Beruflich Dokumente
Kultur Dokumente
THERMODYNAMIC
RELATIONS
S. Krishnan, PhD
Professor of Aerospace Engineering
School of Mechanical Engineering
SRM University
Kattankulathur 603203, Tamil Nadu, India
df f f x x f x
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.
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 x, y y z x, y y z x, y y z x, y
z x y
x y
z z
dz dx dy
Applying the limits of x0 and y0 x y
Professor S. Krishnan, SRM 6
University, India
4. 1. Maxwells Equations
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.
RT p p
p pT , v dp dT dv
v T v v T
300 302
0.287
R
dp dT
RT
dv
0.287
2 2 0.01 0.491kPa
v v2 0.86 0.87 0 . 86 0 . 87
2
2 2
Actual change in pressure = -0.4907kPa
Professor S. Krishnan, SRM 8
University, India
4. 1. Maxwells Equations
4. 1. 2. Partial Derivatives
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.
z z
z z( x , y ) dz dx dy dz Mdx Ndy
x y y x
M 2z N 2z
;
y x x y x y yx
i. Since we are dealing with a continuous function
M 2 z N 2z M N
y x xy x y yx 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.
Professor S. Krishnan, SRM 10
University, India
4. 1. Maxwells Equations
4. 1. 2. Partial Derivatives
z z x x
dz dx dy x x z , y ; dx dz dy
x y z y y z
xy
z x x z
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
University, India
4. 1. Maxwells Equations
4. 1. 2. Partial Derivatives
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 z x y
0 1
x y z Cyclic relation
x y y
x z x 1
Reciprocity relation
1 z x 0 z z
x
s ? v
s s v 300 o C v 200 o C
400 kPa 200 kPa
250 C
p o T
300 kPa 400 200 kPa 300 200 C
o
kJ m3
7.3788 7.7085 kgK 0.87529 0.71629
kg
400 200 kPa 100 K
m3 v
1.6485 10 3 kJ
1.59 10 3 s T p .
kg .K .kPa kgK T p
Entropy change at constant temperature is calculated from the easily
measurable quantities of changes in pressure, specific volume, and
temperature.
Professor S. Krishnan, SRM 17
University, India
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 p s
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.
Professor S. Krishnan, SRM 18
University, India
4.2. Clapeyron Equation
Consider the third Maxwells equation.
p s Critical point
T v v T
p
dp
dp
sg s f
vg v f
T v dT sat dT sat
dp s fg
dT sat v fg
dh Tds vdp l h fg
dp h fg dp dp
h Tv fg h Tv 12
dT sat Tv fg Clapeyron Equation fg dT sat
12
dT sat
Professor S. Krishnan, SRM 20
University, India
4.2. Clapeyron Equation
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
h fg Tv fg
dT sat
h fg Tv g v
dp
f
dT sat
From the Table for R134a
v g v f v fg 0.035238 m 3 kg
p25 o C p15 o C
666.3 489.5 kPa 17.68 kPa
p
T sat 25 o C 15 o C
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
p2 h fg 1 1 p2 2454.1 1 1
ln 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
Professor S. Krishnan, SRM University, India
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
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Note the fundamental definitions of u h
cv cp
T v T p
u cv dT cv T
For approximate calculations
h c p dT c p T
How to calculate rigorously u and h ?
