12-1

Chapter 12
THERMODYNAMIC PROPERTY RELATIONS

Partial Derivatives and Associated Relations

12-1C
z
dz

∂x ≡ dx
(∂z)y
∂y ≡ dy
dz = (∂z ) x + (∂z ) y
(∂z)x

y y + dy
y
dy
x
dx

x +dx

12-2C For functions that depend on one variable, they are identical. For functions that depend on two or
more variable, the partial differential represents the change in the function with one of the variables as the
other variables are held constant. The ordinary differential for such functions represents the total change as
a result of differential changes in all variables.

12-3C (a) (∂x)y = dx ; (b) (∂z) y ≤ dz; and (c) dz = (∂z)x + (∂z) y

12-4C Only when (∂z/∂x) y = 0. That is, when z does not depend on y and thus z = z(x).

12-5C It indicates that z does not depend on y. That is, z = z(x).

12-6C Yes.

12-7C Yes.

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 12-2

12-8 Air at a specified temperature and specific volume is considered. The changes in pressure
corresponding to a certain increase of different properties are to be determined.
Assumptions Air is an ideal gas
Properties The gas constant of air is R = 0.287 kPa·m3/kg·K (Table A-1).
Analysis An ideal gas equation can be expressed as P = RT/v. Noting that R is a constant and P = P(T,v),
 ∂P   ∂P  R dT RT dv
dP =   dT +   dv = −
 ∂T v  ∂v  T v v2
(a) The change in T can be expressed as dT ≅ ∆T = 400 × 0.01 = 4.0 K. At v = constant,
R dT (0.287 kPa ⋅ m 3 /kg ⋅ K)(4.0 K)
(dP )v = = = 1.276 kPa
v 0.90 m 3 /kg
(b) The change in v can be expressed as dv ≅ ∆v = 0.90 × 0.01 = 0.009 m3/kg. At T = constant,
RT dv (0.287 kPa ⋅ m 3 /kg ⋅ K)(400K)(0.009 m 3 /kg)
(dP )T =− =− = −1.276 kPa
v2 (0.90 m 3 /kg) 2
(c) When both v and T increases by 1%, the change in P becomes
dP = (dP)v + (dP )T = 1.276 + (−1.276) = 0
Thus the changes in T and v balance each other.

12-9 Helium at a specified temperature and specific volume is considered. The changes in pressure
corresponding to a certain increase of different properties are to be determined.
Assumptions Helium is an ideal gas
Properties The gas constant of helium is R = 2.0769 kPa·m3/kg·K (Table A-1).
Analysis An ideal gas equation can be expressed as P = RT/v. Noting that R is a constant and P = P(T, v ),
 ∂P   ∂P  R dT RT dv
dP =   dT +   dv = −
 ∂T v  ∂v  T v v2
(a) The change in T can be expressed as dT ≅ ∆T = 400 × 0.01 = 4.0 K. At v = constant,
R dT (2.0769 kPa ⋅ m 3 /kg ⋅ K)(4.0 K)
(dP )v = = = 9.231 kPa
v 0.90 m 3 /kg
(b) The change in v can be expressed as d v ≅ ∆ v = 0.90 × 0.01 = 0.009 m3/kg. At T = constant,
RT dv (2.0769 kPa ⋅ m 3 /kg ⋅ K)(400 K)(0.009 m 3 )
(dP )T =− = = −9.231 kPa
v2 (0.90 m 3 /kg) 2
(c) When both v and T increases by 1%, the change in P becomes
dP = (dP) v + (dP) T = 9.231 + (−9.231) = 0
Thus the changes in T and v balance each other.

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 12-3

12-10 It is to be proven for an ideal gas that the P = constant lines on a T- v diagram are straight lines and
that the high pressure lines are steeper than the low-pressure lines.
Analysis (a) For an ideal gas Pv = RT or T = Pv/R. Taking the partial derivative of T with respect to v
holding P constant yields
 ∂T  P
  = T
 ∂v P R
which remains constant at P = constant. Thus the derivative P = const
(∂T/∂v)P, which represents the slope of the P = const. lines on a
T-v diagram, remains constant. That is, the P = const. lines are
straight lines on a T-v diagram.
(b) The slope of the P = const. lines on a T-v diagram is equal to
P/R, which is proportional to P. Therefore, the high pressure lines
are steeper than low pressure lines on the T-v diagram. v

12-11 A relation is to be derived for the slope of the v = constant lines on a T-P diagram for a gas that
obeys the van der Waals equation of state.
Analysis The van der Waals equation of state can be expressed as
1 a 
T=  P + 2 (v − b )
R v 
Taking the derivative of T with respect to P holding v constant,
 ∂T  1 v −b
  = (1 + 0 )(v − b ) =
 ∂P  v R R
which is the slope of the v = constant lines on a T-P diagram.

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 12-4

12-12 Nitrogen gas at a specified state is considered. The cp and cv of the nitrogen are to be determined
using Table A-18, and to be compared to the values listed in Table A-2b.
Analysis The cp and cv of ideal gases depends on temperature only, and are expressed as cp(T) = dh(T)/dT
and cv(T) = du(T)/dT. Approximating the differentials as differences about 400 K, the cp and cv values are
determined to be
 dh(T )   ∆h(T ) 
c p (400 K ) =   ≅  cp
 dT  T = 400 K  ∆T  T ≅ 400 K h

h(410 K ) − h(390 K )
=
(410 − 390)K
(11,932 − 11,347)/28.0 kJ/kg
=
(410 − 390)K
= 1.045 kJ/kg ⋅ K
(Compare: Table A-2b at 400 K → cp = 1.044 kJ/kg·K) T

 du (T )   ∆u (T ) 
cv (400K ) =   ≅ 
 dT  T = 400 K  ∆T  T ≅ 400 K
u (410 K ) − u (390 K )
=
(410 − 390)K
(8,523 − 8,104)/28.0 kJ/kg
= = 0.748 kJ/kg ⋅ K
(410 − 390)K
(Compare: Table A-2b at 400 K → cv = 0.747 kJ/kg·K)

