ME 267: Advanced Thermodynamics I: Thermodynamic Relations

ME 267: Advanced Thermodynamics I
Thermodynamic Relations
Edwin N. Quiros, Ph.D.

Review of Partial Derivatives
For a function z that depends on two independent variables (x,y) such that
its partial derivative represents the variation of z with respect to one variable while holding the
other variable constant.
The partial derivative of z with respect to x at constant y is
 z   z  z ( x  x, y )  z ( x, y )
   lim    lim
 x  y x0  x  y x0 x
and the partial derivative of z with respect to y at constant x is
 z   z  z ( x, y  y )  z ( x, y )
   lim    lim
 y  x y  0
 y  x y 0 y
ME 267 Advanced Thermodynamics I

∂ represents the partial differential change due to the
variation of a single variable
Also note that the value of the partial derivative
 z 
 
 x  y
in general, is different at different y values.

The Total Differential change of a function reflects the influence of all variables.
Specifically, the total differential change in z(x, y) for simultaneous changes in x and y, is
given by

The Total Differential dz of a function
 z   z  This is the fundamental relation for the total differential of a

dz    dx    dy dependent variable in terms of its partial derivatives with
 x  y  y  x
respect to the independent variables
Note:
The changes indicated by d and ∂ are identical for
independent variables, but not for dependent variables.
For example,
(∂x)y = dx
but
(∂z)y ≠ dz = (∂z)x + (∂z)y

Partial Differential Relations

Partial Differential Relations

Maxwell
Relations

The Clapeyron Equation
Enables us to determine the enthalpy change associated with a phase change
(such as the enthalpy of vaporization hfg ) from a knowledge of P, v, and T data
alone.
 P 
h fg  T v fg  
 T sat

Consider the Liquid-Vapor phase change or Vaporization Process at constant P and T.
Psat = f(Tsat)

Then
The development of the enthalpy change
 P   P 
relation starts with the 3rd Maxwell relation      (1.14)
 T v  T sat
 s   P 
     (1.12) which represents the slope of the
 v T  T v
saturation line on a P-T diagram
For the vaporization process at constant P and T,
P = Psat is a function of T = Tsat only
→ Psat = f(Tsat)

For the vaporization process (sat. liquid to sat. vapor, or f – g, line seen as a point only) at a given
or constant temperature T , P  
   const.
 T sat
so that combining (1.12) and (1.14) gives
 P  sg  s f s fg
   
 T  sat vg  v f v fg
or
 P 
s fg  v fg  
 T sat
The entropy change sfg during vaporization is the product of the change in specific
volume vfg and the slope (∂P/∂T) of the vaporization curve at the vaporization
temperature Tsat .
The enthalpy change for the process is obtained using the relation
dh = T ds + v dP (1.16)
Since the pressure is constant during vaporization, dP = 0.

Integrating eq. (1.16) noting that T = const. = Tsat during vaporization,
 P 
h fg  T v fg   (1.17)
 T sat

The Clapeyron equation is applicable to any phase-change process that occurs at constant
temperature and pressure. It can be expressed in a general form as
 P  h12
   (1.18)
 T sat T v12
where the subscripts 1 and 2 indicate the two phases.
ME 267 Advanced
Some Simplifications:
If all the following conditions exist,
1. At Low Pressures, vg >> vf so that vfg ≈ vg ,

2. and treating the vapor as an ideal gas, vg ≈ RT/P
3. and for small temperature intervals, hfg)T1 ≈ hfg)T2 ≈ hfg ≈ const. , then
for liquid-vapor and solid-vapor phase changes.

