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Hermann Weingärtner 1 , Ernst Ulrich Franck 2 , Gabriele Wiegand 3 ,
Nicolaus Dahmen 4 , Georg Schwedt 5 , Fritz H. Frimmel 6 , Birgit C. Gordalla 7 ,
Klaus Johannsen 8 , R. Scott Summers 9 , Wolfgang Höll 10 , Martin Jekel 11 ,
Rolf Gimbel 12 , Robert Rautenbach 13 , William H. Glaze 14
1 Ruhr-Universität Bochum, Physikalische Chemie II, Bochum,
Federal Republic of Germany
2 Institut für Heiße Chemie, Forschungszentrum Karlsruhe,
Karlsruhe, Federal Republic of Germany
3 Institut für Heiße Chemie, Forschungszentrum Karlsruhe,
Karlsruhe, Federal Republic of Germany
4 Institut für Heiße Chemie, Forschungszentrum Karlsruhe,
Karlsruhe, Federal Republic of Germany
5 Institut für Anorganische und Analytische Chemie, Technische
Universität Clausthal, Clausthal-Zellerfeld, Federal Republic of Germany
6 Engler-Bunte-Institut der Universität Karlsruhe, Bereich
Wasserchemie, Karlsruhe, Federal Republic of Germany
7 Engler-Bunte-Institut der Universität Karlsruhe, Bereich
Wasserchemie, Karlsruhe, Federal Republic of Germany
8 Technische Universität Hamburg-Harburg, Arbeitsbereich
Wasserwirtschaft und Wasserversorgung, Hamburg, Federal Republic of
Germany
9 University of Cincinnati, Department of Civil Engineering,
Cincinnati, Ohio, United States
10 Forschungszentrum Karlsruhe, Institut für Technische Chemie,
Bereich Wasser- und Gastechnologie, Karlsruhe, Federal Republic of
Germany
11 Technische Universität Berlin, Fachgebiet Wasserreinhaltung,
Berlin, Federal Republic of Germany
12 Gerhard-Mercator-Universität Gesamthochschule Duisburg und
Rheinisch-Westfälisches Institut für Wasserchemie und
Wassertechnologie, Mülheim, Federal Republic of Germany
13 Rheinisch-Westfälische Technische Hochschule, Institut für
Verfahrenstechnik, Aachen, Federal Republic of Germany
14 Department of Environmental Sciences and Engineering, School
of Public Health, University of North Carolina, Chapel Hill, NC, United
States
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Copyright © 2002 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights
reserved.
DOI: 10.1002/14356007.a28_001
Article Online Posting Date: June 15, 2000
Abstract
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Full Text: HTML

Abstract

The article contains sections titled:

1.

Water as a Solvent

1.1.

Properties of Pure Water

1.1.1.

Molecular Properties

1.1.2.

Hydrogen Bonding and Water Structure

1.1.3.

Bulk Properties of Liquid Water

1.2.

Aqueous Solutions

1.2.1.

General Solvent Properties

1.2.2.

Solutions of Simple Nonpolar Gases

1.2.3.

Solutes with Hydrophilic Groups

1.2.4.

Electrolyte Solutions

2.

Water at High Pressure and Temperature

2.1.

Properties of Ice

2.1.1.

Thermodynamic Properties

2.1.2.

Transport Properties

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

2.1.3.

Electrolytic Properties

2.1.4.

Mechanical Properties

2.2.

Properties of Fluid Water

2.2.1.

Thermodynamic Properties

2.2.2.

Transport Properties

2.2.3.

Electrolytic Properties

2.2.4.

Other Physical Properties

2.3.

Properties of Water Vapor

2.4.

Water in the Supercritical State

 

3.

Water Analysis

3.1.

Sampling and Sample Preservation

 

3.2.

Physicochemical and Sum Parameters

3.3.

Inorganic Analysis

3.3.1.

Determination of Cations

3.3.2.

Anion Analysis

3.3.3.

Determination of Dissolved Gases

 

3.3.4.

Quick Test Processes

3.4.

Organic Analysis

3.4.1.

Spectrometric Methods

3.4.2.

Gas and Liquid Chromatography

 

3.5.

Biochemical Methods

4.

Hydrological Cycle and Water Use

 

4.1.

World Water Balance

4.2.

Hydrological Cycle

4.3.

Demand for Water

4.4.

Source of Water Used

4.5.

Water Treatment

5.

Adsorption Processes in Water Treatment

5.1.

Introduction

5.2.

Properties of Activated Carbon

 

5.3.

Adsorption Theory

5.4.

Adsorption Equilibrium

5.5.

Adsorption Kinetics

5.6.

Biological Processes

5.7.

Design of GAC Systems

5.8.

Design of PAC Systems

5.9.

Reactivation of GAC

6.

Ion Exchange

6.1.

Fundamentals

6.1.1.

Characterization of the Chemical State of Water

6.1.2.

Representation of the Chemical State of Water

6.1.3.

Ion Exchangers

6.2.

Cation-Exchange Processes

6.2.1.

Strongly Acidic Resins in the Na + Form

6.2.2.

Strongly Acidic Resins in the H + Form

6.2.3.

Weakly Acidic Resins in the Hydrogen Form

6.3.

Anion-Exchange Processes

6.3.1.

Strongly Basic Resins in the Cl Form

6.3.2.

Strongly Basic Resins in the OH Form

6.3.3.

Strongly Basic Resins in the

6.3.3. Strongly Basic Resins in the Form

Form

6.3.4.

Weakly Basic Resins

6.4.

Combined Processes

6.4.1.

Demineralization

6.4.2.

Partial Demineralization

7.

Flocculation

7.1.

Introduction

7.2.

Definitions

7.3.

Chemicals Used in Coagulation and Flocculation

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

7.3.1.

Inorganic Chemicals

7.3.2.

Organic Chemicals

 

7.4.

Kinetics of Aggregation

7.5.

Process Technology for Coagulation and Flocculation

7.5.1.

Dosing

7.5.2.

Rapid Mixing

 

7.5.3.

Reactors for Floc Formation

7.5.4.

Integrated Flocculation Systems

7.5.5.

Operational Aspects

8.

Filtration

8.1.

Introduction

8.2.

Slow Sand Filters

 

8.3.

Polishing Filters

8.4.

Rapid Filters

8.4.1.

Design

8.4.2.

Areas of Application and Modes of Operation

8.4.3.

Filter Performance

 

9.

Membrane Separation Processes in Water Treatment

9.1.

Principles

9.1.1.

Flow, Selectivity, Driving Forces

9.1.2.

Mass Transport Resistance in Front of the Membrane

9.2.

Membranes

9.2.1.

Organic Membranes

9.2.2.

Inorganic Membranes

9.3.

Modules

9.3.1.

Modules with Tubular Membranes

9.3.2.

Modules with a Flat-Sheet Membrane

9.4.

Fouling and Scaling

 

9.4.1.

Membrane Blockage due to Crystallization (Scaling)

9.4.2.

Membrane Blockage due to Contaminants (Fouling)

9.5.

Module Arrangements (Plant Design)

9.6.

Use of Membrane Processes in Water and Wastewater Technology

9.6.1.

Desalination of Seawater and Brackish Water

9.6.2.

Recovery of

9.6.2. Recovery of -Caprolactam

-Caprolactam

9.6.3.

Leachates from Dump Sites

9.6.4.

Wastewater from the Dye Industry

10.

Oxidation Processes in Water Treatment

10.1.

Physical and Chemical Properties of Chemical Oxidants

10.2.

Production of Chemical Oxidants

10.3.

Uses of Chemical Oxidants

10.3.1.

Drinking Water Treatment

10.3.1.1.

Disinfection

10.3.1.2.

Chemical Oxidation

 

10.3.2.

Wastewater Treatment

10.3.3.

Oxidation in Pulp and Paper Treatment

10.3.4.

Advanced Oxidation Processes

10.4.