12-13E Nitrogen gas at a specified state is considered. The cp and cv of the nitrogen are to be determined
using Table A-18E, and to be compared to the values listed in Table A-2Eb.
Analysis The cp and cv of ideal gases depends on temperature only, and are expressed as cp(T) = dh(T)/dT
and cv(T) = du(T)/dT. Approximating the differentials as differences about 600 R, the cp and cv values are
determined to be
 dh(T )   ∆h(T ) 
c p (600 R ) =   ≅ 
 dT T = 600 R  ∆T T ≅ 600 R
h(620 R ) − h(580 R )
=
(620 − 580)R
(4,307.1 − 4,028.7)/28.0 Btu/lbm
= = 0.249 Btu/lbm ⋅ R
(620 − 580) R
(Compare: Table A-2Eb at 600 R → cp = 0.248 Btu/lbm·R )
 du (T )   ∆u (T ) 
cv (600 R ) =   ≅ 
 dT T = 600 R  ∆T T ≅ 600 R
u (620 R ) − u (580 R )
=
(620 − 580)R
(3,075.9 − 2,876.9)/28.0 Btu/lbm
= = 0.178 Btu/lbm ⋅ R
(620 − 580) R
(Compare: Table A-2Eb at 600 R → cv = 0.178 Btu/lbm·R)

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 12-5

12-14 The state of an ideal gas is altered slightly. The change in the specific volume of the gas is to be
determined using differential relations and the ideal-gas relation at each state.
Assumptions The gas is air and air is an ideal gas.
Properties The gas constant of air is R = 0.287 kPa·m3/kg·K (Table A-1).
Analysis (a) The changes in T and P can be expressed as
dT ≅ ∆T = (404 − 400)K = 4 K
dP ≅ ∆P = (96 − 100)kPa = −4 kPa
The ideal gas relation Pv = RT can be expressed as v = RT/P. Note that R is a constant and v = v (T, P).
Applying the total differential relation and using average values for T and P,
 ∂v   ∂v  R dT RT dP
dv =   dT +   dP = −
 ∂T  P  ∂P  T P P2
 4K (402 K)(−4 kPa) 
= (0.287 kPa ⋅ m 3 /kg ⋅ K) −
 98 kPa (98 kPa) 2 
 
= (0.0117 m 3 /kg) + (0.04805 m 3 /kg) = 0.0598 m 3 /kg
(b) Using the ideal gas relation at each state,
RT1 (0.287 kPa ⋅ m 3 /kg ⋅ K)(400 K)
v1 = = = 1.1480 m 3 /kg
P1 100 kPa
RT2 (0.287 kPa ⋅ m 3 /kg ⋅ K)(404 K)
v2 = = = 1.2078 m 3 /kg
P2 96 kPa
Thus,
∆v = v 2 − v1 = 1.2078 − 1.1480 = 0.0598 m3 /kg
The two results are identical.

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 12-6

12-15 Using the equation of state P(v-a) = RT, the cyclic relation, and the reciprocity relation at constant v
are to be verified.
Analysis (a) This equation of state involves three variables P, v, and T. Any two of these can be taken as
the independent variables, with the remaining one being the dependent variable. Replacing x, y, and z by
P, v, and T, the cyclic relation can be expressed as
 ∂P   ∂v   ∂T 
      = −1
 ∂v T  ∂T  P  ∂P v
where
RT  ∂P  − RT P
P= →   = =−
v −a  ∂v  T (v − a ) 2 v −a
RT  ∂ v  R
v= +a  →   =
P  ∂T  P P
P (v − a)  ∂T  v −a
T= 
→   =
R  ∂P  v R
Substituting,
 ∂P   ∂v   ∂T   P  R  v − a 
      = −    = −1
 ∂v T  ∂T P  ∂P v  v − a  P  R 
which is the desired result.
(b) The reciprocity rule for this gas at v = constant can be expressed as
 ∂P  1
  =
 ∂T v (∂T / ∂P)v
P(v − a)  ∂T  v −a
T= →   =
R  ∂P v R
RT  ∂P  R
P= →   =
v −a  ∂T v v −a
We observe that the first differential is the inverse of the second one. Thus the proof is complete.

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 12-7

The Maxwell Relations

12-16 The validity of the last Maxwell relation for refrigerant-134a at a specified state is to be verified.
Analysis We do not have exact analytical property relations for refrigerant-134a, and thus we need to
replace the differential quantities in the last Maxwell relation with the corresponding finite quantities.
Using property values from the tables about the specified state,
 ∂s  ?  ∂v 
  =−  
 ∂P  T  ∂T  P
 ∆s  ?
 ∆v 
  ≅− 
 ∆P  T =80°C  ∆T  P =1200 kPa
 s1400 kPa − s1000 kPa  ?  v 100°C − v 60°C 
  ≅ − 
 (1400 − 1000 )kPa
 (100 − 60 )°C
 
  T =80°C  P =1200kPa

(1.0056 − 1.0458)kJ/kg ⋅ K ? (0.022442 − 0.018404)m 3 /kg

≅−
(1400 − 1000)kPa (100 − 60)°C
− 1.005 × 10 − 4 m 3 /kg ⋅ K ≅ −1.0095 × 10 − 4 m 3 /kg ⋅ K
since kJ ≡ kPa·m³, and K ≡ °C for temperature differences. Thus the last Maxwell relation is satisfied.

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 12-8

12-17 EES Problem 12-16 is reconsidered. The validity of the last Maxwell relation for refrigerant 134a at
the specified state is to be verified.
Analysis The problem is solved using EES, and the solution is given below.

