C  S  C
  = P;   = V
 T  P T  T V T
2. Equation (4.35) gives the total differential of S as
CP  V 
dS = dT −   dP
T  T  P
3. Dividing by dT and imposing the constant volume restriction, the above equation becomes
 S  C  V   P 
  = P −    − − − − − −(4.44)
 T V T  T  P  T V
4. Substitute eq (4.32) into Eq (4.44) so that

Page 10
 UNIT IV
CV C P  V   P 
= −   
T T  T  P  T V
5. This can be rearranged as
 V   P 
C P − CV = T     − − − − − −(4.45)
 T  P  T V
6. Equation (4.38) can be used to replace (P / T )V from this equation. The resulting equation is

 V   P 
2

C P − CV = −T     − − − − − −(4.46)
 T  P  V T
7. If the P-V-T behaviour of the fluid is known either as an equation of state or as a graphical result,
Eq. (4.46) can be used to evaluate the difference between 𝐶𝑝 and 𝐶𝑣 over wide range of
temperature and pressure.
8. Equation (4.46) can be written in terms of coefficient of volume expansion (𝛽) and coefficient of
compressibility (K) which are defined as below.
1  V  1  V 
=   ;  =−  
V  T  P V  P  T
9. Which means that (V / T )P = V and (V / P )T = −V . Using these in Eq. (4.46) the
following equation results:
 2VT
C P − CV = − − − − − −(4.47)

10. Equation (4.47) is the most convenient form for the calculation of C P − CV of solids and liquids.
Equation (4.46) and (4.47) are particularly valuable because most of the laws developed under
statistical thermodynamics on specific heat deal with CV , through these are rarely determined
experimentally. These equations provide useful tools for calculating CV from experimentally
determined valves of C P
Problem 5: Show that for ideal gases 𝐶𝑝 - 𝐶𝑣 = R.
Solution For ideal gases, PV = RT, or V= RT/P, Also,
 V  R RT  P  RT
  = ; P= ;   =− 2
 T  P P V  V T V
Substituting these into Eq. (4.46), we obtain C − C = −T  V   P  − − − − − −(4.46)
2

   
 T  P  V T
P V
2
 R   RT 
C P − CV = T    2  = R
P V 
Problem 6: Show that for a gas obeying van der Waals equation of state,
R
C P − CV =
1 − 2a(V − b) 2 /( RTV 3 )
Where a and b are van der Waals constants.
Solution The van der Waals equation is
 a 
 P + 2 (V − b) = RT
 V 

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 UNIT IV
Differentiate the above equation with respect to V at constant T
 P  2a  a
(V − b)   − 3+P+ 2 =0
 V T V  V
This equation can be rearranged using vander Waals equation as
 P  2a(V − b) 2 − RTV 3
  = − − − − − −(4.48)
 V  T V 3 (V − b) 2
Differentiating vander Waals equation with respect to T at constant P, we obtain
 2a  V    a  V 
(V − b) − 3    +  P + 2   =R
 V  T  p   V  T  p

The above equation can be rearranged to give

 V  − R(V − b)V 3
  = − − − − − (4.49)
 T  p 2a(V − b) − RTV
2 3

Substituting Eqs.(4.48) and (4.49) into Eq.(4.46), we get the following result
R
C P − CV =
1 − 2a(V − b) 2 /( RTV 3 )
Ratio of Heat Capacities:
1. Combining Eqs.(4.31) and (4.32) we see that
C P (S / T )P
= − − − − − − − −(4.50)
CV (S / T )V
2. In order to express this ratio in terms of P-V-T data, let us assume that S=f(P,T) so that
 S   S 
dS =   dP +   dT
 P T  T  P
3. At constant entropy, dS = 0. That is,
 S   S 
  dPS +   dTS = 0
 P T  T  P
 S   S 
  dPS = −  dTS
 P T  T  P
4. Rearranging this equation we get
 S   S   P 
  = −   
 T  P  P T  T  S
5. By assuming S = f (V, T) and proceeding as above, we can show that
 S   S   V 
  = −   
 T V  V T  T  S
6. Substituting the partial derivatives given by the preceding two equations into Eq.(4.50), we see
that
C P (S / P )T (P / T )S  V   P 
= =    − − − − − − − −(4.51)
CV (S / V )T (V / T )S  P T  V  S