Toxicology and Environmental Health

11.

Acknowledgement

 

[Top of Page]

1. Water as a Solvent

Hermann Weingärtner

1.1. Properties of Pure Water

1.1.1. Molecular Properties In comparison to other solvents, water and aqueous solutions in many respects show unique properties that are highly sensitive to temperature and pressure [1-3]. These properties result from the structure and the charge distribution of the water molecule. In a simple four-point-charge model, this charge distribution is depicted as a quadrupole with two protons and two lone electron pairs at the corners of a tetrahedron with oxygen in its center (Fig. 1). In the isolated molecule the O–H

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

internuclear distance is 0.096 nm, with an H–O–H bond angle of 104.3°, which is close to the tetrahedral angle [2], [3]. This nonspherical charge distribution gives rise to electric moments. The dipole moment of the isolated water molecule is 1.85 D (6.14×10 30 C · m), the dipole vector acting along the bisector of the H–O–H angle with the negative end directed toward the oxygen. Thus, water is a highly polar solvent.

toward the oxygen. Thus, water is a highly polar solvent. Figure 1. Four-point-charge model of water

Figure 1. Four-point-charge model of water after [4]. The partial charges

electron pairs. The experimental dipole moment is reproduced with

+ =
+ =

+ refer to the protons, the charges

– to the lone to the lone

= 0.236 e, where e is the elementary charge.

When considering intermolecular interactions, the electrostatic forces have to be supplemented by terms accounting for the core repulsion of the molecules and the attractive dispersion (van der Waals) forces. For water, these terms are often approximated by the corresponding figures for the isoelectronic neon, which has a core radius of 0.14 nm. In computer simulations, models of this type are able to reproduce the major features of the properties of liquid water [4].

1.1.2. Hydrogen Bonding and Water Structure

The molecular geometry and charge distribution of water favor the formation of a hydrogen-bonded network with four O–H–O bonds per molecule. Hydrogen bonding can be proved by infrared and Raman spectroscopy. Three normal vibrations of the

isolated H 2 O molecule occur in the vapor phase: the symmetric stretching mode at a wave number

asymmetric stretching mode at 3756 cm 1 , and the bending mode at 1595 cm 1 (Fig. 2). Hydrogen bonding leads to shifts in the wave numbers of these modes, a change in their band contours, and the appearance of new bands associated with intermolecular vibrations [3]. These spectral features are often used to monitor changes in hydrogen bonding as a function of temperature and pressure or induced by added solutes. In addition, the chemical shift in the 1 H NMR spectrum of water provides a sensitive tool for measurement of hydrogen bonding.

a sensitive tool for measurement of hydrogen bonding. = 3675 cm – 1 , the Figure

= 3675 cm 1 , the

measurement of hydrogen bonding. = 3675 cm – 1 , the Figure 2. Normal vibrations of

Figure 2. Normal vibrations of the water molecule:

mode, and

2. Normal vibrations of the water molecule: mode, and 2 the bending mode 1 is the

2 the bending mode

of the water molecule: mode, and 2 the bending mode 1 is the symmetric stretching mode,

1 is the symmetric stretching mode,

2 the bending mode 1 is the symmetric stretching mode, 3 the antisymmetric stretching The structure

3 the antisymmetric stretching

The structure of hexagonal ice Ih (Fig. 3), which is the stable polymorph of ice at atmospheric pressure, is an ideal representation of this hydrogen-bonded network [3]: Each oxygen is surrounded tetrahedrally by four others at a distance of 0.276 nm, the structure being isomorphous with the tridymite structure of silica. The protons lie approximately along the O–O axes. Because of hydrogen bonding, the intramolecular OH distance (0.101 nm) is greater than in the isolated molecule. If compared with closely packed structures with up to 12 nearest neighbors, the ice Ih structure is very open. The large molar volume of ice Ih is, for example, responsible for the volume contraction of ice upon melting.

responsible for the volume contraction of ice upon melting. Figure 3. Structure of hexagonal ice Ih.

Figure 3. Structure of hexagonal ice Ih. The spheres give the positions of the oxygen atoms.

In the liquid state the long-range order is lost, but short-range positional and orientational correlations are retained, which can be studied by X-ray and neutron scattering [3]. At room temperature a structure is perceptible in the local environment, which extends to about 0.8 nm. On average, one molecule has 4.4 nearest neighbors at a distance of 0.284 nm. These figures and the location of second-nearest neighbors correspond closely to the requirements imposed by the ice Ih structure. However, intermolecular O–O and O–H distances and H–O–H angles show a broad distribution around the average value, and due to thermal reorientation, the lifetime of a given configuration is only of the order of some picoseconds. With increasing temperature, the three-dimensional network gradually breaks down. Thus, with rising temperature, water loses its unique properties, although Raman spectroscopy shows that even at the critical point at 374 °C, some degree of hydrogen bonding is still retained [5].

Any model of liquid water must accommodate these features, but none of the existing models seems to be immune to criticism. For a long time, so-called mixture models have been used to explain the properties of water and aqueous solutions. These models assume the existence of two (or more) physically distinguishable water species, corresponding to molecules

with “broken” and “unbroken” hydrogen bonds [2], [3], according to equilibria of the general form H 2 O (icelike)

(gaslike), which depend on temperature and pressure and are changed by solutes. From the present point of view, the need for such models is overcome largely by the possibility of performing more rigorous model-free analyses based on statistical mechanical methods and computer simulations, so that many of these models are only of historical interest.

methods and computer simulations, so that m any of these models are only of historical interest.

H 2 O

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

1.1.3. Bulk Properties of Liquid Water

A knowledge of the bulk properties of pure water and their anomalous behavior is a prerequisite for understanding its solvent

properties, because many methods and rules for evaluating and predicting data in nonaqueous systems are of little value for aqueous solutions. Most of these anomalies occur near room temperature or up to 100 °C. The significance of these anomalies for processes in nature and in sustaining life has been outlined [3]. Doubtless, these anomalies result from the strong hydrogen bonding that occurs, however, in many other substances as well. Hence, the existence of strong hydrogen bonds cannot fully explain the uniqueness of some properties of water. Rather, it is the existence of the three-dimensional network that distinguishes water from other hydrogen-bonded liquids. Despite great progress in liquid-state theory, the treatment of such hydrogen-bonded systems remains difficult.

Isotopic Composition. Natural (“ordinary”) water is a mixture of isotopic species made up by the hydrogen isotopes

mixture of isotopic species made up by the hydrogen isotopes and (deuterium) and the oxygen isotopes

and

of isotopic species made up by the hydrogen isotopes and (deuterium) and the oxygen isotopes Proton

(deuterium) and the oxygen isotopes Proton exchange equilibria of the form

assumed to be distributed randomly on the oxygens. Then, the four major species of ordinary water occur in the proportions

[6]

, , and
,
, and

. Their masses and natural abundances are compiled in Table 1.

yield further mixed species. The

andare compiled in Table 1 . yield further mixed species. The are usually Table 1. Isotopic

compiled in Table 1 . yield further mixed species. The and are usually Table 1. Isotopic

are usually

Table 1. Isotopic masses and natural abundances of hydrogen and oxygen isotopes [11]

Atomic mass Natural abundance

 

Mol %

wt %

H

(natural)

1.0080

1.0078399.985 99.970

99.985

99.970

2.014100.015 0.030

0.015

0.030

O

(natural) 15.9994

 
15.9995 99.759 99.732

15.9995

99.759

99.732

16.9991 0.037 0.039

16.9991

0.037

0.039

17.9992 0.204 0.229

17.9992

0.204

0.229

16.9991 0.037 0.039 17.9992 0.204 0.229 The molar mass of ordinary water is 18.012 g/mol. The

The molar mass of ordinary water is 18.012 g/mol. The variation of these proportions in water from different natural sources

is usually smaller than variations as a result of water purification, and except in work of the highest accuracy, the properties

of ordinary water can be set equal to the properties of

and

the following, the term “water” is used for ordinary water with natural isotopic composition.