General Relations for du, dh, ds, cv, & cp in
Terms of P, v, and T
 The following discussion presents the development of relations for calculating changes
in internal energy, enthalpy, and entropy in terms of the measurable properties
pressure, specific volume, temperature, and specific heats.
 Once the state of a system is defined by two independent properties (i.e., the state
postulate), the other properties may be calculated using the relations developed here
 An expression relating cp and cv will be developed so that only one of the specific heats
need to be measured – the other specific heat is calculated
 Property values at specified states can be determined after the selection of an arbitrary
reference state (which has “assigned” values of properties)

Internal Energy Change: du
From the state postulate, let u  u (T , v) (1.1)
Its total differential is then

 u   u 
du    dT    dv (1.2)
 T v  v T
Recall that the definition of the specific heat at constant volume is

 u  (1.3)
cv   
 T v
Substituting (1.3) into (1.2),
 u 
du  cv dT    dv (1.4)
 v T

 u 
du  cv dT    dv (1.4)
 v T
In this expression, we want to express
 u 
 
 v T
in terms of P, v, T so that we can finally calculate du in terms of measurable parameters.
Another relationship for du in terms of P, v, T, and s which can be invoked comes from
one of the Gibbs equations:
du  T dS  P dv (1.5)

We now express dS in terms of P, v, T by letting (using the state postulate) entropy be a
function of the same variables (T, v), as was done with internal energy. Thus
s  s (T , v) (1.6)
and its total differential is then
 s   s 
ds    dT    dv (1.7)
 T v  v T
Substituting (1.7) into (1.5) to eliminate ds ,
 s   s  
du  T   dT    dv   P dv
 T v  v T 
or
 s    s  
du  T   dT  T    P  dv (1.8)
 T v   v T 
 u 
du  cv dT    dv (1.4)
 v T
 s    s  
du  T   dT  T    P  dv (1.8)
 T v   v T 
Between eqs. (1.4) and (1.8), the former looks easier to express in terms of P, v, T. Note that
both eqs. (1.8) and (1.4) can independently calculate du which implies that their RHS are
equal. Specifically, the coefficients of dT should be equal; the same is true for the coefficients
of dv . Therefore,
 s  (1.9)
cv  T  
 T v
and
 u   s 
   T   P (1.10)
 v T  v T

Eq. (1.10) is now substituted in eq.(1.4) to obtain
  s  
du  cv dT   T    P  dv (1.11)
  v T 
The partial derivative of entropy in the above equation is then replaced by the Maxwell relation
 s   P 
     (1.12)

 T 
v T v

To finally obtain du in terms of measurable properties P, v, T and cv as
  P  
du  cv dT   T    P  dv (1.13)
  T v 
This can be integrated between two states at (T1, v1) and (T2, v2) to determine (u2 – u1):
T2 v2   P  
u2  u1  T1
cv dT  
v1
T    P  dv
  T v 
(1.14)

Enthalphy Change: dh
From the state postulate, let h  h(T , P ) (1.15)
 h   h 
Its total differential is then dh    dT    dP (1.16)
 T  P  P T
Recall that the definition of the specific heat at constant pressure is

 h 
cp    (1.17)
 T  P
Substituting (1.17) into (1.16),
 h 
dh  c p dT    dP (1.18)
 P T
 h 
dh  c p dT    dP (1.18)
 P T
In this expression, we want to express  h 

 
 P T
in terms of P, v, T so that we can finally calculate dh in terms of measurable parameters.
Another relationship for dh in terms of P, v, T, and s which can be invoked comes from
one of the Gibbs equations:
dh  T ds  v dP (1.19)

We now express dS in terms of P, v, T by letting (using the state postulate) entropy be a
function of the same variables (T, P) as enthalpy. Thus
s  s(T , P) (1.20)
and its total differential is then
 s   s 
ds    dT    dP (1.21)
 T  P  P T
Substituting (1.21) into (1.19) to eliminate ds ,
 s    s  
dh  T   dT  v  T    dP (1.22)
 T  P   P T 

 h 
dh  c p dT    dP (1.18)
 P T
 s    s  
dh  T   dT  v  T    dP (1.22)
 T  P   P T 
Between eqs. (1.18) and (1.22), the former looks easier to express in terms of P, v, T. Note that
both eqs. (1.22) and (1.18) can independently calculate dh which implies that their RHS are
equal. Specifically, the coefficients of dT should be equal; the same is true for the coefficients
of dP . Therefore,
 s 
cp  T   (1.23)
 T  P
and
 h   s 
   v  T  (1.24)
 P T  P T
Eq. (1.24) is now substituted into eq.(1.18) to obtain
  s  
dh  c p dT  v  T    dP (1.25)
  P T 
The partial derivative of entropy in the above equation is then replaced by the 4th Maxwell
relation
 s   v 
     (1.26)

