HSC Chemistry® 5.

0 25 - 1

Peter Björklund June 28, 2002 02103-ORC-T

25. WATER

Figure 1: Pressure-Temperature calculator for water.

The Pressure and Temperature calculator enables a complete thermodynamic description

for a species, by allowing the user to specify not only the temperature, but also the pressure
(partial). This calculator is currently only available for water, since the properties of steam
in particular, deviate significantly from those of the ideal gas, i.e. the heat capacity is
purely a temperature-dependent function. In letting the user specify water/steam pressure,
cases where pressure is of extreme importance can easily be calculated.

This calculator is a very useful replacement for steam table books and Mollier diagrams.
By directly typing the pressure and temperature of the process points, or by simply
clicking on the diagram, the process enthalpy and entropy are calculated along with several
other useful thermodynamic data. The module is also available through the Heat and
Material Balances module (Chapter 11. Heat and Material Balance), where the pressure
correction may be inserted into the worksheet as a cell formula.
 HSC Chemistry® 5.0 25 - 2

Peter Björklund June 28, 2002 02103-ORC-T

25.1 Basic Calculation Procedure
The calculator lets the user specify two process points; point 1 being the starting point and
point 2 the end point. The calculator then calculates the absolute values for the two points
and then the difference between them. The absolute values are mostly useful for density
and heat capacity data, whereas the difference or delta values are useful for enthalpy and
entropy data. A line between the two points may be drawn by selecting Show/Line from the
menu. However, this line does not necessarily represent the actual process path, instead it
makes the visualization of the two points easier. There are two basic ways, which may also
be combined, of specifying the process points:
Specifying points using the mouse:
1. Specify the appropriate units from the comboboxes and the amount (kmol or kg) in the
textbox.
2. Activate one of the points by clicking on the appropriate box in the diagram. A yellow
box indicates the active point and a white box the inactive point.
3. Click on a position in the diagram and the selected point will move to that position and
the data will automatically be recalculated. Note that if a saturated state is selected, the
point will jump to the appropriate saturated curve if possible. It is also possible to use
the drag-and-drop technique to move the selected point.
4. Repeat steps 2 and 3 for the other point.
5. If a point is on a saturated curve, the user may specify the Mixture %, i.e. the percentage
of the first of the two phases in the mixture shown in the combobox on row 3 of the
worksheet. The default value is 50 %.
Specifying points manually:
1. Specify the appropriate units from the comboboxes and the amount (kmol or kg) in the
textbox.
2. Specify pressures and temperatures for the two points by simply typing them into the
cells on columns 1 and 2. Note that if a saturated state is selected, the temperature or
pressure will automatically be calculated. The values that are automatically calculated
are indicated in a black font.
3. If a point is on a saturated curve, the user has to specify the Mixture %, i.e. the
percentage of the first of the two phases in the mixture given in the combobox on row 3.
The default value is 50 %.
4. If a point is on a saturated curve, the user may specify the Mixture %, i.e. the percentage
of the first of the two phases in the mixture shown in the combobox on row 3 of the
worksheet. The default value is 50 %.
Explanation of the p,T-diagram:
The p,T-diagram to the right of the window contains a few labels. These are explained in
the following points:
1. Triple Point
The triple point refers to the point where all three phases of water may exist
simultaneously. This point is at T = 0.01 °C and p = 0.0061 bar. Most steam tables use
this as the reference point, i.e. the absolute enthalpy and absolute entropy are set to zero.
By selecting Edit/Point 2 = Triple Point from the menu, the second process point will
automatically be set to the triple point, which is also the default setting. This means that
 HSC Chemistry® 5.0 25 - 3