"Input Data:"

T=80 [C]
P=1200 [kPa]
P_increment = 200 [kPa]
T_increment = 20 [C]
P[2]=P+P_increment
P[1]=P-P_increment
T[2]=T+T_increment
T[1]=T-T_increment

DELTAP = P[2]-P[1]
DELTAT = T[2]-T[1]

v[1]=volume(R134a,T=T[1],P=P)
v[2]=volume(R134a,T=T[2],P=P)
s[1]=entropy(R134a,T=T,P=P[1])
s[2]=entropy(R134a,T=T,P=P[2])

DELTAs=s[2] - s[1]
DELTAv=v[2] - v[1]

"The partial derivatives in the last Maxwell relation (Eq. 11-19) is associated with the Gibbs
function and are approximated by the ratio of ordinary differentials:"

LeftSide =DELTAs/DELTAP*Convert(kJ,m^3-kPa) "[m^3/kg-K]" "at T = Const."

RightSide=-DELTAv/DELTAT "[m^3/kg-K]" "at P = Const."

SOLUTION

DELTAP=400 [kPa] RightSide=-0.000101 [m^3/kg-K]

DELTAs=-0.04026 [kJ/kg-K] s[1]=1.046 [kJ/kg-K]
DELTAT=40 [C] s[2]=1.006 [kJ/kg-K]
DELTAv=0.004038 [m^3/kg] T=80 [C]
LeftSide=-0.0001007 [m^3/kg-K] T[1]=60 [C]
P=1200 [kPa] T[2]=100 [C]
P[1]=1000 [kPa] T_increment=20 [C]
P[2]=1400 [kPa] v[1]=0.0184 [m^3/kg]
P_increment=200 [kPa] v[2]=0.02244 [m^3/kg]

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 12-9

12-18E The validity of the last Maxwell relation for steam at a specified state is to be verified.
Analysis We do not have exact analytical property relations for steam, and thus we need to replace the
differential quantities in the last Maxwell relation with the corresponding finite quantities. Using property
values from the tables about the specified state,
 ∂s  ?  ∂v 
  =−  
 ∂P  T  ∂T  P
 ∆s  ?
 ∆v 
  ≅−  
 ∆ P  T =800°F  ∆T  P = 400psia
 s 450 psia − s 350 psia  ?  v 900° F − v 700° F 
  ≅ − 
 (450 − 350)psia
 (900 − 700 )°F
 
  T =800°F  P = 400psia

(1.6706 − 1.7009)Btu/lbm ⋅ R ? (1.9777 − 1.6507)ft 3 /lbm

≅−
(450 − 350)psia (900 − 700)°F
− 1.639 × 10 −3 ft 3 /lbm ⋅ R ≅ −1.635 × 10 −3 ft 3 /lbm ⋅ R
since 1 Btu ≡ 5.4039 psia·ft3, and R ≡ °F for temperature differences. Thus the fourth Maxwell relation is
satisfied.

12-19 Using the Maxwell relations, a relation for (∂s/∂P)T for a gas whose equation of state is P(v-b) = RT
is to be obtained.
RT
Analysis This equation of state can be expressed as v = + b . Then,
P
 ∂v  R
  =
 ∂T P P
From the fourth Maxwell relation,
 ∂s   ∂v  R
  = −  =−
 ∂P  T  ∂T  P P

12-20 Using the Maxwell relations, a relation for (∂s/∂v)T for a gas whose equation of state is (P-a/v2)(v-b)
= RT is to be obtained.
RT a
Analysis This equation of state can be expressed as P = + . Then,
v −b v 2
 ∂P  R
  =
 ∂T  v v − b
From the third Maxwell relation,
 ∂s   ∂P  R
  =  =
 ∂v  T  ∂T  v v − b

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 12-10

12-21 Using the Maxwell relations and the ideal-gas equation of state, a relation for (∂s/∂v)T for an ideal
gas is to be obtained.
RT
Analysis The ideal gas equation of state can be expressed as P = . Then,
v
 ∂P  R
  =
 ∂T v v
From the third Maxwell relation,
 ∂s   ∂P  R
  =  =
 ∂v  T  ∂T  v v

The Clapeyron Equation

12-22C It enables us to determine the enthalpy of vaporization from hfg at a given temperature from the P,
v, T data alone.

12-23C It is exact.

12-24C It is assumed that vfg ≅ vg ≅ RT/P, and hfg ≅ constant for small temperature intervals.

12-25 Using the Clapeyron equation, the enthalpy of vaporization of refrigerant-134a at a specified
temperature is to be estimated and to be compared to the tabulated data.
Analysis From the Clapeyron equation,
 dP 
h fg = Tv fg  
 dT  sat
 ∆P 
≅ T (v g − v f ) @ 40°C  
 ∆T  sat,40°C
 Psat @ 42°C − Psat @38°C 
= T (v g − v f ) @ 40°C  

 42°C − 38°C 
 (1072.8 − 963.68)kPa 
= (40 + 273.15 K)(0.019952 − 0.0008720 m 3 /kg) 
 4K 
= 163.00 kJ/kg
The tabulated value of hfg at 40°C is 163.00 kJ/kg.

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 12-11

12-26 EES Problem 12-25 is reconsidered. The enthalpy of vaporization of refrigerant 134-a as a function
of temperature over the temperature range -20 to 80°C by using the Clapeyron equation and the refrigerant
134-a data in EES is to be plotted.
Analysis The problem is solved using EES, and the results are tabulated and plotted below.

"Input Data:"

T=30 [C]
T_increment = 5 [C] 0.35

T[2]=T+T_increment 0.3
T[1]=T-T_increment ]
P[1] = pressure(R134a,T=T[1],x=0) % 0.25
[
P[2] = pressure(R134a,T=T[2],x=0)
r
DELTAP = P[2]-P[1] o 0.2
rr
DELTAT = T[2]-T[1]
E t
n 0.15
v_f=volume(R134a,T=T,x=0) e
cr
v_g=volume(R134a,T=T,x=1) e 0.1
h_f=enthalpy(R134a,T=T,x=0) P
h_g=enthalpy(R134a,T=T,x=1) 0.05
-20 0 20 40 60 80
h_fg=h_g - h_f T [C]
v_fg=v_g - v_f

"The Clapeyron equation (Eq. 12-22) provides a means to calculate the enthalpy of vaporization,
h_fg at a given temperature by determining the slope of the saturation curve on a P-T diagram
and the specific volume of the saturated liquid and satruated vapor at the temperature."

