hydrometallurgy

ELSEVIER

Hydrometallurgy 42 (1996) 209-219

On the catalysis of ferrous sulphate oxidation in

autoclaves by nitrates and nitrites
Susan A. Baldwin a Gus Van Weert b,,
a Department of Bio-Resource and Chemical Engineering, University of British Columbia, Vancouver, B.C.,
Canada
b Faculty of Mining and Petroleum Engineering, Delft University of Technology, Delft, The Netherlands

Received 27 January 1995; accepted 20 September 1995

Abstract
The effect of small concentrations of nitrate (KNO 3, HNO 3) and nitrite (NaNO 2) on ferrous
sulphate oxidation in a sulphuric acid solution under pressure was investigated. Nitrate did not
result in noticeable acceleration of ferrous ion oxidation, whereas the same concentration of nitrite
resulted in significantly catalyzed oxidation. Experimental results also suggested that the nitrosoferrous complex, Fe(NO) 2, if present, does not adversely affect the reaction rate. In addition, gas
venting did not result in a loss of catalyzing effect, and hence NOx species. These results show
that adoption of nitrite-assisted oxidation in autoclaves used for minerals processing could result
in more efficient operations.

1. I n t r o d u c t i o n
Aqueous processing o f minerals often requires high temperatures and pressures,
particularly for refractory sulphides such as pyrite. This is due to slow reaction kinetics
and the low solubility of gaseous oxygen in electrolyte solutions. High oxygen pressures
are often needed so as to increase the driving force for g a s - l i q u i d mass transfer. Thus,
oxidation of these sulphide minerals is carried out in autoclaves. The major operating
costs are due to oxygen consumption, both in the production or purchase of high purity
oxygen and in power consumption o f the agitators. There is, therefore, much incentive to

* Corresponding author. Present address: Oretome Ltd., 16668 Humberstation Road, R.R. #3 Caledon East,
Ont., Canada L0N 1E0. Fax: + 1 905 880 3748
0304-386X/96/$15.00 Copyright 1996 Elsevier Science B.V. All rights reserved.
SSDI 0304-386X(95)00092-5

210

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996) 209-219

improve the reaction kinetics and oxygen transfer, ultimately to enable oxidation of
sulphides with air at much lower temperatures and pressures. Attempts in this direction
have already been made by using nitric acid for aqueous oxidation of auriferous
sulphides, combined with the N O / N O z couple to extract the oxygen from air at
atmospheric pressure [1]. Some industrial operations are already using nitric or nitrous
acid added in small concentrations to their sulphuric acid, oxygen pressure leach
processes. At Sunshine Precious Metals, in Kellogg, Idaho, silver and copper are
recovered from a complex sulphide concentrate at temperatures between 145 and 155C
and a total pressure of 709 kPa [2,3]. There, the nitrous/sulphuric acid leach process is
used with success. The Electrolytic Zinc Co. of Australasia has piloted a process for
atmospheric air or oxygen leaching of zinc concentrates with NO 2 as an oxygen carrier
[4]. A two-stage process was used, similar to those also proposed by Bjorling and Kolte
[5] and Brennecke et al. [6], where the purpose of the second stage leach, with excess
concentrate, was to reduce completely the nitrates in solution. In all these cases, nitric
acid and, in particular for the Sunshine process, nitrous acid were found to enhance the
solubilization of minerals at lower temperatures and pressures. Reasons given for this
effect include the presence of stronger oxidizing agents and faster kinetics as well as
better oxygen transfer with NO 2 as an oxygen carder. The mechanisms and quantification of this catalyzing effect on oxygen transfer by nitrites and nitrates is the topic of the
investigation described in this article. The oxidation of ferrous to ferric ion in sulphuric
acid, which is typically very slow under conventional pressure leaching conditions, was
used to elucidate the effects of small concentrations of nitrates and nitrites. Also, it was
intended to postulate the role of a nitroso-ferrous complex, Fe(NO) 2, which is known
to be stable under ambient conditions, and reportedly interferes with the catalyzing
effect [2,4].

