Thermodynamic Relations by Dr. Krishnan

UNIT 4 (PART A):
THERMODYNAMIC
RELATIONS
S. Krishnan, PhD
Professor of Aerospace Engineering
School of Mechanical Engineering
SRM University
Kattankulathur 603203, Tamil Nadu, India
Reference: Cengal, Y. A. and Boles, M. A., Thermodynamics: An Engineering
Approach, 7th Edition, McGraw Hill. Inc. New Delhi, 2011, pp. 657-676.
Unit 4: Thermodynamic
Relations
Syllabus
Maxwells Equations Clapeyron Equation
General Relations for dh, du, ds, cp, and
cv. Joule Thomson Coefficient Gas
Mixtures Daltons Law of Partial
Pressures. P-v-T Behavior of Gas
Mixtures. Property Calculations
Professor S. Krishnan, SRM

University, India
4. 1. Maxwells Equations
4. 1. 1. Introduction
i.Thermodynamic relations help preparation of property tables.
ii.Directly measurable properties are temperature, pressure,
volume, and mass.
iii.Simple derived properties are density and specific volume.
iv.Not so easy to determine properties are internal energy,
enthalpy, and entropy.
v. Also, with thermodynamic relations we can estimate enthalpy
of condensation (heat of vaporization or latent heat of
evaporation) , and enthalpy of freezing (enthalpy of fusion or
latent heat of melting).
vi. In this Unit we learn the real application of our mathematical
knowledge on partial differential equations to solve engineering
problems.
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f f x
Partial Differentials
f
f x x f x
df
lim
lim
dx x 0 x x 0
x
The derivative of a function f(x) with
respect to x represents the
rate of change of f with x.
The derivative of a function at a specified point

represents the slope of the function at that point.
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Partial Differentials
The variation of z(x, y) with x when

y is held constant is called the
partial derivative of z with respect
to x, and it is expressed as
z x x, y z x, y
z
z
lim lim
x
x y x 0 x y x 0
Geometric representation of
partial derivative (z/x)y.
The symbol represents differential

changes, just like the symbol d.
They differ in that the symbol d
represents the total differential
change of a function and reflects
the influence of all variables,
whereas represents the partial
differential change due to the
variation of a single variable.
The changes indicated by d and
are identical for independent
variables, but not for dependent
variables.

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To obtain a relation for the total differential change in z(x,y) for simultaneous
changes in x and y, consider a small portion of the surface z(x,y) shown in
figure. When the independent variables x and y change by x and y
respectively, the dependent variable z changes by z, which can be expressed
as
z z x x, y y z x, y
z z x x, y y z x, y y z x, y y z x, y
z x, y y z x, y
z x x, y y z x, y y
y
x
z
y
x
Applying the limits of x0 and y0
z
z
dz dx dy
x
y

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z
z
dz dx dy
x
y
This is the fundamental
relation for the total
differential of a dependent
variable in terms of its
partial derivatives with
respect to the independent
variables.
Geometric representation of total

derivative dz for a function z(x, y).
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4. 1. 2. Partial Derivatives
Example 1. Consider air following ideal gas at 300K and
0.86m3/kg. The state of the gas changes to 302K and
0.87m3/kg as a result of some small disturbance. Estimate
the change in the pressure of the air.
RT
p pT , v
v
p
p
dp
dT dv
T v
v T
300 302
0.287
R
RT
0.287
2
0.01 0.491kPa
dp dT
dv
2
2
v
0.86 0.87
v2
0
.
86
0
.
87
Actual change in pressure = -0.4907kPa

