hYDROGEN ION CONCENTRATIOn

One type of ion that is always present in solution is the hydrogen ion H+. This is very
important in controlling many reactions, so much so that the hydrogen on concentration is often treated as a
separate control on reactions. The hydrogen ion concentration is expressed as the pH, which is the log of the
hydrogen ion concentration without the minus sign.
The pH of pure water is 7. A solution with a pH less than 7 is acid, with a greater
value is alkaline. The table below shows the pH of some natural environments:
1/

The solubility of many substances is very much affected by pH. Thus the solubility
of iron is about IOO,OOO times greater at pH 6 than at pH 8'5. Weakly acid iron-bearing
water will therefore precipitate iron when it reaches the alkaline sea. The solubilities
of alumina and silica are very markedly affected by pH as shown in Fig. 15. At very
low pH ( <4) alumina becomes more soluble than silica. Environments at this pH are
very rare, so the removal of alumina to leave a silica residue does not occur. On the
other hand, between pH 5 and 9 alumina is virtually insoluble but silica becomes increasingly soluble, and such
conditions could lead to differential leaching of silica and
the formation of laterite or bauxite.
REDOX POTENTIAL (OXIDATION POTENTIAL,
REDUCTION-OXIDATION POTENTIAL)

Some elements can exist in several oxidation states, e.g. iron, which can be native metal
(oxidation state o), ferrous compounds (oxidation state 2) or ferric compounds (oxidation state 3). The stability in
any oxidation state depends on the energy change involved in adding or removing electrons. This can be
measured quantitatively and expressed relative to the 'oxidation' of hydrogen to hydrogen ions. Oxidation
potentials are symbolised E or Eh.
The Eh varies with the ccncentration of the reacting substances, and if H or
OH is involved, then the Eh varies with the pH of the solution. The Eh becomes
lower as pH increases, and so oxidation proceeds more readily the more alkaline the
solution.
In aqueous solutions in nature, only reactions between Eh 1 '23 volt and Eh 0'00
can occur, for outside these limits water is decomposed, Environments can be plotted
on a diagram of Eh against pH, as shown in Fig. 16.
IONIC POTENTIAL

Ions in solution attract water molecules to them and the hydration of an ion is
proportional to its charge (symbolized Z) and its radius (r). The factor Z/r is known
as the ionic potential, and provides a measure of the behaviour of ions towards
water.
Elements with low ionic potential, such as Na, K and Mg, remain in solution during
weathering; elements with intermediate ionic potential are precipitated by hydrolysis;
elements with still higher ionic potentials form complex anions with oxygen that are
once again soluble (Fig. 17).
'
The concept of ionic potential is useful in explaining which elements occur together
in weathered rocks and which are removed during weathering. For instance, a number
of fairly rare quadrivalent elements are concentrated in the range of ionic potential of
hydrolysate sediments, and so bauxite may be enriched not only in beryllium and
TYPES OF CHEMICAL REACTIONS
Solution
Solution is usually the first stage of chemical weathering. It may take place in running
water, or in a thin film of water around a solid particle. The amount of solution depends on the amount of water passing the surface of the particle, and the solubility of
the solid being dissolved.
Common salt is very soluble, and only survives at the earth's crust in the most arid
regions. Gypsum is less soluble, and carbonates less still. An idea of the weathering
. '..,

of rock can be gained from an analysis of run-off water in rivers or streams. They
usually have carbonates in solutiori, and in warmer 'arcas perhaps silica, indicating
that different elements have different solubilities in different climatic regions.
Solutions mal' precipitate chemicals, which can lead to volume changes and
enhance physical weathering. By carrying ions frorn one place to another solutions'i may lead to more
combinations of reactions than if water did not move, or if there was
no circulation.
,
Smyth (1913) and Polynov (1937) suggest that the direction of weathering as a
'whole would be indexed by the relative mobilities of the elements. To arrive at nurnerical values they compared percentage compositions of salts from river waters with estimated average
compositions of the rocks composing or underlying their drainage basins.
Smyth produced generalisation for all rocks and climates, and Polynov for all igneous
rocks and climates. Their data proved to be comparable, but the order of mobilities
may not hold in all conditions. The generalisation is that the group calcium, sodium,
magnesium and potassium is more mobile than silica, which is more mobile than the
sesquioxides, Polynov concluded that the individual mobility groups are removed
successively during rock weathering, but in fact all three groups are removed simultaneously though at
different rates.
Salt concentrations in rivers frequently reflect the nature of the rack (in a general
sense) of the river basin. It is found in Victoria that the highest salinities are in areas
of Tertary laterite. At first sight It. might appear that the laterites, being already
thoroughly weathered, might have lost their salts. The high figures are probably due
to the considerable degree of percolation of ground water in the old, deep soils and
weathered rock 50 that they have enhanced opportunity to pick up salt, though the
concentration is low. In fresh rocks, percolating water has a much shorter time to pick
up salt.
A literature survey by Davis (1964) suggests silica is less variable in natural water
than other dissolved constituents. This throws doubt on the idea that 'lateritisation'