The Physical Properties of

Hydrothermal Fluids

Module 1

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Contents

1. Introduction ........................................................................................3
2. Temperature, Heat Content and Physical State ..............................4
3. Solutions ............................................................................................6
4. Pressure Gradients, Boiling and Effervescence .............................7
5. Using Steam Tables to Calculate Steam Mass Fraction (X) ...........9
6. Distribution of Gas between Steam and Water .............................10

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1. Introduction

The objective of this section is to review the physical properties of water and other fluids in the
temperature and pressure range that occur in geothermal systems.

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2. Temperature, Heat Content and Physical State

In the SI unit, system temperature is measured with the Celsius (or Centigrade) scale, which has 0 °C
at the freezing point of water at normal atmospheric pressure, and boiling at 100°C. Other scales
which may be used are the Fahrenheit (°F), now little used outside the USA and of no technical
advantage, and the Kelvin (K). In the Kelvin scale the degrees are the same as in the Celsius scale, but
the zero point is approximately 273° lower. The Kelvin scale has advantages when calculating gas
behaviour and is necessary for making thermodynamic calculations, as explained below.

The heat content of an object is a measure of the amount of energy that it contains. It is dependent on
the mass of the object, its physical properties, and the temperature. Heat content is measured in units
of Joules. Heat content per unit mass is called enthalpy and is usually measured in kJ/kg.

One kilogram of a certain material, such as water, will not necessarily have the same heat content as
that of another material, such as rock, at the same temperature, since their physical properties differ.
The amount of heat that can be stored within a material is its specific heat, usually measured in units
of kJ/kg/K. The specific heat of solids is more or less constant over a wide temperature range. The
specific heat of liquids and gases varies with temperature.

If 1 kg of a solid is heated from say 100 K to 200 K, its heat content and hence its enthalpy will
double, provided that its state does not change.

Any material can exist in the states of solid, liquid and vapour (provided that it is chemically stable
through the appropriate temperature and pressure range). For water, these states are commonly
referred to as ice, water and steam. The general term "fluid" can be used for either of the mobile states
(water or steam or a mixture thereof).

For any material, a change of state involves a gain or loss of energy. Thus water at 0°C has a higher
enthalpy than ice does at 0°C, and steam at 100°C has a greater enthalpy than does water at 100°C.
The energy gained in water changing from liquid to vapour is the energy (or latent heat) of
evaporation, or condensation in the other direction.

Energy is conserved in physical processes. This means that if water condenses from steam, there is a
surplus of latent heat released, which must be lost to the surroundings. Boiling in response to a
pressure drop results in a transfer of heat from the liquid phase to a developing steam phase with the
temperature of both declining.

At any temperature there is corresponding pressure at which both water and steam can co-exist, and
vice-versa. These ranges of pressure-temperature combinations are referred to as the saturation
conditions, and are very relevant to geothermal processes. We use steam tables to find out the
physical properties of water and steam at any temperature and pressure: see Appendix 1 and examples
below.

In a closed system containing water, there are several possible combinations of temperature, pressure,
energy and state. If the temperature is below saturation at the prevailing pressure, only water will be
present and the enthalpy will be equivalent to that of liquid water. If it is on saturation, both water and
steam will be present. The enthalpy of each can be read from the steam tables, and the enthalpy of the

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mixture will depend on the relative proportions (by mass) of each which is present. If the temperature
is above saturation, only steam can be present and the fluid is called superheated.

Note that the enthalpy of liquid water is proportional to the temperature, but the enthalpy of saturated
steam remains almost constant over quite a wide temperature range (but the pressure changes, so
steam at a higher temperature can do more work).

The behaviour of solids, liquids and gases in response to changing pressure and temperature is quite
different.

If solids are heated, they will generally expand a little (though a few will contract). They are virtually
incompressible, that is to say they show little change in volume in response to changing pressure.
Liquids exhibit similar behaviour, although quantitatively different.

In contrast, gases exhibit behaviour where volume, pressure and temperature all respond to each other
more or less directly proportionally. The ideal gas law describing this is:

PV = nRT

where: P = pressure
V = volume
n = number of moles of gas present
(i.e.: grams divided by the molecular weight)
R = constant who's value depends on the units used
T = temperature in K

Note the use of K for temperature. This is where the advantage of the Kelvin scale comes in: doubling
the temperature in K will cause the pressure or the volume of a gas also to double, depending on
whether to not it is free to expand.

Real gases show some deviation from ideal behaviour, but over the geothermal temperature range the
theoretical gas law gives a reasonably good approximation except near changes of state.

The loss of energy when gases are allowed to expand is called the Joule-Thomson effect. This is the
basic principle on which refrigerators work. It can sometimes be observed when a cold gas cap is bled
quickly from geothermal wells: the wellhead may acquire a thick coating of ice, and in one example in
the Philippines cooling was sufficient that solid particles of CO2 (dry ice) were discharged.