2. Background
2.1. Ferrous to f e r r i c oxidation

Ferrous to ferric oxidation has been studied extensively, recently at higher temperatures, typical of zinc pressure leaching conditions, by Dreisinger and Peters [7]. In
summary, the rate was found to be second order in ferrous concentration and first order
in oxygen partial pressure. Oxidation of ferrous was also found to be slower at higher
acidities, but faster in the presence of other metal sulphates. The last two observations
were explained by the postulation that ferrous complexed species are oxidized faster
than free ferrous ion, the relative concentrations of which are influenced by solution
chemistry.
No information was found in the literature on the rate of ferrous oxidation by, or in
the presence of, nitrate or nitrite species. A mechanism for the reduction of nitric acid
was proposed, where nitrous acid is produced as an intermediate with an autocatalytic
effect [8]. The very strongly oxidizing ion NO + is produced as an intermediate from the
decomposition of unstable nitrous acid. This ion is thought to be responsible for the
faster rates of dissolution of minerals in nitric acid containing some nitrous acid than in

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996)209-219

211

pure nitric acid. For pure nitric acid solutions a long induction period is observed [2].
The key to the catalytic effect of nitrates and nitrites on oxygen transfer is the
subsequent regeneration of oxidant from the reduction product, NO [2-4]. The important
steps postulated in this process are described below.

2.2. Oxidation of NO to N O 2
Gaseous nitric oxide is readily oxidized to nitrogen dioxide, NO 2. The rate of
oxidation has been found to be second order in NO partial pressure and first order in
oxygen partial pressure:
d PNO2 = kP~o Po2
dt

(1)

where log k = ( 6 4 1 / T ) - 0 . 7 2 5 (T in C) psia -2 min -1 [2]. Nitrogen oxide then

dimerizes in the gas phase to form a mixture of NO 2 and N204.

2.3. Mass transfer

The nitrogen oxides are transferred from the gas to the liquid phase with the
following rate:

r = kLa(C i - Cb) moll -1 s -1

(2)

where the product of the mass transfer coefficient and specific interfacial area, kLa, is a
function of the hydrodynamics, reaction vessel configuration and the diffusivity of the
molecules. C i is the concentration of oxide species at the interface, and C b the
concentration in the bulk. Nitric oxide is more soluble in an electrolyte solution than
oxygen, but much less soluble than nitrogen dioxide. For example, in a mixture of 0.2
mol 1- l ferrous sulphate and 1.0 mol 1-1 sulphuric acid under 101.3 kPa of gas
pressure, the solubility of oxygen is 6.97 10 -4 mol 1-1, nitric oxide is 1.32 10 -3
mol 1- l and nitrogen dioxide is 2.88 10 -2 mol 1-1 [9]. Thus NO 2 is 20 times more
soluble than NO. Therefore, the mass transfer rate of NO 2 will be 20 times faster than
that for NO, and 40 times faster than that for molecular oxygen, assuming the gaseous
concentrations and liquid diffusivities are all similar.

2.4. Oxidizing agent

It is not clear what reactions take place to regenerate the oxidizing species. N O 2 and
N204 are themselves strong oxidizing agents, which are reduced to nitrous acid or all
the way to NO. The overall half-reaction is:
NO 2 + 2H30+ + 2 e - ~

NO + 3 H 2 0

(3)

Probably intermediate reactions occur where NO 2 and N204 react with NO to form
mixtures of nitric and nitrous acid [8]. The oxidizing agent is thought to be NO + , as
postulated previously [2,8], formed from the decomposition of nitrous acid:
HNO2 + H + ~ N O + + H 2 0

(4)

212

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996)209-219

2.5. Formation of nitroso-ferrous ion complex

It was observed in both industrial operations using nitrate/nitrite assisted oxidation
that in the presence of ferrous ion the catalytic effect is extinguished. This is because
NO forms a complex with ferrous ion, called the nitroso-ferrous complex:
KE

Fe E+ + NO ~ Fe(NO) 2+

(5)

This is the complex formed in the well-known brown ring test for nitrates [10]. It is
stable under ambient conditions and ferrous sulphate solutions are often used for the
absorption of NO and NO z [9].

3. Experimental method
A standard 2 1, titanium, Parr autoclave was charged with 1 1 of solution containing:
1.0 M H2SO 4, 0.1-0.2 M FeSO 4, 0-0.112 M Fe2(SO4) 3, 0-0.00389 M NaNO 2,
KNO 3 or HNO 3. The autoclave was sealed and brought to 120C, at which point stirring
was started and the autoclave pressurized with pure oxygen to a total pressure of
608-1013 kPa. Total pressure and temperature were maintained constant throughout the
experiments. Samples were taken every 5 or 10 min and analyzed for Fe 2+ concentration by titration with potassium permanganate. Nitrogen species, such as NO 2 or NO 2
are also oxidized by potassium permanganate, but so slowly that warm solutions are
recommended to enable their analysis [11]. The titrations in this experimental study were
carried out at room temperature and quickly. Therefore, no oxidation of nitrogen species
was assumed to occur and interfere with the analysis of Fe 2+ concentration.

