See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/307011998

Stability of metal cyanide and hydroxide complexes

Conference Paper · September 1997

CITATIONS READS

2 522

1 author:

James Hamilton Kyle

Murdoch University
33 PUBLICATIONS   354 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Nickel laterites View project

New Guinea botany View project

All content following this page was uploaded by James Hamilton Kyle on 27 August 2016.

The user has requested enhancement of the downloaded file.

 tA/orfdGofd '97

1.- 3 SeptemberL997
5ingapore

T h e Au s tra l a s i a n
Insti tuteof Mi ni ngand Metal l urgy
P u b l i c ati on
5eri es l 1o Z/97

P u b l i s h e db v

ThiTAU5TRALA5IAN III5TITUTEOF MIIIINCAIiD METALLURCY

Level 3, 15-31 Pelham5treet, carlton VictoriaAustraria505i
 and HydroxideComplexes
Stabilityof Metal-Cyanide
{
J H Kyle'

SUMMARY 4Au + SNaCN + Oz + ZHzO = 4NaAu(CN)z + 4

NaOH
The aim of the study was to determinethe rangesof stability and
instabilityof the metal hydroxidesand metal cyanidespeciesthat However,cyanide also fbrms complexeswith other metals in
may be formed during the gold extractionprocess,Merrill-Crowe the ore such as mercury, zinc, copper, iron and nickel. These
gold precipitation, and Inco SOz/Air or f'errous ion cyanide metal cyanidesare presentin the tailings solutions and can be
removalprocesses. difficult to treat. This is particularlytrue when the ore contains
Following cyanidedetoxificationby the Inco SOz/Air process, silver, wliich requiresmore aggressiveconditions than gold for
the main componentsof concernin the tailings will be: its recovery,and can lead to higher dissolution of otl'rermetals
liom the ore.
Zinc and copper hydroxide
The zinc (fiom zinc precipitation of gold) hydroxide will be Gold recovery
stablebetweenpH 8.7 and 10.0. Below pH 8.7o,zincwill re-
dissolveinto solution as the aqueouszinc ion, Zn'-. Above pH Gold, especiallyin high silver or high grade gold ores, may be
10.0,the zinc will^begin to re-dissolveas the zincatehyflroxo recoveredfiom solution by the zinc cementation (or Merrill-
complex Zn(OH)a,''.At low cypnide concentrations (10-' M), Crowe) process. This is based on the electrochemicalreaction
zinc is mostly solublebelow l0-- M as fiee zinc or zinc cyanide between zinc powder and the gold cyanide complex in the
complexes. absenceof oxygen:
The copper (from the cyanide detoxifrcation)hydroxide will
Zn + 4 NaCN + NaAu(CN)z = Au + NazZn(CN)q + 2
be stablebetweenpH7.2 and 9.5. Below pHL.2, copperwill re- NaCN
dissolveinto solutionas the aqueousion, Cu'-. Above pH 9.5,
the copper will begin to^ re-dissolve as the cuprate The main change to the solution chemistry during the gold
hydroxo complex Cu(OH)+'-. Soluble copper(l) cyanide precipitationreaction is the replacementof gold-cyanide with
complexeswill be formed above pH 8 at EH's fiom +0.3 zinc-cyanide. All the silver and a portion of the copper are also
to -0.3 V. precipitated.In addition, any iron(III)-cyanide in solution is
reduced to iron(Il)-cyanide. Nickel in solution can lead to a
Heavy metal ferro- and ferricyanides lowering of the liydrogen overvoltageon zinc, leading to high
il zinc consumptionsand poor gold recovery.
The f-errocyanideproduced in the detoxification process will
precipitateas iron, copper or zinc f'errocyanide.Some may be
oxidised to the f'erricyanide. In general terms, the region of Cyanide detoxification
stability of,the iron and heavy metal cyanidesis pH 4 to 8.5, Cyanide may be removed from the tailings slurry solution by a
above lO-oM metal ion concentration (0.05 mg/L), and suitable detoxitlcation process. The solution to detoxification
below l0-'M (2.6 mglD cyanide ion concentration. Soluble
will consist of free cyanide. and the cyanide complexes of
ferro- and t'erricyanidesmay be degradedby photolysis with
iron(ll), zinc, silver, gold and/or copper (a catalyst in
ultra-violetlight into tiee cyanide.
detoxitication processes). The detoxifrcation processeswill
oxidise fiee cyanideto cyanate,destroythe weak and moderately
Thiocyanate, cyanate and ammonia
strong complexesof zinc, copper and silver, precipitating the
Other cyanide-relatedspecies of concern will be thiocyanate, metalsas hydroxides,and precipitatethe strong iron(ll) cyanide
cyanate and ammonia. These have toxicological and chemical complex as a heavymetal f'errocyanide, or iron f-errocyanide.
significance. Thiocyanate can form insoluble salts with gold, As zrnalternative,the cyanide may be removed frorn solution
silver, mercury,lead, copper and zinc. It will break down under
and into tlie solid tailings phase as an iron t'errocyanide
normal conditions of pH and EH to sulphate, carbonate or
precipitate. This can be achievedby t-erroussulphateaddition to
carbon dioxide and ammonia. The ammoniamay hold metals
suchas copperand zinc in solutionas ammoniacomplexes. tlretailingsslurry (Adams,1992)

