HVAC&R Research

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Thermodynamic Properties of Real Moist Air, Dry

Air, Steam, Water, and Ice (RP-1485)

Sebastian Herrmann , Hans-Joachim Kretzschmar & Donald P. Gatley

To cite this article: Sebastian Herrmann , Hans-Joachim Kretzschmar & Donald P. Gatley (2009)
Thermodynamic Properties of Real Moist Air, Dry Air, Steam, Water, and Ice (RP-1485), HVAC&R
Research, 15:5, 961-986

To link to this article: https://doi.org/10.1080/10789669.2009.10390874

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© 2009, American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc. (www.ashrae.org). Published in HVAC&R Research,
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permitted without ASHRAE’s prior written permission.
VOLUME 15, NUMBER 5 HVAC&R RESEARCH SEPTEMBER 2009

Thermodynamic Properties of Real Moist Air,

Dry Air, Steam, Water, and Ice (RP-1485)
Sebastian Herrmann Hans-Joachim Kretzschmar, PhD
Student Member ASHRAE Member ASHRAE
Donald P. Gatley, PE
Fellow/Life Member ASHRAE

Received February 14, 2009; accepted May 6, 2009

This paper is based on findings resulting from ASHRAE Research Project RP-1485.

This research updates the modeling of moist air as a real gas mixture using the virial equation
of state. It includes the Hyland and Wexler model (1983a, 1983b) and considers the Nel-
son-Sauer model (2002). All new National Institute of Standards and Technology reference
equations and the latest International Association for the Properties of Water and Steam
(IAPWS) standards, as well as the current values for the molar masses and gas constants, have
been incorporated. The deviations of the proposed model to the Hyland-Wexler and Nel-
son-Sauer models are very low at ambient pressures but increase with increasing pressures
and temperatures. The range of validity of the new model is in pressure from 0.01 kPa up to 10
MPa, in temperature from –143.15°C up to 350°C, and in humidity ratio from 0 kgw/kga up to
10 kgw/kga. This model was used to produce moist air and H2O saturation property tables for
the psychrometric chapter in the 2009 ASHRAE Handbook—Fundamentals (ASHRAE 2009).
The paper summarizes ASHRAE Research Project 1485 (RP-1485).

INTRODUCTION
The American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc. (ASHRAE)
has long been a leader in the field of psychrometric research, publications, and data. The current psy-
chrometric tables in the 2005 ASHRAE Handbook—Fundamentals (ASHRAE 2005) are now 25
years old and are based on the Hyland-Wexler RP-216 (1983a, 1983b) and the Stewart et al. RP-257
(1983) research projects.
Research completed in recent years has resulted in new data and the new formulations listed
below. The net effect is changes in the properties of moist air and in the saturation properties of
H2O. These changes are small for air-conditioning system psychrometrics, but they are more
significant at higher pressures and temperatures (e.g., the pressures and temperatures encoun-
tered in the compression stage of gas turbines and in compressed-air energy storage applica-
tions). New developments include:

• the fundamental equation of Lemmon et al. (2000) for the calculation of the dry air properties,

Sebastian Herrmann is a doctoral student and Hans-Joachim Kretzschmar is a professor at the Zittau/Goerlitz Uni-
versity of Applied Sciences, Zittau, Germany. Donald P. Gatley is president of Gatley & Associates, Inc., Atlanta, GA.

961
962 HVAC&R RESEARCH

• Henry’s constant from the International Association for the Properties of Water and Steam
Guideline 2004 (IAPWS 2004) in the determination of the enhancement factor,
• the value for the universal molar gas constant from The Committee on Data for Science and
Technology (CODATA) standard by Mohr and Taylor (2005),
• IAPWS Release on an Equation of State for H2O Ice Ih, (IAPWS 2006),
• the air-water second molar cross-virial coefficient from Harvey and Huang (2007),
• the Revised Release 2008 on the Pressure along the Melting and Sublimation Curves of
Ordinary Water Substance (IAPWS 2008), and
• the value for the molar mass of dry air from Gatley et al. (2008).

The objective of this research is to update the ASHRAE real moist air psychrometric
model (Hyland and Wexler 1983a, 1983b; Nelson and Sauer 2002) and incorporate the new
developments listed above. The new model applies over the range of 130 K to 623.15 K
(–143.15°C to 350°C) at pressures from 0.01 kPa to 10 MPa. The deliverables include new
moist air and saturated H2O tables for the psychrometrics chapter of the 2009 ASHRAE
Handbook—Fundamentals (ASHRAE 2009).
RP-1485 is the fourth major ASHRAE psychrometric research project.

UNDERLYING PROPERTIES OF DRY AIR, STEAM, WATER, AND ICE

Thermodynamic Properties of Dry Air
The thermodynamic properties of dry air are calculated using the National Institute of Standards
and Technology (NIST) Lemmon et al. (2000) reference equation as a pseudo pure component. It
consists of a fundamental equation for the molar Helmholtz energy ( a ) as a function of density ( ρ )
and temperature (T). The constants used by Lemmon et al. are given in Table 1.
The dimensionless form of the fundamental equation reads

( ρ, T )
a-----------------
= α ° ( δ, τ ) + α r ( δ, τ ) , (1)
R Lem T

where α° is the ideal-gas contribution to the dimensionless Helmholtz energy and α r is the
residual contribution, δ = ρ ⁄ ρj is the reduced density, and τ = T j ⁄ T is the reciprocal reduced
temperature. The reducing parameters ρ j and Tj are given in Table 1.
All thermodynamic properties for dry air can be derived from Equation 1 by using the appro-
priate combinations of the ideal-gas part α° and the residual part α r of the dimensionless Helm-
holtz energy and their derivatives. The derivatives of Equation 1 are described in detail in
Lemmon et al. (2000) and Herrmann et al. (2008).

Thermodynamic Properties of Steam, Water, and Ice

Overview. For calculating thermodynamic properties of water and steam, the following
IAPWS standards are used:

• IAPWS-95, Release on the IAPWS Formulation 1995 for the Thermodynamic Properties of Ordi-
nary Water Substance for General and Scientific Use (IAPWS 1995; Wagner and Pruß 2002)
• IAPWS-IF97, Revised Release on the IAPWS Industrial Formulation 1997 for the Thermody-
namic Properties of Water and Steam (IAPWS 2007; Wagner and Kretzschmar 2008; Parry et al.
2000)
• IAPWS-06, IAPWS Release 2006 on an Equation of State for H2O Ice Ih (IAPWS 2006;
Feistel and Wagner 2006)
VOLUME 15, NUMBER 5, SEPTEMBER 2009 963

• IAPWS-08, Revised Release 2008 on the Pressure along the Melting and Sublimation Curves
of Ordinary Water Substance (IAPWS 2008; Wagner et al. 2009).

The pressure-temperature diagram in Figure 1 shows in which ranges of state the certain
formulation is applied.
For temperatures T ≥ 273.15 K , the industrial formulation IAPWS-IF97 (IAPWS 2007) is
used both for liquid water, including saturated liquid (region 1), and for superheated steam,
including saturated vapor (region 2). The saturation pressure p97 s (T) is calculated using the
IAPWS-IF97 saturation pressure equation. For practical purposes, the triple-point temperature
Tt = 273.16 K = 0.01°C = 32.018°F of water was rounded to 273.15 K = 0°C = 32°F. Instead of
the triple-point pressure pt = 0.6117 kPa of water, the pressure p = p97
s (273.15 K) = 0.6112 kPa
is used.
For superheated steam, including saturated steam at temperatures T ≤ 273.15 K , the scientific
formulation IAPWS-95 (IAPWS 1995) has to be used because the industrial formulation is only
valid for temperatures T ≥ 273.15 K .
For ice, including the saturation state, the formulation IAPWS-06 (IAPWS 2006) is applied.
The sublimation pressure is calculated from the IAPWS-08 (IAPWS 2008) sublimation pressure
08 (T). Instead of the melting line, the phase boundary between ice and liquid, the
equation p sub
isotherm T = 273.15 K can be used in the pressure range 0.6112 kPa ≤ p ≤ 10 MPa with reason-
able accuracy.
The Formulation IAPWS-95 for General and Scientific Use. To calculate the thermody-
namic properties of water and steam, the international standard for general and scientific use
IAPWS-95 (IAPWS 1995) can be applied. This standard contains an equation for the specific
Helmholtz energy (a) as a function of density ( ρ ) and temperature (T). The equation for the
reduced Helmholtz energy reads