used for ordinary water with natural isotopic composition. . Practically pure (heavy water) and highly enriched

. Practically pure

water with natural isotopic composition. . Practically pure (heavy water) and highly enriched - -labeled water

(heavy water) and highly enriched

-
-
. Practically pure (heavy water) and highly enriched - -labeled water are available commercially, so that

-labeled water are available commercially, so that some data also exist for water of other isotopic compositions [7]. In

p – V – T Data and Invariant Points. Water is the only inorganic substance that, under ambient conditions found in nature, occurs in the solid, liquid, and gaseous states. Its state of aggregation is characterized by the pressure p, the temperature T,

and volume V (or density

properties of the liquid along the saturation curve can be set equal to the properties at atmospheric pressure.

can be set equal to the properties at atmospheric pressure. ). Only the p – V

). Only the p – V – T properties of the liquid phase are discussed here. In most applications, the

The liquid range is limited by the triple point at which solid ice Ih, liquid water, and steam are in equilibrium and by the critical point. The triple point of ordinary water is bound by the definition of the temperature scale to 273.16 K = 0.01 °C. The normal melting and boiling points at 1.01325 bar are 0 and 100 °C, respectively. The triple-point pressure is p t = 6.113×10 2 Pa. Recommended values for the critical temperature, critical pressure, and critical density are [8] t c = 373.98 °C, p c =

22.05 MPa, and

is the mass

density;

thermal pressure coefficient

MPa, and is the mass density; thermal pressure coefficient c = 322 kg/m 3 . Table

c = 322 kg/m 3 . Table 2 lists volumetric properties of the liquid from 0 to 100 °C [8], [9]. Here,

v =
v =
of the liquid from 0 to 100 °C [ 8 ], [ 9 ]. Here, v
of the liquid from 0 to 100 °C [ 8 ], [ 9 ]. Here, v

p = (1/V )( V/ T ) p , the thermal expansion coefficient; and

V / ∂ T ) p , the thermal expansion coefficient; and v = ( ∂

v = ( p/ T ) V can be calculated by

T = (1/V )( V/ p) T , the isothermal compressibility. The

p / T .

Table 2. Density

compressibility. The p / T . Table 2. Density , thermal expansion coefficient p , and

, thermal expansion coefficient

/ T . Table 2. Density , thermal expansion coefficient p , and isothermal compressibility atmospheric

p , and isothermal compressibility

atmospheric pressure [11]

T of ordinary water at T of ordinary water at

t, °C

t , °C , kg/m 3 p ×10 6 , K – 1 T , bar

, kg/m 3

t , °C , kg/m 3 p ×10 6 , K – 1 T , bar

p ×10 6 , K 1

t , °C , kg/m 3 p ×10 6 , K – 1 T , bar

T , bar 1

0

999.84

–68.14

50.88

10

999.70

 

87.90

47.82

20

998.20

206.6

45.90

25

997.05

257.1

45.25

30

995.65

303.1

44.77

992.23

385.4

44.24

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

40

50

60

70

80

90

100

988.03

457.8

44.18

983.19

523.4

44.51

977.76

584.0

45.17

971.79

641.3

46.15

965.31

696.3

47.43

958.36

750.0

49.02

At atmospheric pressure, ice Ih contracts by ca. 8.2 % on melting — from a density of 916.8 kg/m 3 to 999.87 kg/m 3 in the liquid. The slope of the melting pressure curve depends on the volume change on melting. The anomalous volume contraction of water leads to a depression of its melting point with rising pressure. This depression continues up to 207 MPa and –22 °C, where the ice polymorph changes to ice II. Close to 0 °C, a pressure of 133 bar is required to lower the melting point by 1 °C.

The volume contraction on melting continues in the liquid phase up to 3.98 °C, where the density reaches a maximum value and the thermal expansion coefficient changes sign from negative to positive. Over the entire temperature range considered, the thermal expansion coefficient of water is one order of magnitude smaller than that of other liquids. The isothermal compressibility is unusually large and possesses a minimum near 46.5 °C. Both extremes represent anomalous properties of pure water that tend to disappear at high pressure.

Actually, liquid water may be supercooled below the equilibrium melting point [10]. Experiments can be performed fairly easily down to –20 °C, which is roughly the limit of heterogeneous nucleation. With special techniques, temperatures as low as –40 °C have been achieved with liquid water. At 1 bar, homogeneous nucleation sets a limit at –43 °C. Many of the anomalous properties of liquid water become even more unusual in the supercooled, metastable regime [10].

Specific Heat. At the normal melting point, the isobaric specific heat c p increases from 2.072 J K 1 g 1 in the solid to

4.228 J K 1 g 1 in the liquid state, where it remains almost unchanged up to 100 °C [8], [9] (a very shallow minimum is found near 35 °C) (Table 3). The specific heat is particularly amenable to molecular interpretation and has often been used to estimate the extent of hydrogen bonding in water [2], [3].

Table 3. Isobaric specific heat c p , vapor pressure p, latent heat of vaporization at saturation pressure

p , latent heat of vaporization at saturation pressure h , and surface tension of water

h, and surface tension

vaporization at saturation pressure h , and surface tension of water t , °C c p

of water

t, °C

c p , J g –1 K –1 p, bar

c p , J g –1 K –1 p , bar

h, kJ/kg

t , °C c p , J g –1 K –1 p , bar h ,

×10 3 , N/m

0

4.217

0.00611 2500.5

75.64

10

4.191

0.01228 2467.9

74.23

20

4.182

0.02338 2453.4

72.75

30

4.178

0.04245 2429.6

71.20

40

4.178

0.07382 2405.9

69.60

50

4.180

0.12346 2309.9

67.94

60

4.184

0.19936 2357.7

66.24

70

4.189

0.31181 2333.1

64.47

80

4.196

0.47379 2308.2

62.67

90

4.205

0.70123 2282.7

60.82

100

4.216

1.01325 2256.6

58.91

Liquid – Vapor Equilibria. The vapor pressure at saturation is given in Table 3 [9]. The slope of the vapor pressure curve

yields the latent heat of vaporization

decrease in

its values have often been used to estimate the energy of hydrogen bonds in water. Based on comparison with data for similar molecules, the heat of vaporization of non-hydrogen-bonded H 2 O should be ca. 550 kJ/kg, about one-fourth of the

actual values between 0 and 100 °C. The difference is ascribed to the energy of the hydrogen bonds.

difference is ascribed to the energy of the hydrogen bonds. h [ 8 ], [ 9

h [8], [9], which is ca. 2500 kJ/kg at the normal melting point. Up to 100 °C, a slight

kJ/kg at the normal melting point. Up to 100 °C, a slight h is observed (Table

h is observed (Table 3). Compared with other liquids, the latent heat of vaporization is anomalously high, and

The vapor pressure is well investigated for other isotopic compositions — above all heavy water. Vapor pressure data for

other isotopic forms usually are represented by the partition coefficient

the heavier isotopic form. Figure 4 shows the partition coefficient of heavy water as a function of temperature [7]. Over a

of heavy water as a function of temperature [ 7 ]. Over a , where H

, where H 2 O represents light water and x

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

large range of temperature, heavy water is less volatile than light water, so its melting and boiling points (3.82 and 101.42 °C)

are higher than those of

points (3.82 and 101.42 ° C) are higher than those of . The inverse is true

. The inverse is true above 200 °C, and the critical point of

The inverse is true above 200 °C, and the critical point of is about 3 °C

is about 3 °C lower.