INTRODUCTION IRON . CYANIDE COMPLEXES

The aim of the study was to determinethe rangesof stability and The stabilityconstantsof some common metal cyanidespecies
instabilityof the metal hydroxidesand metal cyanidespeciesthat rurepresentedin Table 1.
may be tormed during the gold extractionprocess,Merrill-Crowe The stabilityconstantsare listedin termsof log K, whereK is
gold precipitation,and Inco SOz/Air or other cyanide removal the constanttbr the equilibriurn(fbr f'errocyanidefbr example):
processes.
a, - [Fe(CNu4- )
't
rr--iT
Gold dissolution tt"'* l.[cN-]o
Gold recovery by cyanidation is based on the strong complex 'Ilie
fbrmed between cyanide ion and the gold(l) ion. This is iron cyanide complexes have the highest stability
describedby Elsner'sequation: constantsand are classitiedas very strong complexes.Mercury,
copper, nickel and silver tirrrn medium strength complexes,
whereascadrniurnand zinc torm weak complexes.
l. OretestPtv Ltd. l2 Aitken Wav. KewdaleWA 610-5

W o r l dG o l d' 9 7 C o n f e r e n c e S i n g a p o r e1, - 3 S e p t e m b e1r 9 9 7

J H KYLE

Tasr.B2
stabitityconstants:;:nl rranidecomptexes. Sol ubiLity o.f lrcavv tnetal ferro- und.ferri-cyanides.

Name Formula DissociationConstant

Names Formula Solubility
(Loe K)
(T"C)
Ferricyanide Fe(CN)r,r' -52.0 Copper(I ) Ferricyanide CurFe(CN)r, i n s o l u b l e1 s y
Ferrocyanide Fe(CN)r* 41.0 Copper(lI ) Ferricyanide C u r l F e ( C N ) n l :l.4 H z O i n s o l u b l el n t
Tetracyanomercurate( II) Hg(CN)+1 41.4 Copper(I I ) Ferrocyanide C u z F e ( C N ) r ,H . x2 O i n s o l u b l e1 p 1 1
Tetracyanocuprate(l) Cu(CN)a' 21.3
Tetracyanonickelate( -5x10-'M11,.1
II) Ni(CN)q'' 22.0 Iron(| I) Ferricyanicle Fer[Fe(CN)r,]z i n s o l u b l e1 1 1 y
Dicyanoargentate(l) Ag(CN)4 21.0 Iron(ll) Ferrocyauide FezFe(CN)r, i n s o l u b l e1 H l
Tetracyanocadminate(ll) Cd(CN)q- 16.9 Iron(lll)Ferricyanide Fe[Fe(CN)6,] i n s o l u b l e1 p ;
Tetracyanozincate(
II ) Zn(CN)+' 16.9
l0-" !l {ni
I r o n (I I I ) F e l i o c y a n i d e FealFe(CN)olr 3 x lO-'M 1p11
S o u r c e :C a r u s o( 1 9 7 - 5 ) < l o - l oM 1 p ;
S i l v e r t| ) F e n ' i c y a n i d e AgrFe(CN)r, l0-"M (n)
Silver(l) Ferrocyanide AgaFe(CN)n.HzO insoluble
Z i n c (| | ) F c r r o c y a n i d e Zn2Fe(CN)6, 8x l0-6M1ur
Iron-cyanide complexes , 5x l 0 - ' M 1 r , 1
Zinc(ll) Ferricyanide ZnrlFe(CN)nlz 3 x l 0 - - ' Mr n r
As iron-cyanidehas a diff-erentchemistryto other metal-cyanide
complexes,it is discussedseparately.Iron forms two complexes
with cyanide depending on its oxidation state. Iron(ll) forms S o u r c e :( H ) : H u i a t tc t u l ( l 9 t i 2 ) a n d ( F ) F l v n n a n d H a s l e m( 1 9 9 - 5 ) .
ferrocyanide, Fe(CN)6"-, while iron(III) forms f'erricyanicle,
Fe(CN)o'j-.Thesecomplexesrequirespecialattentionbecauseof KEY
their specialstabilityin the absenceof ultra-violetradiation,ancl H3 f Fe{OH)J{ao)
tl4 "
IFcioF$.l'
their tendencyto dissociatein its presence. OS Fe(OH).(am.aocd)
c71ss Fe:[Fc(cr.r).j,.iH,i1s1
Ferrocyanide, or hexacyanoferrate(Il),is fbrmed by the
L - 5
addition of f'errous ions, or ferrous hydroxide, to a solution 6

containingfiee cyanide. This complex is extremely chemically <9

o-6
J
stable below pH 9.0, but decomposesabove this pH. The
dissociationconstantfor this complex is shown in Table l.
Despite its higher stability constant,excessf'errousion will not
readily displace zinc, copper, or nickel from their cyanide
complexes. o 2 4 6 8 1 0 1 2 1 4
pH
Ferricyanide,or hexacyanof-errate(Ill),is not fbrmed directly
in solution from iron(III) and cyanide, becauseof the greater Ftr; I - The pFe(III)-pH diagram firr p[Fe(CN)r,a-] = 4.0
stability of f'erric hydroxide. It is usually formed by tlie (from Flynn and Haslern, 1995).
oxidationof ferrocyanide. i a