Figure 1. Pressure-temperature diagram with application ranges of the formulations for

steam, water, and ice.
964 HVAC&R RESEARCH

Table 1. Constants and Values Used by Lemmon et al. (2000) in

Their Fundamental Equation for Dry Air
Quantity Symbol Value
Universal molar gas constant R Lem 8.314510 kJ/(kmol⋅K)
Specific gas constant R Lem 0.287117 kJ/(kg⋅K)
Molar mass M Lem 28.9586 kg/kmol
Maxcondentherm molar density ρj 10.4477 mol/dm3
Maxcondentherm temperature Tj 132.6312 K

( ρ, T )
a-----------------
= α° ( δ, τ ) + α r ( δ, τ ) , (2)
R 95 T

where α° is the ideal-gas contribution and α r is the residual part, δ = ρ ⁄ ρc is the reduced den-
sity, and τ = T c ⁄ T is the reciprocal reduced temperature. The reducing parameters ρc and Tc
and the specific gas constant R95 of IAPWS-95 are listed in Table 2.
All thermodynamic properties for water and steam can be derived from Equation 2 by using
the appropriate combinations of the ideal-gas part α° and the residual part α r of the dimension-
less Helmholtz energy and their derivatives. The derivatives of Equation 2 are described in
detail in IAPWS-95 (IAPWS 1995) and in Herrmann et al. (2008).
The Industrial Formulation IAPWS-IF97. In addition to the scientific formulation
IAPWS-95 (IAPWS 1995), the industrial formulation IAPWS-IF97 (IAPWS 2007) for water
and steam can be used for practical calculations. The range of validity of the IAPWS-IF97 is
divided into five calculation regions. The constants and critical parameters of IAPWS-IF97 are
listed in Table 3.
Liquid-Water Region 1. The liquid-water region 1, including saturated liquid line x = 0, is
described by an equation for the reduced Gibbs energy as a function of reduced pressure and
reciprocal reduced temperature. The equation reads:

g 1 ( p, T )
- = γ 1 ( π, τ )
------------------- (3)
R 97 T

where π = p ⁄ p * and τ = T * ⁄ T with p* = 16.53 MPa and T* = 1386 K, and R97 is given in
Table 3.
All thermodynamic properties for water can be derived from Equation 3 by using the appro-
priate combinations of the dimensionless Gibbs energy γ 1 and its derivatives. The derivatives of
Equation 3 are described in IAPWS-IF97 (IAPWS 2007) detail in Herrmann et al. (2008).
Steam Region 2. The steam region 2, including the saturated vapor line, is described by an equa-
tion for the reduced Gibbs energy as a function of pressure and temperature. The equation reads:

g 2 ( p, T )
- = γ 2° ( π, τ ) + γ 2r ( π, τ )
------------------- (4)
R 97 T

where γ 2° is the ideal-gas contribution, γ 2r is the residual part, π = p ⁄ p * is the reduced pressure,
and τ = T * ⁄ T is the reciprocal reduced temperature with p* = 1 MPa and T* = 540 K. R97 is the
specific gas constant of IAPWS-IF97 (IAPWS 2007) given in Table 3.
VOLUME 15, NUMBER 5, SEPTEMBER 2009 965

Table 2. Constants and Critical Values of IAPWS-95 (IAPWS 1995)

Quantity Symbol Value
Universal molar gas constant R 95 8.314371 kJ/(kmol⋅K)
Specific gas constant R95 0.46151805 kJ/(kg⋅K)
Molar mass M95 18.015268 kg/kmol
Critical mass density ρc 322 kg/m3
Critical temperature Tc 647.096 K
Critical pressure pc 22.064 MPa

All thermodynamic properties for steam can be derived from Equation 4 by using the appro-
priate combinations of the ideal-gas part γ 2° and the residual part γ 2r of the dimensionless Gibbs
energy and their derivatives. The derivatives of Equation 4 are described in detail in
IAPWS-IF97 (IAPWS 2007) and in Herrmann et al. (2008).
Thermodynamic Properties of Ice. The IAPWS-06 (IAPWS 2006) formulation for ice
describes the thermodynamic properties of ice in the region Ih (see Figure 1) with an equation
for the specific Gibbs energy as seen here:

g = g ( p, T ) (5)

The constants and triple-point parameters of IAPWS-06 (IAPWS 2006) are listed in Table 4.
All thermodynamic properties for ice can be derived from Equation 5 by using the appropriate
combinations of the Gibbs energy g and its derivatives. The derivatives of Equation 5 are
described in detail in IAPWS-06 (IAPWS 2006) and in Herrmann et al. (2008).
Saturation Pressure and Saturation Temperature of Water. The saturation pressure and
the saturation temperature of the liquid-vapor equilibrium (see Figure 1) are calculated using

Table 3. Constants and Critical Values of IAPWS-IF97 (IAPWS 2007)

Quantity Symbol Value
Universal molar gas constant R 97 8.314510 kJ/(kmol⋅K)
Specific gas constant R97 0.461526 kJ/(kg⋅K)
Molar mass M97 18.015257 kg/kmol
Critical mass density ρc 322.0 kg/m3
Critical temperature Tc 647.096 K
Critical pressure pc 22.064 MPa

the industrial formulation IAPWS-IF97 (IAPWS 2007). It contains an implicit quadratic equa-
tion that can be solved analytically with regard to both saturation pressure or saturation temper-
ature. The solution with regard to the saturation pressure is a function of given temperature T as
seen here:

p w, s = p s97 ( T ) (6)

The solution for the saturation temperature reads:

966 HVAC&R RESEARCH

Table 4. Constants and Values Used in IAPWS-06

(IAPWS 2006; Feistel and Wagner 2006)
Quantity Symbol Value
Universal molar gas constant R 06 8.314472 kJ/(kmol⋅K)
Specific gas constant R06 0.46152364 kJ/(kg⋅K)
Molar mass M06 18.015268 kg/kmol
Triple-point temperature Tt 273.16 K
Triple-point pressure pt 0.611657 kPa

T w, s = T s97 ( p ) (7)

Both equations are valid for temperatures T ≥ 273.15 . Equations 6 and 7 are described in
detail in IAPWS-IF97 (IAPWS 2007) and in Herrmann et al. (2008).
Sublimation Pressure and Sublimation Temperature. The sublimation pressure and the
sublimation temperature of the solid-vapor equilibrium (see Figure 1) are calculated using the
IAPWS-08 (IAPWS 2008) formulation.
The sublimation-pressure equation reads:

08 ( T )
p w, s = p sub (8)

In this work, Equation 8 is used in the temperature range 130 K ≤ T ≤ 273.15 K (see Figure 1).
Equation 8 is described in detail in IAPWS-08 (IAPWS 2008) and in Herrmann et al. (2008).
08 ) is calculated for given pressure p by solving iteratively the
The sublimation temperature ( T sub
08 = T .
sublimation pressure equation (Equation 8) in terms of T sub

PSYCHROMETRIC EQUATIONS
Methodology
The properties of moist air are calculated from the modified Hyland-Wexler model given in
Herrmann et al. (2008). The modifications incorporate:

• the value for the universal molar gas constant from Mohr and Taylor (2005)
• the value for the molar mass of dry air from Gatley et al. (2008) and that of water from
IAPWS-95 (IAPWS 1995; Wagner and Pruß 2002)
• the calculation of the ideal-gas parts of the heat capacity, enthalpy, and entropy for dry air
from the fundamental Lemmon et al. (2000) equation
• the calculation of the ideal-gas parts of the heat capacity, enthalpy, and entropy for water and
steam from IAPWS-IF97 (IAPWS 2007; Wagner and Kretzschmar 2008; Parry et al. 2000)
for T ≥ 273.15 K and from IAPWS-95 (IAPWS 1995; Wagner and Pruß 2002) for
T ≤ 273.15 K
• the calculation of the vapor-pressure enhancement factor from the equation, given by Hyland
and Wexler (1983a, 1983b)
• the calculation of the second and third molar virial coefficients Baa and Caaa for dry air from
the fundamental Lemmon et al. (2000) equation
• the calculation of the second and third molar virial coefficients Bww and Cwww for water and
steam from IAPWS-95 (IAPWS 1995; Wagner and Pruß 2002)
VOLUME 15, NUMBER 5, SEPTEMBER 2009 967