4. Results and discussion

4.1. Ferrous to ferric oxidation in the absence of nitrate / nitrites
Three experiments were done at different stirring speeds: 600, 800 and 1000 min - l ,
with initial concentrations: 1.0 M H2SO 4 and 0.1 M FeSO 4. Fig. 1 shows straight line
plots of 1/[Fe 2+ ] versus time multiplied by oxygen partial pressure, which confirm the
second order rate law with respect to ferrous ion concentration:
d[Fe] 2+
dt
= k2 Po2[Fe2+ ]2

(6)

Above 800 min-~ the improvement in rate was negligible, thus all subsequent experiments were performed using this stirring speed. From the slopes of the lines in Fig. 1,
rate constants, k 2 in Eq. (6), were obtained: 0.0125, 0.0181 and 0.0192 mol 1-1 min -~
for 600, 800 and 1000 min -1, respectively. These were compared with the results
obtained by Dreisinger and Peters [7]. Using an empirical rate expression derived from
their data [12], the rate constant for the same concentrations and temperature was

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996) 209-219

30

213

StizTing Speed (min -1)

"

600

"

800

"~

25

1000

"

'

20
el

10
10

20

30

40

50

60

70

80

90

Time X PO~ X 10 -3 (min kPa)

Fig. 1. Plot of the inverse of ferrous concentration (l mol- l ) versus the product of time (in min) and oxygen
partial pressure (526.7 kPa). The initial solution composition was 1.0 M H2SO4 and 0.1 M FeSO4.
Temperature and total pressure were constant at 120C and 810.4 kPa, respectively.

c a l c u l a t e d , f r o m the D r e i s i n g e r r e s u l t s , as 0 . 0 1 7 0 m o l 1-1 m i n - ] . T h u s , t h e r e s u l t s o f
the present experiments agree well with those of Dreisinger.

4.2. Comparison between nitrate and nitrite assisted oxidation

T h e e x p e r i m e n t s w e r e c o n t i n u e d w i t h 1.0 M H 2 S O 4, 0.2 M F e S O 4, at 120C a n d a
total p r e s s u r e o f 8 1 0 . 4 kPa, w i t h 0 . 0 0 3 8 9 M o f e i t h e r H N O 3, K N O 3 or N a N O 2 a d d e d .

0.1

0.09

no nitrate/ites []
HNO3 n

~"
0.08

KNO3

0.07
=

.2

NAN02

0.06
0.05

0.04

"a"~"n"'~

0.03
~,

0.02
0.01
0

20

40

60
Time (rain)

80

100

120

Fig. 2. The acceleration of ferrous oxidation due to the addition of nitrates and nitrites. The initial solution
composition was: 1.0 M H2SO4, 0.1 M FeSO4 and no nitrates or nitrites (D), 0.00389 M HNO 3 ( 1 ) ,
0.00389 M KNO 3 ( A ) or 0.00389 M NaNO 2 ( ). The temperature and pressure were maintained constant at
120C and 810.4 kPa, respectively.

214

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996)209-219

The results, plotted as ferrous concentration versus time, are presented in Fig. 2. The
beginning point of the reaction is uncertain due to some reaction occurring during the
heating-up period. As can be seen in Fig. 2, ferrous to ferric oxidation rate was
accelerated in the presence of nitrates, but not by much, whereas, nitrites enhanced the
reaction rate substantially. We expect that, once the nitrate or nitrite is reduced to NO,
the mechanism of oxidant regeneration must be the same regardless of whether nitrate or
nitrite was added initially. As nitrate is reduced to nitrite the HNO 3 and KNO 3 curves
should curve down to reflect the increased nitrite content. Since this was not observed,
the difference in rate must be due to the lack of reduction of nitrate under these
experimental conditions. There also appears to be a shift in the rate law, or rate-controlling step. For the HNO 3 and KNO 3 additions, plots of the inverse of ferrous concentration versus time times oxygen pressure yielded straight lines, suggesting that ferrous to
ferric oxidation is still the rate-controlling step. However, in the presence of nitrites,
NaNO 2, the reaction rate becomes independent of ferrous concentration:

d[Fe ]
- - - k
dt

(7)