0.5
Precipitated iron-cyanides 0.3
The iron-cyanidespresent in mining solutions and tailings are
mainly in the mixed ferro- and ferri- forms. They are classifiecl -0.1
E

as 'inert' complexes,becauseof their very low solubility and

uJ
-ne

rates of dissociation. They also form a range of insoluble or -0.5

sparingly soluble precipitates with other metal-cyanide
complexes,the most insoluble of which are the copper(I) and -0.9
copper(Il) f-erricyanides.A compilation of the solubility of a - l - l

range of metal ferri- and f-erro-cyanidesis given in Table 2. o 2 o u 10 12 14

o"u
The heavy metal salts of ferrocyanide are insoluble and
precipitatein water. Smith and Mudder (1991) state that their FIc 2 - TheEs-pH cliagram
for pFe= 2.0andp[Fe(CN)r,a-]
-- 4.0
solubility is not greatly aff-ectedby pH in the range pH 2 to pH (flomFlynnandHaslern, 1995).
Il.
The heavy metal salts of ferrocyanideare considerablymore
soluble than those of their ferricyanide analogues. They are hydrogen), the compound is reduced to f'errous ferricyanide
(C5l2S) and then to f-errousferrocyanide(C3065), with its pH
classified as 'sparingly soluble' or 'insoluble'. The most
insoluble are the iron(lI) ferricyanides. Again, Smith and stability rangeextendingup to pH l0 rnaximum(Figure 2).
Mudder claim that their solubility is mostly independentof pH in This data contradictsto some extent the pH 2 to 10 or I I
the rangepH 2 to pH 11 (seeTable 2). stability range quoted by Smith and Mudder, but is probably
more reliable in that it is more rigorous in its derivation,and is
More recent data is presentedby Flynn and Haslem (1995)
who havedeterminedpH-concentrationstability diagramsfbr the more recent.
iron(lll), iron(Il), copper and zinc ferrocyanide.Thesediagrams Figure 3 showsthe pFe(ll)-pH diagramtbr p[Fe(CN)eo-]= 4.0.
are reproducedin Figures I to 6 overleaf. The diagram indicates that the f'errous ferrocyanide solid
(C3065)ls stableabove an Fe(II) concentrationof 10-6M in the
Figure I shows the pFe(lll)-pH diagram for p[Fe(CN)64-1=
pH range 2 to 9. This range is similar to that reportedby Smith
4.0. The diagram indicatesthat at all concentrationsof Fe(III)
down to l0-vM, the f'erric ferrocyanidesolid phase (C7l8S) is and Mudder (1991). Above this pH range, the compound is
stablebelow pH 7 , and unstablewith respectto ferric hydroxide unstablewith respectto crystallinef'erroushydroxide (OS), and
(OS) above this pH. At low EH (less than zero with respectto below l0-oM Fe(ll), the compounddissolvesinto its constituent
ions. This refersto tlie 'sparinglysoluble'natureof this complex

S i n g a p o r e1, - 3 S e p t e m b e1r 9 9 7 World Gold '97 Conference

 STABILITY OF METAL-CYANIDE AND HYDROXIDE COMPLEXES

vcv
M Fc" K%'
H1 tFc{OH)l'
r.a
Hz
H3
OS
lreiosiitaot
lre(oHll' "
Fc(OH),(cr)
C3o6S Fe.[Fe(CN).1.xH,C{s)
ti {;ilgftf".'
oS ZnO(s)'-
33'Iiil?!1d{if
.xFLo(s)

pH pH

Frc 3 - ThepFe(ll)-pHdiagramfor p[Fe(CN)na

] = 4.0 FIc 6 - The pZn-pH diagramfbr pCN = 5.0 and p[Fe(CN)r.a-]= 4.0
(fromFlynnandHaslem,1995). (fi'om Flynn and Haslem, 1995).