• the calculation of the air-water second molar cross-virial coefficient Baw from Harvey and
Huang (2007)
• the calculation of the air-water third molar cross-virial coefficients Caaw and Caww from Nel-
son and Sauer (2002; Gatley 2005)
• the calculation of the saturation pressure of water from IAPWS-IF97 (IAPWS 2007; Wagner
and Kretzschmar 2008; Parry et al. 2000) for T ≥ 273.15 K and of the sublimation pressure of
water from IAPWS-08 (IAPWS 2008; Wagner et al. 2009) for T ≤ 273.15 K
• the calculation of the isothermal compressibility of liquid water from IAPWS-IF97 (IAPWS 2007;
Wagner and Kretzschmar 2008; Parry et al. 2000) for T ≥ 273.15 K and that of ice from
IAPWS-06 (IAPWS 2006; Feistel and Wagner 2006) for T ≤ 273.15 K in the determination of the
vapor-pressure enhancement factor
• the calculation of Henry’s constant from the IAPWS Guideline 2004 (IAPWS 2004;
Fernández-Prini et al. 2003) in the determination of the enhancement factor, whereas the
mole fractions for the three main components of dry air were taken from Lemmon et al.
(2000). Argon was not considered in the former research projects, but it is now the third
component of dry air.

Virial Equation of State

The mixture moist air is calculated using the following mixing virial equation of state. The equa-
tion contains virial coefficients up to the third virial coefficient. The virial equation of state reads:

pv- Bm Cm
------ = 1 + ------- + ------2- (9)
RT v v

where p is the total pressure of moist air, v is the molar mixture volume, R is the universal
molar gas constant given in Table 5, Bm is the second molar virial mixing coefficient, and Cm is
the third molar virial mixing coefficient. The molar virial coefficients with higher order than the
third one are not considered in Equation 9. The molar virial coefficients Bm and Cm are calcu-
lated as follows:

B m = ( 1 – ψ w ) 2 B aa + 2 ( 1 – ψ w )ψ w B aw + ψ w2 B ww (10)

C m = ( 1 – ψ w ) 3 C aaa + 3 ( 1 – ψ w ) 2 ψ w C aaw + 3 ( 1 – ψ w )ψ w2 C aww + ψ w3 C www (11)

where ψ w is the mole fraction of water vapor in the mixture moist air, and 1 – ψ w = ψ a is the
mole fraction of dry air.
The derivatives of the second and the third molar virial mixing coefficients, with respect to
temperature, are given as follows:

dB dB aa dB aw dB ww
---------m- = ( 1 – ψ w ) 2 -----------
- + 2 ( 1 – ψ w )ψ w ------------
- + ψ w2 ------------- (12)
dT dT dT dT

dC m dC aaa dC aaw dC aww dC www

---------- = ( 1 – ψ w ) 3 --------------
- + 3 ( 1 – ψ w ) 2 ψ w ---------------
- + 3 ( 1 – ψ w )ψ w2 ---------------- + ψ w3 ----------------- (13)
dT dT dT dT dT

The calculation of the molar virial coefficients Baa, Caaa for dry air, Bww, Cwww for water
vapor, and the cross-virial coefficients Baw, Caaw, Caww, and their derivatives are described in
the next section.
968 HVAC&R RESEARCH

Table 5. Constants and Values Used for the Calculation

of Psychrometric Properties of Moist Air
Quantity Symbol Value Reference
Universal molar
R 8.314472 kJ/(kmol⋅K) Mohr and Taylor (2005)
gas constant
Molar mass of dry air Ma 28.966 kg/kmol Gatley et al. (2008)
Molar mass of water Mw 18.015268 kg/kmol IAPWS-95 (IAPWS 1995)
Specific gas constant
R a = R / Ma ≅ 0.287042 kJ/(kg⋅K)
of dry air
Specific gas constant
R w = R / Mw ≅ 0.461524 kJ/(kg⋅K)
of water
Quotient:
ε ≅ 0.621945
Mw ⁄ Ma = Ra ⁄ Rw
Pressure of the
p0 0.101325 MPa
reference state
Temperature of the
T0 273.15 K
reference state

The values for the universal molar gas constant ( R ), the molar mass of dry air (Ma), and the
molar mass of water (Mw) used for the calculation of the psychrometric properties in this section
are given in Table 5.
The specific gas constant for dry air can be obtained using Ra = R / Ma and the specific gas
constant for water can be obtained using Rw = R / Mw. The values given in Table 5 for Ra and Rw
are displayed with six decimal places.
The quotient of the molar masses of water and dry air is defined as

Mw Ra
ε = -------- = ------- . (14)
Ma Rw

Virial and Cross-Virial Coefficients and Their Derivatives

Dry Air. The second and third molar virial coefficients of dry air and their derivatives are cal-
culated using Lemmon et al. (2000) and read

1 ∂α r
B aa ( ρ, T ) = ---- ⎛⎝ ---------⎞⎠ (15)
ρ j ∂δ τ
δ=0

dB aa ( ρ, T ) 1 2⎛ ∂2αr⎞
- τ ------------
--------------------------- = – --------- (16)
dT ρ j T j ⎝ ∂δ∂τ⎠
δ=0

1 ∂ 2 α r⎞
C aaa ( ρ, T ) = -----2- ⎛ ----------- (17)
ρ j ⎝ ∂δ 2 ⎠ τ
δ=0
VOLUME 15, NUMBER 5, SEPTEMBER 2009 969

dC aaa ( ρ, T ) ∂ 3 α r-⎞
1 - 2 ⎛ --------------
------------------------------ = – ---------- τ (18)
dT ρ j T j ∂δ 2 ∂τ⎠
2 ⎝
δ=0

where ρ j is the molar density at Maxcondentherm and Tj is the temperature at Maxcondentherm

(both given in Table 1), τ is the reciprocal reduced temperature, and δ is the reduced density.
The derivatives ( ∂α r ⁄ ∂δ) τ , ( ∂ 2 α r ⁄ ( ∂δ∂τ ) ) , ( ∂ 2 α r ⁄ ∂δ 2 ) τ , and ( ∂ 3 α r ⁄ ( ∂δ 2 ∂τ ) ) are determined
using the residual part of the reduced fundamental Lemmon et al. equation (Equation 1) at the
limit of δ = 0. The fundamental Lemmon et al. equation for dry air and its derivatives are given
in detail in Lemmon et al. (2000) and in Herrmann et al. (2008).
Water Vapor. The second and third molar virial coefficients of water vapor and their deriva-
tives are calculated using IAPWS-95 (IAPWS 1995; Wagner and Pruß 2002) using the follow-
ing equations:

1 ∂α r
B ww ( ρ, T ) = ----- ⎛⎝ ---------⎞⎠ (19)
ρ c ∂δ τ
δ=0

dB ww ( ρ, T ) ∂ 2 α r-⎞
1 - 2 ⎛ -----------
- = – ----------
--------------------------- τ (20)
dT ρ c T c ∂δ∂τ⎠⎝
δ=0