200 °C, and the critical point of is about 3 °C lower. Figure 4. Partition coefficients

Figure 4. Partition coefficients

of is about 3 °C lower. Figure 4. Partition coefficients of light (a) and heavy water

of light (a) and heavy water (b) as a function of temperature

Surface Tension. Below 100 °C, the surface tension

[8], [9] (Table 3) refers to the interface between water saturated with

air and air saturated with water. It is distinctly higher than that of other liquids, including most hydrogen-bonded ones. On the

basis of simple theories, the quantity

This is observed approximately, but for water the temperature function of slope found with most other liquids.

function of slope found with most other liquids. / 2 / 3 should be a function
/
/

2/3 should be a function of the temperature distance T T c from the critical point.

/
/

2/3 does not exhibit the predicted universal

Transport Properties. The dynamic viscosity

data are often used to calibrate viscometers. The dynamic viscosity is higher than that of comparable substances without

hydrogen bonds. The decrease of dynamic viscosity with increasing temperature cannot be described with sufficient

accuracy by the conventional Arrhenius-type expression with two adjustable constants

Arrhenius-type expression with two adjustable constants of liquid water (Table 4 ) is known with great

of liquid water (Table 4) is known with great accuracy [6], [8], [9], and the

) is known with great accuracy [ 6 ], [ 8 ], [ 9 ], and

0 and E

with great accuracy [ 6 ], [ 8 ], [ 9 ], and the 0 and
with great accuracy [ 6 ], [ 8 ], [ 9 ], and the 0 and

unless the energy of the viscous flow E

of viscosity versus the inverse temperature does not yield a straight line, as found for many other liquids. More complex expressions are therefore in use [10]. The temperature dependence of viscosity is of some interest in interpreting processes in supercooled water [10]. The pressure dependence of the dynamic viscosity of water is anomalous as well: Whereas the viscosities of liquids usually increase with increasing pressure, the viscosity of water initially decreases up to a minimum at ca. 60 MPa. This decrease has clear structural implications: the hydrogen-bonded network becomes deformed with rising pressure, and this tends to facilitate molecular motion. An unusually large increase of viscosity (ca. 23 % at 25 °C) is found when ordinary water is replaced by heavy water. At higher temperature, this isotope effect diminishes. This unusually large effect is attributed to a higher structuredness of heavy water.

is attributed to a higher structuredness of heavy water. is assumed to be temperature dependent. In

is assumed to be temperature dependent. In other words, the plot of the logarithm

Table 4. Viscosity

In other words, the plot of the logarithm Table 4. Viscosity and thermal conductivity of liquid

and thermal conductivity

of liquid water at atmospheric pressureof the logarithm Table 4. Viscosity and thermal conductivity t , °C ×10 6 , Pa

t, °C

t , °C ×10 6 , Pa · s , mW K – 1 m –

×10 6 , Pa · s

, mW K – 1 m – 1 1 m 1

0

1792

565

10

1307

584

20

1002

602

25

890.3

30

797.5

617

40

653.2

631

50

547.1

642

60

466.6

652

70

403.9

660

80

353.8

669

90

312.8

675

100

278.3

679

In gases, the thermal conductivity

liquids a linear decrease is found with increasing temperature. In contrast, water shows an anomalous increase in

130 °C [6], [8], [9] (Table 4). Despite its considerable technical importance, understanding of the thermal conductance of liquids on a molecular basis is poorly developed.

of liquids on a molecular basis is poorly developed. is proportional to viscosity, but this correlation

is proportional to viscosity, but this correlation is lost in the liquid phase, where for most

this correlation is lost in the liquid phase, where for most up to ca. The self-diffusion

up to ca.

The self-diffusion coefficient D characterizes the mean-square displacement of water molecules due to thermal agitation. In ordinary water at 25 °C, D = 2.30×10 9 m 2 /s [11], corresponding to a displacement of the order of 10 4 m during 1 s. The temperature and pressure dependence of D and the isotope effects are correlated strongly with those of the reciprocal viscosity.

Autoprotolysis. Self-dissociation of water is characterized by the ion product

A utoprotolysis. Self-dissociation of water is characteriz ed by the ion product or its negative decadic

or its negative decadic

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logarithm. Here

of pure water is

Section Electrolytic Properties). Autoprotolysis is of paramount importance for the Brønsted acid – base concept. According

to this scheme, water is classified as an amphiprotic solvent that, depending on the solute, exhibits acidic or basic properties.

and
and

are the activities of the H + and OH ions. At 25 °C, K w = 1.008×10 14 . Accordingly, the pH value

. The ion product increases with increasing temperature and increasing pressure [12] (see

Electric Properties. Water exhibits a nonvanishing electrical conductance. Values of the specific conductance

3× 10 8 1 cm 1 have been achieved, but in practice, water with

experiments. The discrepancy results from impurities not removable by simple distillation or ion exchange and from dissolved carbon dioxide.

or ion exchange and from dissolved carbon dioxide. as low as ≈ 1×10 – 6 Ω

as low as

or ion exchange and from dissolved carbon dioxide. as low as ≈ 1×10 – 6 Ω

1×10 6 1 cm 1 is used even in accurate

The dielectric constant (relative permittivity)

increasing temperature to 55.44 at 100 °C [13]. The value at 25 °C is 78.46. These high values are attributed to a cooperative alignment of molecules in the hydrogen-bonded network. The dielectric constant is a key quantity for interpreting solute – solvent interactions, above all in electrolyte solutions. Its change with temperature and pressure gives rise to drastic changes in the solvent properties of water.

rise to drastic changes in the solvent properties of water. of water ( = 87.81 at

of water (

changes in the solvent properties of water. of water ( = 87.81 at 0 °C) is

= 87.81 at 0 °C) is very high and decreases substantially with

Other Properties. Refractive Index. At 25 °C, the refractive index of water is 1.3340. It decreases slightly with increasing temperature.

Standard Enthalpy and Entropy of Formation. The standard enthalpy of formation of water at 25 °C and 1 bar is – 286.2 kJ/mol, and the corresponding entropy is 69.98 J mol 1 K 1 [14].

Cryoscopic and Ebullioscopic Constants. The cryoscopic constant K f = 1.853 g K 1 mol 1 characterizes the freezing-point

depression caused by 1 mol dissolved species in 1000 g H 2 O. The ebullioscopic constant K b = 0.515 g K 1 mol 1 characterizes the boiling-point elevation caused by 1 mol dissolved species in 1000 g H 2 O.

1.2. Aqueous Solutions

1.2.1. General Solvent Properties

At ambient conditions, water is a good solvent for many ionic and polar inorganic and organic substances. To some degree, it can even accommodate nonpolar particles and larger nonpolar molecular groups in the interstitial voids of its hydrogen- bonded network. At high temperature the solvent behavior of water can change drastically. Many comparatively inert substances that mix only poorly with water at room temperature become highly soluble or even completely miscible. In contrast, due to the decreasing dielectric constant, water loses its favorable characteristics as a solvent for ionic compounds.

A useful classification distinguishes among three types of hydration, i.e., ion hydration; hydration of organics with polar

functional groups such as OH, C=O, and NH; and “hydrophobic” hydration of inert particles and substances with nonpolar molecular groups. Of these, ion hydration has traditionally received the most interest and is comparatively well characterized. The hydration of substances containing polar functional groups is determined by the extent of solute – solvent hydrogen bonding. In such cases, a highly complex and specific behavior is found. Hydrophobic hydration is a nonspecific “nonbonded” interaction that depends on whether water can build up a stable structure around the inert particle, thereby retaining or strengthening its hydrogen bonds. Hydrophobic effects are therefore determined by the nature of water – water interactions rather than by water – solute interactions, and are driven by a favorable entropy change rather than by energetic contributions. Such processes are very sensitive to temperature, and this strong temperature dependence is one of the essential characteristics of hydrophobic hydration.