as opposed to the more insoluble f'erricyanide(Smith and In general terms, therefbre, these stability diagrams indicate
M u d d e r ,l 9 9 l ) . that the region of stabil{y of the iron and heavy metal cyanides is
Figure 4 refers to the stability of the copper(ll)-f'errocyanide pH 4 to 8.5, above lO-oM metal ion concentration (0.05 mg/L),
solid (FOS). It is only stablein the pH region4 to 6.5. Above and below l0-"M (2.6 mg/L) cyanide ion concentration.
this range,it is unstablewith respectto copper oxide (OS), and
below it begins to dissolve into its constituentions. In reality, Photolysis
copper oxide generally will form only very slowly from the
metastable copper hydroxide. This may extend the actual In the presenceof ultra-violetlight, photolysisand hydrolysisof
stability range of the complex to higher pH values (about pH f-erro-and f-erricyanideoccurs. In laboratory experimentsat high
8.5). The compoundis also sparinglysoluble,decomposinginto UV radiation,ferro- and ferricyanidehave releasedup to 85 per
its constituentions below l0-oM copper(II) concentration. cent and 4L)per cent respectivelyof their cyanide.
The reactioninitially involvesthe loss of only one cyanidqion
per molecule. Tliis intermediateproduct, [Fe(CN).s(HzO)]'-,is
o
KEY also photosensitive,and will break down with time. Continued
M Cu"
-z H1 fCu{OH)l' irradiationin the presenceof oxygen will result in the formation
H3[3113tlt.'t of Prussianblue in acid solution, and iron oxides in alkaline
solution.
a.
ag

(9
33 tcJ{o($)J"
FOS Cu,Fi{CN). xH,O(s) The f-ateof fiee cyanide releasedon decompositionof these
o € speciesby photolysisis unknown. It is suspectedthat much is
J
degradedby normal mechanismsto HCN, CNO-, and CzNz
-8 (Slrarpe,1976).

-t0
HEAVY METAL. CYANIDE COMPLEXES
pH
The heavy rnetalcyanide cornplexescan be classifredinto three
FIc 4 - ThepCu(ll)-pHdiagramfor pCN= 5.0andp[Fe(CN)6,4-]
= 4.0 ciltegoriesbasedon the strengthof the complex.These are:
(fromFlynnandHaslem,1995). l. weak Zn(cN)+2-,Cd(cN):l-, cd(cN)+2-
2. Moclerately Hg(CN)42-, Cu(CN)zl-, Cu(CNh2-
Strong Ni(CN)+'-,and Ag(CN)z-
Figures 5 and 6 refer to the stability of rhe zinc(Il)-
f-errocyanidesolid (FOS). Figure 5 is the pCN-pH diagram for 3. Srrong
Fe(CN)64,, Fe(CN)03-, Co(CN)03-
pZn = 4.0 and p[Fe(CN)o'-] = 4.0. The compound is stable A u ( C N) z ' -
below pH 8.5 and at low cyanide concentrations(less than l0- The complexes fbrm and breakdown in a stepwise manner.
"M). Above pH 8.5, the solid is unstablewith respectto zinc Tlie stepwisestability constants,where available,for the mono-,
oxide (OS) and above 10-'M CN- solublezinc cyanidespecies di-, tri- and tetracyanocomplexesare listed below in Table 3. I
begin to fbrm. Figure 6 indicatesthe same pH stability range, For the iron complexes,the stability constantsfor the penta-and
and that the compound is sp-aringlysoluble (dissolutionof the
complexwill occurbelow l0-oM zinc(Il) concentration).
hexacyano-complexesare listed.
The stepwisestability constzrnts
in orderof increasingstability.
of thesecomplexesare listed
i
i

K€Y The weak complexesbreak down readily in the absenceof

M Zn"
H4 IZn(Oll).1'' cyanide, the moderately strong complexes only release small
os 2ndrst"'
c3 tZn(CNt.t' amounts of cyanide, whereas the strong complexes release
z , C4 lZn{CttJj' almostno cyanideinto solution as the free cyanideconcentration
ces lzn(crullrst
Fos Zn,[Fe(C-N1.;.xH,c4s1 decreases.
(9
O - c

Weak complexes
These are mainly the complexesof zinc and cadmium. They
tbrrn in a stepwise manner as the cyanide concentration in
pH solutronis increased,and will decomposein a likewise manner
as cyanidein solutionis decreasedas occursin a detoxitrcation
-5- The pCN-pH diagram for pZn = 4.0 and p[Fe(CN)r,a-l= 4.O reaction.The stepwisedissociationconstantsare listedabove.
(from Flynn and Haslern,199-5).

W o r l dG o l d ' 9 7C o n f e r e n c e S i n g a p o r e1, - 3 S e p t e m b e r . 1 9 9 7
 J H KYLE