Peter Björklund June 28, 2002 02103-ORC-T

the enthalpy and entropy differences will have the same values as those found in most
steam tables if the phase is set to liquid at the triple point.
2. Critical Point
When the temperature rises above the critical point, it is no longer possible to clearly
distinguish between the liquid and the gaseous phase. Such a condition is referred to as
supercritical. The critical point for water is at T = 373.946 °C and p = 220.64 bar. It is
important to know that above this point the program still specifies the phase of the
point, although there are no longer any actual phase transitions between the phases.
3. Saturated Curves
There are three saturated curves in the diagram. These are gas/liquid, gas/solid and
liquid/solid. A point located on any one of these curves indicates that the two phases are
in equilibrium. The three curves join at the triple point, which is where all three phases
can exist simultaneously. The user may force a point onto the saturated curve by
selecting either Sat. (g,l), Sat. (g,s) or Sat. (l,s) from one of the phase comboboxes on
row 3.
4. Solid Ice
A stability area consisting of several solid ice phases, with different crystal structures,
of which some are shown on the diagram. Data is not, however, available for
the high pressure solid phases.
Calculation worksheet:
The calculation worksheet is to the left of the window. The first four rows are input rows
and the last six rows show the results. The input rows are explained in the following points:
1. Temperature
The temperature unit may be either in °C or in K, depending on the temperature unit
combobox. The temperature is automatically calculatad when the Sat. (l,s) state is
selected.
2. Pressure
The pressure unit may be either in bar or in MPa, depending on the pressure unit
combobox. The pressure is automatically calculatad when the Sat. (g,l) or the Sat. (g,s)
state is selected.
3. Phase
There are three different pure phases available for water: Solid (s), Liquid (l) and Gas
(g). These three phases may be combined on the saturated curves and they are specified
as: Sat. (g,l), Sat. (g,s) and Sat. (l,s). At the triple point a mixture of all of these is
possible, however, only a mixture of two is possible in this module. When a pure phase
is selected, the actual phase is automatically selected according to the user input
(manually or with the mouse). When a saturated state is selected, the temperature or
pressure is automatically calculated, which is then indicated in a black font. For the
gas/liquid and gas/solid mixtures the pressure is automatically calculated and for the
liquid/solid mixture the temperature is automatically calculated. Note that when moving
outside the limits of the saturation curve, the phase will automatically change into the
corresponding pure phase of the specified point.

4. Mixture %
 HSC Chemistry® 5.0 25 - 4

Peter Björklund June 28, 2002 02103-ORC-T

It is possible here to enter the mixture percentage of the saturated state. This is the same
as the dryness percentage of steam when the point is on the saturated gas/liquid curve.
The percentage always refers to the amount of the first phase in the total mixture, e.g.
the gas percentage in a gas/liquid mixture. This is set to 50 % by default and only
visible when a saturated state is specified.

The results of the calculation are shown in the same table below the input. The data
calculated includes:
1. Enthalpy (H) and Entropy (S)
The enthalpies and entropies for the two process points are calculated using the
reference point T = 25 °C and p = 1 bar. This differs from what is normally found in
steam tables, where the reference point is T = 0.01 °C and p = 0.0061 bar (triple point
for water). This means that only the differences in enthalpy and entropy are of
importance, since they are independent of the choice of reference points. Point 2 is
therefore by default set to the triple point, which means that the enthalpy and entropy
differences, indicated by a yellow background, give the values normally found in steam
tables.
2. Specific Enthalpy (H specific)
The specific enthalpies are the enthalpies when the phase transformations are ignored.
In other words the enthalpy released/gained when water is cooled/heated to 25 °C at
constant pressure. Therefore the specific enthalpy is zero at 25 °C.
3. Gibbs Energy (G)
These cells show the Gibbs Energy for the two points.
4. Heat Capacity (Cp)
These cells show the specific heat capacity at constant pressure for the two points.
5. Density
These cells give the densities for the two points. The densities are interpolated or
extrapolated from the Excel file [Link] located in the .\HSC5\PTCalc directory.
Please do not modify this file.
Other important terms:
1. Isentropic process
If the entropy is constant through a process, i.e. the entropy difference is zero, the
process is called isentropic. An isentropic process is an ideal process and real processes
are often compared to the corresponding isentropic process.
2. Isentropic efficiency
An isentropic process generates no entropy and may therefore be considered an ideal
process. It is useful to compare real processes to that of the isentropic through the
isentropic efficiency. The isentropic efficiency for a compressor or pump is defined as
h s
 s ,c  , [1]
h

where h is the real enthalpy difference and hs is the isentropic enthalpy difference.
The isentropic efficiency for a turbine is defined as
 HSC Chemistry® 5.0 25 - 5

Peter Björklund June 28, 2002 02103-ORC-T

h
 s ,t  . [2]
hs

An isentropic process is always adiabatic, however, an adiabatic process is not

necessarily isentropic.

25.2 Calculation examples

25.2.1 Ice melting at high pressure

Figure 2: Melting of ice at a pressure of 500 bar.

The example in Figure 2 shows the enthalpy and entropy change of 1 kg solid ice melting
at a constant pressure of 500 bar, until 90 % of the total mixture is liquid water. The
enthalpy difference is ~290 kJ and the process therefore endothermic. The entropy
difference is ~1.079 kJ/°C and the process therefore generates entropy.
The melting point of ice at 500 bar is automatically calculated, since the point is on the
saturated liquid/solid curve, and it is roughly –4.5 °C. This pressure is achieved, for
example, when pressing a sharp object against an icy surface, which then melts due to the
decreased melting point temperature.