h_fg_Clapeyron=(T+273.2)*v_fg*DELTAP/DELTAT*Convert(m^3-kPa,kJ)
PercentError=ABS(h_fg_Clapeyron-h_fg)/h_fg*Convert(, %) "[%]"

hfg hfg,Clapeyron PercentError T

[kJ/kg] [kJ/kg] [%] [C]
212.91 213.68 0.3593 -20
205.96 206.56 0.2895 -10
198.60 199.05 0.2283 0
190.73 191.07 0.1776 10
182.27 182.52 0.1394 20
173.08 173.28 0.1154 30
163.00 163.18 0.1057 40
151.79 151.96 0.1081 50
139.10 139.26 0.1166 60
124.32 124.47 0.1195 70
106.35 106.45 0.09821 80

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 12-12

12-27 Using the Clapeyron equation, the enthalpy of vaporization of steam at a specified pressure is to be
estimated and to be compared to the tabulated data.
Analysis From the Clapeyron equation,
 dP 
h fg = Tv fg  
 dT  sat
 ∆P 
≅ T (v g − v f ) @300 kPa  
 ∆T  sat, 300 kPa
 (325 − 275)kPa 
= Tsat @300 kPa (v g − v f ) @300 kPa  
 Tsat @325 kPa − Tsat @275 kPa 
 
3  50 kPa 
= (133.52 + 273.15 K)(0.60582 − 0.001073 m /kg) 
 (136.27 − 130.58)°C 
= 2161.1 kJ/kg
The tabulated value of hfg at 300 kPa is 2163.5 kJ/kg.

12-28 The hfg and sfg of steam at a specified temperature are to be calculated using the Clapeyron equation
and to be compared to the tabulated data.
Analysis From the Clapeyron equation,
 dP 
h fg = Tv fg  
 dT  sat
 ∆P 
≅ T (v g − v f ) @120°C  
 ∆T  sat,120°C
 Psat @125°C − Psat @115°C 
= T (v g − v f ) @120°C  

 125°C − 115°C 
 (232.23 − 169.18)kPa 
= (120 + 273.15 K)(0.89133 − 0.001060 m 3 /kg) 
 10 K 
= 2206.8 kJ/kg
Also,
h fg 2206.8 kJ/kg
s fg = = = 5.6131 kJ/kg ⋅ K
T (120 + 273.15)K
The tabulated values at 120°C are hfg = 2202.1 kJ/kg and sfg = 5.6013 kJ/kg·K.

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 12-13

12-29E [Also solved by EES on enclosed CD] The hfg of refrigerant-134a at a specified temperature is to be
calculated using the Clapeyron equation and Clapeyron-Clausius equation and to be compared to the
tabulated data.
Analysis (a) From the Clapeyron equation,
 dP 
h fg = Tv fg  
 dT  sat
 ∆P 
≅ T (v g − v f ) @ 50°F  
 ∆T  sat, 50° F
 Psat @ 60 ° F − Psat @ 40 °F 
= T (v g − v f ) @ 50°F  

 60°F − 40°F 
 (72.152 − 49.776) psia 
= (50 + 459.67 R)(0.79136 − 0.01270 ft 3 /lbm) 
 20 R 
= 444.0 psia ⋅ ft 3 /lbm = 82.16 Btu/lbm (0.2% error)
since 1 Btu = 5.4039 psia·ft3.
(b) From the Clapeyron-Clausius equation,
P  h fg  1 1 
ln 2  ≅  − 
 P1  sat R  T1 T2  sat

 72.152 psia  h fg  1 1 
ln  ≅  − 
 49. 776 psia  0.01946 Btu/lbm ⋅ R  40 + 459 .67 R 60 + 459 . 67 R 
h fg = 93.80 Btu/lbm (14.4% error)

The tabulated value of hfg at 50°F is 82.00 Btu/lbm.

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 12-14

12-30 EES The enthalpy of vaporization of steam as a function of temperature using Clapeyron equation
and steam data in EES is to be plotted.
Analysis The enthalpy of vaporization is determined using Clapeyron equation from
∆P
h fg ,Clapeyron = Tv fg
∆T
At 100ºC, for an increment of 5ºC, we obtain
T1 = T − Tincrement = 100 − 5 = 95°C
T2 = T + Tincrement = 100 + 5 = 105°C
P1 = Psat @ 95°C = 84.61 kPa
P2 = Psat @ 105°C = 120.90 kPa
∆T = T2 − T1 = 105 − 95 = 10°C
∆P = P2 − P1 = 120.90 − 84.61 = 36.29 kPa
v f @ 100°C = 0.001043 m 3 /kg
v g @ 100°C = 1.6720 m 3 /kg
v fg = v g − v f = 1.6720 − 0.001043 = 1.6710 m 3 /kg
Substituting,
∆P 36.29 kPa
h fg ,Clapeyron = Tv fg = (100 + 273.15 K)(1.6710 m 3 /kg) = 2262.8 kJ/kg
∆T 10 K
The enthalpy of vaporization from steam table is
h fg @ 100°C = 2256.4 m 3 /kg

The percent error in using Clapeyron equation is

2262.8 − 2256.4
PercentError = × 100 = 0.28%
2256.4
We repeat the analysis over the temperature range 10 to 200ºC using EES. Below, the copy of EES
solution is provided:

"Input Data:"
"T=100" "[C]"
T_increment = 5"[C]"
T[2]=T+T_increment"[C]"
T[1]=T-T_increment"[C]"
P[1] = pressure(Steam_iapws,T=T[1],x=0)"[kPa]"
P[2] = pressure(Steam_iapws,T=T[2],x=0)"[kPa]"
DELTAP = P[2]-P[1]"[kPa]"
DELTAT = T[2]-T[1]"[C]"

v_f=volume(Steam_iapws,T=T,x=0)"[m^3/kg]"
v_g=volume(Steam_iapws,T=T,x=1)"[m^3/kg]"
h_f=enthalpy(Steam_iapws,T=T,x=0)"[kJ/kg]"
h_g=enthalpy(Steam_iapws,T=T,x=1)"[kJ/kg]"

h_fg=h_g - h_f"[kJ/kg-K]"
v_fg=v_g - v_f"[m^3/kg]"

