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with a rather long S-S bond length of 2.389 A. The S02 planes are almost
parallel and elipsed. This unusual and unstable configuration of the
2_
molecule explains why the S204 ion is unstable in solution (Brasted
1961; Bailar et al. 1973).
2- 2-
2S2°4 + H2° ---- > S203 + 2HS03
(3)
S(+III) S(-II), S(+IV)
S(+VI)
In acid solutions, such hydrolysis is more rapid and follows second order
kinetics. Elemental sulphur is also produced, probably due to the
decomposition of the thiosulphate. S2°3 ion (Moellar 1973) as
_5
This reaction occurs at proton concentrations in excess of 10 M (i .e.,
pH <-5.0). On the other hand. in neutral and alkaline media, the
thiosulphate ion is perfectly stable (Moellar 1973). Therefore, reactions
of dithionite carried out in neutral or alkaline media will not cause
deposition of sulphur. This aspect of the reaction does not appear to
have been comprehended by previous workers (Deb 1950; Mitchell 8
Mackenzie 1954; Mehra 8 Jackson 1960).
21
tS03l2
RT
E E° In ----------------------- (8)
2F [S204)2.[0H]4
or
RT
E E° In
2F
22
2- 2-
when activities of SOg and $2°4 are both etlual to 1. the eqn. (9)
reduces to,
RT 4
E = E° + 2F In [OH] ......... (10)
-14
[H].[OH] 10 (ID
We have,
-14
E E° + In 10 (12)
2F [H]
The values of oxidation potential E for the reaction (5), are thereby
obtained and are as follows :
pH E (in V)
6.0 0.176
7.0 0.294
8.0 0.412
9.0 0.530
10.0 0.648
11.0 0.766
12.0 0.884
13.0 1.002
14.0 1.120
23
to form H2S or S (eqn. 18, 19). Such side reactions can account for the
formation of sulphides (FeS) observed during the reduction of iron oxides
by dithionite (Deb 1950; Mehra 8 Jackson 1960). According to Wayman and
Lem (1970)', the H2S as well S, which are produced, have a catalytic
action on the reaction (eqn. 17 ) and may themselves be consumed in the
process. Thus H2S may react with sulphoxylate, HS02 , to form S.
Wayman and Lem (1970) also pointed out that the white milky cloud of
S which is formed in the initial phase of dithionite decomposition, is
subsequently dissolved over a period of time [wz alt>o ob6zn.vzd Auch a
phznomznon in tkz AyAtzmA Atudizd by ua) . Thus, it would appear that
in dithionite solutions, of slightly acidic to alkaline pH, both H2S as
well as S would only be transient phases. The persistence of FeS during
iron oxide dissolution by dithionite can, therefore, be due to the fact
2+
that H2S reacts with Feforming FeS, which being insoluble, is no
longer available for further reaction (as in eqn. 20). Unless some
chemical agents are present in the system, which can dissolve the FeS
2+
(e.g., strong Fe complexants), the accumulation of FeS is inevitable.
Thus, a knowledge of the chemistry of dithionite can itself provide some
of the prerequisites for efficient dissolution.
The eqn. (22), however, does not take into account, the possibility
that the charge transfer process itself [i.e., M (III) M (II)] may be
rate-limiting. A more general kinetic scheme is (Blesa 6 Maroto 1986) :
k. . Q
i.J.3
M (III) -» M (III) aq
(23)
k. . _
i.J.2
M (II) ■> M (II)
aq
(rate constant)
Thus, ket^may also control the rate process. Studies on dissolution of
iron oxides (Gorichev 6 Kipriyanov 1984) have shown that any one of the
k values in eqn. (23) may be rate-limiting depending on the experimental
conditions.
Thus, the dominant reducing agent is the S09 radical which results from
2- ^
the dissolution of . The S02 is an effective reducing agent for a
wide variety of complexes and reacts by simple outer-sphere electron
transfer (Balahura 8 Johnson 1987).
citrate is removed into the solution phase. At the first stage, the
formation of the surface complex is initially extremely rapid in the
presence of excess adsorbate. The dissolution rate is proportional to the
concentration of adsorbed citrate. Once the reduced FeZ+-citrate species
are formed, they rapidly leave the Y-FeOOH surface, i.e., there is no
significant build up of Fe2+ at the surface.
surface bound then rapidly leaves the surface and goes into solution as
the Fe(II) complex. Since this last stage is very rapid, the reaction rate
would probably be controlled by the stages (i) surface-Fe^+ + complex
3+ 3+
—surface-Fe complex, and (ii) surface-Fe complex + reductant —>-
surface Fe^+ complex. Other factors which would also greatly influence
pH