25.2.2 Evaporation process in a heat recovery boiler

 HSC Chemistry® 5.0 25 - 6

Peter Björklund June 28, 2002 02103-ORC-T

Figure 3: Evaporation process.

The example in Figure 3 shows the evaporation process in a heat recovery boiler, when the
mass flow is 500 t/h (Amount: 500000 kg, Unit: MWh). The temperature is 285 °C and the
pressures are automatically calculated, since the saturated gas/liquid state is selected. The
transferred heat is ~21 MW, when 10 % of the total water flow evaporates. This is
equivalent to a water/steam ratio of 90%/10% = 9. The entropy generation of ~0.038
MW/°C indicates that the process is not isentropic.
 HSC Chemistry® 5.0 25 - 7

Peter Björklund June 28, 2002 02103-ORC-T

25.2.3 Steam turbine process

Figure 4: Steam turbine process.

A simple steam turbine process is shown in Figure 4. The calculation shows that the net
enthalpy for a mass flow of 10 kg/s is –10633 kW and thus exothermic, i.e. the enthalpy is
released in the form of work on the shaft. The entropy generation is 7.5 kW/°C and the
process is therefore not isentropic. By decreasing the Mixture % (in this case ~81.7 %) the
process may be compared with the ideal isentropic process for which there is no entropy
generation. The enthalpy released in the isentropic process is –12903 kW and the isentropic
efficiency is therefore, according to equation 2, s,t = -10633 kW / -12903 kW  0.82.
 HSC Chemistry® 5.0 25 - 8

Peter Björklund June 28, 2002 02103-ORC-T

25.3 Detailed Description

25.3.1 Pressure correction in the database

The pressure-corrected calculations are based on new pressure-specific species in the

database. They are of the form S(XbarP), where S denotes the species, X the pressure
(partial) in bars and P the phase. The phase is only specified for gaseous species. The only
currently available species is H2O (water), and the pressure-corrected species are found in
the database as H2O(0.01bar), H2O(0.01barg), H2O(100bar), H2O(100barg), etc. Note that
if the phase is not specified, it may be either solid or liquid depending on the temperature.
For supercritical steam, that is for T  373.946 °C, a gaseous phase is used for p < 220.64
bar and a liquid phase for p  220.64 bar, although the two phases are impossible to
separate in reality.

Table 1 shows the pressure-corrected water species currently found in the HSC database.

Pressure [bar] Solid/liquid species (ice/water) Gaseous species (steam)

0.01 H2O(0.01bar) H2O(0.01 barg)
0.05 H2O(0.05bar) H2O(0.05 barg)
0.1 H2O(0.1bar) H2O(0.1 barg)
0.5 H2O(0.5bar) H2O(0.5 barg)
1 H2O(1bar) H2O(1 barg)
5 H2O(5bar) H2O(5 barg)
10 H2O(10bar) H2O(10 barg)
20 H2O(20bar) H2O(20barg)
30 H2O(30bar) H2O(30barg)
40 H2O(40bar) H2O(40barg)
50 H2O(50bar) H2O(50barg)
60 H2O(60bar) H2O(60barg)
70 H2O(70bar) H2O(70barg)
80 H2O(80bar) H2O(80barg)
90 H2O(90bar) H2O(90barg)
100 H2O(100bar) H2O(100barg)
200 H2O(200bar) H2O(200barg)
300 * H2O(300bar) *
400 * H2O(400bar) *
500 * H2O(500bar) *
600 * H2O(600bar) *
700 * H2O(700bar) *
800 * H2O(800bar) *
900 * H2O(900bar) *
1000 * H2O(1000bar) *
* Supercritical pressures

Table 1: Pressure-corrected species currently available in the database.

Since water is in a liquid form at the reference temperature of 25 °C for pressures higher
than 0.032 bar, the Cp functions for steam follow the saturated steam curve below the
boiling point. This means that the pressure is not kept constant below this point and thus
the pressure value in the species name, i.e. X in H2O(Xbarg), is no longer valid for these
temperatures. This may be seen from Figure 5, where the Cp functions of steam at different
pressures are shown. When the temperature drops below the boiling point the Cp functions
follow the saturation curve, where the partial pressure also reduces with the temperature.
This also means that the total enthalpy and entropy curves below the boiling point will not
join as expected and therefore these curves are comparable with each other only for values
 HSC Chemistry® 5.0 25 - 9

Peter Björklund June 28, 2002 02103-ORC-T

above or equal to the boiling point. This is, however, not an issue when studying only one
pressure-corrected species at a time since the enthalpy/entropy differences are then still
valid. Naturally this is never a problem in the Pressure and Temperature calculator, since it
automatically chooses the liquid phase when the temperature drops below the boiling point
for a constant pressure.