 T
P  T P

To finally obtain dh in terms of the measurable properties P, v, T and cp as
  v  
dh  c p dT  v  T    dP (1.27)
  T  P 
This can be integrated between two states at (T1, P1) and (T2, P2) to determine (h2 – h1):
T2 P2   v  
h2  h1  T1
c p dT  
P1
v  T 

  dP
 T  P 
(1.28)

Entropy Change: ds
Two general relations for entropy change of a simple compressible system can be developed:
one in terms of T and v, another in terms of T and P.
1st Relation – In terms of ( T, v )
Let s  s (T , v) (1.29)
Its total differential is then

 s   s 
ds    dT    dv (1.30)
 T v  v T

Entropy Change: ds
From the development of a general relation for du, where u = u(T,v), it has been shown that
cv  s 
   (1.31)
T  T v
Also from the 3rd Maxwell relation
 s   P 
     (1.32)

 T 
v T v

Entropy Change: ds
Substituting (1.31) and (1.32) into (1.30) yields
cv  P 
ds  dT    dv (1.33)
T  T v
or
cv v2
 P  dv
 
T2
s2  s1  dT    (1.34)
T1 T v1   T v

Entropy Change: ds
2nd Relation – In terms of ( T, P )
Let s  s(T , P) (1.35)
its total differential is then
 s   s 
ds    dT    dP (1.36)
 T  P  P T

Entropy Change: ds
From the development of a general relation for dh, cP  s  (1.37)
  
where h = h(T,P), it has been shown that T  T P
Also from the 4th Maxwell relation,  s   v  (1.38)

    
 T  P  T  P
Substituting (1.37) and (1.38) into (1.36) yields
cP  v 
ds  dT    dP (1.39)
T  T  P
or
cP  v  dP
 
T2 P2
s2  s1  dT    (1.40)
T1 T P1   T P
Relations for Specific Heats cv and cp
For a general pure substance the specific heats depend on pressure or specific volume as
well as temperature.
Relation Between Zero Pressure (or Ideal Gas) Specific Heats and Higher Pressure
(Real Gas) Specific Heats
 Recall that ideal gas specific heats cv0 and cp0 , which are easier to determine, are valid
for low pressures or high specific volume
 A relation for relating ideal gas specific heats to those at higher pressures can be
developed as follows:

Consider the two relations for entropy change derived previously which contain specific
heats in the equations,
cv  P 
ds  dT    dv (1.33)
T  T v
cP  v 
ds  dT    dP (1.39)
T  T  P

 M   N 
Applying the test for exactness    
 y x  x y
for a differential dz  M dx  N dy
 cv   2 P 
on eqs. (1.33) and (1.39) give    T  2 (1.41)
 v T  T v
 c p    2v 
and     T  2  (1.42)
 P T  T  P

The deviation of cp from cp0 with increasing pressure can be determined by integrating
eq.(1.42) from zero pressure to any pressure P along a constant-temperature process.
Thus
v
c  cp0    T

P 2
p  T 2  dP (1.43)
T 0  P
The P-v-T behavior of the substance is necessary to integrate the RHS of the above
equation.