This is indicated by the linearity of the ferrous concentration versus time plots for all
the experiments involving nitrites. In the presence of nitrites or nitrite-derived species,
the rate of ferrous oxidation must be very fast and the rate-controlling step becomes
either mass transfer or the oxidation of nitrogen species, such as NO to NO 2.
Compared with the initial rates for the experiments without and with nitrate, which
are all similar, the rate with nitrite is 5 times faster at 0.00389 M NaNO 2. But, since the
rate with nitrite is zero order with respect to ferrous concentration, the time to
completion for the oxidation reaction is very much shorter, as can be clearly seen in Fig.
2.
Now, if the nitroso-ferrous complex is stable under these experimental conditions and
interferes, as suggested in [2], with the regeneration of NO 2 from NO, then independence of the rate from ferrous concentration is unexpected. One would expect that, at the
beginning of the experiment, most of the NO would be tied up in the complex and the
reaction rate would be slow. As ferrous is consumed and NO is released from the
complex, the reaction rate would then accelerate. This was not observed and the
importance of this nitroso-ferrous complex was, therefore, explored as explained in the
next section.
4.3. The nitroso-ferrous complex

To speculate on the existence and role of the nitroso-ferrous complex, experiments

were done using different initial ferrous concentrations and various initial ferrous:ferric
concentration ratios. The standard conditions were: 1.0 M H2SO 4, 0.2 M FeSO 4,
0.00389 M NaNO 2, 120C and a total pressure of 810.4 kPa. If the complex prevents
regeneration of NO 2 by tying up NO, then one would expect the initial oxidation rate to
be slower at higher initial ferrous concentrations.

215

S.A. Baldwin, G. Van Weert/Hydrometallurgy 42 (1996) 209-219

0.2

Fe2+ Fe3+ ko tool L -1 min - I

I

"~
.o

0.15

~
~
o

0.1 0.0
0.1 0.1
0.2 0.0
0.2 0.005

""-.."'-..

0.0032
0.0021
0.0025
0.0025

"*

0.I
0.05

0
10

20

30

40

50

60

70

Time (rain)

Fig. 3. Experiments with varying initialferrous and ferric concentrations. Other experimental conditions w c r c :
1.0 M initial H2SO 4 concentration, 0.00389 M NaNO 2, 120(2 and 810.4 kPa total pressure. Ferrous and
ferric conccntrations arc given (in M) on the graph. Zero ordcr rate constants,/co, are also given (in tool I-I

min-l).
Bosio et al. [9] found an equilibrium constant for the complexation reaction (5) at
25C of 450 1 mol -~. This was extrapolated to 120C by using the following formula,
where A H is not a strong function of temperature [13]:
In-- = -K1
R

1)

Tl

T2

(8)

K~ is the equilibrium constant at 7"1, K 2 the equilibrium constant at T2, and R the gas
constant. A H for the reaction (Eq. (8)), found from data given in Latimer [14], is
- 4 3 . 1 kJ mol - l , which gives an equilibrium constant at 120C of 6.78 1 mol - I . Using
this extrapolated equilibrium constant it was calculated that, with a total ferrous
concentration of 0.2 M, 40% of the total NO is unbound, and with a total ferrous
concentration of 0.1 M, 80% of the total NO is unbound. If either bound or free NO
concentration is rate determining, then variations in the ferrous oxidation rate could give
insight into the reaction mechanism. However, from Fig. 3, it can be seen that there was
no significant difference in the rates. This implies that either the complex is unstable and
the extrapolated equilibrium constant inaccurate, or the complex exists but does not
inhibit the regeneration of oxidant. It could even play a part in the reaction mechanism.
The presence of NO 2 as an intermediate species is thought unlikely, since it would
convert nitrites to passive nitrates by the well-established absorption reaction:
3NO 2 + H 2 0 -~ 2HNO 3 + NO

(9)

4.4. Oxygen pressure

Fig. 4 shows the results for experiments performed at three different total pressures:
607.8, 810.4 and 1013.0 kPa. The oxygen partial pressures, calculated from the total

S.A. BaMwin, G. Van Weert/ Hydrometallurgy 42 (1996) 209-219

216

0.2

PT

ko raol L -1 rain -1
607.8 0.0019 "

,.z

810.40.0025

0.15

. 0.0039

0.1

0.05

2
10

20

30

40

50

60

70

T i m e (rain)
Fig. 4. The effect of total pressure on the rate o f ferrous oxidation. Initial concentrations were: 1.0 M initial
H 2 S O 4, 0.2 M FeSO 4 and 0.00389 M N a N O 2. Temperature was constant at 120C.

pressures minus the water vapour pressure, were: 324.2, 526.8 and 729.4 kPa. The rate
constants, found from the slopes of the lines in Fig. 4, are 0.0019, 0.0025 and 0.0039
mol 1-1 m i n - l, respectively. This shows a more or less linear dependence of the rate on
oxygen partial pressure, implying that either the oxidation of NO to NO 2 is rate-controlling or oxygen mass transfer is rate-controlling, when oxygen is transferred to the
aqueous phase.

