Aqueous precipiIaIion and crysIaIIizaIion Ior Ihe producIion oI parIicuIaIe soIids wiIh

desired properIies
C.P. DemopouIos
Dcportmcnt oj Mining onJ Motcriols £nginccring, McCill Univcrsity, Montrcol, Qucbcc, ConoJo HJ/ 282
A 8 s 1 k A c 1 A k 1 I c I I I D I o
/rticlc history:
Keceived 9 OcIober 2008
AccepIed 9 OcIober 2008
AvaiIabIe onIine 28 OcIober 2008
KcyworJs:
Aqueous
Processing
PrecipiIaIion
CrysIaIIizaIion
HydromeIaIIurgy
SupersaIuraIion
Powders
Non-Ierrous meIaIs
Inorganic maIeriaIs
II is Ihe scope oI Ihis paper Io review and appIy Ihe Iheory oI crysIaIIizaIion kineIics Io Ihe anaIysis and
design oI aqueous inorganic hydromeIaIIurgicaI precipiIaIion sysIems. In parIicuIar Ihe criIicaI roIe oI
supersaIuraIion in conIroIIing Ihe properIies ¸crysIaIIiniIysIabiIiIy, parIicIe size and cIeanIiness) oI Ihe
precipiIaIed compounds is emphasized. The approach Iaken is oI generic naIure and noI sysIem-speci c;
however, reIerence is made Io parIicuIar precipiIaIion sysIems such as producIion oI very ne
monodispersed parIicIes, hydroIysisjneuIraIizaIion oI acidic Ierric suIphaIe Iiquors, iron precipiIaIion Irom
zinc process soIuIions, immobiIizaIion oI arsenic in Ihe Iorm oI crysIaIIine scorodiIe, and gypsum
crysIaIIizaIion in wasIe waIer IreaImenI. KeIerence Io Ihese sysIems is noI made wiIh Ihe purpose oI
describing Ihe respecIive processes buI raIher Io reinIorce Ihe vaIidiIy oI Ihe supersaIuraIion-conIroIIed
approach Io indusIriaI inorganic precipiIaIion processes.
© 2008 EIsevier B.V. AII righIs reserved.
1. lntroduction
Aqueous precipiIaIion is one oI Ihe mosI imporIanI and oIIen mosI
negIecIed uniI operaIions in various processes invoIving aqueous
media Ior Ihe purpose oI inorganic maIeriaIs producIion ¸e.g.
hydromeIaIIurgy) or immobiIizaIion oI Ioxic inorganic wasIes ¸e.g.
indusIriaI eI uenI and wasIe waIer IreaImenI). TradiIionaIIy pre-
cipiIaIion has been viewed ¸i) Irom a chemicaI equiIibrium ¸soIubiIiIy
producI) sIandpoinI and ¸ii) Iroman inorganic caIion or anion removaI
sIandpoinI, i.e. Ihe emphasis was on Ihe soIubiIiIy ¸÷aqueous species
concenIraIion) raIher Ihan on Ihe characIerisIics and quaIiIy oI Ihe
precipiIaIed compound. The IaIIer, however, becomes now increas-
ingIy more criIicaI as process chemisIs and engineers are seeking Io
preparejsynIhesize maIeriaIs wiIh speci c properIies ¸vaIue adding
processing) and Io design eI uenI IreaImenI processes IhaI can
immobiIize conIaminanIs in compacI and sIabIe soIids Ihe disposaI oI
which can avoid or minimize adverse environmenIaI eIIecIs ¸cIean
IechnoIogy). This shiII oI Iocus IromIhe soIubiIiIy Io Ihe quaIiIy oI Ihe
precipiIaIed compound caIIs Ior Ihe sIudy and appIicaIion oI Ihe
Iheory oI crysIaIIizaIion Io aqueous precipiIaIion sysIems. This is
indeed Ihe scope and conIenI oI Ihis paper.