Relation Between cp and cv
A relation between cp and cv will be advantageous since only one of the two specific
heats needs to be measured (usually cp) and the other just calculated.
The relation between cp and cv is developed by equating the two entropy change relations
derived earlier
cv  P 
ds  dT    dv (1.33)
T  T v
cP  v 
ds  dT    dP (1.39)
T  T  P

Solving for dT,
T  P / T v T  v / T  P
dT  dv  dP (1.44)
c p  cv c p  cv
This suggests that T  T (v, P ) (1.45)
and  T   T 
dT    dv    dP (1.46)
 v  P  P v
Equating the coefficients of dv or dP of eqs.(1.44) and (1.46) gives
 v   P 
c p  cv  T     (1.47)
 T  P  T v
The previous equation can be expressed in terms of the thermodynamic properties volume
expansivity β and isothermal compressibility α by using the cyclic relation applied to the
P-v-T behavior of a substance:
 P   T   v 
       1
 T v  v  P  P T
or  P   v   P 
       (1.48)
 T v  T  P  v T
Substituting eq. (1.48) into (1.47),
 v   P 
2
c p  cv   T     (1.49)
 T P  v T
Recalling the definitions
1  v 
Volume Expansivity    (1.50)
v  T  P
1  v 
Isothermal Compressibility     (1.51)
v  P T
and substituting these into eq.(1.49) gives
vT  2
c p  cv  (1.52)

vT  2
c p  cv  (1.52)

Notes:
1. Since α is positive for all substances in all phases and β2 is also always
positive, then
(1.53)
2. cp approaches cv as the temperature approaches absolute zero.
3. For incompressible substances, i.e., v = const. (α = 0, β = 0), then cp ≈ cv . The

differences are usually neglected for solids and liquids.

Throttling Process
Flow through a restriction resulting to a pressure drop. The

flow is characterized as ∆q ≈ 0, ∆w = 0, ∆KE ≈ 0, ∆PE ≈ 0.
Application of the 1st Law to the steady-state throttling process

shows it is isenthalpic.
h1 = h2

Temperature After Throttling Process
The 1st Law for throttling is
h1 = h2
u1 + P1v1 = u2 + P2v2
internal energy + flow energy = constant
Then
1. If (P2v2 > P1v1)  u2 < u1  T2 < T1
2. If (P2v2 < P1v1)  u2 > u1  T2 > T1
3. For ideal gas, h = h(T)  T2 = T1

The Joule-Thomson coefficient is a measure of the change
in temperature with pressure during a constant-
enthalpy process.
 T 
   (1.54)
 P h
It represents the slope of h = constant lines on a

T-P diagram

 T 
   (1.54)
 P h
A throttling process proceeds along a constant-enthalpy

line in the direction of decreasing pressure, that is, from
right to left.

 Only some of the constant-enthalpy lines have a point of
zero slope or zero Joule-Thomson coefficient.
 The line that passes through these points is called the

Inversion Line, and the temperature at a point where a
constant-enthalpy line intersects the inversion line is
called the inversion temperature.

 During a throttling process, the temperature increases
on the right-hand side of the inversion line, decreases
on the left-hand side of the inversion line.
 It is clear from this diagram that a cooling effect cannot

be achieved by throttling unless the fluid is below its
Maximum inversion temperature.

An expression for the Joule-Thompson coefficient in terms of
P-v-T can be developed from the relation for dh
  v  
dh  c p dT  v  T    dP (1.55)
  T  P 
Noting that dh = 0 for a throttling process, this equation after

re-arrangement becomes
1   v    T 
 v  T         JT (1.56)
cp   T  P   P h

General Relations for du, dh, & ds
of Real Gases
• Real gas behavior deviates significantly from ideal gas behavior at higher pressures.
• The deviation from ideal gas behavior should be accounted for in the calculation of
dh, du, & ds for real (non-ideal) gases.
• The approach taken to accomplish this is the use of the relations developed earlier
for ideal gases together with the compressibility factor Z to account for the real gas
(or deviation from ideal gas) behavior.