1 ∂ 2 α r⎞
C www ( ρ, T ) = -----2- ⎛ ----------- (21)
ρ c ⎝ ∂δ 2 ⎠ τ
δ=0

dC www ( ρ, T ) 1 2 ⎛ ∂3 αr ⎞
- τ ---------------
-------------------------------- = – ----------- (22)
dT ρ c2 T c ⎝ ∂δ 2 ∂τ⎠ δ=0

where Tc is the critical temperature, ρ c is the molar critical density, τ is the reciprocal reduced
temperature, and δ is the reduced density. The derivatives ( ∂α r ⁄ ∂δ ) τ , ( ∂ 2 α r ⁄ ( ∂δ∂τ ) ) ,
( ∂ 2 α r ⁄ ∂δ 2 ) τ , and ( ∂ 3 α r ⁄ ( ∂δ 2 ∂τ ) ) are determined using the residual part of the reduced funda-
mental equation of IAPWS-95, Equation 2, at the limit of δ = 0. The fundamental equation for
water and steam from IAPWS-95 and its derivatives are given in detail in IAPWS-95 (IAPWS
1995) Herrmann et al. (2008).
Air Water. The second molar virial coefficient of air-water molecule interactions (Baw) is
calculated using the calculation proposed by Harvey and Huang (2007). They determined the
temperature-dependent second molar virial coefficient of air and water (Baw) and its first deriva-
tive (dBaw/dT) to be:

3
1
B aw ( T ) = -----* ∑ a i θ bi (23)
ρ
i=1

3
dB aw ( T ) 1 b –1
- ∑ ai bi θ i
--------------------- = ----------- (24)
dT ρ T * *
i=1

where θ = T/T* with T* = 100 K and ρ * = 10 3 mol/dm3. The coefficients a1…a3 and b1…b3
are given in Harvey and Huang (2007) and in Herrmann et al. (2008).
970 HVAC&R RESEARCH

Nelson and Sauer (2002) determined the third molar cross-virial coefficients of air-water
Caaw and Caww as follows:

5
1 -
C aaw ( T ) = ------------ ∑ ci θ 1 – i (25)
( ρ* )2
i=1

5
dC aaw ( T ) 1
- ∑ c i ( 1 – i )θ –i
------------------------ = ------------------ (26)
dT ( ρ* )2 T*
i=2

4
1 - ⎛ ⎞
C aww ( T ) = – ------------ exp ⎜ ∑ d i θ 1 – i⎟ (27)
(ρ ) * 2
⎝i = 1 ⎠

4 4
dC aww ( T ) 1 ⎛ ⎞
------------------------ - exp ⎜ ∑ d i θ 1 – i⎟ ∑ d i ( 1 – i )θ –i
- = – ------------------ (28)
dT ( ρ* )2 T* ⎝ ⎠
i=1 i=2

where θ = T/T* with T* = 1 K and ρ * = 10 3 mol/dm3. The coefficients c1…c5 and d1…d4 are
given in Herrmann et al. (2008); also see Gatley (2005).

Saturation State of Moist Air

Equation for the Saturation Partial Pressure of Water. The partial pressure of water (ps)
in saturated moist air is calculated using the following equation:

p s = fp w, s (29)

where f = f(p,T) is the vapor-pressure enhancement factor, and pw,s = pw,s(T) is the saturation
pressure of pure water. Therefore, ps depends on total pressure (p) and temperature (T). The next
section comprises the calculation of f.
The saturation pressure of pure water (pw,s) is calculated for given temperature T as follows:

p w, s = p s97 ( T ) for T ≥ 273.15 K from Equation 6 (30)

08 ( T ) for T ≤ 273.15 K from Equation 8

p w, s = p sub (31)

where p s97 (T) is the saturation-pressure equation of water obtained from IAPWS-IF97
(IAPWS 2007), Equation 6, and p sub 08 (T) is the sublimation-pressure equation of water

obtained from IAPWS-08 (IAPWS 2008), Equation 8.

Using the saturation partial pressure of water (ps), the saturation mole fraction of water ( ψ w,s)
is calculated using the following equation:

ps fp w, s
ψ w, s = ----- = ------------ . (32)
p p

Equation for the Enhancement Factor. The vapor-pressure enhancement factor (f)
describes the enhancement of the saturation pressure of water in the air atmosphere under ele-
vated total pressure. The calculation of the enhancement factor as a function of total pressure (p)
and temperature (T) is given by this equation:
VOLUME 15, NUMBER 5, SEPTEMBER 2009 971

ln ( f ) = ( RT ) – 1 [ ( 1 + κ T p w, s ) ( p – p w, s ) – 0.5κ T ( p 2 – p w2 , s ) ]v w, s + ln [ 1 – β H ( 1 – ψ w, s )p ]
+ ( RT ) – 1 { ( 1 – ψ w, s ) 2 pB aa – 2 ( 1 – ψ w, s ) 2 pB aw – [ p – p w, s – ( 1 – ψ w, s ) 2 ]pB ww }

+ ( RT ) –2 { ( 1 – ψ w, s ) 3 p 2 C aaa + 3 [ 0.5 – ( 1 – ψ w, s ) ] ( 1 – ψ w, s ) 2 p 2 C aaw

– 3 ψ w, s ( 1 – ψ w, s ) 2 p 2 C aww – 0.5 [ ( 3 – 2ψ w, s )ψ w2 , s p 2 – p w2 , s ]C www (33)

– ψ w, s ( – 2 + 3ψ w, s ) ( 1 – ψ w, s ) 2 p 2 B aa B ww – 2 ( – 1 + 3ψ w, s ) ( 1 – ψ w, s ) 3 p 2 B aa B aw
+ 6 ψ w2 , s ( 1 – ψ w, s ) 2 p 2 B aw B ww – 1.5 ( 1 – ψ w, s ) 4 p 2 B aa
2

– 2 ψ w, s ( – 2 + 3ψ w, s ) ( 1 – ψ w, s ) 2 p 2 B aw
2 – 0.5 [ p 2 – ( 4 – 3ψ
w, s w, s )ψ w, s p ]B ww }
3 2 2

where T is the temperature of the mixture moist air, p is the total pressure, ψ w, s is the mole frac-
tion of water in saturated moist air, and R is the current value of the universal molar gas con-
stant from Mohr and Taylor (2005) given in Table 5.
Furthermore, p w, s = p s97 (T) is the saturation pressure for temperatures T ≥ 273.15 K obtained
using Equation 6 of IAPWS-IF97 (IAPWS 2007). For temperatures T ≤ 273.15 K, p w, s = p sub 08 (T) is

the sublimation pressure from Equation 8 of IAPWS-08 (IAPWS 2008). (For practical purposes, the
triple-point temperature T t = 273.16 K = 0.01°C = 32.018°F of water was rounded to
273.15 K = 0°C = 32°F . Therefore, instead of the triple-point pressure pt = 0.6117 kPa, the pres-
sure p = ps97(273.15 K) = 0.6112 kPa is used for water.)
For temperatures T ≥ 273.15 K , the molar volume of saturated liquid water is calculated using
IAPWS-IF97 (IAPWS 2007) using the following equation:

R T ∂γ 1
97
v w, s = ------------ π ⎛⎝ --------⎞⎠ (34)
p w, s ∂π τ

where π is the reduced pressure, and τ is the reciprocal reduced temperature (see Equation 3).
The saturation pressure of water pw,s = ps97(T) is obtained using Equation 6, and R 97 is the
molar gas constant of IAPWS-IF97, given in Table 3. The derivative ( ∂γ 1 ⁄ ∂π ) τ is formed from
the reduced Gibbs equation of IAPWS-IF97, Equation 3. More details about this fundamental
equation and its derivatives are given in Herrmann et al. (2008).
For temperatures T ≤ 273.15 K , the molar volume of saturated ice is calculated using
IAPWS-06 (IAPWS 2006) using the following equation

∂g
v w, s = M 06 ⎛⎝ ------⎞⎠ (35)
∂p T

where ( ∂g ⁄ ∂p ) T is the derivative of the specific Gibbs equation of IAPWS-06, Equation 5, and
M 06 is the molar mass of IAPWS-06, given in Table 4. Details about this Gibbs equation and its
derivatives are given in Herrmann et al. (2008).
The calculation of the second molar virial coefficients Baa, Baw, Bww, and of the third molar
virial coefficients Caaa, Caaw, Caww, Cwww is described in the previous section.
The quantity κ T in Equation 33 is the isothermal compressibility of saturated liquid water for
temperatures T ≥ 273.15 K and that of saturated ice for temperatures T ≤ 273.15 K . The follow-
ing section contains the algorithms for both cases of temperatures.
In Equation 33, β H is the Henry’s law constant. Equation 38 contains its calculation.
Using Equation 33, the enhancement factor (f) has to be calculated iteratively because the sat-
uration mole fraction of water ( ψ w, s ) in Equation 33 depends on f via Equation 32.
972 HVAC&R RESEARCH