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 UNIT IV
7. It is to be noted that it is impossible to write the ratio of heat capacities in terms of P-V-T data
alone; entropy appears in at least one of the partial derivatives.
Effect of Pressure and Volume on CP and CV
1. The change in entropy with changes in temperature and pressure is given by Eq.(4.35)
CP  V 
dS = dT −   dP
T  T  P
2. The above equation reduces to the Maxwell’s equation, Eq.(4.24), under constant temperature (i.e.
when dT=0) and the heat capacity relation, Eq.(4.31), under constant pressure(i.e. when dP = 0).
 S   V 
  = −  − − − − − −(4.24)
 P  T  T  P
 S  C
  = P − − − − − − − (4.31)
 T  P T
3. Differentiate Eq.(4.24) with respect to temperature, keeping the pressure constant and
Eq.(4.31)With respect to pressure keeping the temperature constant. This results in Eqs.(4.52) and
(4.53) respectively.
2S   2V 
= − 2  − − − − − −(4.52)
TP  T  P
2S  C / T  1  C 
= P  =  P  − − − − − −(4.53)
PT  P  T T  P  T
4. Compare Eq.(4.52) with Eq.(4.53). The right-hand sides of these equations are equal. That is,
 C P    2V 
  = −T  2  − − − − − −(4.54)
 P T  T  P
5. As (C P / P )T can be written as (C P / V )T (V / P )T , Equation (4.54) becomes

 C P    2V   P 
  = −T  2    − − − − − −(4.55)
 V T  T  P  V  T
6. Eqs.(4.54) and (4.55) represent the effect of pressure and volume on CP.
7. The following two equations that give the effect of pressure and volume on CV and derived in a
manner similar to that used for the derivation of Eqs.(4.54) and (4.55)
 CV   2P 
  = T  2  − − − − − −(4.56)
 V  T  T V

 CV    2 P   V 
  = T  2    − − − − − −(4.57)
 P  T  T V  P T
8. Eqs. (4.54)- (4.57) hold good for any homogeneous substance; however, they are usually applied
to gases.
Problem 7:
Show that CP and CV of ideal gases are independent of pressure and volume.
Solution: Since PV= RT,
 V  R   2V 
  = ,  2  = 0
 T  P P  T  P
Page 13
 UNIT IV
 P  R  P
2

  = ,  2  = 0
 T V V  T V
On substituting these results into Eqs.(4.54)-(4.57), we see that
 C p   C   C   C 
  =  p  =  V  =  V  = 0
 P  T  V  T  V  T  P  T
This means that, for ideal gases CP and CV depend only on temperature.
Problem 8:
A certain gas is found to obey the following equation of state.
RT C D
V = − 2 + 3
P T T
(a) Develop a relation to predict the effect of pressure on Cp
(b) What is CP -CV?
Solution: Equation (4.54) gives the effect of pressure on Cp. The partial derivatives in this equation
are evaluated first.
RT C D
V = − 2 + 3
P T T
 V  R 2C 3D   2V  6C 12 D  V  RT
  = + 3 − 4,  2  = − 4 + 5 ,   =− 2
 T  P P T T  T  P T T  P  T P
(a) Substituting these results in eqn (4.54),
 C P  6C 12 D
  = 3 − 4
 P  T T T
(b) Substituting the necessary partial derivatives in eqn (4.46), we get
2
1 2C 3D 
C P − CV =  + − 4 
RP 2
 
3
P RT RT
Problem 9: A gas obeys the relation P (V-b ) = RT and has a constant Cv. Show that
(a) U is a function of temperature alone
(b)  is a constant
(c) P (V-b)  is constant for a reversible adiabatic process.
Solution: (a) To prove that U depends only on temperature, it is enough to show that U does not
change with P or V at constant T. Consider eqn (4.40). At Constant temperature this equation can be
simplified to
 U   (V / T ) P   P 
  = − P + T  =T  − P ------ (4.58)
 V  T  (V / P) T   T V
Since the eqn of state is P (V-b) = RT,
 P  R
  =
 T V V − b
Substituting this in eqn (4.58)