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i.Any state of a simple compressible substance is
completely specified by any two independent intensive
properties.
pv RT
z z ( x, y )
z
z
dz dx dy
x y
y x
ii.z is a dependent variable and x and y are independent

variables
iii. In the case of the ideal-gas equation of state any two of
the three (p, v, and T) can be taken as independent
variables and the third becomes the dependent variable.
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z z( x , y )
z
z
dz dx dy
x y
y x
2z
M

y x x y
dz Mdx Ndy
2z
N
;

x y yx
i. Since we are dealing with a continuous function

2 z N
2z
M

y x xy x y yx
M
N
y x x y
ii. In fact this is the test that we used to do in mathematics to

check dz is an exact differential or inexact differential.
Differential of a continuous function will be an exact differential.
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x
x
z
z
x
x
z
,
y
;
dx
dz
dy

dz dx dy
y z
z y
y
x y
x
x z
z x
dz dz dy dy
x y z y
y z y x
z x z
x z
x y y dy 1 z x dz
i.y and z are independent variables. For example y or z can be

held constant (dy = 0 or dz = 0) and the other can be varied ( dz
0 or dy 0 ).
ii.Therefore for the above equation to be valid the bracketed
terms should be equal toProfessor
zero.S. Krishnan, SRM
11
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z x z
x z
x y y dy 1 z x dz
i.Therefore for the above equation to be valid the bracketed

terms should be equal to zero.
z x z
0
x y y
x z
1 z x 0
z x y
1
x y z
Cyclic relation
x
1
Reciprocity
relation
z z
x
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1 Reciprocity relation
x
z z
x
Cyclic relation
z x y
1
x y z
Example 2. Using the ideal-gas equation of state, verify (a) the

cyclic relation and (b) reciprocity relation at constant p.
p
RT v R T v
;
2
v
T p p R
v
R
v
R
1
1
;
T T
p
p p
v
R
RT
p
R
p
dp dv
dT
dv
dT Mdv NdT
2
v T
v v
T v
v T
RT
RT
pv
p
;v
;T
v
p
R
p v T
RT R v
p
1
2
p
v T p
v pR
2 p
R
M

T v vT
v2
2 p
R
N

v T Tv
SRM
v2
Professor S. Krishnan,
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13
4. 1. 2. Maxwells Equations
i.Maxwells equations relate the partial derivatives of p, v, T, and
s of a simple compressible systems.
ii. The two Gibbs equations that we have already
discussed are as per below. These are also known as First Tds
and Second Tds equations.
dh Tds vdp
du Tds pdv
iii. There are two functions of combination properties, known as

Helmholtz function (F) and Gibbs function (G). They are
frequently used in chemical equilibrium analyses and are
defined as per below.
F U TS ;
f u Ts
G H TS ; g h Ts
iv. Differentiating Helmholtz function and Gibbs function
df du Tds sdT sdT pdv

dg dh Tds sdT sdT vdp

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df sdT pdv
dg sdT vdp
14
v. Therefore we have now four Gibbs equations:
du Tds pdv
dh Tds vdp
df sdT pdv dg sdT vdp

vi. The above four Gibbs equations are of the form
dz Mdx Ndy
which will satisfy
M
N

y x x y
since they contain properties u, h, f, g, p, v, T, and s. du,

dh, df, and dg are all exact differentials. Thus we derive
the Maxwells equations.
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f u Ts
g h Ts
du Tds pdv dh Tds vdp
df sdT pdv dg sdT vdp

T
T
p
v
v
p
s
s
v
s s p
Problem: 12.15
s
s
p
v
v
T
p
T
T
v T
vii.
viii.
The above are the Maxwells Equations applicable for

simple compressible systems.
Note that in all the above equations, the non-measurable
quantity entropy can be calculated from the easily
measurable quantities, viz, p, v, and T.
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16
s
v
Example 3. Verify the validity of the Maxwells equation
for
p
T
o
p
T
steam at 250 C and 300kPa.
? v
v 300 o C v 200 o C
s
s
s
400
kPa
200
kPa

o
o
p
T
250 C
300 kPa 400 200 kPa
300 200 C
kJ
m3
0.87529 0.71629
7.3788 7.7085 kgK

kg
400 200 kPa

100 K
v
kJ
m3
3
3
s
p
.
1.6485 10
1.59 10
T
p
kg .K .kPa
kgK
Entropy change at constant temperature is calculated from the easily
measurable quantities of changes in pressure, specific volume, and
temperature.
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4.2. Clapeyron Equation