25
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Internal Energy Changes
u uT , v s sT , v
u
du
T v
dT
u
dv
v T
u
du cv dT dv
v T
s
ds
s
dT dv
T v v T
du Tds pdv
s s u
du T dT T p dv du cv dT v dv
T v v T T
s u s s p
cv
v
T p
T v T
T T
v v T T v
u p p
T p du cv dT T p dv
v T T v T v 26
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Internal Energy Changes
u uT , v s sT , v
u u u
du dT dv du cv dT dv
T v v T v T
u p
T p
v T T v
p
du cv dT T p dv
T v
T2 v2
p
u2 u1 cv dT T p dv
T 1 v T v
1
27
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
T2 v2
p
u2 u1 cv dT T p dv
T 1 v T v
1
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 p T p T p0
T v v T
s s h
dh T dT v T dp dh c pdT dp
T p p T p T
v
dh c pdT v T dp
T p
p2
v
T2
h2 h1 c pdT v T dp
T1 p1 T p
h2 Professor u1 SRM
h1 u2S. Krishnan, p2 v 2 p1v1 30
University, India
4.3. General Relations for
dh, du, ds, cp, and cv
p v
du cv dT T p dv dh c pdT v T dp
T v T p
p2
v
T2 v2 T2
p
u2 u1 cv dT T p dv h2 h1 c pdT v T dp
T v T v T1 p1 T p
1 1
h2 h1 u2 u1 p2 v 2 p1v1
Problem: 12.34
Professor S. Krishnan, SRM 31
University, India
4.3. General Relations for
dh, du, ds, cp, and cv
s sT , v Entropy Changes
s
ds
s s cv s
p
dv
T v
dT
v T T v T
T
v T v
T2 v2
p p
c cv
ds v dT dv s2 s1 dT dv
T T v T T 1 v T v 1
s sT , p
s c p s v
s s
ds dT dp
T p T p T
T p
T p p T
T2 c p2
ds
cp v
dT dp s2 s1
p
dT
v
dp
T T p T1 T p1 T p
Professor S. Krishnan, SRM 32
University, India
4.3. General Relations for
dh, du, ds, cp, and cv
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
T
cv
p
dv v T
T 2
M 2
z N
2
z ds dT
v
T T v
y x xy x y yx cp v c p 2v
ds dT dp T
T T p p T T 2
p
p 2 p 2
cv cv 0 T T
p dv
T 2
c p c p0 T T v
dp
2
0 v 0 T p
33
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Specific Heats cv and cp
Between cv and cp, if one is known how to find the other??
c p cp v cv p cp v
ds v dT dv ds dT dp dT dv dT dp
T T v T T p T T v T T p
T T T p T v T v T p
T T v , p dT dv dp dT dv dp
v p p v c p cv c p cv
v p p T v p v p
c p cv T 1
T p T v T v v p p T T v T p v T
2
v p
c p cv T
T p v T
34
Professor S. Krishnan, SRM University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Specific Heats cv and cp
Between cv and cp, if one is known how to find the other??
2 Definition of volume
v p expansivity and
1 v 1 v
;
c p cv T isothermal v T p v p T
T p v T
compressibility .
2
v p 1 v 2 v vT 2
c p cv T T 2
T p v T v T p
1 v v
p T
Meyers Relation
vT 2 1 v 1 v
c p cv ;
v T p v p T
Professor S. Krishnan, SRM 35
University, India
4.3. General Relations for
dh, du, ds, cp, and cv
Specific Heats cv and cp
Meyers Relation
The volume
vT 2 expansivity
c p cv (also called the
coefficient of
volumetric
1 v 1 v expansion) is a
;
v T p v p T measure of the
change in
volume with
temperature at
constant
pressure.
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
cv 2 p RT p R 2 p
T 2 p ; ; 2 0 uideal gas uT
v T T v v T v v T
v
vT 2 0 c p cv c c p 2v
T 0
c p cv
p T 2
T p
2
For an ideal gas pv=RT. v p
c p cv T
T p v T
RT v 2 R
2 RT p RT p
v ; p
;
p T p p v v T 2
v v
2
R p TR 2
c p cv T R
p v pv
T
p h
0 Temperatur e increases
0 Temperatur e remains cons tan t
0 Temperatur e decreases
Professor S. Krishnan, SRM 42
University, India
4.4. The Joule-Thomson
Coefficient
T
p h
0 Temperatur e increases
0 Temperatur e remains cons tan t
0 Temperatur e decreases
T 1 v
JT v T
p h c p T p
JT JT c p , p , v ,T c p c p JT , p , v ,T
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.
Professor S. Krishnan, SRM 46
University, India
4.4. The Joule-Thomson
Coefficient
Example 9. Show that the Joule Thomson coefficient of an ideal
gas is zero.
T 1 v
JT v T
p h c p T p