Page 14
 UNIT IV
 U 
  =0 - - - - - - - - - -(4.59)
 V T
Since
 U   U   P 
  =  = 
 V T  P T  V T
and as is evident from the equation of state, (P / V )T  0 , we have

 U 
  = 0 − − − − − −(4.60)
 P T
Equations (4.59) and (4.60) together mean that U depends only on T
(b)Equation (4.46) gives CP – CV as

 V   P 
2

C P − CV = −T    
 T  P  V T
 V  R  P  RT
Here,   = ,   =−
 T  P P  V  T (V − b) 2
Thus
 
2
R RT
C P − CV = −T    −  = R a constant
P  (V − b)
2

It is given that Cv is constant. Therefore, Cp and hence,  = Cp / Cv are also constant.
(c) Here
 V  R  P  R
  = ,   =
 T  P P  T V V − b
Consider S as a function of P and V. That is, S = f (P, V)
 S   S 
dS =   dP +   dV
 P V  V  P
At constant S, we have
 S   S 
  dP +   dV = 0
 P V  V  P
Rearranging this, we get
 P  (S / V ) P (S / T ) P (T / V ) P C p (T / V ) P P/R P
  =− =− =− * = − = −
 V  S (S / P)V (S / T )V (T / P)V CV (T / P)V (V − b) / R V −b
This can be written as
dP dV
= −
P V −b
d ln P = − d ln (V − b )


Or d ln P (V − b ) = 0


i.e,

Page 15
 UNIT IV
P (V − b ) = C


Where C is a constant.
Joule- Thomson Coefficient
1. The Joule- Thomson expansion is employed for cooling and liquefying of gases. It involves
adiabatic throttling of a gas .The enthalpy remains constant during the process. The Joule-
Thomson coefficient (µ) is the fall in temperature associated with a unit decrease in pressure
under this condition.
 T 
 =  − − − − − − − (4.61)
 P  H
2. Generally, a gas cools on throttling, so that the Joule- Thomson coefficient is positive. However, it
may take negative values if the temperature increases with the expansion of the gas.
3. The gas, which is initially at a state represented by the point P in Fig. 4.3, is undergoing Joule-
Thomson expansion. It will experience a rise in temperature till the point Q is reached, and
thereafter the temperature decreases with further decrease in pressure.
4. The slope of the isenthalp is equal to the Joule- Thomson coefficient as per the defining relation
eqn. (4.61). It is positive only in the region where pressure is less than that at Q and is zero at
point Q, where there isenthalp exhibits a maximum.
5. The locus of the maximum in the isenthalp curves forms the Joule- Thomson inversion curve as
show in the figure. To the left of this, µ is positive and to the right it is negative. Figure 4.4 shows
the complete range of a typical Joule- Thomson inversion curve.

Page 16
 UNIT IV
6. The region bounded by this curve and the temperature axis indicates the conditions under which
the gas would cool on Joule-Thomson expansion, whereas in the region outside this curve
throttling process results in increase in temperature.
7. The Joule-Thomson coefficient may be calculated from the P-V-T behaviour and specific heat data
as detailed below. The modified differential of enthalpy [Eq. (4.41)] may be taken as the starting
point.
  V  
dH = C P dT + V − T    dP − − − − − − − −(4.41)
  T  p 
8. As noted above, for Joule-Thomson expansion dH = 0. Imposing this condition on Eq. (4.41) we
get
  V  
C P dT + V − T    dP = 0
  T  p 

or
 T  T (V / T ) p − V
  ==
 P  H Cp

 V 
C p = T   − V − − − − − −(4.62)
 T  P
Gibbs-Helmholtz Equation:
1. The Gibbs-Helmholtz equation provides the effect of temperature on Gibbs free energy. Consider
Eq. (4.18).
dG = − SdT + VdP − − − − − −(4.18)
2. At constant pressure, the above equation reduces to
 G 
  = − S − − − − − − − (4.63)
 T  p
3. Even though this equation gives the effect of temperature on G it will be convenient for practical
calculations to replace S in terms of measurable quantities. This can be done as follows.
4. Nothing that d (u / v) = (vdu − udv) / v 2 , the derivative of G/T can be written as
  (G / T )  T (G / T ) p − G
  =
 T  p T2