The maIeriaI covered here is oI generic naIure and can be appIied
Io pracIicaIIy any aqueous precipiIaIion sysIem spanning Irom Ihe
removaI and rejecIion oI iron Irom hydromeIaIIurgicaI soIuIions
¸DuIrizac and Monhemius, 1985; DuIrizac and Harris, 1995; DuIrizac
and Kiveros, 2005), Io Ihe producIion oI aIumina, and Irom Ihe
producIion oI uIIra ne monodispersed powders oI meIaIs ¸SugimoIo,
1987) Iike Cu, Ag, Pd eIc. used in Ihe eIecIronics indusIry and Ihe
synIhesis oI precursor compounds Ior producIion oI high IemperaIure
superconducIors ¸copper, barium and yIIrium oxaIaIes) ¸Dirksen and
King, 1991) Io Ihe IreaImenI oI eI uenIs Ior Ihe immobiIizaIion oI
conIaminanIs Iike As and P ¸Krause and EIIeI, 1989; KamaIho, 198J). In
Ihis paper reIerence Io a number oI speci c precipiIaIion sysIems is
made because on one hand Ihis heIps Io reinIorce crysIaIIizaIion
Iheory wiIh speci c exampIes and on Ihe oIher because Ihis re ecIs
currenI research inIeresIs oI Ihis auIhor.
2. Crystallization thcory ol prccipitation
According Io crysIaIIizaIion Iheory, precipiIaIion is de ned as
reacIive crysIaIIizaIion. This de niIion is preIerred as iI emphasizes
Ihe IormaIion oI Ihe soIid producI via a chemicaI reacIion insIead oI
Ihe cIassicaI de niIionwhich Iocuses on Ihe meIaI ion removaI aspecIs
oI Ihe process. In Ihe anaIysis IhaI IoIIows Ihe emphasis is given Io Ihe
IacIors which conIroI Ihe properIies oI Ihe soIid producI, nameIy
composiIion, crysIaIIiniIy, parIicIe size, morphoIogy, and cIeanIiness.
The correIaIion oI Ihe precipiIaIion processing condiIions Io producI
properIies is deIermined via Ihe sIudy and conIroI oI Ihe IoIIowing
aspecIs oI Ihe process: ¸a) soIidIiquid equiIibria; ¸b) crysIaIIizaIion
kineIics, i.e. supersaIuraIion, nucIeaIion and growIh; ¸c) coIIoid-
surIace chemisIry, i.e. Ihe aggregaIion oI parIicIes and Ihe adsorpIion
HydromeIaIIurgy 95 ¸2009) 199214
£-moil oJJrcss: george.demopouIos@mcgiII.ca.
0J04-J85XjS  see IronI maIIer © 2008 EIsevier B.V. AII righIs reserved.
doi:10.1015jj.hydromeI.2008.10.004
Contents |ists avai|ab|e at ScienceDirect
HydromeIaIIurgy
j our na| homepage. vvv. e| sevi er. com/ | ocat e/ hydr omet
oI impuriIies; and IasI buI noI IeasI ¸d) reacIor seIecIion and design.
FuII aIIenIion Io aII Ihese issues is oI criIicaI imporIance in ensuring
exceIIenI resuIIs. This inIegraIed approach Io aqueous precipiIaIion
research is iIIusIraIed in Fig. 1.
2.1. Prccipitotion phosc cquilibrio
When we consider Ihe precipiIaIion oI a compound we have Io
examine rsI Ihe phase equiIibria oI Ihe sysIem, i.e. Io de ne Ihe
condiIions, IemperaIure, pressure and acIiviIies  concenIraIions
which Iavour Ihe IormaIion oI one or Ihe oIher phase Irom a
Ihermodynamic poinI oI view. PrecipiIaIion or soIubiIiIy diagrams
have Io be consuIIed as parI oI Ihis examinaIion. As an exampIe Ihe
soIubiIiIy diagram oI goeIhiIe ¸ -FeOOH) aI 25 "C is given in Fig. 2
¸Baes and Mesmer, 1985). This diagram by no means, however, can be
inIerpreIed as an indicaIion oI Ihe IeasibiIiIy oI producing goeIhiIe ¸i.e.