Isothermal Compressibility. For temperatures T ≥ 273.15 K , the isothermal compressibility

( κ T ) of liquid water is calculated for total pressure and temperature using the expression

1 ∂ γ 1⎞ ⎛ ------- ∂γ 1⎞ –1
2
κ T = – --- π ⎛⎝ ---------- - , (36)
p ∂π 2 ⎠ τ ⎝ ∂π ⎠ τ

where π is the reduced pressure, and τ is the reciprocal reduced temperature (see Equation 3).
The derivatives ( ∂γ 1 ⁄ ∂π ) τ and ( ∂ 2 γ 1 ⁄ ∂π 2 ) τ are formed using the reduced Gibbs equation of
IAPWS-IF97 (IAPWS 2007) region 1, Equation 3. Details about this fundamental equation and
its derivatives are given in Herrmann et al. (2008).
For temperatures, T ≤ 273.15 K is determined using IAPWS-06 (IAPWS 2006) for ice as
seen here:

∂ g ∂g 2 –1
κ T = – ⎛ --------2⎞ ⎛ ------⎞ , (37)
⎝ ∂p ⎠ T ⎝ ∂p⎠ T

where ( ∂g ⁄ ∂p ) T and ( ∂ 2 g ⁄ ∂p 2 ) T are the derivatives of the specific Gibbs equation, Equation 5.
Details about this fundamental equation and its derivatives are given in Herrmann et al. (2008).
In the iteration process of the enhancement factor via Equation 33, κ T is set to zero for
p w, s ( T ) > p .
Henry’s Law Constant. Henry’s law constant β H is calculated using IAPWS-04 (IAPWS 2004;
Fernández-Prini et al. 2003) for the three main components of dry air:

ψ ψO ψ ⎞
1 ⎛ N Ar
β H = ------------------- ⎜ ---------2 + ---------2 + ---------⎟ (38)
1.01325 ⎝ β N βO β Ar ⎠
2 2

where ψ N , ψ O , and ψ Ar are the mole fractions of nitrogen, oxygen, and argon in dry air. The
2 2
calculation of the three terms β N , β O , and β Ar for the Henry’s law constant for each solvent
2 2
are described in detail in Herrmann et al. (2008).
β H is set to zero for T ≤ 273.15 K or T > Tw,s (p), where Tw,s is the saturation temperature of
pure water calculated using Equation 7.
Graphical Representation of the Enhancement Factor. Values of the vapor-pressure
enhancement factor f calculated using Equation 33 for several total pressures are plotted over
temperature t for t > 0°C in Figure 2. In the figure, the enhancement increases with increasing
total pressure (p). Each curve p = const starts at f = 1.0 and the saturation temperature of pure
water. The vapor-pressure enhancement factor at 0.101325 MPa is 1.0041 at 0°C and is often
disregarded in air-conditioning calculations. The vapor-pressure enhancement factor must be
included for many industrial process calculations (e.g., at a total pressure of 10 MPa the
vapor-pressure enhancement factor is 1.4638).

Psychrometric Properties of Moist Air

Humidity Ratio. The humidity ratio (W) is defined as the quotient of the mass of water (mw)
divided by the mass of dry air (ma) in the mixture moist air as seen here:

mw mw
W = ------- = ---------------------- (39)
ma ( m – mw )

where m is the mass of the mixture moist air.

VOLUME 15, NUMBER 5, SEPTEMBER 2009 973

Figure 2. Values of the vapor-pressure enhancement factor f calculated using Equation 33

for several total pressures plotted over Celsius temperature t.

With the mole fraction ψ w of water one obtains

ψw
W = ε --------------------- , (40)
( 1 – ψw )

where ε is the quotient of the molar masses of dry air and water, Equation 14. By solving
Equation 40 in terms of ψ w one obtains

W
ψ w = ------------------ . (41)
(ε + W)

Using ψ w , the molar mass of moist air (M) is calculated using the equation

M = ( 1 – ψ w )M a + ψ w M w (42)

where Ma and Mw are the molar masses of dry air and water, given in Table 5.
Relative Humidity of Unsaturated or Saturated Moist Air. In addition, for unsaturated and
saturated moist air, the water content can be specified by the quantity relative humidity:

ψw
ϕ = ----------- (43)
ψ w, s

with the definition range 0 ≤ ϕ ≤ 1 , the value ϕ = 0 for dry air, and the value ϕ = 1 for saturated
moist air.
974 HVAC&R RESEARCH

With the partial pressure of water vapor p w = ψ w p and the saturation partial pressure of
water p s = ψ w, s p , according Equation 29 one obtains

pw
ϕ = ------ . (44)
ps

This equation is valid for p w ≤ p s .

Using the previous equations the following equation is obtained:

ϕp s
W = ε ---------------------- (45)
( p – ϕp s )

with ε as quotient of the molar masses of water and dry air, Equation 14, and ps calculated using
Equation 29.
Saturation State. The saturation state of moist air is characterized by

p w = p s ( p, T ) according to Equation 29,

ψ w = ψ w, s according to Equation 32,

ϕ = 1,

and therefore by

ψ w, s
W s = ε ------------------------- (46)
( 1 – ψ w, s )

where ψ w, s is the mole fraction of water vapor in saturated moist air, and ε is given in Equation 14.
Molar and Air-Specific Volume. The molar volume ( v ) (or molar density ρ = 1 ⁄ v ) for
moist air can be calculated iteratively for given pressure p, given temperature T, and mole frac-
tion of water vapor ψ w using the expression

Bm Cm
p ( T,v,ψ w ) = ------- ⎛⎝ 1 + ------- + ------2-⎞⎠ ,
RT
(47)
v v v

where R is the universal molar gas constant given in Table 5, and Bm and Cm are the second
and third molar virial coefficients of the mixture given by Equations 10 and 11. The mole
fraction of water vapor ψ w can be calculated from given humidity ratio W using Equation 41.
Herrmann et al. (2008) comprises a detailed description of the algorithm.
In the case of ψ w = 0 , the molar volume of dry air is obtained from Equation 47. (The
molar volume for dry air obtained from Equation 47 differs from that of the fundamental
Lemmon et al. (2000) equation, Equation 1, because only the second and the third virial coef-
ficients are used.)
The air-specific volume (v) or specific density ( ρ ) can be obtained using the iteratively calcu-
lated molar volume ( v ) as follows:

( 1 + W )v (1 + W)
v = ---------------------- and ρ = ------------------- (48)
M v
VOLUME 15, NUMBER 5, SEPTEMBER 2009 975

where M is the molar mass of the mixture calculated using Equation 42, and W is the humidity
ratio, Equation 40.
Molar and Air-Specific Enthalpy. The molar enthalpy ( h ) for moist air is calculated using
the ideal-gas parts of dry air and water vapor and the real-gas correction from the virial equation
for moist air. Equation 49 can be used for this calculation:

h ( T, v, ψ w ) = h 0 + ( 1 – ψ w )h ao + ψ w h wo
(49)
dB m 1 T dC m 1
+ RT ⎛⎝ B m – T ----------⎞⎠ --- + ⎛⎝ C m – --- ----------⎞⎠ ----2-
dT v 2 dT v

where ψ w is the mole fraction of water vapor, h ao is the ideal-gas molar enthalpy of dry air and
h wo is the ideal-gas molar enthalpy of water vapor—both described below, v is the molar vol-
ume of the mixture moist air calculated iteratively using Equation 47, Bm and Cm are calculated
using Equations 10 and 11, dBm/dT and dCm/dT are calculated using Equations 12 and 13, and
R is the universal molar gas constant given in Table 5. The mole fraction of water vapor ( ψ w )
can be calculated from given humidity ratio W using Equation 41. Herrmann et al. (2008) com-
prises a detailed description of the algorithm. The value of h 0 results from the adjustment of the
molar enthalpy to zero at p0 and T0, given in Table 5. The value is h o = 2.924425468 kJ/kmol.
Using the fundamental Lemmon et al. (2000) equation, the molar ideal-gas enthalpy for dry
air is calculated as follows:

∂α o
h ao = h 0Lem + R Lem T 1 + τ ⎛ ---------⎞ (50)
⎝ ∂τ ⎠ δ

where R Lem is the universal molar gas constant used by Lemmon et al. (and given in Table 1),
τ is the reciprocal reduced temperature, and δ is the reduced density. The derivative
( ∂α o ⁄ ∂τ ) δ is determined using the ideal-gas part of the reduced fundamental Lemmon et al.
equation, Equation 1, and described in detail in Herrmann et al. (2008). The value
h 0Lem = – 7914.149298 kJ/kmol results from shifting the reference state to T0 = 273.15 K used for
moist air.
The IAPWS-IF97 (IAPWS 2007) formulation is used to calculate the molar ideal-gas
enthalpy for water vapor at temperatures T ≥ 273.15 K :

∂γ 2o
h wo = h 097 + R 97 Tτ ⎛ --------⎞ (51)
⎝ ∂τ ⎠ π

where R 97 is the molar gas constant of IAPWS-IF97, given in Table 3, π is the reduced pres-
sure, and τ is the reciprocal reduced temperature. The derivative ( ∂γ 2o ⁄ ∂τ ) π is determined using
the ideal-gas part of the reduced fundamental equation of IAPWS-IF97, Equation 4, and is
described in detail in Herrmann et al. (2008). The value h 097 = – 0.01102142797 kJ/kmol results
from shifting the reference state.
The IAPWS-95 (IAPWS 1995) formulation is used to calculate the molar ideal-gas enthalpy
for water vapor at temperatures T ≤ 273.15 K as follows:

∂α o
h wo = h 095 + R 95 T 1 + τ ⎛⎝ ---------⎞⎠ (52)
∂τ δ
976 HVAC&R RESEARCH

where R 95 is the molar gas constant of IAPWS-95, given in Table 2, τ is the reciprocal reduced
temperature, and δ is the reduced density. The derivative ( ∂γ 2o ⁄ ∂τ ) π is determined using the
ideal-gas part of the reduced fundamental equation of IAPWS-95, Equation 2, and described in
detail in the report of Herrmann et al. (2008). The value h 095 = – 0.01102303806 kJ/kmol results
from shifting the reference state.
The air-specific enthalpy (h) can be obtained using the molar enthalpy ( h ) calculated using
Equation 49 via h = h ( 1 + W ) ⁄ M , where M is the molar mass of the mixture calculated using
Equation 42, and W is the humidity ratio, Equation 40.
Molar and Air-Specific Entropy. The molar entropy s for moist air is calculated using the
ideal-gas parts of dry air and water vapor and the real-gas correction from the virial equation for
moist air. The equation reads

s ( T, v,ψ w ) = s 0 + ( 1 – ψ w )s ao + ψ w s wo

⎛ B + T dB dC m⎞ 1 (53)
---------m-⎞ 1--- + ⎛ C m + T ---------- --------
–R ⎝ m dT ⎠ v ⎝ dT ⎠ 2v 2
+ ( 1 – ψ w ) ln ( 1 – ψ w ) + ψ w ln ( ψ w )

where ψ w is the mole fraction of water vapor, s ao is the ideal-gas molar entropy of dry air s wo is
the ideal-gas molar entropy of water vapor—both described below, v is the molar volume of
moist air calculated iteratively using Equation 47, Bm and Cm are calculated using Equations 10
and 11, dBm/dT and dCm/dT are calculated using Equations 12 and 13, and R is the universal
molar gas constant, given in Table 5. The mole fraction of water vapor ( ψ w ) can be calculated
from given humidity ratio W using Equation 41. Herrmann et al. (2008) comprises a detailed
description of the algorithm. The value of s 0 results from the adjustment of the molar entropy to
zero at p0 and T0, given in Table 5. The value is s 0 = 0.02366427495 kJ/(kmol ⋅ K).
Using the fundamental Lemmon et al. (2000) equation, the molar ideal-gas entropy for dry air
is calculated as follows:

∂α o ⎛ v a⎞
s ao = s 0Lem + R Lem τ ⎛ ---------⎞ – α o + R Lem ln ⎜ ----o-⎟ (54)
⎝ ∂τ ⎠ δ ⎝v ⎠ a

where R Lem is the universal molar gas constant used by Lemmon et al., given in Table 1, τ is
the reciprocal reduced temperature, δ is the reduced density, α o is the ideal-gas part of the
reduced fundamental Lemmon et al. equation, Equation 1, and ( ∂α o ⁄ ∂τ ) δ is its derivative,
described in detail in Herrmann et al. (2008). The molar volume of dry air ( v a ) is calculated iter-
atively for given total pressure p and temperature T from the following equation:

R Lem T ⎛ B aa C aaa⎞
p = ---------------- ⎜ 1 + -------- + -----------⎟ (55)
va ⎝ va v a2 ⎠

where Baa and Caaa are the second and third molar virial coefficients of dry air calculated using
Equations 15 and 17. The ideal-gas molar volume of dry air v ao results from v ao = R Lem T 0 ⁄ p 0 ,
where p0 and T0 are the values at the reference state given in Table 5. The value
s 0Lem = – 196.1375815 kJ /(kmol ⋅ K) results from shifting the reference state used for moist air.
VOLUME 15, NUMBER 5, SEPTEMBER 2009 977

The IAPWS-IF97 (IAPWS 2007) formulation is used to calculate the molar ideal-gas entropy
for water vapor at temperatures T ≥ 273.15 K :

∂γ 2o
s wo = R 97 τ ⎛⎝ --------⎞⎠ – γ 2o (56)
∂τ π

where R 97 is the molar gas constant of IAPWS-IF97 given in Table 3, π is the reduced pres-
sure, τ is the reciprocal reduced temperature, γ 2o is the ideal-gas part of the reduced fundamen-
tal equation of IAPWS-IF97, Equation 4, and ( ∂γ 2o ⁄ ∂τ ) π is its derivative, described in detail in
Herrmann et al. (2008).
The IAPWS-95 (IAPWS 1995) formulation is used to calculate the molar ideal-gas entropy
for water vapor at temperatures T ≤ 273.15 K as follows:

∂α o
s wo = R 95 τ ⎛⎝ ---------⎞⎠ – α o , (57)
∂τ δ

where R 95 is the molar gas constant of IAPWS-95, given in Table 2, α o is the ideal-gas part of
the reduced fundamental equation of IAPWS-95, Equation 2, ( ∂α o ⁄ ∂τ ) π is its derivative, and τ
is the reciprocal reduced temperature. The reduced density δ = ρwo ⁄ ρ c is calculated using
95
ρ wo = p 0 ⁄ ( R T ) with p0, given in Table 5, and ρ c = ρ c ⁄ M 95 with ρ c and M95, given in Table 2.
Herrmann et al. (2008) comprises a detailed description of the algorithm.
The air-specific entropy s can be obtained from the molar entropy s calculated from Equa-
tion 53 using s = s ( 1 + W ) ⁄ M .
Compressibility Factor. The compressibility factor Z = pv ⁄ R T for moist air results from
the following equation:

Bm Cm
Z ( T, v,ψ w ) = 1 + ------- + ------2- (58)
v v

where ψ w is the mole fraction of water vapor, v is the molar volume of moist air calculated iter-
atively from Equation 47, Bm and Cm are the second and third molar virial coefficients of the
mixture, given by Equations 10 and 11. The mole fraction of water vapor ( ψ w ) can be calculated
from given humidity ratio W using Equation 41. Herrmann et al. (2008) comprises a detailed
description of the algorithm.
Dew-Point Temperature and Frost-Point Temperature. The dew-point temperature
( T ≥ 273.15 K ) or the frost-point temperature ( T ≤ 273.15 K ) is calculated iteratively using the
following equation:

p w = f ( p, T d )p w, s ( T d ) (59)

where f(p,Td) is the vapor-pressure enhancement factor calculated using Equation 33 for given
total pressure p and dew-point or frost-point temperature Td. The quantity pw,s is the saturation
pressure of pure water, calculated for T = Td using Equation 30 or Equation 31, respectively. In
Equation 59, the partial pressure of water vapor in moist air (pw) is calculated for total pressure
p and humidity ratio W or the mole fraction of water vapor ( ψ w ) using the following equation:

W
p w = ψ w p = -------------- p , (60)
ε+W
978 HVAC&R RESEARCH

where ε is the quotient of the molar masses of dry air and water, Equation 14. Herrmann et al.
(2008) comprises a detailed description of the algorithm.
For calculating dew-point or frost-point temperature Td for given total pressure p and given
humidity ratio W or given mole fraction of water vapor ψ w , Equations 59 and 60 in connection
with Equations 33, 30, or 31 have to be solved iteratively. The iterative calculation is also
required, when determining humidity ratio W or mole fraction of water vapor ψ w for given total
pressure p and given dew-point temperature or frost-point temperature Td.
Wet-Bulb Temperature and Ice-Bulb Temperature. The wet-bulb temperature
( T ≥ 273.15 K ) or ice-bulb temperature ( T ≤ 273.15 K ) is calculated using the following equation:

h ( p, T, W ) = h wb, s ( p, T wb, W wb, s ) + ( W – W wb, s )h w ( p, T wb ) (61)

where h is the air-specific enthalpy of unsaturated moist air at total pressure p, dry-bulb temper-
ature T, and humidity ratio W. The quantity hwb,s is the air-specific enthalpy of saturated moist
air at wet-bulb or ice-bulb temperature Twb, and hw is the specific enthalpy of liquid water or ice
at wet-bulb or ice-bulb temperature. The humidity ratio (Wwb,s) of saturated moist air at
wet-bulb temperature can be calculated using the following equation:

p wb, s
W wb, s = ε --------------------------- (62)
( p – p wb, s )

with

p wb, s = f wb p wb, w, s (63)

where ε is the quotient of the molar masses of dry air and water, Equation 14, fwb(p,Twb) is the
vapor-pressure enhancement factor calculated using Equation 33 for given total pressure p and
temperature Twb, and pwb,w,s is the saturation pressure of pure water, calculated for T = Twb
using Equation 30 or Equation 31, respectively. Herrmann et al. (2008) comprises a detailed
description of the algorithm.
For calculating wet-bulb or ice-bulb temperature Twb for given total pressure p, dry-bulb tem-
perature T, and humidity ratio W, Equation 61 in connection with Equations 62, 63, 33, 30, or 31
have to be solved iteratively. This is also true when calculating humidity ratio W of dry-bulb state
for given total pressure p, dry-bulb temperature T, and wet-bulb or ice-bulb temperature Twb.

COMPARISON OF THE NEW ALGORITHM WITH EXPERIMENTAL DATA

This section contains comparisons that were carried out between experimental data for the
partial pressure of water vapor of saturated moist air available in the literature (not from this
paper) to values calculated from the algorithm developed in this work (abbreviated as HKG) for
the thermodynamic properties of moist air. In addition, models developed by Hyland and Wex-
ler (1983a, 1983b), Rabinovich and Beketov (1995), and Yan et al. (Ji et al. 2003a; Ji and Yan
2003b; Ji and Yan 2006) are included in these comparisons.
In Figure 3, the deviations of values calculated using the above-mentioned models, except the
model of Yan (YAN), in comparison with the experimental data from Pollitzer and Strebel (1924)
at 323 K as well as from Webster (1950) at 273 K and 288 K are plotted over total pressure. The
deviation of the new algorithm (HKG) is smaller than that of the Hyland and Wexler model (HW).
The deviations of the values obtained from the Rabinovich and Beketov model (RB) compared
with the experimental data are similar to that of the HKG model, except at 273 K.
VOLUME 15, NUMBER 5, SEPTEMBER 2009 979

Figure 3. Deviations of values for the saturation partial pressure of water calculated
using different models compared with experimental data provided by Pollitzer and
Strebel (1924) at 323 K and Webster (1950) at 273 and 288 K plotted over total pressure.
Considered models: HKG—this work, HW—Hyland and Wexler (1983a, 1983b), and
RB—Rabinovich and Beketov (1995).

Figure 4 shows deviations of values calculated using the considered models compared with
experimental data from Hyland and Wexler (1973) at 303 K, 313 K, and 323 K, as well as from
Hyland (1975), at 343 K, plotted over total pressure. It is obvious that the new model agrees
with the experimental data for pressures below 6 MPa. Above this pressure, the values for the
saturation partial pressure of water calculated using the new model and using the model by
Hyland and Wexler are greater than the experimental data, while the Rabinovich and Beketov
and Yan (YAN) models do not follow this trend.
Figure 5 illustrates the deviations of values calculated using the models included in these
comparisons to experimental data from Wylie and Fisher (1996) at 293 K, 323 K, and 348 K
plotted over total pressure. All models show good agreement with the experimental data. Again,
at high pressures the model presented in this work calculates values for the partial pressures,
which are greater than the experimental data. The largest deviation shows Rabinovich and Beke-
tov’s model at 293 K and 348 K.

COMPARISON OF THE NEW ALGORITHM WITH OTHER MODELS

Figure 6 shows deviations of values for the density of moist air calculated from different
models compared with density values calculated from the model presented in this work. The
deviations were plotted for several total pressures from 0.1 to 10 MPa over mole fractions from
0 to 0.5 mol/mol. The models and algorithms listed in Table 6 are considered in the compari-
sons. The zero lines in the diagrams of Figure 6 represent the model proposed in this work.
As can be seen, the YAN model is not able to describe the density of dry air ( ψ w = 0 ) accu-
rately. At ambient pressure, no model differs more than –0.03% from the model presented in this
980 HVAC&R RESEARCH

Figure 4. Deviations of values for the saturation partial pressure of water calculated
using different models compared with experimental data provided by Hyland and Wexler
(1973) at 303 K, 313 K, and 323 K and Hyland (1975) at 343 K plotted over total pressure.
Considered models: HKG—this work, HW—Hyland and Wexler (1983a, 1983b), RB—
Rabinovich and Beketov (1995), and YAN—Yan (Ji et al. 2003a; Ji and Yan 2003b; Ji and
Yan 2006).

Figure 5. Deviations of values for the saturation partial pressure of water calculated using
different models compared with experimental data provided by Wylie and Fisher (1996) at
293 K, 323 K, and 348 K plotted over total pressure. Considered models: HKG—this
work, HW—Hyland and Wexler (1983a, 1983b), RB—Rabinovich and Beketov (1995),
and YAN—Yan (Ji et al. 2003a; Ji and Yan 2003b; Ji and Yan 2006).
VOLUME 15, NUMBER 5, SEPTEMBER 2009 981

Figure 6. Deviations of values for the density of moist air calculated using different mod-
els compared with values calculated using the model presented in this work for several
total pressures plotted over mole fraction. Considered models: Zero line—this work, –––
Hyland and Wexler (1983a, 1983b), •••••• Rabinovich and Beketov (1995), ----- Yan (Ji et al.
2003a; Ji and Yan 2003b; Ji and Yan 2006), – • – • – Kretzschmar et al. (2005), – •• – •• –
Herrmann et al. (2009).
982 HVAC&R RESEARCH

work. The new model shows only small deviations compared with the HW model, because both
models are based on the virial approach. The YAN and RB models show different behaviors
compared to the new model, especially at higher pressures. While YAN deviates up to 1.2% at
10 MPa and ψ w = 0 , the RB model deviates up to –2.1% at 10 MPa and ψ w = 0 . With increas-
ing pressure, the deviations of the ideal-mixture models HuAir and SKU to the new model
increase up to –1% at ψ w = 0 . The model for calculating thermodynamic properties of moist air
proposed in this work shows reasonable behavior when compared to other models.
In addition, ASHRAE RP-1485 (Herrmann et al. 2008) comprises detailed results for compar-
isons of the developed algorithm with the model of Hyland and Wexler model (1983a, 1983b)
for the thermodynamic properties enthalpy, entropy, dew-point temperature, and wet-bulb tem-
perature of moist air.