5. Use Eq. (4.63) to eliminate (G / T ) p from the above equation.

  (G / T )  − TS − G
  =
 T  p T2

6. Since by definition, G = H –TS, the above equation can be simplified as

 (G / T )  H
  = − 2 − − − − − − − (4.64)
 T  p T
7. Equation (4.64) is known as Gibbs – Helmholtz equation and it finds wide application in the
analysis of chemical reaction equation. Integration of Eq. (4.64) yields
G H
= −  2 dT + G '− − − − − − − − −(4.65)
T T
Page 17
 UNIT IV
Method of Jacobians:
1. Jacobians are determinants, the elements of which are partial derivatives. The method of Jacobians
can be used as a very powerful but simple tool for deriving the relationship between
thermodynamic properties.
2. In the earlier sections we have developed these relationships through partial derivatives. All these
relation may be derived using the method of Jacobians. Here we discuss the method in general,
and derive a few typical equation which were derived in previous section using the method of
partial derivatives.
Properties of Jacobians:
1. Let us consider three variables, x, y and z, each of which is a function of the independent variables
u and v. Then,
x = x(u, v), y = y(u, v), z = z(u, v)
2. The Jacobian of x and y, denoted by [x, y] / [u, v], is defined as,
 x   y  
   
x, y  =  u V  u V  =  x   y  −  x   y 
        - - - - - -(4.66)
u, v  x   y    u V  v  u  v  u  u V
    
 v  u  v  u 
3. The following are some of the properties of the Jacobians that are useful in derivation of
thermodynamic relationships.
Property 1: x, y = −y, x − − − − − − − −(4.67)
Property 2: x, x = 0 − − − − − − − −(4.68)
Property 3: x, y =  x, y − − − − − − − (4.69)
Property 4: In Jacobians notation, the partial derivative (y / x )Z can be expressed as
 y  y, z  − − − − − − − (4.70)
  =
  Z x, z 
x

Property 5:
x, y  = x, y /s, t  − − − − − − − (4.71)
u, v u, v/s, t 
Property 6: The exact differential equation, dz = Mdx + Ndy, in terms of Jacobians becomes
z, u = M x, u + Ny, u − − − − − − − −(4.72)
Property 7: The exact differential equation, dz = Mdx + Ndy, may be put in another form as

dz =
z, y  dx + z, x dy − − − − − − − −(4.73)
x, y   y, x 
4. The properties 1-5 can be easily verified by writing the Jacobians as determinants and expanding
them. To verify property 6 consider the total differential:
dz = Mdx + Ndy − − − − − −(4.74)
5. Divide this by dv, keeping u constant we get,
 z   x   y 
  = M   + N 
 v  u  v  u  v  u
6. Using the property 4, the partial derivatives in the above equation may be eliminated in favour of
the Jacobians as:
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 UNIT IV
z, u  = M x, u  + N y, u 
v, u  v, u  v, u 
7. The above result can be written in simplified notation as in Eq. (4.72). Nothing that in Eq. (4.74),
 z   z 
M =  , N =  
 x  y  y  x
and using the property 4, Eq. (4.73) can also be easily verified.
8. Another relationship among Jacobians which is found to be extremely useful in the derivation of
thermodynamic relations may be developed as follows. Divide Eq. (4.73) by dv, keeping u
constant and express the result in terms of Jacobians.
 z  z, y  x  + z, x  y 
  =    
 v  u x, y   v  u  y, x  v  u
z, u  = z, y  x, u  + z, x y, u 
v, u  x, y  v, u  y, x v, u 
That is,
z, ux, y = z, yx, u− z, xy, u
Or
x, , uy, z + y, uz, x + z, ux, y = 0 − − − − − − − −(4.75)
Thermodynamic Relations through the Method of Jacobians:
Fundamental property relations:
Consider the differentials of the energy properties that were developed and are given by (4.14,
4.16, 4.17 and 4.18). Using property 6, these equations may be expressed in terms of the Jacobian Eqs.
(4.76) – (4.79) respectively, as
U , w = T S , w − PV , w − − − − − − − −(4.76)
H , w = T S, w + V P, w − − − − − − − −(4.77)
A, w = −ST , w − PV , w − − − − − − − −(4.78)
G, w = −ST , w + V P, w − − − − − − − −(4.79)
In Eqs. (4.76) – (4.79), “w” stands for any thermodynamic property other than the energy property.
Maxwell’s equation:
It can be shown that all Maxwell’s equations can be expressed as [P,V] = [T,S]. For example,
consider Maxwell’s equation, Eq.(4.23)
 P   S 
  =  − − − − − − − −(4.23)
 T V  V T
Using property 4, eq.(4.70), the partial derivatives in eq. (4.23) may be replaced by the Jacobians.
P,V  = S , T 
T ,V  V , T 
Using the property 1, this becomes
P,V  = − S , T 
T ,V  T ,V 