General Relations for du, dh, & ds of Real Gases
These processes are:
1 – 1* isothermal process from actual initial

pressure to zero pressure
1* - 2* isobaric process with change in

temperature, ideal gas behavior
2* - 2 isothermal process from zero pressure to

actual final pressure

Although these series of processes is more complicated than the
actual process, the calculations are greatly simplified because
one property remains constant in any segment of the entire
process.
The general relation
 
  v  
T2 P2
h 2  h1  c p dT  v  T    dP (1.57)
T1 P1   T  P 
is applied to process 1 – 1* - 2* - 2 .

Thus,
  
h 2  h1  h2  h2*  h2*  h1*  h1*  h1    (1.58)
Evaluating the RHS using Eq. (1.57) (noting that P1* = P2* = P0 ),
 
  v     v  
P2 P2
h2  h2*  0   v  T    dP   v  T    dP
P2*   T  P  T T P0   T  P  T T
2 2
(1.59)

 
  v     v  
P2 P2
h2  h  0 
*
v  T    dP  v  T    dP
 T  P  T T  T  P  T T
2
P2*  2
P0  2
(1.59)
 
T2 T2
h*2  h1*  c p dT  0  c p 0 (T ) dT (1.60)

T1 T1
P1*
 
  v     v  
P1
h1*  h1  0   v  T    dP    v  T    dP
P1   T  P  T T P0   T  P  T T
1 1
(1.61)

Now define the Enthalpy Departure such that
Enthalpy Departure = ( h* - h )T
= the difference in enthalpy of a real gas at ( P, T ) and
ideal gas at ( P0 , T ) , where P0 ≈ zero pressure
For a real gas with compressibility factor Z ,
𝑃𝑣
𝑍=
𝑅𝑇

The compressibility factor Z chart
𝑃𝑣
𝑍=
𝑅𝑇

The compressibility factor Z
chart
𝑃𝑣
𝑍=
𝑅𝑇

The compressibility factor Z
chart
𝑃𝑣
𝑍=
𝑅𝑇

The enthalpy departure at any temperature T and pressure P can be expressed as

P
 Z  dP
h*
h 
T
  RT 2

 T

P P
(1.62)
0
By expressing the pressure and temperature P and T in terms of the reduced pressure
and reduced temperature defined as
𝑃𝑟 = 𝑃/𝑃𝑐𝑟 and 𝑇𝑟 = 𝑇/𝑇𝑐𝑟

The enthalpy departure can be expressed in non-dimensional form called
Enthalpy Departure Factor
 h*  h  T

 Z 
PR
Zh   d  ln PR  (1.63)
2

 TR  PR
R
RuTcr 0
 The integral on the RHS of the above equation can be evaluated graphically or numerically
using data from the compressibility charts.

Generalized Enthalpy Departure Chart
A plot of Zh = Zh ( PR , TR ) used to evaluate

enthalpy departure of a real gas at an actual
temperature T and pressure P.
h h  T

*
 Z 
PR
Zh   d  ln PR 
2

 TR  PR
R
RuTcr 0

Generalized Enthalpy Departure Chart
A plot of Zh = Zh ( PR , TR ) used to evaluate

enthalpy departure of a real gas at an actual
temperature T and pressure P.
h h  T

*
 Z 
PR
Zh   d  ln PR 
2

 TR  PR
R
RuTcr 0

The enthalpy change of a Real Gas from (T1, P1) to (T2, P2) on a molar basis is then

h2  h1  h2  h1 ideal
 RuTcr  Zh 2  Z h1  (1.64)
or a mass basis

h2  h1  h2  h1 
ideal
 RTcr  Zh2  Zh1  (1.65)
where
(h2 – h1)ideal is evaluated using ideal gas behavior from T1 to T2 .