1.2.2. Solutions of Simple Nonpolar Gases

The solubility of simple low-polarity gases (noble gases, aliphatic hydrocarbons such as methane or ethane, or inert inorganic compounds such as SF 6 ) in water at 25 °C is lower than in most organic liquids [15] (Fig. 5). Moreover, in contrast to the normal behavior found with other solvents, the solubility decreases as a function of temperature. Only at high temperature (e.g., >100 °C) does the solubility pass through a minimum and then have a positive temperature coefficient like that of normal solvents [16]. Extensive tabulations of gas solubilities in water are available [17].

of gas solubilities in water are available [ 17 ]. Figure 5. Solubility of simple gases

Figure 5. Solubility of simple gases in water and cyclohexane; x 2 is the mole fraction of the gas (reproduced from [21] by permission)

The thermodynamics of dissolution of inert gases in water and the structural properties of such systems have received wide attention [18], [19], because they are often used to model the hydration of nonpolar groups in more complex molecules. The same interactions play an important role in determining the properties of colloidal and macromolecular solutions, and in the manner in which proteins acquire their native structure [19], [20]. The various properties may be investigated by considering the transfer of 1 mol inert solute from a nonaqueous to an aqueous environment. The latter solutions are nonideal in the sense that the changes in volume and enthalpy on dissolution are negative. However, this is counteracted by a very large negative change of the excess entropy over the entropy of ideal mixing. This dominance of the entropy over the enthalpy term leads to a strongly positive free energy of mixing and, hence, to the low solubility of inert gases in water.

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FRANK and EVANS [21] have explained this process by an ordering of water molecules and an increase in the degree of hydrogen bonding around the inert solute. This assumption is supported mainly by the existence of solid hydrates of gases and of other small molecules with definite cage structures (clathrates) [22]. In liquid water, the environment of inert gases and inert molecular groups such as the methyl group are now believed to exhibit some residues of the clathrate structure.

At higher solute concentrations, a second important effect occurs: so-called hydrophobic interactions or hydrophobic bonding [18-20]. This term denotes the formation of close-encounter configurations between two inert solutes or molecular groups that are stabilized by a favorable common water structure around the pair (Fig. 6). With larger solutes the configuration shown in Figure 6 may, for example, correspond to the encounter of two methyl groups or larger side chains accompanied by

a decrease in the number of nearest water molecules. Hydrophobic bonding may include not only configurations with direct

solute contact but also configurations in which one layer of water molecules is located between the hydrophobic pair. Since this association process annihilates solute – water contacts, the association is analogous to that expected if an inert solute is removed from an aqueous environment. Thus, the thermodynamic parameters characterizing hydrophobic bonding have signs opposite to those discussed for hydrophobic hydration.

signs opposite to those discussed for hydrophobic hydration. Figure 6. Schematic representation of a hydrophobic

Figure 6. Schematic representation of a hydrophobic association process

A) Two methane molecules form a dimer; B) Stabilization of the conformation of a biopolymer by hydrophobic bonding between two methyl groups or side chains

The spheres represent methyl groups or side chains. The shaded area indicates that the processes occur only in an aqueous environment.

1.2.3. Solutes with Hydrophilic Groups The hydration of polar groups is highly specific, and with molecules carrying both polar groups and inert residues, distinguishing between the various effects is usually difficult. Some insight is often obtained by considering the variation of solution properties within homologous series. Typical examples of such systems include aqueous solutions of alcohols, amines, ketones, ethers, fatty acids, nitriles, or polar gases.

A useful classification that may establish some order in this confusing field is based on the strength and number of proton-

accepting groups of the nonaqueous interaction partner [23]. For example, nitriles and ketones are weak proton acceptors, and mixing with water is endothermic. In combination with the entropic term, such solutions are slightly stable thermodynamically and liquid – liquid immiscibilities with upper consolute points are usually found, except for the lowest members of the homologous series. If the solute is capable of accepting stronger hydrogen bonds, the mixing process may become exothermic over some temperature ranges, and a tendency exists for a lower consolute point or a closed miscibility gap. Such behavior is often found with alcohols, ethers, or amines. Finally, in some mixtures, hydrogen bonding is very strong. These are thermodynamically very stable and never separate into two liquid phases. Examples are mixtures with polyhydric alcohols such as glycerol and amides.

Even though knowledge of the hydration of comparatively simple systems is imperfect, the results are of major importance for interpreting the role of water in more complex systems of biological interest. There, hydrophobic hydration and hydrophobic interactions have gained wide attention because these nonbonded interactions play a major role in determining the stability of conformations of biomolecules (e.g., proteins) in solution [19], [20].

1.2.4. Electrolyte Solutions Traditionally, electrolyte solutions have received far more attention than nonelectrolyte systems [24]. The dissolution of a salt in a solvent may be visualized by two steps consisting of (1) dissociation of the salt into gaseous ions and (2) solvation of these ions in the solvent. Consequently, to achieve dissolution, the free energy of solvation must overcome the lattice energy. The polarity and high dielectric constant of water near room temperature favor this process. This, at least qualitatively, explains why the solubility of many salts is higher in water than in nonaqueous solvents. The resulting heats of solution are low, compared to the lattice energies, and in total, the solution process can be exothermic or endothermic.

The dissolution of ions changes the water structure, because the electric field associated with the ionic charge favors definite orientation of the water molecules near the ions. However, other effects also must be accounted for, such as ion – water hydrogen bonds and conditions imposed by the need to form hydrogen bonds with water molecules beyond the first sphere. For anions, most experiments, including neutron-scattering studies [25], give evidence that a hydrogen-bonded configuration

in which one of the water protons is directed toward the anion (Fig. 7, right) is preferred to that favored by electrostatic

arguments (Fig. 7, left).

to that favored by electrostatic arguments (Fig. 7 , left). Figure 7. Possible configurations of an

Figure 7. Possible configurations of an anion – water pair

With larger univalent ions such as K + or I , even the water configuration in the first hydration sphere may be quite isotropic. This leads to the structure-breaking effect: On dissolution of the salt, water behaves as if its temperature were increased, corresponding to a decrease in the solvent structure. This picture is derived from thermodynamic data such as hydration entropies [21], transport coefficients such as viscosity [24], and spectroscopic data [26], [27]. An illustrative example of the quite unusual effects obtained by the addition of structure-breaking salts is the concentration dependence of viscosity at room temperature. For salts such as potassium iodide, the viscosity decreases with increasing salt concentration, in contrast

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to the usual expectations. Salts that follow this pattern are termed structure breakers as opposed to structure formers. This structure-breaking effect exhibited by alkali-metal ions (except Li + ) and halide anions (except F ) constitutes an anomalous property of aqueous solutions. Multivalent cations and most multivalent anions are structure formers.

Because of the high dielectric constant of water near room temperature, most salts of univalent ions are dissociated completely even at high concentration. At high dilution of the salt, the Debye – Hückel theory of electrolyte thermodynamics and its extensions to transport processes provide a correct description of such systems [24]. In the strict sense, these are, however, limiting laws for vanishing salt concentration, as exemplified by the famous Debye – Hückel limiting law for the mean ionic activity coefficient, the logarithm of which exhibits a square-root dependence on salt concentration [24].

Progress in statistical mechanics has also led to an understanding of concentrated electrolyte solutions. Although such theories are notoriously complex, PITZER and coworkers have derived rather simple semiempirical equations for electrolyte thermodynamics that fit, within experimental accuracy, a variety of data on pure and mixed electrolytes in aqueous solutions over wide ranges of salt concentration and temperature [28].

At elevated temperature, where the dielectric constant of water is low, extensive ion pairing may occur [16]. The same is true for electrolytes of higher valence such as sulfates of alkali, alkaline-earth, and transition-metal ions, because the Coulombic interactions between the ions are stronger than in the case of unielectrolytes [24]. In addition, very specific association can be observed, for example, with zinc, cadmium, or mercury halides, where stable complexes are formed [24]. To a certain degree, such ion pairing can be incorporated in PITZER's approach. A more common way, however, is a description in terms of equilibria between distinct ionic species, which are then treated by a simple law of mass action and the corresponding thermodynamic relations [24].