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 UNIT IV
So that
P,V  = −S , T 
Or
P,V  = T , S  − − − − − − − (4.80)
University Question:
1. Explain the fundamental differential equations for the energy properties: List their canonical
variables for U, H, A and G. (16) May 2014 & R8

2. Derive the quations from fundamentals for dE and dH equation and Prove that dH = CpdT& dE =
CvdT. Nov 2011 & R8

3. Derive Maxwell's equations and discuss about their importance in establishing relationships
between thermodynamic properties. (16) May 2014 & R8
Derive Maxwell's relationship using Mnemonic Diagram. (16) NOV 2014 & R8
Derive Maxwell's relations from thermodynamic principles NOV 2013 & R8
State and prove Maxwell's Equations. NOV 2013 & R7, May 2012 & R7
Derive all Maxwell's relations from fundamental property relations. (10) May 2013 & R7, May
2017 & R8
Derive Maxwell relations from fundamentals (10) Nov 2010 & R7, Nov 2011 & R8
Derive Maxwell relations from first principles.(8) May 2011 & R8
Write any two Maxwell's relation and explain its significance. (2) May 2013 & R7, Nov 2017
& R8
Mention any two important applications of Maxwell relations. (2) May 2014 & R8
Derive Maxwell equations and also mention the applications. (16) Nov 2015 & R8, Nov 2017 &
R8
Derive Maxwell's Relations using the method of partial derivatives. (16) May 2015 & R7
Derive Maxwells equations. May 2015 & R7, Nov 2017 & R13
Write any two Maxwell's relations. (2) May 2016 & R8
State the necessity of Maxwell's relations.(2) May 2017 & R13

4. Show that Cp and Cv of an ideal gas depends on temperature alone. (6) NOV 2013 & R7, May
2012 & R7, May 2015 & R7
Show that Cp and Cv of ideal gases are independent of pressure and volume. (2) Nov 2012 & R7,
May 2012 & R7
Show that for a gas obeying van der Waals equation  CV  = 0 ( NOV 2013 & R8), NOV 2013 &
 V T
R7, May 2012 & R7, May 2015 & R7, May 2016 & R13

5. Cp- Cv= ? (derive from entropy Equation) (6) Nov 2011 & R8
Show that the difference between Cp and Cv .(8) Nov 2010 & R7
State the relationship between Cp and Cv. (2) NOV 2013 & R8
What is the relation between Cp and Cv? Derive it. (2) May 2016 & R8
Explain the Cp - Cv relationship for solids and liquids.(8) Nov 2017 & R8

6. Why is the specific heat at constant pressure Cp always greater than that at constant volume Cv ?
(2) May 2015 & R7

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 UNIT IV

7. Derive the following relation between Cp and Cv using the method of Jacobians: (16) Nov 2015
& R13

8. What are thermodynamic formulations? (2) NOV 2013 & R8

9. Prove that Joule Thompson coefficient is given by =  1 T  V  − V  and obtain its value for
C 
an ideal gas.  P   T  P 
May 2011 & R8, NOV 2014 & R8, May 2016 & R13

