Physical Properties of Water

K M Stewart, State University of New York, Buffalo, NY, USA

ã 2009 Elsevier Inc. All rights reserved.

Introduction these unusual properties and provide examples of

Water is an indispensable and remarkable substance how these properties may help us understand the
world of inland waters.
that makes all forms of life possible. Speculation
about possible past or present life on other planets
within our solar system, or on any extraterrestrial
body somewhere within the universe, is conditioned Density
on the evidence for or against the existence of past Density may be simply defined as the amount of
or present water or ice. Humans can and did survive weight or mass contained in a specific volume. If
and evolve without petroleum products (gas and the volumes of all substances could be standardized
oil) but cannot survive and evolve without water. to one size, e.g., one cubic centimeter (cm 3), then a
Water is the most important natural resource. measure of the weight or mass in that fixed volume
By far the greatest volume~ ( 76%) of water on gives the density. Table 1 lists a few comparative
Earth is in the oceans. A smaller fraction
~ ( 21%) is densities (rounded to two decimals) of two liquids
found within sediments and sedimentary rocks. A (water and mercury) and some selected solids.
still smaller fraction ( 1% of the overall volume) is Density differences in inland waters may be
~ and of that 1%, about 73% is in the
freshwater, caused by variations in the concentrations of
form of ice (mostly contained within the Greenland dissolved salts, by changes in the water
and Antarctic ice caps), and only about 23% of that temperature, and in pressure. For the vast majority
1% is liquid fresh- water. If we consider further that of inland lakes, only vertical differences in salt
about one-fifth of the world’s liquid freshwater is concentrations and temperatures are of significant
contained within the five St. Lawrence Great Lakes influence to mixing processes. Fixed or uniform
in North America, and another approximately one- additions of salts to the water tend to cause linear
fifth is contained within the deepest freshwater lake
on Earth, Lake Baikal, in Russia, we are left with an increases in the density of water. In contrast, fixed
unevenly distributed re- source. It is obvious that if or uniform changes in the temperature (both below
the expanding human popu- lations around the and above 4 ○C) of water cause nonlinear changes
world do not conserve and manage this precious in the density of water (see Table 2). The density of
resource very carefully, they put them- selves at pure water is maximum at a temperature of 4 ○C
great peril. (3.98 ○C to be precise). It is at this temperature that
Liquid water can be formed through some the interatomic and intermolecular motions and
hydrogen bonding and electrostatic attraction of intermolecular distances of water molecules are least.
two slightly positively charged atoms of the One consequence of this reduction is that more
gaseous hydrogen mole- cules of H2O can fit into a fixed space at 4 ○C
(H) and one slightly negatively charged atom of the than at any other temperature. This compaction
gaseous oxygen (O) to form one molecule of water allows the most mass per unit volume and thus the
(H2O). Figure 1 provides two views of that polar greatest den- sity. It is especially noteworthy that the
molecule. Figure 1(a) and 1(b) show the somewhat temperature at which water has the maximum
lopsided or asymmetrical arrangement of two density is above its freezing point.
smaller hydrogen atoms, separated by an angle of Because the differences in densities, within a few
105○, and a larger oxygen atom. Figure ~ 1(a) is a degrees above and below 4 ○C, are very slight, it
simple ‘ball and spoke’ representation whereas takes relatively little wind energy to induce
Figure 1(b) shows the shared electron orbits, positive substantial ver- tical mixing when water
( ) and negative ( ) poles, andþthe number (eight temperatures are within those ranges. An example
each) of protons and neutrons in the nucleus of the period, for those lakes that become covered with ice
oxygen atom. in the winter, would be shortly before an ice cover
The relative elemental simplicity of water is develops and shortly after the ice cover departs.
some- what deceptive because of the great However, it takes much more energy to cause
influence that some of the unusual properties of extensive mixing when the den- sity differences are
water have on the physics, chemistry, and biology high, such as is common between the usually warm
of the world gener- ally, and on the distribution of upper waters and colder lower waters of Temperate
life specifically. The following discussion will Zone lakes during summer.
describe briefly some of

