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This introductory chapter is about liquid water and some of its important
properties - those that enable it to act as a good solvent for ionic and
polar substances.
I.I Introduction
A
consists of a
dissolved in a
. The solute is
recoverable from the solution, e.g. sodium chloride dissolved in water is
OH
1.2
Liquid Water
Figure
(a) The structure Of
the water molecule; (b) the water
molecule dipole moment
w2
70.8% of the Earths surface] with only 2% existing in the solid state as
polar ice and glaciers. Ground water, aquifers, lakes, soil moisture and
rivers account for the very small remainder. Like all liquids and solids,
water exerts a vapour pressure and at any time there are about 1.3 x 1019
grams in the atmosphere (0.0009% of the Earths total) and it is
replenished every 12 days or s0.l This amount seems to be rather small,
but if all the water vapour were to be precipitated evenly over the Earths
surfzice instantaneously as rain there would be a layer 2.5 cm thick. The
vapour is responsible for a substantial fraction of global warming, the
retention of energy in the atmosphere, in the absence of which the Earths
surface would be some 33 C cooler on average.
The triatomic water molecule has a bond angle of 104.5 in its electronic
ground state, and the O-H bond lengths are 96 pm. Its structure is shown
in Figure 1.2(a). The electronegativity coefficients (Allred-Rochow)2 of
hydrogen (2.1) and oxygen (3.5) are sufficiently different to make the
molecule
with a
of 1.84 D [l Debye (D) = 3.33564
x
C m]. The
of the molecule is shown in Figure 1.2(b), the
oxygen end being negative with respect to the two hydrogen atoms. In
addition to the normal van der Waals intermolecular forces that operate
between molecules, the relatively bare protons of the water molecule
and the electronegative - and so relatively electron-rich - oxygen
atom allow the formation of hydrogen bonds between adjacent molecules in the liquid and solid states. Hydrogen bonds in water have bond
enthalpies of about 20 kJ mol- I , which is weak compared with the
strengths of single covalent bonds, which lie in the region 44 (Cs-Cs) to
570 (H-F) kJ mol-. However, H-bonds are responsible for the
abnormally high values of the melting and boiling points of water,
considering its low relative molar mass of 18.
2 x 96 x
6.19 x lo-''
x cos( 104.5/2) x 1.602 x
= 0.33e
Over many years, rivers have carried the results of weathering of the rocks
to the oceans, which have an enormous total ionic content as indicated by the
data given in Table 1.2. Typically, when 1 dm3 of seawater is evaporated to
dryness, 42.8 grams of solid are produced, which contains sodium chloride
(58.9%), magnesium chloride hexahydrate [MgC12.6H20](26.1 YO),sodium
sulfate decahydrate [Na2S04.10H20] (9.80/0), calcium sulfate (3.2%) and
potassium sulfate (2%). Other compounds are present in minute amounts.
~~~~
Element
Chlorine
Sodium
Magnesium
Sulfur
Calcium
Potassium
Bromine
Carbon (as carbonate and
hydrogen carbonate ions)
Strontium
Boron
SiIicon
Fluorine
Concentrabon/mg dmP3
19,400
10,800
1290
905
412
399
67
28
8
4.4
2.2
1.3
The major physical properties of water are given in Table 1.3. The
abnornially high melting and boiling points already referred to are
caused by hydrogen bonding in the solid and liquid phases, respectively.
The structure of solid water (ice) formed at 0 " C and 100 kPa pressure,
called ice-I,,, is shown in Figure 1.4.
Value
1 Siemen (S) = 1 SZ
0 "C,
273 15 K
100 "C,
373 15 K
4 "C,
277.13 K
999 975 kg m
997 048 kg m - 3
78 54
5.5 x
S"m
1 008 x 10-l 4
5583 kJ mol
-285 83 kJ rnol-237.1 kJ rnol
'
'
-'
'
' (reciprocal o h m )
oo'.
\
0
'
\
0-0
Compound
Water
Methanol
Liquid ammonia
Propanone
cc14
Benzene
Hexane
Temperature1 C
Relative permittivitL; E ,
25
78.54
32.63
22.4
20.7
2.24
2.28
1.89
25
- 33.4 (b.p.)
25
20
20
20
million times higher than that of water. This illustrates the effect of the
dissociation of ionic substances when they are dissolved in water:
Na'C1- (s) +. Na+ (aq)
+ C1- (aq)
(1.3)
(1.4)
in which liquid water dissociates slightly to give equal concentrations of
hydrated protons and hydrated hydroxide ions. The equilibrium constant
for the reaction is:
( 14
Kw = ~ H - c I O H -
= yc/a"
where c is the molar concentration (in mol dm-') of the solute, y is the
and u"is the standard molar activity of 1 mol dm-3.
In very dilute solutions, y may be taken to be 1.O and the autoprotolysis
constant may be formulated as:
'
H+(aq)
+ OH-(aq)
is thermodynainically spontaneous.
---$
H20( 1)
(1.9)
10
Equation (1.9) is also one of the most rapid chemical reactions. The
second-order rate constant is one of the largest on record, 1.4 x 10"
dm3 mol
s at 25 * C. The reaction rate is diffusion controlled, i.e. the
rate depends on the rate of diffusion of the reactants towards each other
rather than their chemical characteristics, and there is a reaction every
time the reactants meet.
The very negative values of the thermodynamic properties of water
given in Table 1.3 (the standard enthalpy of formation, AfH", and the
standard Gibbs energy of formation, Afi") indicate the considerable
thermodynamic stability of the substance compared with the constituent
elements in their standard states. The contributions to the value of the
standard enthalpy of formation of liquid water may be calculated from
data for bond energy terms and the known enthalpy of vaporization
(latent heat) of the liquid. The formation of gaseous water from
dihydrogen and dioxygen in their standard states may be represented
by the equations:
' '
H,(g)
2H(g)
+ 2H(g)
+ O(g) -+
2A,H"(H? g)
=2
x 218 kJ molF'
-926 kJ mol-'
(1.10)
(1.12)
H2k) + '/202(g)
H20k)
(1.13)
'.
H20(1)
(1.14)
'.
11
12