 V  
10. Show that dH = CP dT + V − T    dP (6) May 2013 & R7
  T  P 

11. Show that  CP  = T   V2 

2
(6) May 2013 & R7
 T 
 P T  P
Show that dT  V  (6) ( NOV 2013 & R8)
dS = CP −  dP
T  T  P

12. The equation of state of a certain substance is given by the expression V = RT / P − C / T 3

and the specific heat is given by the relation C P = A + BT where A, B and C are constants.
Derive expressions for changes in internal energy, enthalpy and entropy for an (i) Isothermal
process (ii) an isobaric process. NOV 2012 & R8, NOV 2013 & R8

13. A gas obeys the relation P(V-b) = RT and has a constant Cv. Show that (i) U is function of
temperature alone (ii) γ is constant (iii) P(V-b)γ is constant for a reversible adiabatic process. May
2016 & R8
1 − 2a(V − b )2 
14. Show that for a gas obeying Vander Waals equation of state: C P − CV = R /  
 RTV 3 
NOV 2016 & R13

15. Show that for a gas obeying the equation of state PV (1- bp) =RT. (Nov 2012 & R8)
P2 (1 − bP1 ) P2 (1 − bP1 ) RT RT
(i ) G = RT ln (ii) A = RT ln − +
P1 (1 − bP2 ) P1 (1 − bP2 ) (1 − bP2 ) (1 − bP1 )

16. Write the fundamental property relations. (2) NOV 2013 & R7, Nov 2017 & R13

17. What are the fundamental differential equations for the energy properties? (2) Nov 2012 & R8,
NOV 2015 & R13

18. Develop differential equations for entropy in terms of measurable quantities. (8) May 2016 & R8

19. Name and write the equation that provides the effect of temperature of Gibbs free energy. (2)
NOV 2013 & R7

20. Write clayperon equation and its significance. (2) May 2014 & R8
Write Clausius - Clapeyron equation and give its physical significance. (2) Nov 2012 & R7,
May 2012 & R7

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 UNIT IV

21. How are the thermodynamic properties classified? (2) Nov 2012 & R7, May 2012 & R7

22. What is thermodynamic property? Give proper example for each classification. (2) May 2016 &
R13

23. What are derived properties? (2) Nov 2010 & R7, NOV 2014 & R8

24. Define ' Reference properties' (2) NOV 2016 & R13

25. Define Helmholtz function.(2) May 2015 & R13

26. Define Gibbs and Helmholtz free energies. (2) May 2014 & R8
Write the expression for Helmholtz free energy and Gibbs free energy. NOV 2014 & R8, May
2016 & R13
Explain the following terms briefly: (1) Helmholtz free energy (2) Gibbs free energy (4+4) May
2016 & R8

27. What are residual properties? (2) May 2015 & R13, Nov 2017 & R13

28. Derive the residual property relations for Gibb,s free energy. Helmholtz free energy and entropy.
(16) May 2015 & R13

29. List the fields of application of different types of thermodynamic diagrams.(2) NOV 2015 & R13

30. Discuss the different types of thermodynamic diagrams briefly and explain the construction of any
one thermodynamic diagrams in detail. (16) NOV 2015 & R13

31. Express the coefficient of thermal expansion and isothermal compressibility in terms of
measurable properties. (2) NOV 2016 & R13

32. Derive the following fundamental property relations from basics (i) dG = -SdT + VdP (ii) dH =
TdS + VdP (iii) dU = TdS - PdV (iv) dA = -SdT - PdV (4*4 = 16) NOV 2016 & R13

33. Derive the following equations May 2017 & R8

  V  
dH = CP dT + V − T    dP
  T  P 
CP  V 
dS = dT −   dP
T  T  P
  V  
dU = CP dT −  PdV + T   dP 
  T  P 

34. Give any two methods by which the fugacity coefficient of a real gas is estimated. (16) May 2017 & R8
35. Derive any three T-dS relations (13) Nov 2017 & R13
36. Derive how the energy properties were measured.(8) Nov 2017 & R8
37. List the properties of jacobians. (2) May 2017 & R13

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