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3. Solutions

A mixture of one chemical species in another that cannot be physically separated is a solution. Gases
are totally inter-miscible: they will dissolve into each other in all proportions. The ability of a liquid
to dissolve solids, liquids or gases varies very widely. Water will dissolve at least some of many
gases, other liquids and solids. Other solids are effectively insoluble: if mixed with water they will
form suspensions but not dissolve. Two liquids with a limited capacity to dissolve each other, such as
oil and water, are immiscible.

The amount of any substance that will dissolve in water at a particular temperature (and pressure,
when referring to gases) is defined by the saturation solubility. If less than this amount is present, an
under-saturated solution will be formed and more can be dissolved (though not necessarily
instantaneously). If more than this is dissolved the solution is super-saturated, and the excess will
precipitate: though once again, not necessarily rapidly.

The solubility of many substances in water is strongly temperature dependent. Most solids have
prograde solubility with increasing temperature. Thus if a saturated solution is formed at one
temperature, and then allowed to cool, there will be a tendency for the solid to be precipitated. For
example, geothermal fluids become saturated with silica at high temperatures at depth, and then when
brought to the surface and cooled, silica tends to precipitate. Controlling this reaction is a major
constraint on geothermal development since the precipitated silica can clog up pipes and reinjection
wells. In contrast, it is rare to get similar problems with halite (NaCl), because there is usually not
enough available in the reservoir to form a saturated solution as it is much more soluble than silica.

A few important substances, however, have inverse solubility. One of the most important examples in
geothermal systems is calcium sulphate, or anhydrite. If a solution saturated with anhydrite is heated,
some will precipitate.

Most gases have inverse solubility in water. They are more soluble in cold water than in hot water.

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4. Pressure Gradients, Boiling and Effervescence

To understand fluid processes in hydrothermal systems, we need to understand boiling and

effervescence. For any fluid such as water, at any particular temperature, there is a theoretical vapour
pressure. This is the pressure, which will be present above a free water surface in an evacuated
container (Figure 1a). If there is less pressure than this confining the fluid, fluid will evaporate until
equilibrium is reached. In a finite system, where the vapour phase can be removed, if the confining
pressure is reduced to less than the saturated vapour pressure or the temperature rises to where the
saturated vapour pressure is higher than the confining pressure, fluid will suddenly turn to vapour, that
is to say "flash" or "boil". The process will continue until either the temperature falls enough that the
saturated vapour pressure becomes less than the confining pressure, or the pressure rises to reach the
saturated vapour pressure, or the fluid supply is exhausted.

Figure 1 Physical Properties of Geothermal Reservoirs

A similar situation holds for dissolved gases. At any particular temperature, there is a theoretical
saturated vapour pressure for the gas. Since water vapour is also present, this is referred to as the gas
partial pressure. But remember that except at very high pressures or concentrations, gases in a
container act independently: the total pressure is made up of the sum of the partial pressures. So the
gas effectively "ignores" the water vapour pressure. If the confining pressure is less than the saturated
partial pressure, gas will come out of solution. This is the process known as "effervescence".
Conversely, if the partial gas pressure exceeds saturation, more gas will dissolve in the liquid.

"Effervescence" and "boiling" are physically similar. They both have the same cause, i.e. partial
pressure exceeding confining pressure. It is simply that "boiling" conventionally refers to the major
phase (solvent), and "effervescence" conventionally refers to the minor phase (solute). In any mixture
(solution) they take place together.

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The pressure at any depth in a column of water is equivalent to the weight of the water above. Thus
pressures increases with depth, on a hydrostatic gradient. For fresh water at surface temperatures, the
pressure increases by one atmosphere roughly every 10 metres (Figure 1b). Hot water is less dense
than cold water, so the pressure gradient in a hot water column is smaller than in cold water, but the
difference is small. In a column of gas, the same principle applies, but the increase in pressure with
depth is much smaller because the gas is much less dense.

The boiling point of water increases with increasing pressure (Figure 1c). Another way of putting this
is to say that boiling occurs when the confining pressure is less than or equal to the saturated vapour
pressure of the water (Figure 1a). Therefore at depth in a column of water, the boiling point is higher
than on the surface, where boiling occurs when the vapour pressure equals atmospheric pressure
(100°C at sea level). Gases dissolved in the water can significantly increase the depth at which first
boiling occurs because a greater head of water is required to keep the gas in solution (Figure 2). This
also implies that, at any one depth, the boiling point is less. Ionic solutes such as salts raise the boiling
point a small amount.