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 12-15

"The Clapeyron equation (Eq. 11-22) provides a means to calculate the enthalpy of vaporization,
h_fg at a given temperature by determining the slope of the saturation curve on a P-T diagram
and the specific volume of the saturated liquid and satruated vapor at the temperature."

h_fg_Clapeyron=(T+273.15)*v_fg*DELTAP/DELTAT*Convert(m^3-kPa,kJ)"[kJ/kg]"
PercentError=ABS(h_fg_Clapeyron-h_fg)/h_fg*100"[%]"

hfg hfg,Clapeyron PercentErro T

[kJ/kg] [kJ/kg] r [C]
[%]
2477.20 2508.09 1.247 10
2429.82 2451.09 0.8756 30
2381.95 2396.69 0.6188 50
2333.04 2343.47 0.4469 70
2282.51 2290.07 0.3311 90
2229.68 2235.25 0.25 110
2173.73 2177.86 0.1903 130
2113.77 2116.84 0.1454 150
2014.17 2016.15 0.09829 180
1899.67 1900.98 0.06915 210
1765.50 1766.38 0.05015 240

2600

2500 hfg calculated by Clapeyron equation

2400

]
g 2300
k/
J hfg calculated by EES
k[ 2200
g
f
h 2100

2000

1900

1800

1700
0 50 100 150 200 250
T [C]

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 12-16

12-31 The sublimation pressure of water at -30ºC is to be determined using Clapeyron-Clasius equation
and the triple point data of water.
Analysis The sublimation pressure may be determined using Clapeyron-Clasius equation from
 Psub,CC  hig  1 1 
ln = 
 R T − T

 P1   1 2 
where the triple point properties of water are P1 = 0.6117 kPa and T1 = 0.01ºC = 273.16 K (first line in
Table A-4). Also, the enthalpy of sublimation of water at -30ºC is determined from Table A-8 to be 2838.4
kJ/kg. Substituting,
 Psub,CC  hig  1 1 
ln =

 − 
 P1  R  T1 T2 
 Psub,CC  2838.4 kJ/kg  1 1 
ln =
  − 
 0 . 6117 kPa  0.4615 kJ/kg.K  273. 16 K − 30 + 273. 15 K 
Psub,CC = 0.03799 kPa
The sublimation pressure of water at -30ºC is given in Table A-8 to be 0.03802 kPa. Then, the error
involved in using Clapeyron-Clasius equation becomes
0.03802 − 0.03799
PercentError = × 100 = 0.08%
0.03802

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 12-17

General Relations for du, dh, ds, cv, and cp

12-32C Yes, through the relation

 ∂c p   2 
  = −T  ∂ v 
 ∂P   ∂T 2 
 T  P

12-33 It is to be shown that the enthalpy of an ideal gas is a function of temperature only and that for an
incompressible substance it also depends on pressure.
Analysis The change in enthalpy is expressed as
  ∂v  
dh = c P dT + v − T   dP
  ∂T  P 
For an ideal gas v = RT/P. Then,
 ∂v  R
v −T  = v − T   = v −v = 0
 ∂T  P P
Thus,
dh = c p dT

To complete the proof we need to show that cp is not a function of P either. This is done with the help of
the relation
 ∂c p   2 
  = −T  ∂ v 
 ∂P   ∂T 2 
 T  P
For an ideal gas,
 ∂ 2v 
 ∂v 
  =
R
and   =  ∂ ( R / P )  = 0
∂  ∂T 2 
 T P P   P  ∂T  P
Thus,
 ∂c P 
  = 0
 ∂P T
Therefore we conclude that the enthalpy of an ideal gas is a function of temperature only.
For an incompressible substance v = constant and thus ∂v/∂T = 0. Then,
dh = c p dT + v dP

Therefore we conclude that the enthalpy of an incompressible substance is a function of temperature and
pressure.

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 12-18

12-34 General expressions for ∆u, ∆h, and ∆s for a gas that obeys the van der Waals equation of state for
an isothermal process are to be derived.
Analysis (a) For an isothermal process dT = 0 and the general relation for ∆u reduces to
T2 v2   ∂P   v2   ∂P  
∆u = u 2 − u1 = ∫ T1
cv dT + ∫v 1
T 
 v

  ∂T  − P dv =

∫v 1
T  
  ∂T  − P dv
 v 
The van der Waals equation of state can be expressed as
RT a  ∂P  R
P= − 2 
→   =
v −b v  ∂T v v − b
Thus,
 ∂P  RT RT a a
T  −P= − + 2 = 2
 ∂T v v −b v −b v v
Substituting,
v2 a  1 1 
∆u = ∫v 1 v2
dv = a − 
 v1 v 2 
(b) The enthalpy change ∆h is related to ∆u through the relation
∆h = ∆u + P2v 2 − P1v 1
where
RTv a
Pv = −
v −b v
Thus,
 v v   1 1 
P2v 2 − P1v 1 = RT  2 − 1  + a − 
 v 2 − b v1 − b   v1 v 2 
Substituting,
 1 1   v v 
∆h = 2a −  + RT  2 − 1 
 v1 v 2   v 2 − b v1 − b 
(c) For an isothermal process dT = 0 and the general relation for ∆s reduces to
T2 cv v2  ∂P  v2  ∂P 
∆s = s 2 − s1 = ∫T1 T
dT + ∫v 1
  dv =
 ∂T  v ∫v 1
  dv
 ∂T  v
Substituting (∂P/∂T)v = R/(v - b),
v2 R v −b
∆s = ∫v 1 v −b
dv = Rln 2
v1 − b

