A Warning for Frost Diagrams Users

J e s ~ i M.
s Martinez de llarduya and Fernando Villafaiie
Departamento de Quimica Inorganica, Universidad de Valladolid, 47005 Valladolid, Spain
Frost diagrams ( I ) are widely used to study the redox A New Reduction Potential and Reference
properties and the behavior in aqueous solutions of the dif- Explaining this discrepancy requires a look at the refer-
ferent species of an element. They are shown in most inor- ence potential. These diagrams (a and b) have been made
eanic chemistrv textbooks to eive a visual remesentation from standard reduction potentials, that is, in reference to
zf the free energy changes assGciated with redox processes.
Amoncr the more extended books, those of Greenwood and E O ~ + l l i z=, O
~ a r n s h u w(2)and Shriver et al. (3, use them thoroughly
for most of the elcmcnts in the periodic table. Acid-solution which is represented as an a m w of slope zero in the upper
diagrams are extensively s h o d and unambiguously dis- left comer of the diaerams. Phillios and Williams defined
cussed, but there is some controversy on the basic-solution a new reduction pt&tial for basic- solution^,^ Eo(OH),as
diagrams, as we show below.
Reduction Potentials and References
Acid-Solution Diagrams This definition comes after considering the potential of
the couple H20/H2,0H- (-0.828 V) as a new reference, in-
Acid-solution Frost diagrams for nitrogen and chlorine stead of HIM2.The representation of these new reduction
are depicted in Figures l a and 2a, respectively These are potentials for basic solutions gives rise to the diagrams de-
the result of plotting the volt equivalents associated with picted in Figures l c (for nitrogen) and 2c (for chlorine). The
each species against the oxidation state. The volt equiva- slope associated with the couple H20/H2,0H-shown in the
lents are defined as the product of the oxidation state of upper left corner of the diagrams now has zero value, as
the element in the compound considered and its reduction can be immediately inferred from eq 1. The diagram ob-
potential with respect to the element (nEo).Thus, they are tained in Figure l c coincides with that shown in ref 3 (p
a measurement of its free energy (nEo= -AG"IF). Further- 248) and in ref 4 where this element is chosen for the defi-
more, the slope of the line joining any two species in the nition of EYOH).
diagram is the potential associated with this couple. The
values of the reduction potential used to construct the dia-
prams shown in F i m e s l and 2 have been taken from the
excellent review inref .?, which shows a complete collection Therefore, two different Fmst diagrams for basic solu-
of Larimer dia,qams for all the chemical elements, both in tions can be constmcted and are shown in some textbooks.
acid and basicsolutions. This would not create any trouble if the type chosen were
clearly stated. However, some problems may appear if the
A Discrepancy in Basic-Solution Diagrams reader realizes that both types of diagrams are given in the
textbooks, without any indication of which basic-solution
If we take the reduction potentials in basic solutions potential (Fobor Eo(OH))was used to construct them.
(a)
from these Latimer diagrams for the same elements,
In fad, as stated above, in ref 3 Eg is used for halogens
we can construct a new Frost diagram. The representation
thus obtained is shown in Figures l b and 2b for nitrogen but EYOH) for nitrugen. This appears on the page just be-
and chlorine. In the books cited above, only the chlorine fore the diagram for oxygen, made instead with Eg. Fur-
diagram agrees with this representation (ref 2, p 1002; ref thermore, the reference H+/H2with slope zero is only
3, p 4161, whereas that of nitrogen is clearly different (ref shown in the nitrogen diagram, where&: (reductionpoten-
3, p 248). tials in acid solutions) and EO(OH) are depicted, but this

Oxidation state
Figure 1. Frost diagrams for nitrogen. (a)Acid solution. (b) Basic solution, from e.(c)Basicsolution, from ,!?(OH),
480 Journal of Chemical Education
 Oxidation state

Figure 2. Frost diagrams forchlorine. (a)Acid solution. (b) Basicsolution,from P. (c)Basicsolution, from @(OH).