[Top of Page]

2. Water at High Pressure and Temperature

Ernst Ulrich Franck, Gabriele Wiegand, Nicolaus Dahmen

Water plays a part in many technical processes and is used in a wide range of temperatures and pressures. The critical point above which liquid phase and vapor phase no longer coexist is determined by the critical data t c = 373.98 °C, p

c = 22.05 MPa, and

data t c = 373.98 °C, p c = 22.05 MPa, and c = 322 kg/m

c = 322 kg/m 3 (see Section Bulk Properties of Liquid Water).

2.1. Properties of Ice

2.1.1. Thermodynamic Properties

Twelve modifications of ice are known [29-31]. The phase diagram of ice in the p T projection in the temperature ranges – 100 to +600 °C and pressures up to >10 4 MPa is shown in Figure 8 [32], [33]. The densities at 500 °C have also been entered for comparison. Natural ice exists as ice Ih and crystallizes hexagonally. In general, only this modification is of interest for technical processes. A metastable cubic variant of this modification also exists. In Figure 8, ice IV (a metastable modification, which occurs in the phase region of ice V) and ice VIII (with a triple point at ca. 5 °C and 2100 MPa, which is formed from ice VI or ice VII at higher pressure and lower temperature) are not shown. Ice IX and ice XII have also been excluded from Figure 8 because they lie outside the temperature and pressure region depicted in this figure. All known triple points are listed in Table 5 [31], [34].

Table 5 shows that modification II, for example, is not formed directly from liquid water on cooling or compression but can originate only from modifications Ih, III, V, or VI. An anomaly of water is that the melting pressure curve for ice Ih exhibits a negative slope up to the triple point Ih – III – liquid at 207 MPa and –22 °C. The values of the melting pressure curve ice Ih liquid water are summarized below in tabular form down to this triple point [35]. e

t, °C

p, MPa

0.0098

6.1156×10 4

0.0

0.10132

–5.0

59.8

–10.0

110.8

–15.0

155.9

–20.0

193.2

–22.0

207.4

The following equation describes the melting pressure curve of ice Ih in equilibrium with water [36]:

pressure curve of ice Ih in equilibrium with water [ 36 ]: The sublimation pressure curve

The sublimation pressure curve of ice Ih – water vapor is known down to –110 °C:

t, °C

p×10 3 , hPa 0 6108

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10

20

30

50

70

90

–110

2597

1032

380.1

39.37

2.59

0.093

0.0013

Table 5. Triple points of ice and water modifications

Coexistent phases Pressure, MPa Temperature, °C

Ih

– liquid – gaseous 6.1×10 –4

Ih

– liquid – III

207

Ih

– II – III

200

Ih

– II – VI

1050

Ih

– VI – XII

1550

II

– III – V

350

II

– V – VI

970

III

– liquid – V

346

V

– liquid – VI

626

VI

– liquid – VII

2200

VI

– VII – VIII

2100

0.01 *

22 *

30.15 **

120.15 **

168.15 **

21.15 **

100.15 **

17.0 *

0.16 *

81.6 *

5 *

* from [34]. ** from [31].

* ≈ 5 * * from [ 34 ]. * * from [ 31 ]. Figure

Figure 8. Pressure – temperature phase diagram of water in the solid and liquid states

Densities at 500 °C have been included for comparison.

The heat of fusion of ice Ih – water is 333.69 kJ/kg at 0 °C, and the heat of sublimation of ice Ih – water vapor is 2838 kJ/kg at 0 °C [37], [38].

The molar heat capacity C p of ice was investigated for ice Ih. Down to –140 °C, the following equation is valid [39]:

Down to –140 °C, the following equation is valid [ 39 ]: The parameters of this

The parameters of this equation were determined by fitting the data of GIAUQUE and STOUT [35].

T, K

C p , J mol 1 K 1

10

0.276

20

2.050

50

7.931

100

15.879

150

22.025

200

28.211

250

34.829

270

37.481

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2.1.2. Transport Properties

For the thermal conductivity

2.1.2. Transport Properties For the thermal conductivity of ice, the following equation is valid in the
2.1.2. Transport Properties For the thermal conductivity of ice, the following equation is valid in the

of ice, the following equation is valid in the temperature range 0 to –170 °C [37], [38]:

The self-diffusion coefficient D is [34]

[ 37 ], [ 38 ]: The self-diffusion coefficient D is [ 34 ] 2.1.3. Electrolytic

2.1.3. Electrolytic Properties

Relative Permittivity. The relative permittivity

Properties Relative Permittivity. The relative permittivity was determined on polycrystalline ice at a frequency of =

was determined on polycrystalline ice at a frequency of

was determined on polycrystalline ice at a frequency of = 0 Hz: t , °C –0.1

= 0 Hz:

t, °C –0.1

polycrystalline ice at a frequency of = 0 Hz: t , °C –0.1 91.5 –20.9 –44.7

91.5

–20.9 –44.7 –65.8

97.4

104

133

The relative permittivity increases with decreasing temperature. The phase change from one ice modification to the next-

denser one is always accompanied by a jump in

liquid water [32]. Within one modification region, the relative permittivity increases only slightly with pressure. The more

densely the water molecules are packed, the higher is the value of

the water molecules are packed, the higher is the value of to cons iderably higher values

to considerably higher values along the phase equilibriumcurves with

.
.

The relative permittivity

information on the rotation of dipole molecules in the lattice. The dielectric relaxation time is a measure of how fast the polarization caused by an electrical field decays after the field is turned off. Reorientation times of the water molecules can also be determined by NMR studies [34].

molecules can also be determined by NMR studies [ 34 ]. depends on the frequency of

depends on the frequency

determined by NMR studies [ 34 ]. depends on the frequency of an applied electrical field.

of an applied electrical field. This frequency dependence provides

The electrical conductivity

frequency dependence provides The electrical conductivity of ice was determined, e.g., at –10 °C [ 34

of ice was determined, e.g., at –10 °C [34], [40]:

of ice was determined, e.g., at –10 °C [ 34 ], [ 40 ]: 2.1.4. Mechanical

2.1.4. Mechanical Properties

The mechanical properties of ice provide information on its stability and load capacity. The mechanical properties of ice Ih are listed below [37], [38]:

Mohs scratch hardness

at freezing point

2

at –78.5 °C

6

Tensile strength (–10 °C)

Compressive strength (–10 °C) 3 – 6 MPa

1 – 2 MPa

Young's modulus (–16 °C)

9.42 GPa

Shear strength (–16 °C)

3.55 GPa

Poisson ratio (–16 °C)

0.33

(average)

2.2. Properties of Fluid Water

2.2.1. Thermodynamic Properties

For water in the fluid state, equations of state are developed on the basis of experimental p V T data and fixed points (e.g., critical data). Exact and sometimes very comprehensive equations of state exist, especially for technical applications [41]. They must sometimes by subdivided for different phase regions. Equations of state that are restricted to parameters interpretable by molecular physics must take into account the high dipole moment of the water molecules and hydrogen bonds between them, especially when the equations apply to moderate temperatures and very high densities [42], [43].

The three-dimensional phase diagram of water is depicted in Figure 9.

phase diagram of water is depicted in Figure 9 . Figure 9. Three-dimensional p – V

Figure 9. Three-dimensional p V T phase diagram of water; the coexistence liquid – gaseous region lies in the darkly marked area [44]

C.P. = Critical point

Tabular compilations list p V T data up to a maximum pressure of 3000 MPa and maximum temperature of 2000 °C [44-

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46]. They are based on International Association for the Properties of Steam (IAPS) recommendations and on the International Formulation Committee (IFC) Formulation for Industrial Use. Selected data for temperature and pressure under

saturation conditions are presented in Table 6. Corresponding volumes of the gas and liquid phase along the vapor-pressure curve up to the critical point are included [45]. A comparison between the data listed in the SI steam tables [45] and those compiled in the NBS – NRC steam tables [46] shows that for <300 °C, the values deviate from each other by only ca. 0.1 %.