148
 Properties of Water _ Physical Properties of Water 149

105°
The greater the top-to-bottom differences in temper-
ature, the greater the top-to-bottom differences in
density and, consequently, greater are the energies
105°
required for wind-induced mixing.
+ + There is an old, but still valid, cliche´ in the northern
hemisphere that ‘. . . it is cold up north and warm
down south.’ Water temperatures in more northerly
8+ Temper- ate Zone lakes tend to average cooler than
8n those of more southerly tropical lakes. Interestingly,
although the upper-water summer temperatures in
tropical lakes are somewhat higher than those of
Temperate Zone lakes, the lower-water temperatures
(a) (b) in tropical lakes
Figure 1 Two schematic representations (a) and (b) of a water are substantially higher than those ordinarily found in
molecule. (Modified from various sources.) the lower waters of Temperate Zone lakes. It might
there fore seem that there would be an easy top-to-
bottom mix of the water in tropical lakes. Indeed
Table 1 Some comparative densities of water and other
some shallow tropical lakes, with only slight top- to-
substances or elements
bottom temperature differences, may have this.
However, because of the nonlinear increases in water
Substance Densities (g cm—3) density with temperature, tropical lakes can be
surpris- ingly stable and resistant to much vertical
Wood mixing. Table 2 provides a listing of some
Seasoned balsa 0.11–0.14 comparative densi- ties. Let us consider two
Seasoned maple 0.62–0.75 hypothetical lakes with just a 2 ○C spread between
Seasoned ebony 1.11–1.33 their lower and upper waters. For example, if a
Water 1.00 Temperate Zone lake in the spring, not long after the
Calcium 1.55 ice departed, had lower and upper waters of 4.0 and
Aluminum 2.70 6.0 ○C, respectively, the density difference would be
Iron 7.87 ¼ —3. In
1.00000 – 0.99997 0.00003 g cm
Lead 11.34
contrast, a warmer tropical lake whose lower and
Mercury 13.55
upper water temperatures may be 26.0 and 28.0 ○Cs
Uranium 18.95
would have density differences that are much
Platinum 21.45
greater (0.99681 – 0.99626 0.00055 g cm—3).
Thus, the top- ¼
Information from multiple sources.
to-bottom ratio or density difference of these two
lakes with a temperature difference of just 2 ○C
Table 2 Comparative densities of average ocean water (salinity would ~ be 55/ 3 or 18 times as great in the tropical
~35%), freshwater ice, and pure distilled water at different lake as in the Temperate Zone lake. The example
temperatures above is only hypo- thetical but it shows the
nonlinear influence of density changes with
Temperatures (○C) Densities (g cm—3) temperature, a property of water that influences, to
varying degrees, the stratification and
20.0 1.02760, ocean water (salinity 35%)
0.0 0.9168, freshwater ice
0.0 0.99987, pure water (from here on) mixing of lakes around the world.
2.0 0.99997
3.98–4.00 1.00000
6.0 0.99997
8.0 0.99988 Heat Capacity/Specific Heat
10.0 0.99973
12.0 0.99952 Heat is a form of energy and, as such, we can
measure
14.0 0.99927 changes in the temperature of a given volume of a
16.0 0.99897 substance and determine its heat capacity. Water is
18.0 0.99862 the common standard used and its heat capacity
20.0 0.99823
22.0 0.99780 (arbitrarily defined as the heat needed to increase
24.0 0.99733 the temperature of 1 g of water by 1 ○C) is
32.0 0.99505 compara-—1
26.0 0.99681 is 1 callarge.
tively g . That
Whenquantity may
the mass not seem
is also like much
considered then
Values from Hutchinson (1957), Pinet (1992), and Weast and Astle but,
(1979).
the compared to other materials, the heat capacity
or
150 Properties of Water _ Physical Properties of Water