4.5. Nitrite concentration

The effect of nitrite concentration on the rate of oxidation was investigated. Experimental results for three different nitrite concentrations: 0.00389 M, 0.002 M and 0.001
M, are shown in Fig. 5. Other experimental conditions were: 1.0 M and 0.2 M initial
HzSO 4 and FeSO 4 concentrations, respectively, 120C and 810.4 kPa. It was observed
that the rate was reduced by almost one half when the nitrite concentration was more or
less halved from 0.00389 to 0.002 M. However, no perceptible change in reaction rate
was noticed when the nitrite concentration was halved further to 0.001 M. This
non-linear effect of nitrite concentration on the reaction rate seems to suggest that
nitrogen species oxidation is rate-controlling. The rate law for NO to NO 2 oxidation,
presented earlier (Eq. (5)), is proportional to the square of the NO partial pressure.

4.6. Gas phase venting

In industrial pressure oxidation processes, the gas phase has to be vented continuously to prevent the build-up of inerts, which enter with the oxygen, or to prevent the
build-up of CO 2, which may be released due to carbonate dissolution. This could also
result in loss of some NOx, which would, in turn, slow the oxidation reaction. To
investigate the effect of gas venting, two additional experiments were performed with

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996) 209-219

0.2

i
i

[NaNO2] ko tool L-I rain -1

0.00389 0.0024 0.002 0.0014

~
~

0.15 -

217

0.1

0.05

0
0

10

20

30

I~

40
50
Time (min)

60

70

80

Fig. 5. The effect of nitrite concentration on the rate of ferrous oxidation. Initial concentrations were: 1.0 M
H2SO4, 0.2 M FeSO4 and 0.00389 M NaNO2 (D), 0.002 M NaNO2 ( I ) or 0.001 M NaNO2 (ix).
Temperature and pressure were constant at 120C and 810.4 kPa, respectively.

1.0 M H 2 S O 4, 0.2 M F e S O 4, 0.00389 M N a N O 2, at 120C and 810.4 kPa total

pressure. In the one case, after the autoclave had reached 120C, the gas phase was
purged from the autoclave, prior to pressurizing with oxygen. In the second case, the gas
was also purged at the beginning and again, after 30 min, by depressurizing and then
repressurizing. The results are shown in Fig. 6. Unexpectedly, the reaction rate was
slightly faster for the experiments with gas purging. If a significant amount of N O x was
in the gas phase and was lost during purging then the reaction rate should have been
slower thereafter. This was not the case, which lead us to conclude that most of the

0.2

I
~

no purging a

purge at beginning :

0 . 1 5 ~ . . ~

purge at be~nning and middle

0.1

0.05

,
10

,
20

l
30

40

Time (min)

50

80

70

Fig. 6. The effect of purging of the gas phase on the rate of ferrous oxidation. Initial concentrations were: 1.0
M initial H 2 S O 4 , 0.2 M FeSO4 and 0.00389 M N a N O 2 . Temperature and pressure were constant at 120C
and 810.4 kPa, respectively.

218

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996) 209-219

nitrogen species were in solution. The solubility of NO is not that high, however. As
mentioned previously, at 25C, NO solubility at 101.3 kPa NO pressure is 0.00132 mol
1-~ . This decreases with temperature. Thus, we can only speculate that the nitroso-ferrous complex is actually stable, keeping the NO in solution, and that the oxidation of
NO somehow takes place in the solution. Unfortunately, there was no opportunity to
analyze the vent gases for nitrogen species. In any case, these results indicate that, for an
industrial process operating under these conditions, gas venting appears not to result in
making nitrite-assisted oxidation impractical. The possibility of utilizing air pressure
oxidation on sulphides, as mentioned in the introduction, remains, therefore, worthy of
investigation.