The deviations increase with increasing temperature and can reach 1 %. The enthalpy of vaporization

h is calculated from

the saturation data; it is zero at the critical point. Table 7 shows specific volumes for selected pressures and temperatures in technically relevant regions and also in the supercritical state.

relevant regions and also in the supercritical state. Table 6. Dependence of pressure p , specific

Table 6. Dependence of pressure p, specific volume v of water (l) and water vapor (g), and enthalpy of vaporization h on the temperature in the saturation state at temperatures <100 °C [45]

in the saturati on state at temperatures <100 °C [ 45 ] t , °C p

t, °C

p, MPa

v 1 ×10 3 , m 3 /kg v g , m 3 /kg

v 1 ×10 3 , m 3 /kg v g , m 3 /kg

h, kJ/kg

110

0.14327 1.0519

1.210

2230.0

120

0.19854 1.0606

0.8915

2202.3

130

0.27013 1.0700

0.6681

2173.6

140

0.3614

1.0801

0.5085

2144.6

150

0.4760

1.0908

0.3924

2113.3

160

0.6181

1.1022

0.3068

2081.2

170

0.7920

1.1145

0.2426

2048.0

180

1.0027

1.1275

0.1938

2013.2

190

1.2551

1.1415

0.1563

1976.8

200

1.5549

1.1565

0.1272

1938.5

210

1.9077

1.1726

0.1042

1898.4

220

2.3198

1.1900

0.08604

1856.2

230

2.7976

1.2087

0.07145

1811.8

240

3.3478

1.2291

0.05965

1764.6

250

3.9776

1.2513

0.05004

1714.5

260

4.6943

1.2756

0.04213

1661.5

270

5.5058

1.3025

0.03559

1604.7

280

6.4202

1.3324

0.03013

1543.6

290

7.4461

1.3659

0.02554

1477.6

300

8.5927

1.4041

0.02165

1406.0

310

9.8700

1.4480

0.01833

1327.6

320

11.289

1.4995

0.01548

1241.1

330

12.863

1.5615

0.01299

1143.7

340

14.605

1.6387

0.01078

1030.7

350

16.535

1.7411

0.008799

895.8

360

18.675

1.8959

0.006940

721.2

370

21.054

2.2136

0.004973

452.6

371

21.306

2.2778

0.004723

407.4

372

21.562

2.3636

0.004439

351.3

373

21.820

2.4963

0.004084

273.5

374

22.081

2.8407

0.003458

108.7

374.15 22.120

3.1700

0.003170

0.0

Table 7. Pressure and temperature dependence of specific volume v (10 3 m 3 /kg) of water and superheated steam up to 800 °C and 100 MPa [45]*

p, MPa

t, °C

 

0

100

150

200

250

300

350

400

500

600

700

800

0.1

1.0002 1696

1936

2172

2406

2639

2871

3102 3565 4028 4490 4952

1.0

0.9997 1.0432 1.0904 205.9

232.7

258.0

282.4

306.5 354.0 401.0 447.7 494.3

5.0

0.9977 1.0412 1.0877 1.1530 1.2494 45.30

51.94

57.79 68.49 78.62 88.45 98.09

10

0.9953 1.0386 1.0843 1.148

1.2406 1.3979 22.42

26.41 32.76 38.32 43.55 48.58

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15

20

25

30

40

50

60

15.66 20.80 24.88 28.59 32.09

0.9904 1.0337 1.0779 1.1387 1.2247 1.3606 1.6662 9.947 14.77 18.16 21.11 23.85

0.9928 1.0361 1.0811 1.1433 1.2324 1.3779 11.46

0.9881 1.0313 1.0748 1.1343 1.2175 1.3453 1.6000 6.014 11.13 14.13 16.63 18.91

0.9857 1.0289 1.0718 1.1301 1.2107 1.3316 1.5540 2.831 8.681 11.44 13.65 15.62

0.9811 1.0244 1.0660 1.1220 1.1981 1.3077 1.4896 1.909 5.616 8.088 9.930 11.52

0.9767 1.0200 1.0605 1.1144 1.1866 1.2874 1.4438 1.729 3.882 6.111 7.720 9.076

0.9723 1.0157 1.0552 1.1073 1.1761 1.2698 1.4083 1.632 2.952 4.835 6.269 7.460

0.9682 1.0116 1.0501 1.1005 1.1663 1.2541 1.3793 1.567 2.467 3.972 5.257 6.321

0.9641 1.0076 1.0452 1.0941 1.1573 1.2401 1.3547 1.518 2.188 3.379 4.519 5.481

0.9602 1.0037 1.0405 1.0880 1.1488 1.2273 1.3335 1.479 2.013 2.967 3.964 4.841

100 0.9565 0.9999 1.0359 1.0821 1.1408 1.2155 1.3148 1.446 1.893 2.668 3.536 4.341

70

80

90

* The horizontal lines denote the transition between liquid and gaseous state.

Figure 10 shows the specific heat capacity at constant pressure c p as a function of pressure and temperature. The specific heat capacity at the critical point approaches infinity. In the critical region, the isobars show a pronounced maximum as a function of temperature. For increasing pressures, the maxima become smaller but disappear only above 300 MPa.

the maxima become smaller but disappear only above 300 MPa. Figure 10. Specific heat capacity of

Figure 10. Specific heat capacity of water up to 800 °C and 100 MPa; saturated vapor: x = 1, saturated liquid: x = 0 [45]

Values for the isobaric expansion coefficient for temperatures in the range 200 – 1000 °C and pressures between 1 and 100 MPa are listed in Table 8. They pass through a maximum between 300 and 600 °C. The isothermal compressibility defined as

300 and 600 °C. The isothermal compressibility defined as T is Table 9 shows the dependence
300 and 600 °C. The isothermal compressibility defined as T is Table 9 shows the dependence

T is

Table 9 shows the dependence of

is ±0.016×10 5 MPa 1 . The isothermal compressibility and the isobaric expansion coefficient are quantities derived from the p V T data.

T on temperature and pressure in the pressure range 1 – 100 MPa. The maximum error

in the pressu re range 1 – 100 MPa. The maximum error Table 8. Isobaric expansion

Table 8. Isobaric expansion coefficient

The maximum error Table 8. Isobaric expansion coefficient p in 10 – 3 K – 1

p in 10 3 K 1 of water and water vapor as a function of pressure and

temperature [44] *

p, MPa

t, °C

200

300

400

600

800

1000

1.0

10

20

30

40

50

60

70

80

90

2.714 1.926

1.317 3.167

1.255 2.63

1.201 2.295 36.75

1.153 2.060

1.111 1.884

1.073 1.745

1.038 1.631

1.007 1.537

0.979 1.456

1.563 1.168 0.941 0.789

2.711 1.398 1.023 0.825

7.030 1.720 1.121 0.866

2.105 1.223 0.906

7.972 2.538 1.325 0.944

4.890 2.976 1.423 0.982

3.711 3.343 1.512 1.016

3.068 3.563 1.589 1.047

2.655 3.602 1.650 1.073

2.363 3.491 1.694 1.095

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

100 0.952 1.386

2.144 3.288 1.721 1.112

*

The horizontal line denotes the transition between liquid and gaseous state.