The change in internal energy of a real gas is calculated from the
change in enthalpy. Thus,
 
u 2  u 1  h 2  h1  Ru  Z 2T2  Z1T1  (1.66)

Because of the dependence of ideal gas entropy change on
both pressure and temperature, a pathway similar to enthalpy
change calculation cannot be applied for entropy change
because it involves the value of entropy at zero pressure,
which is infinity.
The pathway chosen for calculating entropy change

from (P1 , T1) to (P2 , T2) is shown in the figure:
1 - a* - 1* - 2* - b* - 2
Where * indicates ideal gas state

For process 1 – a* - 1* - 2* - b* - 2 ,
P0 ≈ zero pressure (ideal gas conditions)
P1 = real gas P1 T1 = real gas T1

Pa* = P0 Ta* = T1
P1* = P1 T1* = T1
P2* = P2 T2* = T2
Pb* = P0 Tb* = T2
P2 = real gas P2 T2 = real gas T2
1 – a* - 1* , isothermal process
2 – b* - 2* , isothermal process
1* - 2* , ideal gas behavior
The entropy change from (P1 , T1) to (P2 , T2) is then

ENTROPY DEPARTURE
The entropy difference (s – s) between the actual state at

(P, T) and the corresponding ideal gas state at the same
pressure and temperature (P = P, T = T) is called the
Entropy Departure at (P, T) which can be expressed as

If the specific volume for the real gas and ideal gas are
respectively
ZRT RT
v and v
P P
the Entropy Departure can be expressed as

ENTROPY DEPARTURE FACTOR
By expressing temperature and pressure in terms of reduced pressure PR , reduced

temperature TR , and critical temperature and pressure Tcr , Pcr ,
T = Tcr TR and P = Pcr PR
the entropy departure can be expressed in non-dimensional form called the Entropy
Departure Factor as

• Values of Zs as a function of PR and TR
are shown in the Generalized Entropy
Departure Chart.
• Note that Zs = 1 for an ideal gas.

Generalized Entropy Departure Chart
(Sonntag et. al)

The entropy change of a real gas from state (P1, T1) to (P2, T2) on a molal or mass
basis respectively is therefore

ME 267: Advanced Thermodynamics I: Thermodynamic Relations

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ME 267: Advanced Thermodynamics I

Edwin N. Quiros, Ph.D.

The partial derivative of z with respect to x at constant y is

and the partial derivative of z with respect to y at constant x is

ME 267 Advanced Thermodynamics I

Also note that the value of the partial derivative

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

 z   z  This is the fundamental relation for the total differential of a

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

Since the pressure is constant during vaporization, dP = 0.

ME 267 Advanced Thermodynamics I

where the subscripts 1 and 2 indicate the two phases.

If all the following conditions exist,

1. At Low Pressures, vg >> vf so that vfg ≈ vg ,

for liquid-vapor and solid-vapor phase changes.

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

Its total differential is then

Recall that the definition of the specific heat at constant volume is

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

Eq. (1.10) is now substituted in eq.(1.4) to obtain

ME 267 Advanced Thermodynamics I

To finally obtain du in terms of measurable properties P, v, T and cv as

ME 267 Advanced Thermodynamics I

Recall that the definition of the specific heat at constant pressure is

In this expression, we want to express  h 

ME 267 Advanced Thermodynamics I

Substituting (1.21) into (1.19) to eliminate ds ,

ME 267 Advanced Thermodynamics I

Eq. (1.24) is now substituted into eq.(1.18) to obtain

ME 267 Advanced Thermodynamics I

To finally obtain dh in terms of the measurable properties P, v, T and cp as

ME 267 Advanced Thermodynamics I

1st Relation – In terms of ( T, v )

Its total differential is then

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

Substituting (1.31) and (1.32) into (1.30) yields

ME 267 Advanced Thermodynamics I

2nd Relation – In terms of ( T, P )

Let s  s(T , P) (1.35)

its total differential is then

ME 267 Advanced Thermodynamics I

Also from the 4th Maxwell relation,  s   v  (1.38)

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

ME 267 Advanced Thermodynamics I

This suggests that T  T (v, P ) (1.45)

Equating the coefficients of dv or dP of eqs.(1.44) and (1.46) gives

and substituting these into eq.(1.49) gives

2. cp approaches cv as the temperature approaches absolute zero.

h2  h1  c p dT  0  c p 0 (T ) dT (1.60)