5. Conclusions
The results of this study show that small concentrations of nitrates, alone, do not
result in noticeable acceleration of high temperature ferrous oxidation in a 1.0 M
H2SO 4 solution. The same small concentrations of nitrites resulted in significantly
catalyzed oxidation. The reaction in solution, with nitrite addition, was so much faster
that the rate-controlling step shifted to oxygen mass transfer or nitrogen species
oxidation. Initial rates were found to be 5 times faster with 0.00389 M NaNO 2 present.
However, since the reaction order for nitrite assisted oxidation is zero with respect to
ferrous ion, the times to completion are much shorter.
The rate of nitrite-catalyzed ferrous oxidation was found to be linear with respect to
oxygen pressure and non-linear with respect to nitrite concentration. This suggests that
oxidation of nitrogen species may be the rate-controlling step.
Surprisingly, increased initial ferrous concentrations did not adversely affect the
reaction rates by binding the NO in a nitroso-ferrous complex. Also, unexpectedly, gas
venting did not result in loss of catalyzing effect, and hence of NOx species. This seems
to suggest that most of the nitrogen species are in solution, bound perhaps as Fe(NO) 2,
and that oxidation must somehow take place there and not in the gas phase. The
presence of gaseous NO 2 as an intermediate seems unlikely.
Thus, adoption of nitrite-assisted oxidation in autoclaves used for mineral processing
could result in more efficient operations. Smaller autoclaves used at lower temperatures
and pressures, and even the use of air, can be considered. From this study, gas venting
and the presence of ferrous ion do not inhibit the nitrite-catalyzed process.

Acknowledgements
S.A. Baldwin wishes to express her appreciation to the Board of Deans of Delft
University of Technology for granting a Research Fellowship allowing this work to be
carried out Fall 1994 at the Faculty of Mining and Petroleum Engineering.

S.A. Baldwin, G. Van Weert / Hydrometallurgy 42 (1996) 209-219

219

References
[1] Van Weert, G., Fair, K.J. and Aprahamian, V.H., Design and operating results of the NITROX process.
In: Gold Mining '88. SME, Littleton, Colo. (1988), pp. 286-302.
[2] Anderson, C.G., Harrison, K.D. and Krys, L.E., Process integration of sodium nitrite oxidation and fine
grinding in refractory precious metal concentrate pressure leaching. Pre-print SME Ann. Meet. (Albuquerque, New Mexico, Feb. 14-17, 1994), 94-45.
[3] Anderson, C.G., et al., US Pat. 5096486 (1992).
[4] Adams, R.W., Mangano, P., Roche, E.G. and Carpenter, S.J., Direct leaching of zinc concentrates at
atmospheric pressure. In: T.S. Mackey and R.D. Prengaman (Editors), Lead-Zinc 90. TMS, Warrendale,
Pa. (1990), pp. 351-372.
[5] Boding, G. and Kolta, G.A., Wet oxidation as a method of utilization of chalcopyrite, sphalerite and
molybdenite, J. Chem. U. A. R., 12(3) (1969): 423-435.
[6] Brennecke, H.M., Bergmann, O., Ellefson, R.R., Davis, D.S., Lueders, R.E. and Spitz, R.A., Nitricsulphuric acid leach process for recovery of copper from concentrate. Min. Eng., August (1981):
1259-1266.
[7] Dreisinger, D.B. and Peters, E., The oxidation of ferrous sulphate by molecular oxygen under zinc
pressure-leach conditions. Hydrometallurgy, 22(1,2) (1989): 101-119.
[8] Heckner, H.N., Potentiostatic switching experiments for the cathodic reduction of nitrous acid in
perchloric acid with the addition of nitric acid. Electroanal. Chem. Interfacial Chem., 44 (1973): 9-20.
[9] Bosio, S., Ravella, A., Saracco, G.B. and Gemon, G., NOx absorption by ferrous sulphate solutions. Ind.
Eng. Chem. Process Res. Dev., 24 (1985): 149-152.
[I0] Sienko, M.J. and Plane, R.A., Chemical Principles and Properties. McGraw-Hill, Kogakusha, 2nd ed.
(1974), p. 617.
[11] Jeffery, G.H., Bassatt, J., Mendlam, J. and Denney, R.C., Vogel's Textbook of Quantitative Chemical
Analysis. Longman Scientific and Technical, New York, 5th ed. (1989), p. 373.
[12] Baldwin, S.A. and Demopoulos, G., Mathematical modelling of the zinc pressure leach process. Metall.
Trans. B (submitted).
[13] Stumm, W. and Morgan, J.J., Aquatic Chemistry. Wiley-Interscience, New York (1970), p. 54.
[14] Latimer, W.M., The Oxidation States of the Elements and their Potentials in Aqueous Solutions.
Prentice-Hall, Englewood Cliffs, N.J. (1952).