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Pourbaix Diagrams (EpH Diagrams) are an excellent to the left of 0 represent one mole of acid per number,
means of visualizing the what, where, and when of in other words one mole of acid would represent a pH
chemical reactions. First it would be advantageous to of 0,01 and a second mole would take the pH to -1.0.
explain a few things for those readers who are not
familiar with these diagrams. The suffix following each chemical species denotes its
state of existence. When there is no parenthetic tetter
Down the Left side you will see the Eh listed as a the species is a solid crystal. Inmost EpH diagrams
voltage. Chemical species by chemical species, the following designations are used: (a) aqueous, (1)
element by element; these are the same as you would liquid {such as mercury], (g) gas, (none) solid.
find in the electromotive series as listed in CRC, or
some other reference book. Usually the diagram is Across the top the first element listed is the element
drawn showing from +2.00 to -2.00 volts but we wish of interest and the diagram is used to show its
to have a clear view of the area of interest so we ask behavior under the chemical, physical and thermal
the computer to draw only that area above 0.00 volts. situation as defined by the temperature (at the top
right) and pressure (at the bottom). By performing
Across the bottom pH is listed and again we have literally millions of calculations the diagram emerges
made a request that instead of the traditional 0 to 14 and we can see the status of (in this case) chlorine (as
listing we required an extra two molar on the acid side combined for SSN) at any pH and Eh combination.
and only pH 8 on the alkaline side. The minus We have darkened the small area at the upper left so
numbers that cationic chlorine will not be overlooked.
Molality m Pressure p
mol / kg bar
CI 4.000E+00 CI I.OOOE+00
Na 6.000E+00 Na I.OOOE+00
N 1440E+00 N I.OOOE+00
Did you notice that there were chlorine atoms SSN leach solution contains in this instance
that were no longer associated with sodium about 1.44 molar nitric acid, therefore, you
would expect to see a pH 0 when it is mea-
chloride? If you did not go back and look at
sured. This is not the case. Actually the pH
the diagram again.
reads from pH 0.8 to pH 1.5. So far there is
The behavior of nitric acid (70%) in SSN is nothing spectacular in the EpH diagrams, so
the topic for this diagram. Nitrogen is there- let's introduce a metal into the solution.
fore the element of interest. We are again
working at 80°C so that the maximum advan-
tage of the chemistry will be well defined. Do
not misconstrue that last statement for the
reaction is the same at 25° C but the tempera-
ture difference will come into play in the next
diagram and if the temperature remains the
same there is less chance of some one misun-
derstanding.
Molality m Pressure p
mol / kg bar
Au l.0OOE*0O Aul J.OO0E+00
N I.440E+00 N I.OOOE+00
Na 6.000E+00 Na I.OO0E+00
CI 1.O0OE+00 CI I.OOOE+00