can only be used for diagrams constructed fromE0,or Eg, as fill eq l (0.73 = -0.13 + 0.828). From the value obtained in
explained before. eq 4, it might be inferred that nitrate is also a good oxidant
On the other hand, ref 2 shows the same diagram with in basic media. However, the potential obtained in eq 3 in-
Eg for the halogens (p 1002). However, that of P, As, and Bi dicates that its reduction to form NO is not thermodynami-
(p 673) has been made from ,!?(OH) values. This is not cally favored. Then which of these two predictions is true?
specified in the text, although the reference potentials Obviously, the answer is both, once the reference poten-
shown in the upper left comer of the diagrams coincide tials (shown in the upper left corner of the diagrams) are
with the representation chosen. Therefore, because two considered in each case.
different Frost diagrams can be constructed for basic solu- Figures l b and l c (and eqs 3 and 4) indicate that the
tions, it is important to always use the same criteria. Oth- potential in basic solution of the couple NOmO is lower
erwise, an explicit statement of the diagram type chosen than that of
would be very valuable in avoiding erroneous predictions. HIM2 -0.13 < 0
Correct Use of the Diagrams but higher than that of
Below we illustrate how the use of the correct diagram H20M2,0K g:4.13 > -0.828arE"(0H):0.73 > 0
prevents wrong conclusions, or how some predictions de-
pend on the nse of each type of basic-solution diagram. Thus, the observation of diagrams l a and l c (or both
plotted in the same set of axes, a s depicted in refs 2 and 4)
Is Nitrate Ion a Stmng Oxidant in Basic Media Also? without remembering the reference potentials could lead
The h o w n oxidative character of nitric acid is shown by to the conclusion that the oxidative trend of nitrate is simi-
the positive value of the slope associated with the NO-NO lar in acid and basic solutions.
couple (consideringNO as the reduced species) in acid so- Are the Potentials of the Ch/Cr and NO& Couples
lutions. From Figure la, we get Invariable with pH?
The previous example reflects the well-known fact that
most potentials depend on the pH ofthe solution, but some
couples do not. The two systems chosen in this example
serve to show what "same slope in acid and basic dia-
However, the value o~E&;~No)
in basic media depends on grams" means, depending on the type of basic diagram
the diagram used. chosen.
From Figure lb, we get The couple CI&- shows the same slope in Figures 2a
and 2b.

From Figure lc, we get

This means that the potential does not change with pH,
as seen in the half-reaction.

Obviously, these are approximate values because they The representation of this reduction potential as a func-
have been calculated from the diagrams, but they must ful- tion of pH is thus a horizontal line, as depicted in Figure 3.

Volume 71 Number 6 June 1994 481

 The representation of this potential with respect to pH
gives rise to a straight line of slope -0.06, which is the
same as that of the reference couple Ht/H2(or H20/H2,0H-
for basic media), as depicted in Figure 3.
2H' + 2 e + Hz

Therefore, we conclude that the potential of a couple that

shows the same slopes in diagrams of types a and c (from
E: and EYOH)) varies with pH as the reference. This also
could have been inferred from Figures l a and l c because
the slope of the NO/& couple remains invariant with re-
spect to the reference potentials shown in the upper left
corners of the diagrams. On the other hand, the mainte-
nance of the slope in diagrams of types a (from g )and b
(from @) indicates that the potential of the couple (such as
C1&-) does not change with pH.
Figure 3. Variation of the reduction potentials of the reference, and of
the couples CI&-and NOIN, with pH. Conclusions
It is evident that Fmst diagrams for acid solutions may
The value found in Figure 2-2, P(OH), for this couple is just be interpreted by themselves, allowing us to draw conclu-
the result of addine- 0.828 V to the value of P. as follows sions about the redox behavior of the species represented.
from eq 1. However, two different Frost diagrams can be constructed
In contrast to C11lCl-. which shows the same s l o ~ in
e dia- for basic solutions. Their interpretation requires knowing
grams of types a(fro& E:) and b (from ~ g )tde , couple which representation has been chosen, that is, which ref-
NO/& shows the same slope in diagrams l a and lc, that erence potential was used for the diagram. This can be eas-
is, from E: and EYOH). ily achieved by comparing the value of the slope associated
with any couple with the value found in tables or Latimer
diagrams for basic-solution reduction potentials. If they
coincide, it is a Eg diagram (type b in the figures). If the
slope is the result of adding 0.828 V to the value found in
This value is different from that found in Figure l b tables or Latimer diagrams, it is aEYOH) diagram (type c
(0.8 V) from @, indicating that this potential does change in the fwres).
with pH. The variation of the potential ar a function of pH Liierature Cited
is immediately inferred after applying the Nernst equation 1. Fmst, A. A.J Am. Cbm. Soe. I951,73,2680.
(when all the species present except H+are considered 1M 2. Gremwood, N. N.;Eamshaai,A. Cbrnislry~f1bEhrn"te: pe~gamon,19%.
3. Shriuer, D. F.;Atkina, P W:I a n g f d , C. H. Inorganic Cbmiatry; Oxford Univerjity.
or 1atm). 7
Lam".
4. Phillips, C. S. G.; Williama,R. J. P Inorganic Cbrnisfri; O x f d Univekq, 119% Vol
I. pp 31P321.

482 Journal of Chemical Education