Ihe crysIaIIine compound -FeOOH) aI 25 "C. This is so because
precipiIaIiondissoIuIion reacIions are noI necessariIy reversibIe,
especiaIIy when iI comes Io Ihe degree oI crysIaIIiniIy oI Ihe
compound and aIso because in Ihis Iype oI Ihermodynamic repre-
senIaIion Ihere are ineviIabIy a number oI assumpIions and resIric-
Iions associaIed wiIh iI.
LeI us consider Ihe generaI case oI precipiIaIion oI a compound
AB¸s):
A
aq
+ B
aq
+ X
aq
+ I
aq
+ H
2
OAB
s
+ ?   ABX andor IB ABOH eIc  
1
where X is Ihe maIrix anion and I represenIs oIher ionic species.
DespiIe Ihe IacI IhaI a simpIe Ihermodynamic anaIysis mighI
indicaIe IhaI Ihe IormaIion oI Ihe soIid producI AB is IeasibIe, side
reacIions may be occurring simuIIaneousIy Ieading Io producIion oI
addiIionaI phases. A good exampIe in Ihis respecI is Ihe Fe¸III)SO ¸II)
H O sysIem where a range oI iron ¸III)  conIaining phases can Iorm
upon hydroIysis, depending on IemperaIure and soIuIion composiIion;
such as hemaIiIe, -goeIhiIe, basic Ierric suIphaIe, jarosiIe, IerrihydriIe
or IoIaIIy amorphous hydrous Ierric oxide ¸Posnjak and Merwin, 1922;
VoigI andCöbIer, 1985; ]ambor and DuIrizac, 1998; DzombakandMoreI,
1990).
However, iI is noI onIy Ihe possibIe IormaIion oI more Ihan one
crysIaIIine phase IhaI compIicaIes maIIers; Ihere is aIso Ihe possibIe
IormaIion oI meIasIabIe phases ¸i.e. phases enjoying a kineIic sIabiIiIy
despiIe Iheir Ihermodynamic insIabiIiIy). In oIher words, in Ihe
domain oI Ihermodynamic sIabiIiIy oI a compound, a Iess sIabIe phase
may Iormdue Io IavourabIe kineIics. UsuaIIy Ihis meIasIabIe phase is a
precursor phase, which evenIuaIIy, given Ihe Iime, shouId converI Io
Ihe sIabIe one. For exampIe, hydroxycarbonaIe saIIs ¸i.e. M ¸OH) CO )
Iend Io Iorm ahead oI Iheir carbonaIe counIerparIs ¸i.e. MCO ) wiIhin
Ihe domain oI sIabiIiIy oI Ihe IaIIer, or jarosiIe Iends Io IormwiIhin Ihe
domain oI Fe O , ¸see shaded area in Fig. J) ¸ZereIIa eI aI., 198J) during
pressure Ieaching oI suIphide IeedsIocks.
AI Ihis poinI iI is worIhy Io remind ourseIves IhaI in generaI aII
equiIibriumdiagrams Iike Ihe ones menIioned here have Io be IreaIed
wiIh cauIion noI onIy because Ihey negIecI Ihe kineIics ¸aIIer aII Ihey
are equiIibriumdiagrams) buI because many oI Ihemare based ondaIa
noI coIIecIed wiIh reIiabIe experimenIaI procedures or simpIy because
Ihey were buiII on Ihe basis oI a number oI simpIiIying assumpIions.