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 12-19

12-35 General expressions for ∆u, ∆h, and ∆s for a gas whose equation of state is P(v-a) = RT for an
isothermal process are to be derived.
Analysis (a) A relation for ∆u is obtained from the general relation
T2 v2   ∂P  
∆u = u 2 − u1 = ∫ T1
cv dT + ∫v 1
T  
  ∂T  − P dv
 v 
The equation of state for the specified gas can be expressed as
RT  ∂P  R
P= →   =
v −a  ∂T v v − a
Thus,
 ∂P  RT
T  −P = −P = P−P = 0
 ∂T v v −a
T2
Substituting, ∆u = ∫T1
cv dT

(b) A relation for ∆h is obtained from the general relation

 ∂v  
v − T 
T2 P2
∆h = h2 − h1 = ∫ T1
c P dT + ∫ P1 

 dP
 ∂T  P 
The equation of state for the specified gas can be expressed as
RT  ∂v  R
v= +a 
→   =
P  ∂T P P
Thus,
 ∂v  R
v −T  = v − T = v − (v − a ) = a
 ∂T  P P
Substituting,
T2 P2 T2
∆h = ∫ c p dT + ∫ a dP = ∫ c p dT + a(P2 − P1 )
T1 P1 T1

(c) A relation for ∆s is obtained from the general relation

T2 cp P2  ∂v 
∆s = s 2 − s1 = ∫
T1 T
dT − ∫P1
  dP
 ∂T  P
Substituting (∂v/∂T)P = R/T,
T2 cp P2 R T2 cp P2
∆s = ∫
T1 T
dT − ∫P1
  dP =
 P P ∫T1 T
dT − R ln
P1
For an isothermal process dT = 0 and these relations reduce to
P2
∆u = 0, ∆h = a(P2 − P1 ), and ∆s = − Rln
P1

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 12-20

12-36 General expressions for (∂u/∂P)T and (∂h/∂v)T in terms of P, v, and T only are to be derived.
Analysis The general relation for du is
  ∂P  
du = cv dT +  T   − P dv
  ∂T  v 
Differentiating each term in this equation with respect to P at T = constant yields
 ∂u    ∂P   ∂v   ∂P   ∂v   ∂v 
  = 0 +  T   − P   = T    − P 
 ∂P  T   ∂T  v  ∂P  T  ∂T  v  ∂P  T  ∂P  T
Using the properties P, T, v, the cyclic relation can be expressed as
 ∂P   ∂T   ∂v   ∂P   ∂v   ∂v 
      = −1 
→     = − 
 ∂T  v  ∂v  P  ∂P  T  ∂T  v  ∂P  T  ∂T  P
Substituting, we get
 ∂u   ∂v   ∂v 
  = −T   − P 
∂P
 T  ∂T P  ∂P  T
The general relation for dh is
  ∂v  
dh = c p dT + v − T   dP
  ∂T  P 
Differentiating each term in this equation with respect to v at T = constant yields
 ∂h    ∂v   ∂P   ∂P   ∂v   ∂P 
  = 0 + v − T     =v  −T   
 ∂v  T   ∂T  P  ∂v  T  ∂v  T  ∂T  P  ∂v  T
Using the properties v, T, P, the cyclic relation can be expressed as
 ∂v   ∂T   ∂P   ∂v   ∂P   ∂T 
      = −1 
→     = − 
 ∂T  P  ∂P  v  ∂v  T  ∂T  P  ∂v  T  ∂P  v
Substituting, we get
 ∂h   ∂P   ∂T 
  =v  +T 
 ∂v T  ∂v T  ∂P  v

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 12-21

12-37 Expressions for the specific heat difference cp-cv for three substances are to be derived.
Analysis The general relation for the specific heat difference cp - cv is
2
 ∂v   ∂P 
c p − cv = −T    
 ∂T  P  ∂v  T
(a) For an ideal gas Pv = RT. Then,
RT  ∂v  R
v= 
→   =
P  ∂T P P
RT  ∂P  RT P
P= 
→   =− 2 =−
v  ∂v  T v v
Substituting,
2
 P   R  TR
c p − cv = −T  −    = R=R
 v   P  Pv
 a 
(b) For a van der Waals gas  P + 2 (v − b ) = RT . Then,
 v 
1 a   ∂T  1  2a  1 a 
T=  P + 2 (v − b ) 
→   =  − 3 (v − b ) +  P + 2 
R v   ∂v  P R  v  R v 
2a (b − v ) T
= +
Rv 3 v −b
 ∂v  1
Inverting,   =
 ∂T  P 2 a (b − v )+ T
Rv 3 v −b
RT a  ∂P  RT 2a
Also, P= − 
→   =− + 3
v −b v 2  ∂v T (v − b ) v
2

Substituting,
2
 
   RT
1 2a 
c p − cv = T    − 3
 2a (b − v ) T   (v − b ) 2
v 
 +  
 Rv 3 v −b 
(c) For an incompressible substance v = constant and thus (∂v /∂T)P = 0. Therefore,
c p − cv = 0

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 12-22

12-38 The specific heat difference cp-cv for liquid water at 15 MPa and 80°C is to be estimated.
Analysis The specific heat difference cp - cv is given as
2
 ∂v   ∂P 
c p − cv = −T    
 ∂T  P  ∂v  T
Approximating differentials by differences about the specified state,
2
 ∆v   ∆P 
c p − cv ≅ −T    
 ∆ T  P =15 MPa  ∆v  T =80°C
2
 v 100°C − v 60°C   (20 − 10)MPa 
= −(80 + 273.15 K )   
  
 (100 − 60)°C  P =15 MPa  v 20MPa − v 10 MPa  T =80°C
2
 (0.0010361 − 0.0010105)m 3 /kg   10,000 kPa 
= −(353.15 K )   
 40 K   (0.0010199 − 0.0010244)m 3 /kg 
   
= 0.3114 kPa ⋅ m 3 /kg ⋅ K = 0.3214 kJ/kg ⋅ K

12-39E The specific heat difference cp-cv for liquid water at 1000 psia and 150°F is to be estimated.
Analysis The specific heat difference cp - cv is given as
2
 ∂v   ∂P 
c p − cv = −T    
 ∂T  P  ∂v  T
Approximating differentials by differences about the specified state,
2
 ∆v   ∆P 
c p − cv ≅ −T    
 ∆T  P =1000psia  ∆v  T =150° F
2
 v 175° F − v 125° F   (1500 − 500)psia 
= −(150 + 459.67 R )   
  