Temperature (°C)
100 150 200 250 300 350
0

200

400
← 10% NaCl

600

800

Depth (m)
1000
Pure Water

1200
1% CO
2

1400

1600

1800

4% CO
2

2000

Figure 2 Hydrostatic boiling-point versus depth relations of hydrothermal fluids, showing the
contrasting effects of salinity and gas content.

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5. Using Steam Tables to Calculate Steam Mass
Fraction (X)

Steam tables are the basis for many important calculations involving geothermal fluids. The most
common is probably when estimating how much water and how much steam will be formed when a
high-temperature, single phase geothermal fluid is allowed to flash (boil) at a lower temperature and
pressure at the surface. The basic principle is that mass and energy are conserved.

Derivation:
hf = enthalpy of liquid water (kJ/kg)

hg = enthalpy of saturated steam (kJ/kg)

hfg = enthalpy of evaporation (hg - hf)

For a two-phase water and steam mixture, with a steam mass fraction (X), the total enthalpy (Ht) is
then:
Ht = X hg + (1-X) hf
= X h g + hf - X h f
= X (hg - hf) + hf

solving for X: X = (Ht - hf) / (hg - hf)

X = (Ht - hf) / hfg

Example: if liquid water at 300°C boils to 200°C what is the resulting steam mass fraction:

Ht = hf at 300°C
= 1345 kJ/kg (from steam tables)

hf (200°C) = 850 kJ/kg (steam tables)

hfg (200°C) = 1940 kJ/kg (steam tables, or subtract hf200 from hg200)

therefore: X = (1345 - 850) / 1940

= 0.25

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6. Distribution of Gas between Steam and Water

When liquid containing dissolved gas boils the gas moves preferentially into the steam phase and only
a small fraction remains dissolved in the liquid phase. The distribution of gas between liquid and
vapour phases, or the solubility, can be described by mass distribution coefficients which are defined
as follows:
B = CVAP / CLIQ

Where CVAP is the concentration of gas in the vapour phase and CLIQ is the concentration in the liquid
phase (molar units). The trends of distribution coefficients with temperature for the major gases are
shown in Figure 3. The most soluble gas is NH3 followed by H2S and CO2. The low molecular
weight gases N2, CH4 and H2 are less soluble. The coefficients decrease continuously with increasing
temperature, so at higher temperatures gas is increasingly concentrated in the liquid phase when steam
is present. The distribution coefficients can be used to calculate the rate of degassing of liquid when
boiling occurs. Figure 4 shows the loss of CO2 and H2S from water boiling from 240°C to 100°C,
where the steam remains in contact with the water (single-step steam separation). H2S is lost more
slowly because it is a more soluble gas. Gas is lost more quickly with multi-step boiling where steam
is removed from the water continuously.

100,000

CH 4 , H 2
N2
10,000
CO 2

1,000 H2 S
B (C / C )
VAP LIQ

100

NH 3
10

1
0 50 100 150 200 250 300
Temperature (°C)

Figure 3 Vapour-liquid distribution coefficients for geothermal gases

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 1.00

0.90

0.80

0.70

0.60
TOT

/C
0.50
CL

0.40

CO 2
0.30
H2S

0.20

0.10

0.00
100 120 140 160 180 200 220 240 260

Temperature (°C)

Figure 4 Degassing of CO2 and H2S from 250°C water, boiling without steam separation down to
100°C.

For dilute solutions of gas in water, the partial pressure of the dissolved gas increases linearly with
increasing gas concentration. This relationship is called Henry’s Law and is expressed numerically as
follows (for CO2):
PCO2 = KH XCO2

where KH is the Henry’s Law coefficient and XCO2 is the mole fraction of CO2 in solution. Henry’s
Law and the mass distribution coefficients (B) are related through the following expression:

KH = B Pv / Zv

where Pv is the water vapour pressure and Zv is the compressibility factor for pure steam. In turn:

ZV = PVVV / RTn

where VV is the molar volume of steam,

so: KH = nBRT / VV

For CO2, B is a continuously decreasing function and 1/VV a continuously increasing function of
temperature. As a result KH for CO2 passes through a maximum at about 175°C (Figure 5). This can
be considered a solubility minimum. An important consequence of the solubility minimum is that
CO2-saturated water at temperatures above 175°C will de-gas upon cooling, possibly initiating boiling.

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 7000

6000
(bars/mole fraction)

5000
CO2
4000

3000

2000
H2 S
K

1000

0
0 50 100 150 200 250 300 350

Temperature (°C)

Figure 5 Temperature trends of Henry’s Law constants for CO2 and H2S

CO2 can be very important in controlling reservoir temperatures and pressures and, as a result, the
phase conditions at production depths. These effects are imposed by the high partial pressures of CO2.
Using both Henry’s Law and the mass distribution coefficients it is possible to construct theoretical
boiling-point-for-depth (BPD) profiles for geothermal reservoirs with known gas content (eg: Figure
2).

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