Tasr,B3 TlnlB 5
Stability constants of metal-cyanide complexes in water. Solubil ity cotlstantso.f'metal- thiot:\,anatecompounds
Metal LogKr Log Kz Log K.r Los Ko

iilt$
Cornpound Los K Conrpound
Cd Loe K
6.0 Il.l 15.6 ll.9
Zn < A
l l.t
Cu(CNS) l-) Ag(CNS) 12.0
sif 16.0 19.6 Pb(cNS)
$r:' Ag 9.7 20.5 1 l A
21.4 Zn(CNS)
Au(CNS) 14.0
t" Cu(ll) 22.6
Cu(l) I0.,5 zl 7 27.0 28.5
Ni 30.2
Hg 17.0 32.8 36.3 39.0
Au l8 31.0
Metal Log K3 Log lfu Log K5 C N + S - C N S -
Log K6
Fe(ll) 11 A
3-s.4 Thiocyanate car form insorubre sarts witrr gold, sirvcr,
Fe(llI) 34.8 42.3 mercury,leiid,copperand zinc as shown below in Table 5._
Thiocy^nate is chemically or biotogically degradable to
Source: Flynn and Haslem 0 99-5).
ammoniumion, carbonate(or carbonclioxide)and suiphate. The
equation,unbalanced and simplified,is writtenbelow:
SCN- + ZHzO +Oz = NH+* + CO:2- + SOa2-
Moderately strong complexes
Figures7 and 8 show the Eg-pH stabilitydiagramsfbr sulpliur
Thesearethecomplexes
of copper,nickelanclsilver. (includingthiocyanate)at cyanidei.n concentrations
of tti
sv
(pCN = 5.0) and lO-'M lpCN = 2.0). They show
very little
Strong complexes difl'erence in thiocyanate stability xt the two cyanije lon
concentratrons.
Thesearethecomplexes of iron(Il),iron(III),cobaltandgorcr.
The dissociationconstants givenin Table3 abovecanbe used 0.5
KEY
to calculatethe concentrations of fiee cyanidereleasedwhen 0.3 AA HSQ,'
tlresecomplexes arein solutionat pH 7.0 anclz5oc. Thesecrata AB SO.''
DC SCN'
arepresented in Table4 overleaf. 0.1 EA H,S{aq)
EB SH'
-n1
E
Tnst,n 4 LLI
{.3
Free cyanide released from metal-cyanide complexes
in water at
1tH 7.0 at various levels of a metal cyanide complex (in mg/L). {.5

Complex I mgtL l0 mgl[, r00 mg/L 1000mg/L r0 000 4.7

ms/L -0.9
Hg(CN)r2' 0.00002 0.00003 0.0000-5 0.00007 0.00018
AsICN)r- 0.00009 0.0002 0.0004 0.0009 0.004t pH
C;(CN)31 0.0003 0.00054 0.0001 0.0017 0.00-s4
Fe(CN)ar- 0.0002 0.0032 0.0004 0.0006 0.0012 Ftc 7 - Eu-pH dragramfor S with pCN= 5.0
Fe(CN)a"- 0.0012 0.0016 0.0022 0.0031 0.0061 ( f l o m F l y n n a n d H a s l e r n .1 9 9 5 ) .
ttti(CI'l)+'"- 0 . 13 5 0.215 0.340 0.-539 t.324
Cd(CN)a'- all 2.30 3.64 5.77 14.49
Zn(CN)+2- all' 2.26 3.-59 -5.68 14.28 0.5
KEY
0.3 AA HSO.'
all - complex is completelyionised Source: Caruso AB SO."
( 197,5) DC SCN'
0.1
In general,the amount of cyanidereleasedwill increaseas pH -0.1
[$ $pet<r
decreases. Also, the extent of breakdown will increaseas the .E
ut
concentrationof the complex decreases. -0.3

{.5
Other cyanide compounds
{.7
A number of other compounds related to cyanide are formed
during cyanidationof gord ores. Cyanate (cNo-) and ammonia {.9
(NH:) are fbrmed by the natural degradationof u z o uo, u 10 12 14
cyanide, and
thiocyanate(cNS-) is formed by the reaction of cyanide with
sulphide in the ores. These compoundsare important from
a Frc 8 - TheEs-pHdiagramfor S wirh pCN = 2.6
toxicological viewpoint, and must be considered during the (fiomFlynnandHaslern.
1995).
designof wastewatertreatmentfacilities.

Thiocyanate The region of thiocyanatestability decreasesin EH as the pH

increases.At pH 9, thiocyanateis unstableabove an Eg of -0.2.
Thiocyanate is fbrmecl by the reaction of cyaniclewith labile Normally, the Es in the storagedam would be expectedto be
sulphur atoms in the ore, which in turn are formed by the attack above zero, meaning that in all except highly acidic conditons
of lime or cyanideon pyrrhotiteor other labile sulphiie minerals. (pH), thiocyanatewill be unstablewith respectto sulphate
ion.
This means that tliiocyanatewill, unclernormal conditions. be

S i n g a p o r e1, - 3 S e p t e m b e1r 9 9 7
W o r l dG o l d ' 9 7C o n f e r e n c e
 /66f laqualdas g - 1'atodeburg acuarafuoc/6, ploe ppoM