specific heat of water (1.00 cal g —1) and ammonia

(1.23 cal g—1) are much greater than that of most higher terrain during winter, when enhanced snows
other substances (Table 3). Consequently, these permit additional winter skiing, snowmobiling, and
two liquids are commonly used to exchange heat in other winter sports.
refrig- erators and air conditioners. However, some influences of a lake’s heat capacity
Along with its ever changing and mesmerizing aes- have ‘detrimental economic consequences’. There
thetic qualities, inland waters are of immense impor- are costs involved with snow removal, increased
tance in the storage and release of heat. In terms of vehicu- lar accidents (because of slippery roads), the
freshwater lakes, the influence of their heat capacity corro- sion of cars (attributable to road salts), and the
can be seen most easily around very large lakes potential long-term ecological changes associated
located in Temperate Zone latitudes and more inner with lake and stream salinization. There are also
continental areas. It is in these areas that even larger greater heating costs in spring as cooler water bodies
swings in seasonal air temperature would ordinarily extend their cooling influence inland. In late fall and
occur in the absence of those lakes. Parts of the winter, before an ice-cover develops, heavy snows
immediate surrounding areas of Lake Baikal in may result when water vapor, being formed by evap-
Russia (this is actually the world’s deepest orative processes off a relatively warm lake, is buoyed
freshwater lake as well as one with the greatest into much colder Arctic air (northerly Temperate
volume of water) and the five St. Lawrence Great Zone) crossing the lake. The rising water vapors
Lakes of North America are prime examples of the may freeze, coalesce to ice crystals, and be carried
‘thermal buffer- ing’ these large lakes provide to down wind to shore areas where they fall out as
their surroundings because of their large heat snow. Perhaps the most dramatic of all the detrimen-
capacity. tal consequences is seen following the sometimes
paralyzing effect of occasional, but intense, ‘lake-
For humans, this may mean some ‘beneficial eco- effect’ snow storms of mesoscale proportions. The
nomic consequences’ as portions of a lake’s heat lake- effect snow storms tend to have their greatest
capacity are slowly released or ‘shed’ to down-wind impact at the downwind end of the St. Lawrence Great
regions as the fall and winter seasons progress. The Lakes after very cold Arctic air ( 13 ○C colder than the
immense thermal capacity of Lake Baikal is such that tem- perature of the lake) has moved across a long axis of
the lake and its immediate environments are roughly the lakes and deposited its snows. These deposits or
10 ○C warmer in December and January, and about drops of snow may be in a broader synoptic pattern, but
7 ○C cooler in June and July, than in the cities of sometimes they are in very ≤ narrow bands of thick
Irkutsk (about 50 km to the west of the southern snow that may bring auto traffic, schools, and busi-
half of Lake Baikal) and Ulan-Ude (about 70 km to nesses to a stop. In the St. Lawrence Great Lakes region
the east of the lake). Several coastal and near-coastal of North America, three of the better known areas
regions of the St. Lawrence Great Lakes also provide where unusually heavy deposits of lake-effect snows
impressive beneficial evidence of the influence of the may occur are (1) portions of the Upper Peninsula of
Great Lake’s heat capacity. There may be reduced Michigan on the southeastern shore of Lake Superior,
costs associated with home and business heating in
some coastal regions. An extended or milder autum- (2) the southeasterly and easterly shores of Lake
nal period permits greater production in near-shore Ontario, especially the Tug Hill Plateau area of New
plantations of fruit trees and vineyards. Economic York State, and (3) the easterly end of Lake Erie,
benefits may also accrue in some coastal regions of around Buffalo, NY. Indeed, the St. Lawrence Great
Lakes have been considered ‘weather factories’
capable of causing twists of climate found in few
Table 3 The specific heat (cal g—1) of selected substances other parts of the world.
compared to that of ice, pure water, and ammonia
Aluminum 0.215 Heat of Fusion/Melting
Copper 0.092
Gold 0.030 This is just the amount of heat exchanged during a
Lead 0.030 phase shift from either liquid water to solid ice, or
Silver 0.056 from solid ice to liquid water. One gram of water at
Zinc 0.092 0.0 ○C can be converted to ice at 0.0 ○C if 80 cal
Ethyl alcohol 0.60 (79.72 cal g—1 to be precise) are released in the pro-
Ice (at 0 ○C) 0.51 cess. The same quantity, i.e., 80 cal, is required to melt
Water 1.000 that 1 g of ice back to 1 g of water. No further
Ammonia 1.23 caloric additions or subtractions are needed to effect
Information from multiple sources. the phase shift.
 Properties of Water _ Physical Properties of Water 151