Maxwells equations are frequently used to derive useful
thermodynamic relations.
The Clapeyron equation, derived from one of the Maxwells
equations, helps us to calculate the latent heat involved in a
phase change (say enthalpy of vaporization) from the known
values of p, v, and T
s
p
Consider the third Maxwells equation. T v v T

During phase transition, at a pressure (saturation pressure
or vapor pressure) the temperature (saturation temperature)
is constant independent of change in specific volume. At
some other pressure there is a corresponding constant
temperature during the phase transition despite the changes
in specific volume.
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18
Consider the third Maxwells equation.

s
p
T v v T
Critical point
During phase transition, at a pressure

(saturation pressure or vapor pressure)
the temperature (saturation
temperature) is constant independent
of change in specific volume. At some
other pressure there is a
corresponding constant temperature
during the phase transition despite the
changes in specific volume.
Therefore, psat f Tsat . .Hence,
The slope of the saturation curve

on a P-T diagram is constant at a
constant T or P.
dp
sg s f
vg v f
dT sat
s fg
dp

dT sat v fg
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p
dp
T v dT sat
19
Therefore, psat f Tsat .Hence,
dp
dp
p
sg s f
vg v f
dT sat
T v dT sat
s fg
dp
dT sat v fg
dh Tds vdp
l h fg
Since p = constant, vdp =0. Therefore,
dh T ds h fg Ts fg
The slope of the saturation curve

on a P-T diagram is constant at a
constant T or P.
h fg
dp
dp
dp
Tv
h
Tv
fg
12
12
dT sat Tv fg Clapeyron Equation fg
dT sat
dT sat
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20

Example 4. Using the Clapeyron equation estimate the value of the latent
heat of vaporization of the refrigerant R134a at 20oC and compare it with
the tabulated data.
dp
dp
h fg Tv fg
h
T
v
fg
g
f
dT sat
dT sat
From the Table for R134a
v g v f v fg 0.035238 m 3 kg
p25 o C p15 o C
p
T sat 25 o C 15 o C
666.3 489.5 kPa 17.68 kPa
10 K
K
m3
kPa
kPa .m 3
kJ
h fg 293 K 0.035238
17.68
182.541
182.541
kg
K
kg
kg
Tabulated hfg value = 182.345 kJ/kg.

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4.2.1. Clapeyron-Clausius Equation
Clapeyron equation can be simplified for liquidvapor or
solidvapor changes noting at low pressures vg vf or vg
vs.
Therefore v v or v v . Treating the vapor as
fg
sg
an ideal gas, v fg v g RT p , Clapeyron equation can be

simplified as
ph fg dp
h fg dT
dp
dp
h fg Tv fg
2
2
dT
dT
sat RT p
sat
R T sat
sat
Assuming hfg to be constant for small temperature intervals,

we get the Clapeyron-Clausius equation
ln
h fg 1
p2
1
p1 sat
R T1 T2 sat
Example 11.3 of Nag
Professor S. Krishnan, SRM University, India
22

Example 5. Estimate the saturation pressure of water at 15oC, using
the data available in the steam table. R = 0.4619 kJ/kg-K.
Note that the Clapeyron-Clausius equation is applicable at low
pressures
v fg v g or v sg v g
and low temperature intervals where the change of hfg values is
negligibly small. h fg or hsg cons tan t
ln
h fg 1
p2
1
1
p2 2454.1 1
ln
p1 sat
R T1 T2 sat
2
.
3385
0
.
4619
293
288
p2 1.7069 MPa against 1.7051 MPa
Example 6. Estimate the saturation pressure of R134a at -33oC,

using the data available in the refrigerant table at 30oC. Specific
gas constant for R134a = 0.08149kJ/kg-K. Tabulated value of
saturation pressure at -33oC = 73.7kPa.
23
4.3. General Relations for

dh, du, ds, cp, and cv
Recall that the state of a simple compressible system is
completely specified by any two independent intensive
properties, and hence we can calculate all the properties
of the system.
We will develop some general relations for u , h , s
(which cannot be directly measured) in terms of pressure,
specific volume, temperature, and specific heats.
Note that when we calculate changes, u , h , s
we have to prescribe reference state.
The choice of reference state is quite arbitrary.
24

