CHAPTER 10

Thermodynamic and Transport Properties

0/ Fluid Water
G. S. Keil
Division 0/ Chemistry
National Research Council 0/ Canada
Ottawa, Canada

1. INTRODUCTION

The engineers of remotest antiquity provided water for their cities. In the
Middle Ages the use of water mills flourished in Europe. In these activities
practical knowledge of the properties of water-density, volatility, and
viscosity-preceded the development of scientific understanding. Similarly,
Watt patented the condenser, making the steam engine practica1, in 1769,
before the discovery of the compound nature of water, shown by Cavendish
in 1781, and weIl before the development of thermodynamics in the nine-
teenth century.
Today, the properties of water playa key role in, for example, ocea-
nography and Iimnology, hydraulics, biochemistry, and physical chemistry.
UsuaIly, it is the thermodynamic and transport properties that have this
practical importance. Indeed, for many applications, values of properties are
needed with high precision, even though their relation to structure on a
molecular scale is poorly understood. Accordingly, many measurements
and tabulations have been made for particular purposes, the most note-
worthy being steam tables for the design of power plants.
In the present chapter the thermodynamic and transport properties
of the fluid phases, liquid and vapor, are examined from a molecular point
of view when this is available-macroscopic thermodynamics alone seems
inadequate for the study of ions in solution or of the hydration of proteins-

363

F. Franks (ed.), The Physics and Physical Chemistry of Water

© Plenum Press, New York 1972
364 Chapter 10

experimental work is surveyed, and reliable values, inc1uding those suitable

for calibration, are indicated. The liquid and vapor are considered over their
range of stability at temperatures up to the critical point at 374°C. It is
true that observations have been made on the liquid at 24°C below the
freezing point, (448) and at negative pressures of 270 bars, (124) but the liquid
and vapor will be considered here primarily in their regions of stability.
One school of thought sees liquid water as composed of distinguishable
species, with the properties reflecting equilibria among those species. This
theory has existed since about 1900, when the components were called
hydrol, dihydrol, etc. The mathematics has evolved remarkably little.
Another school(590) sees the properties ofthe liquid as reflecting distributions
of oxygen-oxygen distances and of oxygen-oxygen-oxygen angles. Both
explanations are consistent with the thermodynamic properties of the liquid;
accordingly thermodynamics does not choose between them, and structural
discussions based on these properties are idle. On the other hand, for the
low-pressure vapor the forces between molecules can be determined with
sufficient precision that it is natural to phrase the treatment in molecular
terms.
The needs of international trade in the field of thermal power genera-
tion led representatives of a number of nations to agree, in 1934, to a skeleton
table of values of the thermodynamic properties of water and steam; the
detailed tables to be used in design work were required to be within the
tolerances specified by the skeleton table at the points it gave. In 1963
the Sixth International Conference on the Properties of Steam, meeting
in New York, adopted a revised and enlarged skeleton table giving thermo-
dynamic values from 0 to 800°C and at pressures to 1 kbar, (995) as weIl as
viscosity and thermal conductivity(996) over narrower ranges. It also estab-
lished an International Formulation Committee (IFC) to obtain, for com-
puter use, formulations that were within the tolerances of the skeleton
table. (547 ,548) It is a need of the thermal power industry that the design
tables should remain unchanged for long periods-as from 1934 to 1963.
Political considerations are also said to influence the method of arriving
at the values and tolerances of th~ skeleton table. Thus, steam tables should
not be considered critical compilations for other purposes and, in particular,
they should be differentiated only with caution. Their utility for others is
that they tabulate properties over a wide range of conditions and are
available in various engineering units. *

• Tables agreeing with the 1963 skeleton table: The N.E.L. "Steam Tables 1964"(45)
give temperatures in degrees Celsius, pressures in bars, specific volumes in cubic cen-