Because of the heat needed to melt ice, the spring period can delay the date the ice
researchers might intuitively expect to see a brief disappears. However, with increasing amounts of
but substantial drop in the mean or weighted lake- solar radiation, rising air temperatures, melting
water temperature when the ice cover of a lake snows, and darkening ice, the water below the ice
melts in the spring season. For example, assume may be gaining some heat from solar inputs at the
there is a hypothetical northerly latitude and a 20-m same time it is losing some heat in melting an
deep lake in late winter (March). Consider that the overlying ice cover. Moral of the story: Do not
lake is covered with 50 cm of ice at 0.0 ○C. expect a big drop in mean water tem- perature as an
Consider further that the weighted mean ice cover melts on a lake.
temperature of the 1950 cm (essentially 1950 g)
water column below the ice is 3.0 ○C. The heat
content of that water column would be 5850 cal
(1950 g 3 cal g—1 5850 cal). Assuming that there
are no further gains or losses of heat to the lake, the Heat of Vaporization/Condensation
×
amount of heat required to melt the ice would be As was the case for ‘Heat of Fusion/Melting,’
3680 cal (80 cal g—1 50 cm of ice 0.92 g cm—1, the heat of vaporization/condensation also
allowing for density of pure ice rounded to two represents the amount of heat exchanged during a
deci- mals 3680 cal). × ×
If some of the caloric content phase shift. For vaporization, it is the quantity of
of the water column could be used to melt all the heat (540 cal g—1) needed to convert 1 g of water to
ice, ¼the total caloric content would drop to 2170 1 g of water vapor. The same amount of heat is
cal (5850 cal – 3680 cal 2170 cal). If those 2170 exchanged or released in the phase shift during the
cal were now equally distributed within a 1-cm 2 condensation of 1 g water vapor to 1 g of water.
square and 20-m (2000 cm, essentially 2000 g) Aquatic scientists may be naturally impressed
deep water column, ¼the mean water temperature with the large amount of heat exchanged (80 cal g—
would need to drop from 3 to 1.08 ○C (2170 1
) in the phase shift from water to ice, or from ice
cal/2000 cal 1.08 ○C). A drop of about 2 ○C during to water, but the amount of heat exchanged (540 cal
the melting of ice would be large! g—1) in the phase shift from water to water vapor, or
As it turns out, the hypothetical example ¼ in the water vapor to water is 6.75 times larger (540/80
above paragraph is not realistic. Some background 6.75). Although the importance of this large ¼ amount
follows. Many years ago as a graduate student, I of heat exchange via vaporization or condensation
took daily measurements of ice thickness and top- may be underappreciated by humans, it is huge. On
to- bottomwater temperatures for two winters and a small but critical scale for life, water evaporating
right through the spring ice break up in a off perspiring warm-blooded animals, including
Midwestern U.S. lake. From conversations with humans, helps maintain body temperatures within
others, I was told to expect, and did anticipate, a narrow survivable limits. On a global scale, the
substantial drop in mean water temperature as the seemingly endless phase shifts between liquid water
ice melted... especially in the last few days of ice and water vapor in the atmosphere are key
cover when the ice thinned rapidly. However, I did determinants in the redistribution of water and heat
not measure any big drops in lake temperature and, within the hydrological cycle around the world.
in retrospect, should not have anticipated them. The
reasons researchers do not see large decreases in
lake temperatures with ice loss reflect some
interacting physics. For example, there may be
somewhat differing weather patterns each spring. Isotopes
The ice generally melts over an extended period of An isotope is one of two or more forms of the same
time, from several days to several weeks, not chemical element. Different isotopes of an element
suddenly. Half or more of the total ice thickness have the same number of protons in the nucleus,
may be lost from the top of the ice by melting from giving them the same atomic number, but a
warming air temperatures above the ice, not different number of neutrons giving each elemental
necessar- ily from waters that are just above isotope a different atomic weight. Isotopes of the
freezing below the ice. Because of its albedo same element have dif- ferent physical properties
(percent of incoming solar radiation that is (melting points, boiling points) and the nuclei of
reflected back into space) dark or open water some isotopes are unstable and radioactive. For
generally reflects only a small fraction of the water (H2O), the elements hydro- gen (atomic
incoming solar radiation, whereas white snow cover number 1) and oxygen (atomic number 16) each
on a frozen lake can reflect a large fraction of have three isotopes: 1H, 2H, and 3H for hydrogen;
16
incident radiation. Indeed, snow cover extending O, 17O, and 18O for oxygen. In nature, the 1H and
into
152 Properties of Water _ Physical Properties of Water