'5^el3u 'saxeldruocapruefc alqnlos

rr.uoperd NJnJ elqnlosLr I Jo uorlsruJo.Iaql Jo asnuseqasBeJcur
Hd srql ^\oleg 'g't e^oqu alqnlos oru soxelduoc eprue^:)
,{eu sluleur eql .Jo ,{1r1rqn1os aql ueql .luaseld sr apruu,(c;1
Hd
(1):addocn t'0+ ol t'0- '{tlllqut.lo uor8e:(l)nJ eqr ur 'rena^\oLl 'luaserdeJusruoturueto eprue,{J
su qJns
'(II)nJ ,{q pau:o.y eru slue8eSurxeldruocou Surunssesr srql .9'01 le aseuu8uerupuu
saxalduor opruu,{c ou .-recldoc.rog
'L'g
's-eluultuopaJd L'6 te tunrrupco l€ JUr.z,V.glr?Ie{Jru ,7,.LHd 1u palplldrcard
xelduoc oxo:p,{q eqt 'Hd srllt e^oqv .g.01 ot g ,{11e1o1aq 11rmraddor tcr.ll a]urrpur S alqul ur utep eqJ
Hd uor8e,r 'l puu
eql ur W
o_0Jtnoqu zlroleq(Sl UO 73) xelduoc eprue,(ceqt I 91 se:n8rgur u/y\oqsare
sp alqnlossr rurz lpqt os plo.Iporpunqeuo tnoqu(96) eprxoourz 11dsns:e,t,(11rqn1os Jurz puu reddocyo suer8urp palrulaperotu
.Jo,{tlllqnlos elll asueJJurol sr epruu,{c.Joloe.+.}e eql ,Jurz joC aq1 'ura1s,{s srLIlur uJeJuoJ.Iosploru eql Jo.i,6 a'tn8rgur u/y\oqs
' ruu.l8erp,{11rqn1os-11d
'(l o l u uo u^\oqstsaq sr .xalduoc oxo:p,(q uu
c - 0 1 r - 0 1 )s u o t l u r l u a r l l o r sp uortnlossrp-eJ puu 'uorlulrdrca:daprxorp,{qIo a8uu: gd aq1
epruu,{cA\ol Jo ecuesa;datll ur uet>-is e(Uus orlt qlr,tr pa:ucluor
sr ure1s,{seprxo:p,(q-luleu eql JO.lsuorSe: Ktlllqutr^eql ersqA\ 'sexalduocoxorp,{qelquls
tsotu aql u.ro;:addoc
'sl ol
zl )-aJnSrc ur u^\oqsur soptxoJp,(q lulau puu suor lBlaur
puu curz leLJlueas eq uBJ ll .€lup eql uoJc .A\olaqs
"{;ncJeur
oql Jo ,{lr1rqn1os eql .recldocilull Jurz joC
aql uo epruu,{c.JotJa-I.ia olqel ur u/y\or{s
oslu eJuuorlcEeJsrql JoJsluulsuoJ,(tlllqetsaql

_,t(HO)nl = -Hoz + z(Ho)m

',lol puu,{a11a1g
ra13u) :s3uellrJ/(eq ueJ uorlnlossrpsrql JoJuorlJeeJ1e:eue8
Gtel
'saxalduroo
oxo.rp,{qsuuorlnlossrpa.t eqJ 'sexalduoc oxo:p,{q Jo uorlpruJoJeqt ot enp .Hd q8pl
prrcseprxoJp,{q
susplaur,(,a.caq;o _6 DrC
uollelrclrral4 aql .sploru etuosJoC
te ellossrp oslu uuJ elulrdrcardaprxo.rp,(q

Hd , [ _ H o l ' I h t-_r J4 ,A
..
ZL ol B I ? z re)y{1
:suuenrJi\\eq ueJ tuplsuoJ{tlllqets OLIJ .g elquJ ul
t'o patsrloslEare urosuot lo slutatueql JoJsluelsuos,{tillqetsaqJ
'9 atqEJur polsrl gd
sr s1q1.(f,nqn-gt
Jo uorlurtuaruorleleu
:o; ,{1lunsn;gd relncrgudu se palsr1a{ uuJ pue ,e8uu:
m 11dryro:reu
-l p reAo rncro ,{lpraua8 .alulrdrca;daql
III^\ sIt{I Jo uor]nlossrp
eql Sursnec ,{ypnluena ,espeJJeplllA\ t_HO] eLlt .sesue:cap
t- 'elulrdrcerdeprxo:p,{t1
gd eqt sy aql .lo luutsuor ,{1r1rqu1s
r o
vn . > eq1'{q uanr8 sr e^lossrplpm alelrdrcardsrqt r{JILI^\1e gd aL11
o
z z(HO)lAI = _HOz +
o +zW
m
z-{ :sd\olloJsu ueDrJ/t\aq uuJ
uorlelrdrca:deq1ro.;uortJueJ1u:aua8eql .uorloueJuortuclirxotep
f)
eqt.Io gd arJttu seprxorp,{qsu elelrdrca:d,{11unsnIII,t\asoduocap
--l
sexeldruooepruc,(cuorl/( uorlnlos olur pesueleJslulel'u ,(,rueg
ot o
z SgXg.IdhIOJ
3 -OXOUOAH
ONV SSOIXOUOAH lVJ,gI^I
to

