J. A.
Campbell
R. A. Whiteker A Periodic Table Based
Harvey Mudd College
Claremont, California 91711 on Potential-pH Diagrams
Diagrams presenting aqueous solution
equilibria in terms of species present as a function of
pH and & have been known for almost twenty years
(1-9). Individual diagrams for all of the elements
have now been presented, the most useful that we know
of being those in reference (9). The usefulness of these
diagrams can be considerably enhanced if they are
viewed in the form of a Periodic Table as in Figure 1.
The vertical dashed lines represent the pH at which
two species containing the element under consideration
can be present in equilibrium at unit activity. The
horizontal and slanted solid lines represent the pH-&
values a t which two species of different oxidation num-
her can he in equilibrium when each species is at unit
activity. The lines enclose regions in which the ratio
of the activity of the species indicated to that of any
other species on the diagram is unity or greater. The
equation for each solid line is
where n is the number of electrons involved in the half
reaction for reducing the higher oxidation state to the
lower, &" is the standard reduction potential and m
is the number of hydrogen ions used up in the corre-
sponding half reaction. Note that m may be negative
if hydrogen ions are produced. The species involved
may be aqueous ions, aqueous neutral molecules, or
solid phases. Figure 1 indicates species by oxidation
number only. Figures 2 and 3 identify each species in
terms of its chemical formula. Figure 2 covers most
of the Group a metals and the nonmetals. Figure 3
covers mostly the Group b (transition) metals. The
diamond-shaped area for each element outlines the
pH-& range in aqueous solution between pH 0 and 14
readily obtainable without oxidizing or reducing the
water under equilibrium conditions.
We refer the reader to the Literature Cited, especially
references (5) and (9), for the methods used in con-
structing these diagrams. We constructed our own
mainly from data in references (10) and (11) and then
checked them against other available diagrams espe-
cially those of Pourbaix (9). Only minor differences
exist between those we have used here and those pre-
sented by Pourbaix, to whom we refer the reader for
details on any element. We realize that more recent
data exist hut doubt they would greatly change most of
the features shown.
Trends in aqueous solution chemistry are apparent
both for acid-base and redox equilibria. The general
increase in basicity with atomic number is particularly
marked in families I I a and IIIb, and the existence of
polyprotic acids is especially apparent in families VIb,
90 / Journal of Chemical Education
IIIa, and Va. The increase in acidity with increasing
atomic number, as one moves from left to right in the
rows in the Periodic Table is also apparent in moving
from family I a through family IVb. The variation of
acidity with oxidation states can be illustrated with
vanadium, chromium, and iron, for example, but most
of the elements do not have sufficient stable species to
make this trend apparent.
Examination of Figure 1 makes it apparent that
complexities in redox behavior occur to the greatest
extent in Groups V and VI, both a and b, and VIIb.
Much simpler behavior is noticed a t the ends of the
rows and in the I I b and I I I a elements. This is, of
course, consistent with the variation in availability of
electrons and orbitals as atomic number changes.
The Pourbaix diagrams cover only equilibrium sys-
tems but they can provide interesting insights into
kinetic effects as well. Compare, for example, the
nitrogen and the phosphorus diagrams. The nitrogen
diagram is rather simple and only a few of the common
species are found in it, but all the common species except
the element are found in the phosphorus diagram. Ap-
parently kinetic effects are important in nitrogen chem-
istry and many species are produced which are not
thermodynamically stable. This deduction is, of
course, consistent with the observation that kinetic
effects become less and less important as atomic number
increases in the N, P, As, Sb, Bi family. I n the same
way the chromium diagram shows a region marked
CrOl(,,, a species seldom found in the laboratory.
Thermodynamically CrOsc,, should form but kinetic
effects prevent this.
Construction of a Pourbaix diagram is also an excel-
lent method of checking the internal consistency of
equilibrium data and of determining areas in which such
data are missing. A considerable number of the lines
drawn in the figures are in doubt and it is almost cer-
tainly true that many more acid-base and redox equi-
libria exist than have yet been measured, for example,
M2+i",, + OH-i.,, = MOHti&,,
for the alkaline earth ions.
It seems to us that Pourbaix diagrams are especially
effective in presenting information concerning aqueous
solution chemistry in a fashion understandable by
students. The effectiveness is even greater when the
diagrams are collected in a periodic table. It would
seem feasible to explore having wall charts made avail-
able in this form. As a move in this direction we solicit
additional information which would improve the dia-
grams used here. For example, there is still disagree-
ment as to the existence of the CrOz, Mn203,and MnaOn
regions.
 Figure 2. Diagrams of pH versus & for most of the Group o metolr ond the nonmetal..

Figure 3. Diogroms of pH versus & for the transition metals.

92 / Journal o f Chernicol Education