For the solid/liquid phases, i.e. H2O(Xbar), this reference point does not cause any
problems, since at least one of the two phases (liquid and/or solid) exist below 25 °C and at
pressure X. They can therefore easily be extrapolated up to 25 °C when necessary.
Extrapolation above the boiling/sublimation points at different pressures are shown as
dotted curves in diagrams, which also means that the liquid/solid phase does not exist at
these temperatures.

Figure 5 also shows that the ideal gas approximation, indicated by the label H2O(g), is
generally more accurate for low pressures and high temperatures. The ideal gas curve can
be seen below the constant pressure curves. The rule of thumb is that the accuracy of the
ideal gas approximation increases the further away you move from the critical point.

Figure 5: Cp functions for steam at different pressures.

 HSC Chemistry® 5.0 25 - 10

Peter Björklund June 28, 2002 02103-ORC-T

25.3.2 Basic theory

In order to calculate the enthalpy and entropy at different pressures, slight modifications
have to be made to the enthalpy of formation and standard entropy at 25 °C, i.e. the H f
-term of equations 1 and 3 in Chapter 8. Introduction. Most steam tables use the triple
point of water (T = 0.01 °C, p = 0.0061 bar), instead of the standard reference point used in
HSC (T = 25 °C, p = 1 bar), therefore the absolute enthalpies and entropies will be
different from those found in steam tables. However, since point 2 is by default set to the
triple point, the enthalpy and entropy differences (cells C5 and C6) are the same as the
absolute values found in steam tables and diagrams. This is achieved by selecting
Edit/Point 2 = Triple Point from the menu and choosing the liquid phase.

The pressure corrected enthalpy at temperature T and pressure p is calculated as

T
H ( T , p )  H 'f ( 298.15 K , p )   Cp T , p  dT   H
298.15 K
tr , [3]

where H’f (298.15K, p) is the modified enthalpy of formation at pressure p and H tr is the
enthalpy of a phase transformation. The entropy at pressure p may be calculated in a
similar manner as

Cp  T , p 
T
H
S ( T , p )  S ( 298.15K , p ) 
'
0  dT   tr , [4]
298.15 K
T Ttr

where S’0 (298.15K, p) is the modified standard entropy at pressure p and H tr is the
enthalpy of a phase transformation at temperature T tr.

The Cp function still utilizes the Kelley equation, but the coefficients are now pressure-
dependent according to

Cp T , p   A p   B p   10 3  C  p   105  T 2  D p   10 6  T 2 , [5]

where A(p), B(p), C(p) and D(p) are the coefficients fitted at different pressures p. See
Table 1 for a list of the current pressures available.

The temperature or pressure of a saturated curve is calculated through either one of the
equations 6-8. The pressure for a saturated gas/liquid mixture is

p( T ) = 0.1 ⋅ exp(
11 .78(
T − 372.79 )(
/ T − 43.15)
), [6]

where T is the temperature in K and p the pressure in MPa. The pressure for a saturated
gas/solid mixture is

p( T ) = 1010.5380997 - 2663.91 / (T + 0.01) / 10000 , [7]

where T is the temperature in K and p the pressure in MPa. The temperature for a saturated
liquid/solid mixture is

T ( p ) = −0.009 p + 273.16 , [8]

 HSC Chemistry® 5.0 25 - 11

Peter Björklund June 28, 2002 02103-ORC-T

where T is the temperature in K and p the pressure in MPa. These equations correspond to
the saturated curves in the p,T-diagram and are utilized in the module whenever a saturated
state is selected.

In order to calculate the influence of pressure on the enthalpy and entropy below the
freezing point, a pressure correction term is used. The correction term is

ΔhT =const = (
1 − T f α v ,ice )
ν ice (
p f − p0 )
,
[9]

where Tf is the temperature at the freezing point, p f is the pressure at the freezing point,
α v ,ice is the coefficient of thermal expansion and ν ice is the specific volume.

25.4 Limitations
- The current pressure range is –200 °C to 2000 °C and 0.001 bar to 1000 bar.
- Accuracy in cp-values and density values decreases close to the critical point.
- Accuracy in saturated liquid/gas pressure decreases close to the critical point.
- Uncertainties in cp-values for ice at different pressures.
- The high temperature and pressure region (800 °C - 2000 °C and 100 bar - 1000 bar) is
extrapolated.
- The low pressure region (0.001 bar - 0.01 bar) is extrapolated.