 (175 − 125)°F  P =1000 psia  v 1500 psia − v 500 psia  T =150° F
2
 (0.016427 − 0.016177)ft 3 /lbm   1000 psia 
= −(609.67 R)   
 50 R   (0.016267 − 0.016317)ft 3 /lbm 
   
= 0.3081 psia ⋅ ft 3 /lbm ⋅ R = 0.0570 Btu/lbm ⋅ R (1 Btu = 5.4039 psia ⋅ ft 3 )

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 12-23

12-40 Relations for the volume expansivity β and the isothermal compressibility α for an ideal gas and for
a gas whose equation of state is P(v-a) = RT are to be obtained.
Analysis The volume expansivity and isothermal compressibility are expressed as
1  ∂v  1  ∂v 
β=   and α = −  
v  ∂T  P v  ∂P  T
(a) For an ideal gas v = RT/P. Thus,
 ∂v  R 1 R 1
  = 
→ β = =
 ∂T  P P v P T
 ∂v  RT v 1 v  1
  =− 2 =− → α = −  −  =
 ∂P T P P v  P P
(b) For a gas whose equation of state is v = RT/P + a,
 ∂v  R 1 R R
  = 
→ β = =
 ∂T  P P v P RT + aP
 ∂v  RT v −a 1  v −a v −a
  =− 2 =− 
→ α = −  − =
 ∂P T P P v  P  Pv

12-41 The volume expansivity β and the isothermal compressibility α of refrigerant-134a at 200 kPa and
30°C are to be estimated.
Analysis The volume expansivity and isothermal compressibility are expressed as
1  ∂v  1  ∂v 
β=   and α = −  
v  ∂T  P v  ∂P  T
Approximating differentials by differences about the specified state,
1  ∆v  1  v 40°C − v 20°C 
β≅   =  

v  ∆T  P = 200 kPa v  (40 − 20)°C  P = 200 kPa
1  (0.12322 − 0.11418)m 3 /kg 
=   = 0.00381 K −1
0.11874 m 3 /kg  20 K 

and
1  ∆v  1  v 240 kPa − v 180 kPa 
α≅−   = −  

v  ∆P  T =30°C v  (240 − 180)kPa  T =30°C
1  (0.09812 − 0.13248)m 3 /kg 
=−   = 0.00482 kPa −1
0.11874 m 3 /kg  60 kPa 


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 12-24

The Joule-Thomson Coefficient

12-42C It represents the variation of temperature with pressure during a throttling process.

12-43C The line that passes through the peak points of the constant enthalpy lines on a T-P diagram is
called the inversion line. The maximum inversion temperature is the highest temperature a fluid can be
cooled by throttling.

12-44C No. The temperature may even increase as a result of throttling.

12-45C Yes.

12-46C No. Helium is an ideal gas and h = h(T) for ideal gases. Therefore, the temperature of an ideal
gas remains constant during a throttling (h = constant) process.

12-47 The equation of state of a gas is given to be P(v-a) = RT. It is to be determined if it is possible to
cool this gas by throttling.
Analysis The equation of state of this gas can be expressed as
RT  ∂v  R
v= +a 
→   =
P  ∂T  P P
Substituting into the Joule-Thomson coefficient relation,
 ∂v  
v − T 
1 1  R 1
µ=−    = − v − T  = − (v − v + a ) = − a < 0
cp   ∂T  P  cp  P cp cp
Therefore, this gas cannot be cooled by throttling since µ is always a negative quantity.

12-48 Relations for the Joule-Thompson coefficient and the inversion temperature for a gas whose
equation of state is (P+a/v2) v = RT are to be obtained.
Analysis The equation of state of this gas can be expressed as
v  a   ∂T  v  2a  1  a  2av T RTv − 2a
T= P + 2   →   = − 3  +  P + 2  = − + =
R v   ∂v P R  v  R  v  Rv 2 v Rv 2
Substituting into the Joule-Thomson coefficient relation,
 ∂v    2 
v − T  v − RTv
1 1 =− 2 av
µ=−    = −  
cp   ∂T P  c p  RT v − 2 a  c p ( 2 a − RTv )
The temperature at µ = 0 is the inversion temperature,
2 av
µ=− =0  → v = 0
c p (2a − RTv )
Thus the line of v = 0 is the inversion line. Since it is not physically possible to have v = 0, this gas does
not have an inversion line.

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 12-25

12-49 The Joule-Thompson coefficient of steam at two states is to be estimated.

Analysis (a) The enthalpy of steam at 3 MPa and 300°C is h = 2994.3 kJ/kg. Approximating differentials
by differences about the specified state, the Joule-Thomson coefficient is expressed as
 ∂T   ∆T 
µ=  ≅ 
 ∂P  h  ∆P  h = 2994.3 kJ/kg
Considering a throttling process from 3.5 MPa to 2.5 MPa at h = 2994.3 kJ/kg, the Joule-Thomson
coefficient is determined to be
 T3.5 MPa − T2.5 MPa  (306.3 − 294)°C
µ =  
 = = 12.3 °C/MPa
 (3.5 − 2.5) MPa  h = 2994.3 kJ/kg (3.5 − 2.5) MPa
(b) The enthalpy of steam at 6 MPa and 500°C is h = 3423.1 kJ/kg. Approximating differentials by
differences about the specified state, the Joule-Thomson coefficient is expressed as
 ∂T   ∆T 
µ=  ≅ 
 ∂P  h  ∆P  h =3423.1 kJ/kg
Considering a throttling process from 7.0 MPa to 5.0 MPa at h = 3423.1 kJ/kg, the Joule-Thomson
coefficient is determined to be
 T7.0 MPa − T5.0 MPa  (504.8 − 495.1)°C
µ =  
 = = 4.9 °C/MPa
 (7.0 − 5.0) MPa  h =3423.1 kJ/kg (7.0 − 5.0) MPa