5 :eddo.lpuu Jurz.llpqoJ,le{Jru,{1euuu.sexelduoc
eluoru(uuelqpls rujo-Ileql esoql eJs uJacuoJJo slelel.uurul'UeqJ
'sexelduoc l?ruotutup
o0L eqt ,{q ,0.6 gd anoqe
olqnlosJo uorleruJo.I
seprxo:p,{r1
se slelau .;o uorleydrca:daqt tlqlqul ue, uorlnlos
ur eruourruuoe4 .Io eJuesaJdaqt .,{lrcrxol sll ruoJ-Iyedy
( t t f - , t ) f o l p u c , { e 1 1 a 1pgu u ( ! 6 6 J ) u r a y s c l p
l u c u u , { 1 gr e r , n r o : ^ (perurrluq
rou)ZoJ + rHN =
OzH+ _ONJ
-ONJZ = +
ts,{1u1ur L71 + _NJZ
v'9r .t(Ho)nJ
0'91 t(HO)nO z'L t' 8r z(uo)nl nJ 'eprxorpuoqJuJpuB
uruoruruu
II zt(HO)tN tuJo.Iot sas,{1o:pfqueql uor ateue,{J .uorleprxourn sesodurocap
ZI t(Ho)tt t v'8 Z'LI z(uo)tN IN tl su eprurz,{c.1o lcnpord un\op{earq lertrur aLlt sr a1uuu,(3
s'91 ,n(Ho)tr7
6'tI 1(Ho)uz t'8 21119)u7 uz
L'91 aluue,{3
0'8 _zt(HO)p:)
8't -c(Ho)pc L O {'vl z(r-ro)pc PJ 'PruoI'Uruu
xalduoco1q 9'0r z(Ho)uy\ ,{11un1uane
8'Zl TIIAI
ov z(Ho)Bv puu a1uuu,{o'slcnpo.rd ultopluaJq sll ,,{1lrrxo1
v'9r ozBv 3y .}o tsqt puu
6 ' 8r .t(Ho)BH slr eJu e1cuu,{corql qlrn\ suJecuoclelueuuoJr,rua,(:uuud
6'07, z(no)fH
-i(Ho)3s 8'IZ 3g t O S z H S + _ O N J = O z H S + T . O , + z O S , + "qJ
xeldruoJ _NJS
'eurl peppEeq1,{q pasrluJlnau
x 3o'I oxo.rpd11 gd clsy 3o1
sr luLllprcu or:nqdlnspuu aleue,(c
aprxorp,{11 IBIAIAI .ssaco:d JIV/ZOS
eJu slJnpo.rdu,nop>1ueJq eql eql ur tuoJ
nd 97 tnoqu.Ioluelxe eql ol uA\opsIBeJq,{1uoe1uuu,(Jorqt eLlJ
'alquJeplsuoc aq ,{uru.:enarvroq.aur11
9 S'r{rvJ
slqJ 'urr:ps8urlrutoqt ur oturl Je^o u,rop puu alqulsun
lueJq

SAX!I'IdhIOJIICIXOUCAHCNV iICINVAJ--IVJA'! CO AU-]ITIVJS

J H KYLE

KEY
M Zn''
Hz IZn(OH),](aq)
H3 [Zn(OH),]-
10G H4 {Zn(OH).)'
OS ZnO(s)
106

pH

Frc l2 - The pZn-pH diagrarnfor no ligands

( f r o r nF l y n n a n d H a s l e r n ,1 9 9 5 )

M Zn"

HLr$?$l$
lc.ctl6r:
Cu(ottl+-cu#+0tt- K-lo{
Ei[itlEM#"''
C2S Zn(CN),(s)
cu(Ott)Zr-cu*-zOt' trp'?rlo-19
cu(o(l;-Gu*+!oK- K-5.?rl0'I5
q/(O+t);-Cu*+{ot' (-t.7rt0-17
cu(or)f-2cu*+r0n- r - 1s-ll

pH

Ftc l0 - Coppersolubility versuspH l3 - The pZn-pH diagranrfor pCN = 4.0.

(from Ritcey, 1989) (l'romFlynn and Haslem, 199-5)

KEY
M Cu"
111 {Cu(ol1)l'
t12 (cu(Oll)J(aq)
H3 lCu(OH).1
H4 [Cu(OU)]'
U
?-4 OS CuO(s)
if
o
J
-6

.B
o
€
z -10
I
t-
E pH
F
zTJ
o
z
Frc l4 - The pCu(ll)-pH diagramwith no ligands
o ( f l o m F l y n n a n d H a s l e r n ,1 9 9 - 5 ) .
u
o
zN

_ _1::.r..o l---\
lH€oRer.c^L t . l
RNGE
I
T-
v KEY
0.9 M2' Cu"
u-l
0.5
33:tc$?g)r'
Qz tCu(CN)1.
0.3 c3 lculcMl'
Lrctlo.rt: C 1 S b u c N ( d' i
- 0.1 MS Cu(s)'
Zn(Ox)+-Zn*+61.J- --0.1
K-9.lr10-6
Z^(ofiret-ln*+2gfi' (rp'l'5rlo'll -0.3
Zr(ott);-Zn#+3s41' -0.5
K-1.75r10-ll
zn(on);-In++491.1' -o.7
K-311s-16
-0.9
- 1. 1