Note the fundamental definitions of
u
cv
For incompressible liquids and solids

For compressible fluids
h
cp
cv c p
c p cv
For approximate calculations
u cv dT cv T
h c p dT c p T
How to calculate rigorously u and h ?
25

Internal Energy Changes
u uT , v
u
u
du
dT
dv
v T
T v
s sT , v
u
du cv dT dv
v T
s
s
du Tds pdv
ds
dT dv
v T
T v
s
u
s
du T
dT T p dv du cv dT v dv
T
T v
v T
s
cv
u
p
s
s
T
p
T T
T v T
v T T v
p
u
T

v T T v
p
du cv dT T

T v
p dv
26

Internal Energy Changes
u uT , v
s sT , v
u
u
du
dT dv
T v
v T
u
du cv dT dv
v T
p
u
T
p
v T T v
p
du cv dT T
p dv
T v
T2
v2
p
u2 u1 cv dT T

T
v T v
1
p dv
27

T2
v2
p
u2 u1 cv dT T

v T v
T
1
p dv
Example 7. Show that the internal energy of (a) an ideal gas and (b) an
incompressible substance is a function of temperature only, u = u(T).
(a) For an ideal gas pv=RT.
p
R
p
T

p0
T v
v
T
(b) For an incompressible substance dv = 0.

Is cv a function of v or p??!!
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Enthalpy Changes
h hT , p s sT , p
h
h
h
dh
dT dp c pdT dp
T
p
p T
p T
s
s
ds
dT dp
T p
p T
dh Tds vdp
h
s
s
dh T
dT v T dp dh c pdT dp
T p
p T
p T
c p h
s s
v h
v
s
v T
v T

T p p T
T p
T p T p T
p T p T
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v
dh c pdT v T
dp
T p
29

Enthalpy Changes
h hT , p
s s T , p
h
h
h
dh
dT dv c pdT dp
T
p
p T
p T
s
s
dh T
dT v T dp
T p
p T
h
dh c pdT dp
p T
v
dh c pdT v T
dp
T p
T2
p2
v
h2 h1 c pdT v T
dp
T p
T1
p1
h2 Professor
h1 u2S. Krishnan,
u1 SRM
p2 v 2 p1v1
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30

p
du cv dT T

T v
T2
v2
p dv
p
u2 u1 cv dT T

v T v
T
1
v
dh c pdT v T
dp
T p
T2
p2
v
p dv h2 h1 c pdT v T dp
T p
T1
p1
h2 h1 u2 u1 p2 v 2 p1v1
Problem: 12.34
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s sT , v
Entropy Changes
s
s
ds
dT
dv
v T
T v
c
p
ds v dT
dv
T
T v
s sT , p
s
s
ds
dT
dp
T p
p T
v
ds
dT
dp
T
T p
cp
cv
s
T v T
p
s
v
T
T2
v2
cv
p
s2 s1 dT
dv
T T
v T v
1
c p s
v
s

T p
T p T p T
T2 c
p2
v
s2 s1
dT
dp
T1 T
p1 T p

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32

Specific Heats cv and cp
Recall that the specific heat of ideal gas depends only on temperature.
For a general pure-substance, however, the specific heat depends on

specific volume or pressure and temperature.
Zero-pressure or ideal gas specific heats: cv0 and cp0 are those that we
are familiar with and are applicable for pressures below critical pressure
and temperature above critical temperature.
2
cv
p
cv
p
T 2
dv v T
dT
ds
2
2
z
z
N
T

y x
xy
cv cv 0 T
x y
yx
p 2
p
dv
T
T 2
0
v
v
ds
dT
dp
T
T
p
cp
2v
c p
T
T 2
p T
p
p 2
v
c p c p0 T T
dp
2
T
0
p
33