Table 9. Pressure and temperature dependence of the isothermal compressibility

temperature depe ndence of the isothermal compressibility T of water (in 10 – 5 MPa –

T of water (in 10 5 MPa 1 ) [47]

p, MPa

t, °C

 
 

0.0

10

20

30

40

60

80

100

49.461 46.564 44.725 43.633 43.100 43.287 44.778 47.426

48.093 45.358 43.604 42.546 42.015 42.135 43.492 45.942

46.772 44.196 42.527 41.507 40.982 41.048 42.285 44.555

45.498 43.077 41.492 40.514 39.998 40.020 41.151 43.257

43.076 40.955 39.542 38.652 38.167 38.129 39.080 40.902

40.815 38.979 37.737 36.943 36.500 36.434 37.243 38.830

100 38.699 37.135 36.063 35.371 34.980 34.911 35.612 37.002

10

20

30

40

60

80

In the area of technical thermodynamics, the enthalpy – entropy diagram (h s) presented in Figure 11 is of interest. It is especially important in the design and operation of power plants.

important in the design and operation of power plants. Figure 11. Enthalpy – entropy diagram of

Figure 11. Enthalpy – entropy diagram of water [44]. x = 1: saturated vapor (x = 0 would correspond to the saturated liquid)

The velocity of sound w in water also depends on pressure and temperature. In the liquid state and at atmospheric pressure (0.1 MPa), it increases with increasing temperature. In the gaseous region and at constant higher pressure (isobaric), the sound velocity passes through a maximum at ca. 100 °C. At constant temperature, the velocity of sound increases with increasing pressure. Values for the sound velocity up to 600 °C and 100 MPa are listed in Table 10 [46].

Table 10. Sound velocity w in m/s in water and water vapor up to 600 °C and 100 MPa [46]

p, MPa

t, °C

0.0

20.0

100

200

300

400

600

0.1

1.0

10

20

30

40

60

80

1401.0 1483.2

472.8

533.7

585.7

632.2 713.9

1402.6 1484.8 1543.8

517.9

578.4

628.2 712.5

1418.1 1500.6 1564.3 1361.3

919.7

581.0 698.9

1434.9 1517.6 1586.2 1396.4 1004.4

505.8 684.8

1451.3 1534.2 1607.1 1429.1 1073.0

419.0 672.7

1467.9 1550.6 1627.3 1459.7 1131.3

627.3 664.1

1501.9 1583.0 1665.7 1515.8 1228.1

850.7 666.1

1538.1 1615.5 1701.9 1566.4 1307.6

990.8 702.9

100 1577.1 1648.6 1736.2 1612.7 1375.8 1096.7 767.3

*

The horizontal lines denote the transition between liquid and gaseous state.

2.2.2. Transport Properties

Thermal Conductivity. The thermal conductivity

Properties Thermal Conductivity. The thermal conductivity of water as a function of pressure and temperature in

of water as a function of pressure and temperature in the range 200 –

800 °C and 10 – 100 MPa is shown in Table 11. Experimental data for higher temperatures and pressures exist: for 250 °C

up to 300 MPa [48] and for 250 to 510 °C up to 95 MPa [49]. The values in Figure 12 have been taken from international

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

tabular compilations [45]. The tolerances are around 1.5 % for 0.1 MPa and 0 °C, but they reach 8 % for 100 MPa and 600 ° C. A characteristic feature is that the thermal conductivity of water shows a very pronounced peak at the critical point. This indicates that the change in structure of water is especially great at the critical point. For the supercritical region, the isobars pass through a minimum up to about 50 MPa. This minimum is more pronounced, the lower the pressure. Above ca. 50 MPa, the isobars decrease monotonously without passing through a minimum.

Table 11. Thermal conductivity of water and water vapor (10 3 Wm 1 K 1 ) as a function of pressure and temperature in the range 200 – 800 °C and 1 – 100 MPa [45] *

p, MPa

t, °C

 

200

300

400

500

600

800

1.0

35.9

44.3

56.0

68.0

81.0 108.6

10

675

557

66.9

75.6

89.4 118.1

20

684

576

104.9

91.6

98.6 122.7

30

692

593

337

114.1 112.3 130.2

40

700

608

399

152.9 129.2 139.3

60

715

634

476

277 176

161

80

729

653

521

346 235

185

100

742

672

561

412 288

215

* The horizontal line denotes the transition between liquid and gaseous state.

denotes the transition between liquid and gaseous state. Figure 12. Self-diffusion coefficient of water up to

Figure 12. Self-diffusion coefficient of water up to 700 °C and 150 MPa [51]

a)

25 °C; b)

200 °C; c)

400 °C; d) 500 °C; e)

600 °C; f )

700 °C

Dynamic Viscosity. The dynamic viscosity

300 MPa and 500 °C [50]. Figure 13 shows the temperature dependence of dynamic viscosity for various pressures in the sub- and supercritical regions. These data have been taken from SI steam tables [45]. Like other liquids, liquid water has the

highest viscosity at low temperature and high pressure (i.e., the region of high density). The viscosity of water decreases rapidly with increasing temperature, even at high pressure. In water vapor, the viscosity increases at low pressure and density with increasing temperature. Between these two limits with, on the one hand, a high and, on the other hand, a low density, a large region exists in which the viscosity of water barely changes (see Section Bulk Properties of Liquid Water).

changes (see Section Bulk Properties of Liquid Water ). of water has been studied experimentally in

of water has been studied experimentally in the high-pressure region up to

studied experimentally in the high-pressure region up to Figure 13. Dynamic viscosity of water up to

Figure 13. Dynamic viscosity of water up to 800 °C and 100 MPa [45]

Table 12 shows the viscosity, thermal conductivity, and isothermal compressibility of water [45] along the saturation curve of liquid and vapor in the temperature range 150 – 374 °C.

Table 12. Dynamic viscosity

range 150 – 374 °C. Table 12. Dynamic viscosity , thermal condu ctivity , and isothermal

, thermal conductivity

374 °C. Table 12. Dynamic viscosity , thermal condu ctivity , and isothermal compressibility the saturation

, and isothermal compressibility

the saturation state [45]

, and isothermal compressibility the saturation state [ 45 ] T of water ( ′ )

T of water ( ) and steam ( ) in

t, °C

×10 6 , Pa · s

) and steam ( ″ ) in t , °C ′ ×10 6 , Pa ·

×10 6 , Pa · s

) in t , °C ′ ×10 6 , Pa · s ×10 6 , Pa

t , °C ′ ×10 6 , Pa · s ×10 6 , Pa · s

×10 3 , W K

, Pa · s ×10 6 , Pa · s ″ ′ ×10 3 , W

×10 3 , W K

, Pa · s ″ ′ ×10 3 , W K ″ ×10 3 , W

T ×10 3 ,

×10 3 , W K ″ ×10 3 , W K T ′ ×10 3 ,

T ×10 3 ,

 

–1 m –1

–1 m –1

MPa 1

MPa 1

0.0 1793

9.216

561.0

17.07

0.5101

1 636 700

Water : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

25

890.5

9.866

607.1

18.55

0.4523

316 020

50

547.1

10.62

643.5

20.36

0.4421

92 124

100

281.9

12.27

679.1

25.09

0.4909

10 029

150

182.5

13.99

682.1

31.59

0.6215

2 205

200

134.4

15.71

663.4

40.10

0.8856

722.4

250

106.2

17.49

621.4

51.23

1.470

322.1

300

85.96

19.65

547.7

69.49

3.211

195.0

350

65.88

23.81

447.6

134.6

16.67

215.2

374

43.2

At the critical point, the thermal conductivity and specific heat capacity extend to infinity.

With increasing temperature, the compressibility increases in liquids but decreases in the gas phase. At the critical point, it approaches infinity.

Self-Diffusion. Very few investigations have been conducted on the diffusion coefficient of water in technically relevant regions of high pressure and temperature [51]. The self-diffusion coefficient as a function of pressure up to 150 MPa and temperature from 25 to 700 °C is shown in Figure 12. In this region, a pressure increase always results in a decrease in the self-diffusion coefficient.

2.2.3. Electrolytic Properties

The ion product (see Section Bulk Properties of Liquid Water) has been the subject of diverse studies and discussions. The dependence of the ion product on temperature and pressure is presented in Table 13 [52]. It shows that the logarithmic ion product (e.g., at 400 °C and 100 MPa) assumes a value of approximately 10.8 compared with a value of about 14.0 under