16
O (usually just given as O) isotopes are by far the
most common. In water, the water molecule may be
Surface Tension and Cohesiveness
given as 1H2O or hydrogen oxide, 2H2O or deuterium Surface tension may be regarded as the resistance
oxide, and 3H2O or tritium oxide, the radioactive one. offered by liquid water to forces attempting to
Both of the latter two are sometimes called heavy water deform or break through the surface film of water.
because of their increased mass. However, the phrase It is an interesting property and, for water, the
‘heavy water’ gained notoriety primarily because of surface ten- sion measured in Newton’s per meter
(N m—1), is high
and shows a slight increase as the temperature falls
the association of 2H2O or deuterium oxide, also
called the deuterated form of water, in the develop- from 100 (0.0589 N m—1 ) to 0 ○C (0.0765 N m —1
).
ment of nuclear weapons. Many elements have iso- The molecules of water are strongly attracted to
topes, but the isotopes of hydrogen and oxygen are of each other through their cohesiveness (attraction of
particular interest because fractionation occurs in like substances). The properties of surface tension
vapor–liquid–solid phase changes. Heavier molecu- and cohesiveness work together in water in shaping
lar ‘species’ tend to be enriched in the condensation the small rounded water droplets seen on a table top
phase and lighter molecular ‘species’ in the or a car windshield. The same properties help to
vapor phase. Some isotopes can be used to great form the slightly flattened to spherically-shaped
advantage as tracers in understanding water raindrops as they fall through the air.
movements and exchanges within atmospheric, The primary force for restoring larger wind-gener-
oceanic, lake, stream, and ground water systems. ated surface and internal waves of lakes is gravity, but
the primary force for restoring the much smaller cap-
illary waves or ripples on a lake’s surface seems to be
surface tension of the water itself.
Sublimation The surface tension of water is sometimes used to
advantage in parlor games in which someone claims
Water is said to be sublimated, sublimed, or that he/she can float a more dense (than water) steel
undergo sublimation when it passes directly from a needle on less dense water. When the needle is low-
solid (ice) stage to a gas (vapor stage) without ered slowly and carefully with its long axis paralleling
becoming a liquid in between. The latent heat of the surface of the water, it may be possible to ‘float
sublimation, i.e., the heat required to make the form the needle’ because the high surface tension of
of water change from ice to a water vapor, is 679 the water may prevent the needle from sinking. Do
cal g—1. This quantity is larger than the heat not try this by lowering one of the sharp ends of the
required to melt ice (80 cal g—1) and vaporize water needle first because a point application of the needle
(540 cal g—1) com- bined (80 540 620 cal g—1). will exceed the surface tension of the water film, and
Because there
þ may be multiple heat sources and the needle will sink rapidly.
sinks (e.g., the air above the ice and the water When responding to a ‘fire call’ in fire trucks,
below the ice) associated with changing ice water is the most common and practical substance
thickness on frozen Temperate Zone lakes, it is a used by firemen. Water is cool, it suppresses heat, it
challenge to assess the quantitative role that puts out fires and sometimes there is much water to
sublimation may play in those changes. spare. However, the high surface tension of water
Some practical effects of sublimation may be can reduce its effectiveness in suppressing some
visual- fires. Surfactants are compounds that reduce the
ized by observing a reduction in the volume of surface tension of water. In their response to a ‘fire
some dry ice (solid CO 2) or camphor. In another call’ fire- men often quickly attach hoses to street
example, after several weeks of continuing fire hydrants and spray water from that source on a
subfreezing tem- peratures and deep frost, and burning struc- ture. Although the addition of tiny
assuming that no deicing salts were used, quantities of sur- factants to water may help put out
sublimation is most likely responsible for the slow fires, it is not practical (or safe) to add surfactants
disappearance of an ice sheet over the surface of a to an entire distribution system of a city. However,
frozen sidewalk. Sublimation is also the main the addition of tiny quantities of surfactants to the
process by which wet clothes, which were hung out volume (roughly 1.89 m3 or 500 gallons in the
to dry in subfreezing temperatures, may dry. In the United States) of water being carried in the fire
latter case, the water on the clothing quickly freezes truck would make that truck water ‘wetter.’ Some
to ice, but then slowly vaporizes through combustibles could be penetrated more easily by this
sublimation, and the clothes dry. In more recent wetter water of reduced surface tension and selected
years, freeze-dried vegetables, fruits, and other fires could be put out more rapidly.
products (including instant coffee) provide other
examples where the prac- tical application of
sublimation is utilized to both market and preserve
food.
 Properties of Water _ Physical Properties of Water 153