Between
cv and cp, if one is known how to find the other??
cp
c
p
v
ds v dT
dv ds
dT
dp
T
T v
T
T p
cp
cv
p
v
dT
dT
dv
dp
T
T
T v
T p
T v T p
T
T p T v
T
T T v , p dT
dp dT
dv
dv
dp
v p
c p cv
c p cv
p v
v p
c p cv T

T p T v
p
v p
p T v

1

T v
T p v T
T v v p p T
p
c p cv T

T p v T
34

Between
v
c p cv T
T
Definition of volume
expansivity and
p

isothermal
p v T
compressibility .
2
1 v 2
v p
c p cv T
T 2

T p v T
v T p
c p cv
vT 2
1 v
1 v
;
v T p
v p T
v
vT 2
1 v v
p T
Meyers Relation
1 v
1 v
;
v T p
v p T

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Meyers Relation
c p cv
The volume
expansivity
(also called the
coefficient of
volumetric
expansion) is a
measure of the
change in
volume with
temperature at
constant
pressure.
vT 2
1 v
1 v
;
v T p
v p T

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36

Between
Meyers Relation
cp
Volume expansivity and isothermal compressibility .
2
1 v
1 v
vT ;
0; 0
v T p
v p T
cv
c p cv
vT 2
c p cv 0 as T 0
For incompressible substances (solids and liquids) cp cv
37

T2
v2
p
u2 u1 cv dT T

T
v T v
1
p dv
Example 7 (extension): Show that the internal energy of (a) an ideal gas
and (b) an incompressible substance is a function of temperature only, u
= u(T).
(a) For an ideal gas pv=RT.
p
R
p
T
p T p T p 0
T v
v
T
(b) For an incompressible substance dv = 0.

Is cv a function of v or p??!!
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38

T2
v2
1 v
1 v
p
u2 u1 cv dT T
p
dv
v
T
v
p
v
p T
T1
v1
Is cv a function of v??!!
(a) For an ideal gas
T2
u2 u1 cv dT
T1
2 p
2 p
RT
p
R
cv
T 2 p
; 2 0 uideal gas uT
v T v v T
v T
T v
v
(b) For an incompressible substance, v = constant and hence dv=0
vT 2 0 c p cv c
c p cv
2v
c p
0
T
2
p T
T p
uincompress ible substns u( T ) uideal gas uT

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39

The internal energies and
specific heats of ideal
gases and
incompressible
substances depend on
temperature only. cp and
cv for liquids and cp and
cv solids are almost of
same values.

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40

Example 8. Show that cp- cv = R for ideal gas.
v p
c p cv T

p v T
For an ideal gas pv=RT.
RT v 2 R
v
;

p T p p
RT
RT p
p
p
;
2
v v T
v
v
2
R p TR 2
c p cv T
R
pv
p v
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4.4. The Joule-Thomson

Coefficient
The temperature behavior

of a fluid during a throttling
(h = constant) process is
described by the JouleThomson coefficient.
T

p h
The temperature of a fluid may increase,

decrease, or remain constant during a
throttling process.
p h
0 Temperatur e increases
0 Temperatur e remains cons tan t
0 Temperatur e decreases
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Coefficient
T
p h
0 Temperatur e increases
0 Temperatur e remains cons tan t

The development of an h = constant

line on a P-T diagram.

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Coefficient
0 Temperature increases
T

p h
The development of an h = constant

line on a P-T diagram.
0 Temperature remains cons tan t
Constant-enthalpy lines of a substance

on a T-P diagram.