One such case was Ihe earIy soIubiIiIy daIa and diagrams IhaI were
pubIished Ior FeAsO ·2H O IhaI were based on Fe as opposed Io As
soIuIion concenIraIion measuremenIs ¸Krause and EIIeI, 1989). In a
reviewpaper ¸Cheng and DemopouIos, 1997) deaIing wiIh Ihe anaIysis
oI Ihe hemaIiIe precipiIaIion sysIemiI has been shown IhaI signi canI
discrepancies occur wiIh a number oI precipiIaIion diagrams reIerring
IoIhe sysIemFe¸III)SO ¸II)H O. InconnecIionwiIhIhe IaIIer iI mighI
be added here IhaI iI is commonIy accepIed IhaI hemaIiIe can be
produced onIy aI IemperaIures above 1J0 "C ¸see aIso Fig. J). However
Ihe IemperaIure aI which hemaIiIe precipiIaIion is Iavoured is highIy
dependenI onIhe concenIraIionoI Ihe ironsoIuIions, on Ihe meIhodoI
precipiIaIion, e.g. direcI hydroIysis vs oxydroIysis or on Ihe maIrix oI
Ihe soIuIion, i.e. suIphaIe vs. chIoride vs. niIraIe media. KeIer Ior
exampIe Io VoigI and CöbIer ¸1985), Cheng and DemopouIos ¸1997)
and DuIrizac and Kiveros ¸1999). To expIain Ihese diIIerences iI is
imporIanI Io resorI Io Ihe anaIysis oI Ihe crysIaIIizaIion kineIics oI iron
precipiIaIion and inparIicuIar Ihe eIIecI oI supersaIuraIionon Ihe Iype
and quaIiIy oI Ihe precipiIaIed compound. Hence, pubIished equiIi-
briumdaIa and diagrams have Io be inIerpreIed wiIh cauIion and onIy
as providing generaI Irends.
lig. 1. A new paradigm Ior aqueous precipiIaIion research.
lig. 2. The soIubiIiIy diagram oI -FeOOH ¸25 "C). The numbered Iines reIer Io Ihe Fe
OH aqueous compIexes ¸reproduced Irom Baes and Mesmer ¸1985)).
lig. 3. CoeIhiIejarosiIehemaIiIe equiIibria as a IuncIion oI IemperaIure ¸adapIed
Irom ZereIIa eI aI. ¸198J)).
200 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
2.2. Supcrsoturotion
2.2.1. Soturotion rotio
According Io crysIaIIizaIion Ihermodynamics, a soIid phase Iorms
ouI oI a soIuIion when
C ÷ k! 
o
 0 2
where C: moIar Cibbs Iree energy; k: Ihe universaI gas consInaI; !:
Ihe absoIuIe IemeraIure; : acIiviIy oI Ihe soIuIe in Ihe iniIiaI
soIuIion; and : acIiviIy oI Ihe soIuIe in Ihe naI soIuIion ¸i.e. in
equiIibrium wiIh Ihe soIid phase).
We de ne Ihe raIio j as Ihe saIuraIion raIio, S. II we Iake ¸a
raIher gross simpIi caIion) acIiviIies equaI Io concenIraIions we have:
S ÷ 
o
CC
eq
J
where C : equiIibriumconcenIraIion; when S1 we have C0. This
is Ihe condiIion oI supersaIuraIion. We de ne Ihe supersaIuraIion
raIio equaI Io
C C
eq
C
eq
÷ S 1 4
ThereIore, supersaIuraIion is Ihe driving Iorce Ior crysIaIIizaIion.
For Ihe case oI reacIive crysIaIIizaIion, i.e. A +B AB¸s), Ihe
saIuraIion raIio is de ned as;
S ÷ A B K
sp
5
where K ÷|A| |B| ÷exp¸ C"jk!).
II musI be added here IhaI Ihe soIubiIiIy oI a compound ¸K 
vaIue) is noI onIy a IuncIion oI iIs crysIaIIiniIy ¸i.e. amorphous vs
crysIaIIine precipiIaIes) buI as weII a IuncIion oI Ihe crysIaIIiIe size in
Ihe case oI nanocrysIaIIine precipiIaIes. This is described by Ihe
CibbsThomson equaIion ¸SugimoIo, 1987):
C
eq
÷ C 
2 v
m
rk!