There is a specialized community of organisms,

sometimes called neuston, associated with the Colligative Properties
surface film. For many observers of nature, it is These are the four special properties of water that
always fascinating to see small insects such as pond are significantly altered or modified when solutes
skaters or water-striders (Gerris sp., within the are added to and dissolve in water. The alterations
insect Order Hemiptera), and whirligig beetles or modifications of a colligative property (regarded
(Gyrinus sp. and Dineutes sp., within the insect as a binding property) may be predictable in dilute
Order Coleoptera), running around on the surface solu- tions when the number of solute particles is
of ponds, sheltered lakes, and some streams. known. It is the number of solute particles, not their
Because of padded ends to the long middle and chemical nature, that determines the extent to
hind feet of water striders, and the much shortened which a property is modified.
but paddle-like feet of the whirli- gig beetles, the The four colligative properties of water are vapor
high surface tension of the water is such that the pressure (when water is in equilibrium with its
insects may dimple, but not break through, the own vapor), osmotic pressure (the pressure
surface film. controlling the diffusion of a solvent across a
One of the easiest ways of getting popcorn into semipermeable mem- brane), boiling point (the
your mouth is by touching your tongue to some temperature at which water undergoes a phase shift
pop- corn in a container. Here again it is the surface to a gas), and freezing point (the temperature at
tension of the water on your tongue that lets you
‘hold on’ to the light popcorn easily. which water undergoes a phase shift to a solid).
Even at standardized pressures and temperatures,
the extent to which a property is modified depends
on the number of solute particles added. Generally,
Viscosity if we add a fixed number of solute particles of a
sugar or salt to a liter of pure water, there would be
This property may be thought of as the internal fric- some consequences. The vapor pressure would be
tion or resistance exerted on one substance (gas, liq- lowered but the osmotic pressure would rise. The
uid, or solid) as that substance tries to flow or move boiling point (also termed boiling-point ele-
through the same or another liquid. One way of vation) would be elevated a bit above the usual
visualizing the influence that liquids or semiliquids boiling point of 100.0 ○C. In the latter case, a
of progressively greater viscosities might exert watery mixture with solutes (e.g., a well-mixed
would be to take three glass marbles (same diameter soup being heated for a meal) would have to get
and density) and drop one in each of three similar- hotter than the boiling point of pure water before it
sized glasses, one glass containing water, one light oil, would boil. The free- zing point would be lower
and one honey, all at the same temperature. The than 0.0 ○C. A practical application of this (also
marble would descend quite rapidly in water, more termed freezing-point depres- sion) is easily seen,
slowly in the light oil, and very much more slowly in in parts of the northerly Temperate Zone in winter,
the glass of honey. In this example, honey would following the application of deicing salts to melt
obviously exert the most friction or resistance to the ice and snow on roads and sidewalks. Although
movement through it and have the greatest viscosity. not a colligative property as such, a simple increase
Viscosity is usually measured in poises (N s m —2) or in physical pressure also lowers the melting point
centipoises ( 0.01 P). Water at 20 ○C has a viscosity of ice ( 0.007 ○C/atm) and helps form snowballs
of 0.01002 P or 1.002 cP. (when the snow is not too cold) and form a
The rate of passive descent through a liquid ~
lubricating layer of water under the blade of an ice
¼
reflects the density of the liquid itself as well as the skate.
surface area and density of the substance moving
through it. Viscosity changes with water
See also: Ice; The Surface Mixed Layer in Lakes and
temperature in that viscosities decrease as water
temperatures rise and increase as water Reservoirs.
temperatures fall. Many fish are powerful enough,
slippery from mucous on their skin, and shaped so
they can ‘slip through’ water relatively easily. In
contrast tiny zooplankton, with multiple projections Further Reading
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