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44

Coefficient
T
p h
Constant-enthalpy lines of a
substance
on a T-P diagram.
i.
Temperature of a fluid increases due to

throttling on the right hand side of the
inversion line.
ii. The temperature of a fluid will
decrease due to throttling on the left
hand side of the inversion line.
iii. A cooling effect cannot be achieved by
throttling unless the fluid is of
temperature well below its maximum
inversion temperature. For example
hydrogen has the maximum inversion
temperature of -68oC and hence to
achieve cooling effect, the hydrogen
must have the temperature well below
-68oC.
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45

Coefficient
T
JT
p h
Develop
JT JT c p , p , v ,T
v
dh c pdT v T
dp
T p
v
0 c pdT v T
dp
T p
1
T
v
JT v T
c p
T p
p h
JT JT c p , p , v ,T
c p c p JT , p , v ,T
Throttling process is constant

enthalpy process. Therefore,
Using the above equation Joule Thomson Coefficient can be calculated

from the known values of cp, p, v, and T. Alternatively, if Joule Thomson
coefficient is known (this is easy to determine), cp can be determined.
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Coefficient
Example 9. Show that the Joule Thomson coefficient of an ideal
gas is zero.
1
T
v
v
T

c p
T p
p h
JT
For an ideal gas
RT
p
R
v
;
p p
1
R
T
v T 0
cp
p
p h
JT
Enthalpy is pure function of temperature for an ideal gas. Enthalpy

being held constant for Joule Thomson coefficient, temperature is
a constant and hence temperature differential is zero.
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UNIT 4 (PART A):

Professor S. Krishnan, SRM

The derivative of a function at a specified point

The variation of z(x, y) with x when

The symbol represents differential

Professor S. Krishnan, SRM

Applying the limits of x0 and y0

Professor S. Krishnan, SRM

Geometric representation of total

Actual change in pressure = -0.4907kPa

ii.z is a dependent variable and x and y are independent

i. Since we are dealing with a continuous function

ii. In fact this is the test that we used to do in mathematics to

i.y and z are independent variables. For example y or z can be

i.Therefore for the above equation to be valid the bracketed

Example 2. Using the ideal-gas equation of state, verify (a) the

iii. There are two functions of combination properties, known as

iv. Differentiating Helmholtz function and Gibbs function

df du Tds sdT sdT pdv

Professor S. Krishnan, SRM

df sdT pdv dg sdT vdp

since they contain properties u, h, f, g, p, v, T, and s. du,

du Tds pdv dh Tds vdp

df sdT pdv dg sdT vdp

The above are the Maxwells Equations applicable for

Example 3. Verify the validity of the Maxwells equation

7.3788 7.7085 kgK

400 200 kPa

4.2. Clapeyron Equation

Consider the third Maxwells equation. T v v T

4.2. Clapeyron Equation

Consider the third Maxwells equation.

During phase transition, at a pressure

The slope of the saturation curve

Professor S. Krishnan, SRM

4.2. Clapeyron Equation

Therefore, psat f Tsat .Hence,

Since p = constant, vdp =0. Therefore,

The slope of the saturation curve

4.2. Clapeyron Equation

From the Table for R134a

666.3 489.5 kPa 17.68 kPa

Tabulated hfg value = 182.345 kJ/kg.

Professor S. Krishnan, SRM

4.2. Clapeyron Equation

an ideal gas, v fg v g RT p , Clapeyron equation can be

Assuming hfg to be constant for small temperature intervals,

Example 11.3 of Nag

Professor S. Krishnan, SRM University, India

4.2. Clapeyron Equation

p2 1.7069 MPa against 1.7051 MPa

Example 6. Estimate the saturation pressure of R134a at -33oC,

4.3. General Relations for

4.3. General Relations for

For incompressible liquids and solids

For approximate calculations

How to calculate rigorously u and h ?

4.3. General Relations for

Professor S. Krishnan, SRM University, India

4.3. General Relations for

Professor S. Krishnan, SRM University, India

4.3. General Relations for

(b) For an incompressible substance dv = 0.

4.3. General Relations for