OH

Flc I I - Zinc solubility versuspH l 5 - T h e E s - 1 r Hd i a g r a mf o r p C u ( l l ) = 4 . 0 a n d p C N = . 5 . 0

(frorn Ritcey, 1989). (fr-orn F l y n n a n d H a s l e l n ,1 9 9 5 )

S i n g a p o r e1, - 3 S e p t e m b e1r 9 9 7 World Gold

'97
Conference
 STABILITY OF METAL-CYANIDE AND HYDROXIDE COMPLEXES

CONCLUSIONS Z. Other cyanide-related species of concern will be

tliiocyitnate, cyanate and ammonia. Tliese have
The main conclusionsthat can be drawn fiom the trboveare as toxicological and chemical significance. Thiocyanate can
fbllows: form irtsoluble salts with gold, silver, mercury, lead, copper
l. Following cyanide detoxiflcationby the Inco SOz/Air ancl zinc. It will break down under normal conditions of En
process,the main componentsof concernin tl-retailings ancl pH to sulphate, carbonate and ammonia. The ammonia
will be : rnay hold metals such as copper and zinc in solution as
lmm,rnia complexes.
a. Zinc and copperhYdroxide.
3. Silver will be totally precipitated at pH 4.0, copper at 7.2,
The zinc hyclroxidewill be stablebetweenpH 8.7 ancl
nickel at 8.4, zinc at 8.7. cadmium at9.7 and manganese at
10.0.Below pH 8.7, zinc will re-dissolveinto solution
10.(r. This is assuming no complexing agents such as
as the aqueouszinc ion, Zn"- . AbovepH 10.0,the zinc
cyanide or etmmonia are Present.
will begin to re-dissolve as the zincate hydroxo
complex Zn(OH)q"-. At low cyanide concentrations
(10-4M), zinc is mostly solublebelow l0-- M as free RBFERENCBS
zinc or zinc cyanidecomPlexes.
Adams,M D, 1992. The Removlrlof Cyanidefrom Aqueous Solutionby
The copper hydroxide will be stable betweenpH 7.2 tlre Use ()f Ferrous Sulphate,.l\urrutl ofthe South At'iirun Institute ttl
zrncl9.5. Below pH 7.2, coppe.r, will re-dlssolveinto M ining und M atullurgy,92(l). l'l -25.
solutionas the aqueousion, Cu". Above pH 9.5, the Cartrso,S C. 1975. The chemi.rtrltqfcyunide C\mprturtd.sund Their
copperwill begin to re-dissolveas the cuprtrtehydroxo Behttviourin thc AcluttticEnvintnment,(CarnegieMellon Instituteof
complex Cu(OH)+'-. Soluble copper(l) cyanide Research ).
's from
complexeswill be fbrmed above pH 8 at Es Flynn, C M and Haslem, S M, 199-5. Cyanide Chemistry - Precious
+0.3 to -0.3 v. Metals Processingand WasteTreatment,Information Circular 9429,
U S B u r e a uo f M i n e s .
b. Heavy Metal Ferro- and Ferricyanides Hrriatt, J, Kelrigan, J, Olson, F and Potter, G, 1982. Pntceedingsttl
The f-errocyanide produced in the detoxiftcation CyunidaWrkshtry, (US Bureauof Mines: Salt Lake City' Utah).
process will precipitate as iron. copper or zinc Ritcey,G, M, 1989. Tbiting,sMttilugement- Problemsuncl Solutionsin
ferrocyanide. Some may be oxidised to the t he M irtitt14I ndu,stry,(Elsevier).
ferricyanide. In generalterms,the region of stabilityof Slrarpe,A G, 1976. The Chemistt't,tf cyuno complexes ol tlrc Trunsition
the iron and heavy metal cyanidesis pH 4 to 8.5, above M etuls,Academic,302 PP.
l0-6M metal ion concentration(0.05 mg/L), and below Skelley and Loy, 1973. Processes.Proceduresand Methods to control
l0-4M (2.6 mglL) cyanide ion concentration. The Pollutionfrom Mining Activrties,USEPA 43019-73-OlI' Washington
copper and zinc f'errocyanides are more stablethan the DC.
' iron f'errocyanides. Srnitlr. A and Mudcler,f, l99l . Cfiemistry und Treutmenttf'Cyunidution
Wtste,s, (Mining JournalBooks: London)'
Photolysis of the f'errocyanideand f-erricyanidewitli
ultra-violetlight can lead to its decomposttion.The
clecompositionproducts are unknown, but it must be
assumecl that free cyanide is produced' at least
transiently,until its further decomposition.

W o r l dG o l d ' 9 7C o n f e r e n c e S i n g a p o r e1, - 3 S e p t e m b e1r 9 9 7

View publication stats