THE MODEL’S RANGE OF VALIDITY

Table 7 shows the model’s range of validity for the thermodynamic properties of moist air
described in this section.

Table 6. Models and Algorithms for Calculating Thermodynamic Properties of Moist Air
Used in the Comparisons Carried Out in This Work
Abbr. Model References
HW Virial equation for the mixture Hyland and Wexler (1983a, 1983b)
RB Virial equation for the mixture Rabinovich and Beketov (1995)
Modified Redlich-Kwong equation of state Yan (Ji et al. 2003a; Ji and Yan 2003b;
YAN
for the mixture Ji and Yan 2006)
Ideal mixture of the real fluids, dry air, and
HuAir water and Nelson-Sauer model for the satura- Kretzschmar et al. (2005)
tion state
Modified ideal mixture of the real fluids, dry
SKU air, and water and Nelson-Sauer model Herrmann et al. (2009)
for the saturation state

Table 7. Range of Validity of the Presented Model

Property Range of Validity

Pressure 0.00001 ≤ p ≤ 10 MPa

Temperature –143.15 ≤ t ≤ 350 °C
Humidity ratio 0 ≤ W ≤ 10 kgw/kga
Mole fraction
0 ≤ ψw ≤ 0.94145 kmolw/kmol
of water vapor
(decimal
Relative humidity 0 ≤ ϕ ≤ 1
ratio)
Dew-point temperature –143.15 ≤ t ≤ 350 °C
Wet-bulb temperature –143.15 ≤ t ≤ 350 °C
VOLUME 15, NUMBER 5, SEPTEMBER 2009 983

UNCERTAINTY OF THE MODEL

The model presented in this work utilizes improved correlations for the properties of dry air
and water applied to the basic underlying virial model of Hyland and Wexler (1973, 1983a,
1983b). By using improved correlations, the uncertainties of the new model are slightly less than
the Hyland and Wexler model uncertainties.
The accuracy of the presented model is greater than that of Nelson and Sauer (2002) because
the fitted polynomials for the ideal-gas parts of heat capacity, enthalpy, and entropy for dry air
have been replaced by the fundamental equation of Lemmon et al. (2000). Instead of the fitted
polynomials for virial coefficients for dry air and steam of Nelson and Sauer, the fundamental
equations of Lemmon et al. and of IAPWS-95 (IAPWS 1995) are used in the ASHRAE RP-1485
model. In addition, the equation for the second Nelson and Sauer cross-virial coefficient (Baw)
has been replaced with the more accurate Harvey and Huang equation (2007). Furthermore, the
fitted polynomials for the isothermal compressibility of liquid water and for Henry’s constant in
the calculation of the enhancement factor have been replaced by the IAPWS-IF97 (IAPWS 2007)
and the IAPWS Guideline 2004 (IAPWS 2004) equations. Finally, the current values for the uni-
versal molar gas constant and the molar masses for dry air and water are used in this work.
The uncertainties of selected properties calculated using the presented model are listed in
Table 8.
For moist air with a higher humidity ratio than 0.1 kgw/kga uncertainties cannot be given
because no experimental data are available.

TABLES OF PROPERTY VALUES CALCULATED USING THE MODEL

Tables including the following thermodynamic properties calculated using the algorithms of
this paper are available at www.thermodynamics-zittau.de and in “Publications”:

• Saturation properties Ws, vs, hs, and ss of moist air for temperatures from –60°C to 90°C at
atmospheric pressure (0.101325 MPa)
• Properties twb, v, h, and s of moist air for humidity ratio W from 0 to 1 kgw/kga at 200°C and
320°C for pressures 0.101325, 1, 2, 5, and 10 MPa.

SUMMARY AND CONCLUSION

This research updates the modeling of moist air as a real gas using the virial equation of state.
All of the latest IAPWS standards and NIST publications for dry air, steam, water, ice, and cal-
culating virial coefficients for moist air were used. Therefore, the accuracy of the new model is
improved compared to the Hyland-Wexler (1973, 1983a, 1983b) and Nelson-Sauer (2002) mod-
els. The range of validity of the new model is in pressure from 0.01 kPa up to 10 MPa, in tem-
perature from 130 K up to 623.15 K, and in humidity ratio from 0 up to 10 kgw/kga.
Tables containing values for thermodynamic properties calculated using the algorithm of this
paper are available at www.thermodynamics-zittau.de under the “Publications” tab.
The new model was used to produce moist air and H2O saturation property tables for the psy-
chrometric chapter in the 2009 ASHRAE Handbook—Fundamentals (ASHRAE 2009), which is

Table 8. Uncertainty of the Presented Model

Property Uncertainty
Density 0.1% (dry air) ≤ Δρ ⁄ ρ ≤ 0.3% (moist air with W = 0.1 kgw/kga)
Isobaric heat capacity 1.0% (dry air) ≤ Δc p ⁄ c p ≤ 3.0% (moist air with W = 0.1 kgw/kga)
Enthalpy 2 kJ/kg (dry air) ≤ Δh ≤ 3 kJ/kg (moist air with W = 0.1 kgw/kga)
984 HVAC&R RESEARCH

the first update of these tables since 1985. This new moist air table is close to the 1985 table,
because moist air at ambient pressure behaves essentially as an ideal gas; also the underlying
data used by Hyland and Wexler was quite accurate. Greater deviations to the former models
occur at higher pressures and temperatures.
The following subjects are of interest for further investigations. The third cross-virial coeffi-
cients for air-water interactions can be improved. The GERG-2004 equation (Kunz et al. 2007)
should be considered in the development of new algorithms for the thermodynamic properties of
moist air.
The algorithms for calculating thermodynamic properties of moist air proposed in this paper
are implemented in the property library LibHuAirProp, which can be requested from the authors
(see www.thermodynamics-zittau.de).

ACKNOWLEDGMENTS
The authors would like to thank ASHRAE, the sponsor of RP-1485, and ASHRAE Technical
Committee 1.1, which approved the project. Particular acknowledgment should also be given to
the members of the project monitoring subcommittee: R.M. Nelson (Chairman), R. Crawford,
A. Jacobi, T.H. Kuehn, and V.W. Peppers.

NOMENCLATURE
a = specific Helmholtz energy v = specific volume, air-specific volume
B = second molar virial coefficient W = humidity ratio
C = third molar virial coefficient Z = compressibility factor (real gas factor)
cp = isobaric heat capacity α = reduced Helmholtz energy
f = vapor-pressure enhancement factor βH = Henry’s law constant
g = specific Gibbs energy γ = reduced Gibbs energy
h = specific enthalpy, air-specific enthalpy δ = reduced density
ε = ratio of the molar mass of water and
m = mass
dry air
M = molar mass, molar mass of the mixture θ = reduced temperature
p = pressure κT = isothermal compressibility
R = specific gas constant π = reduced pressure
R = universal molar gas constant ρ = mass density
s = specific entropy, air-specific entropy τ = reciprocal reduced temperature
t = Celsius temperature ϕ = relative humidity
T = Kelvin temperature ψ = mole fraction

Superscripts
Lem = value taken from Lemmon et al. (2000) 06 = value taken from
o = ideal-gas part the IAPWS-06 (IPAPWS 2006) formu-
r = residual part lation for ice
95 = value taken from 08 = value taken from
the scientific formulation IAPWS-95 the IAPWS-08 (IAPWS 2008)
(IAPWS 1995) formulation for ordinary water
97 = value taken from substance
the industrial formulation IAPWS-IF97 ¯ = molar property
(IAPWS 2007) * = reducing quantity

Subscripts
a = dry air m = mixture property
c = critical s = saturation state
d = dew point sub = sublimation state
j = maxcondentherm t = triple point
VOLUME 15, NUMBER 5, SEPTEMBER 2009 985

w = water (water vapor, liquid water, or 0 = reference state

ice) 1, 2 = regions of IAPWS-IF97
wb = wet-bulb (IAPWS 2007)

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