5
where
C soIubiIiIy oI crysIaIIine parIicIes
C soIubiIiIy oI an in niIe size crysIaI
speci c surIace energy ¸] m )
v moIar voIume oI Ihe crysIaI ¸m moI )
r radius oI Ihe parIicIe ¸m)
AppIicaIion oI Ihis equaIion Io scorodiIe precipiIaIes reveaIed IhaI
Ihe soIubiIiIy increases aI IeasI 2 Iimes when Ihe crysIaIIiIe size
decreases Irom 200 Io 10 nm ¸DemopouIos eI aI, 1994).
2.2.2. Supcrsoturotion stotc
The sIaIe oI Ihe supersaIuraIed soIuIion is noI necessariIy Ihe same
as IhaI in a diIuIe ionic soIuIion. In diIuIe soIuIions we have ionic
species ¸Iree or compIexed) soIvaIed wiIh H O. As Ihe concenIraIion oI
Ihe soIuIe increases exIensive ion-associaIion occurs ¸usuaIIy due Io a
decrease in Ihe acIiviIy oI waIer) which Ieads Io Ihe IormaIion oI
eIecIricaIIy neuIraI ion-pairs ¸aIways soIvaIed wiIh waIer). When Ihe
soIuIion becomes supersaIuraIed we have aggregaIionpoIymeriza-
Iion oI Ihe soIuIe species, which Ieads Io Ihe IormaIion oI cIusIers oI
ion-pairsjmoIecuIes ¸101000 monomers per cIusIer). This cIusIer is
Ihe precursor oI Ihe parIicIe ¸FIynn, 1984).
2.J. Kinctics oj crystollizotion
2.J.1. Nuclcotion
The IormaIion oI a soIid phase ouI oI a soIuIion invoIves Ihe
phenomena oI nucIeaIion, growIh and aggregaIion oI parIicIes. Depend-
ing on Ihe siIe on which nucIeaIion occurs we have diIIerenI nucIeaIion
mechanisms ¸Carside, 1985), Ihree oI whichare Ihe mosI imporIanI ones:
¸i) homogeneous, i.e. primary producIion oI nucIei in Ihe absence
oI a surIace
¸ii) heIerogeneous, i.e. primary producIion oI nucIei on a Ioreign
surIace and
¸iii) surIace, i.e. secondary producIion oI nucIei on Ihe surIace oI a
soIid oI Ihe same kind wiIh Ihe one which precipiIaIes.
OIher secondary nucIeaIion mechanisms invoIve IragmenIaIion oI
crysIaIs ¸apparenI nucIeaIion) and deposiIion on reacIor waIIs
¸conIacI nucIeaIion)  Ihe IaIIer is discussed in SecIion 2.10.
2.J.1.1. Homogcncous nuclcotion. The moIecuIes or ion-pairs oI Ihe
supersaIuraIed soIuIion combine IogeIher Io Iorm cIusIers or embryos
consisIing oI 101000 moIecuIesjcIusIer. These embryos consIanIIy
Iorm and disappear unIiI Ihey assume a criIicaI size ¸r ) above which
Ihey are sIabIe, i.e. Ihey do noI go back inIo soIuIion. According Io
crysIaIIizaIionIhermodynamics ¸DirksenandKing, 1991) Ihe Ireeenergy
change associaIed wiIh Ihe IormaIion oI Ihe embryo is given by:
C r   ÷ C
voI
C
surI
7
where Ihe rsI Ierm is Ihe Iree energy change associaIed wiIh Ihe
generaIion oI voIume and Ihe second Ierm is associaIed wiIh Ihe
generaIion oI surIace. The rsI Ierm, i.e. C is negaIive buI Ihe second
one is posiIive. So, iI is onIyaIIer a cerIain size r IhaI | C | | C | and
C¸r) becomes negaIive. A graphicaI represenIaIion oI Ihe C¸r)
IuncIion is given in Fig. 4 ¸MuIIin, 199J). The C represenIs an
acIivaIion energy barrier.
