RHENIUM

The Eh-pH diagrams for rhenium species are shown in Figs. 53 and 54. The
thermodynamic data for important rhenium species are given in Table 39.
Figure 53 shows the stability fields for phases in the system Re-O-H.
Similar to Tc, the important species of Re(VII) is soluble ReOi ion, which occupies much of the high-Eh part of the diagram at all pH values. Important
Re valences are (0, III, IV, VI, and VII). Under mildly reducing conditions, and
above the sulfide-sulfate boundary, Re(VII) is reduced first to Re(VI) and then
to Re(IV,III) oxides. Native Re forms at lower Eh.
With the addition of sulfur, the phases in the system Re-S-O-H are shown
in Fig. 54. Here, the field of native Re is replaced by ReS2 and most of the
Re203 and some of the Re02 and Re03 fields are replaced by ReS2 as well.
Not shown are phases such as Re304 and Re2S3 for which only questionable
data exist. The total space occupied by solids as opposed to aqueous species
in both the Tc(S)-O-H and Re-(S)-O-H systems is essentially the same. Further, Re and Tc possess the same valences and exhibit almost identical crystal
chemical behavior (Brookins 1984), hence Re is often used as an analog for
Tc in predicting Tc behavior from hypothetically breached radioactive wastes
(Brookins 1986b, 1987a).

Table 39. Thermodynamic data for rhenium

Species (state)

LtG? (kcal/gfw)

Reference

Re203 (c)
Re02 (c)
Re0 3 (c)
ReOl- (aq)
ReS 2 (c)

-138.64
- 87.95
-127.96
-165.99
- 38.10

Zoubov and Pourbaix (1966)

Wagman et al. (1982)
Calculated a
Wagman et al. (1982)
Calculated a

Abbreviations see Table 1

Method of calculation described in Brookins (1983 a)

100
D. G. Brookins, Eh-pH Diagrams for Geochemistry
Springer-Verlag Berlin Heidelberg 1988

--

>
i5

-0.5

DH

ReO.-

10
12

14

Fig. 53. Eh-pH diagram for part of the system Re-O-H.

Assumed activity for dissolved Re = to- 8
See text for discussion

0.5

1.0

>
iii

-0.5

0.5

1.0

pH

10

12

14

Fig. 54. Eh-pH diagram for part of the system Re-S-O-H.

Assumed activities for dissolved species are: Re = 10- 8 ,
S = 10- 3 See text for discussion