12-50E [Also solved by EES on enclosed CD] The Joule-Thompson coefficient of nitrogen at two states is
to be estimated.
Analysis (a) The enthalpy of nitrogen at 200 psia and 500 R is, from EES, h = -10.564 Btu/lbm. Note that
in EES, by default, the reference state for specific enthalpy and entropy is 0 at 25ºC (77ºF) and 1 atm.
Approximating differentials by differences about the specified state, the Joule-Thomson coefficient is
expressed as
 ∂T   ∆T 
µ=  ≅ 
 ∂P  h  ∆P  h = −10.564 Btu/lbm
Considering a throttling process from 210 psia to 190 psia at h = -10.564 Btu/lbm, the Joule-Thomson
coefficient is determined to be
 T190 psia − T210 psia  (499.703 − 500.296) R
µ =  
 = = 0.0297 R/psia
 (190 − 210) psia  h = −10.564 Btu/lbm (190 − 210) psia

(b) The enthalpy of nitrogen at 2000 psia and 400 R is, from EES, h = -55.321 Btu/lbm. Approximating
differentials by differences about the specified state, the Joule-Thomson coefficient is expressed as
 ∂T   ∆T 
µ=  ≅ 
 ∂P  h  ∆P  h = −55.321 Btu/lbm
Considering a throttling process from 2010 psia to 1990 psia at h = -55.321 Btu/lbm, the Joule-Thomson
coefficient is determined to be
 T1999 psia − T2001 psia  (399.786 - 400.213) R
µ =  
 = = 0.0213 R/psia
 (1990 − 2010) psia  h = −55.321 Btu/lbm (1990 − 2010) psia

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 12-26

12-51E EES Problem 12-50E is reconsidered. The Joule-Thompson coefficient for nitrogen over the
pressure range 100 to 1500 psia at the enthalpy values 100, 175, and 225 Btu/lbm is to be plotted.
Analysis The problem is solved using EES, and the results are tabulated and plotted below.

Gas$ = 'Nitrogen'
{P_ref=200 [psia]
T_ref=500 [R]
P= P_ref}
h=50 [Btu/lbm]
{h=enthalpy(Gas$, T=T_ref, P=P_ref)}
dP = 10 [psia]
T = temperature(Gas$, P=P, h=h)
P[1] = P + dP
P[2] = P - dP
T[1] = temperature(Gas$, P=P[1], h=h)
T[2] = temperature(Gas$, P=P[2], h=h)
Mu = DELTAT/DELTAP "Approximate the differential by differences about the state at h=const."
DELTAT=T[2]-T[1]
DELTAP=P[2]-P[1]

h = 100 Btu/lbm
P [psia] µ [R/psia]
100 0.003675
275 0.003277
450 0.002899
625 0.00254
800 0.002198
975 0.001871
1150 0.001558
1325 0.001258
1500 0.0009699

0.004

0.003

0.002
h = 100 Btu/lbm
0.001

] 0
ai
s
p/ -0.001
R[ -0.002 h = 175 Btu/lbm
µ
-0.003

-0.004
h = 225 Btu/lbm
-0.005

-0.006
0 200 400 600 800 1000 1200 1400 1600
P [psia]

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 12-27

12-52 The Joule-Thompson coefficient of refrigerant-134a at a specified state is to be estimated.

Analysis The enthalpy of refrigerant-134a at 0.7 MPa and T = 50°C is h = 288.53 kJ/kg. Approximating
differentials by differences about the specified state, the Joule-Thomson coefficient is expressed as
 ∂T   ∆T 
µ=  ≅ 
 ∂P  h  ∆P  h = 288.53 kJ/kg
Considering a throttling process from 0.8 MPa to 0.6 MPa at h = 288.53 kJ/kg, the Joule-Thomson
coefficient is determined to be
 T0.8 MPa − T0.6 MPa  (51.81 − 48.19)°C
µ =  
 = = 18.1 °C/MPa
 (0.8 − 0.6)MPa  h = 288.53 kJ/kg (0.8 − 0.6)MPa

12-53 Steam is throttled slightly from 1 MPa and 300°C. It is to be determined if the temperature of the
steam will increase, decrease, or remain the same during this process.
Analysis The enthalpy of steam at 1 MPa and T = 300°C is h = 3051.6 kJ/kg. Now consider a throttling
process from this state to 0.8 MPa, which is the next lowest pressure listed in the tables. The temperature
of the steam at the end of this throttling process will be
P = 0.8 MPa 
 T2 = 297.52°C
h = 3051.6 kJ/kg 
Therefore, the temperature will decrease.

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 12-28

The ∆h, ∆u, and ∆s of Real Gases

12-54C It is the variation of enthalpy with pressure at a fixed temperature.

12-55C As PR approaches zero, the gas approaches ideal gas behavior. As a result, the deviation from ideal
gas behavior diminishes.

12-56C So that a single chart can be used for all gases instead of a single particular gas.

12-57 The enthalpy of nitrogen at 175 K and 8 MPa is to be determined using data from the ideal-gas
nitrogen table and the generalized enthalpy departure chart.
Analysis (a) From the ideal gas table of nitrogen (Table A-18) we read
h = 5083.8 kJ/kmol = 181.48 kJ/kg ( M N 2 = 28.013 kg/kmol)

at the specified temperature. This value involves 44.4% error. N2

(b) The enthalpy departure of nitrogen at the specified state 175 K
is determined from the generalized chart to be 8 MPa
T 175 
TR = = = 1.387 
Tcr 126.2  (hideal − h ) T , P
and  → Z h = = 1 .6
P 8  Ru Tcr
PR = = = 2.360
Pcr 3.39 

Thus,
h = hideal − Z h Ru Tcr = 5083.8 − [(1.6)(8.314)(126.2)] = 3405.0 kJ/kmol
or,
h 3405.0 kJ/kmol
h= = = 121.6 kJ/kg (3.1%error)
M 28.013 kg/kmol

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