The criIicaI nucIei size, r is a IuncIion oI Ihe saIuraIion raIio
¸decreases as Ihe IaIIer increases) and may vary beIween 40 Io 200 Å.
In pracIicaI Ierms Ihen a high degree oI supersaIuraIion is expecIed Io
yieId a Iarge popuIaIion oI uIIra- ne parIicIes.
AnoIher criIicaI IeaIure oI Ihe dependency oI Ihe nucIeaIion raIe
on saIuraIion raIio is Ihe IacI IhaI nucIeaIion sIarIs onIy when a criIicaI
S vaIue ¸S ) is exceeded ¸Fig. 5). Beyond Ihis S vaIue Ihe
nucIeaIion raIe increases sharpIy, reaching quickIy iIs maximum raIe.
A commonIy used IogIog pIoI oI Ihe dependency oI Ihe nucIeaIion
raIe on saIuraIion raIio is shown in Fig. 5 ¸SohneI and Carside, 1992).
The Iorm oI Ihe nucIeaIion raIe equaIion resembIes IhaI oI Ihe
Arrhenius equaIion ¸Dirksen and King, 1991):
j ÷ 2DJ
5
 C
max
k
8
!   8
where
j is expressed in number oI nucIei per uniI voIume ¸m ) per
uniI Iime¸s),
D is Ihe diIIusiviIy oI Ihe soIuIe species ¸m s )
J is Ihe moIecuIar diameIer oI Ihe soIuIe species ¸m),
and
k is Ihe BoIIzman consIanI; 1.J8×10 ]·K .
The maximum raIe is a very Iarge number oI Ihe order oI 10
nucIei cm s .
II appears, IhereIore, IhaI as soon as homogeneous nucIeaIion
sIarIs, iI propagaIes quickIy and in a raIher shorI Iime we have Ihe
IormaIion oI an uIIra- ne coIIoidaI precipiIaIe.
S is an inIrinsic kineIic properIy oI each precipiIaIed
compound IhaI may vary Irom as Iow as S÷ 1.1 Io as high as more
Ihan 10,000. II has been Iound IhaI S is a IuncIion oI Ihe size oI
Ihe precursor poIymeric species; more speci caIIy S decreases
wiIh increasing n , where n ÷number oI monomers IhaI make up Ihe
criIicaI nucIeus. ConverseIy S decreases as Ihe speci c surIace
energy oI Ihe precipiIaIing soIid increases ¸reIer Io Fig. 5).
201 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
Thus Ior compounds preceded by sponIaneous poIymerizaIion, as is
Ihe casewiIhIerric ¸oxy)hydroxides ¸n 100), S is Iess Ihan10and
Ihis expIains Ihe diI cuIIy oI obIaining crysIaIIine and weII behaving
precipiIaIes. OnIhe oIher handBaSO Iorms smaII poIymers ¸n ~10) and
Ihis resuIIs in a very high S vaIue weII above 1000. In oIher words
homogeneous crysIaIIizaIionoI BaSO occurs wiIhouI a probIemevenaI
ambienI condiIions and Ihis expIains Ihe success oI Ihe gravimeIric
meIhod oI suIphaIe deIerminaIion IhaI invoIves accuraIe precipiIaIion
and separaIion oI BaSO crysIaIs.
2.J.1.2. Hctcrogcncous onJ surjocc nuclcotion. NucIeaIion on an
exisIing surIace is Iavoured as Ihe surIace energy is Iower Ihan IhaI oI
a new nucIeus and C is Iower Ioo. The resuII is Ihe criIicaI
saIuraIion raIio Io decrease as weII. Thus we have Ihe IoIIowing order:
1S
cr surIace
S
cr heIero
S
cr homo
The order oI criIicaI saIuraIion raIios is indicaIive oI Ihe order oI
Ihe acIivaIion energy which conIroIs Ihe nucIeaIion raIe. FinaIIy, Ihe
raIe equaIion Ior surIace or heIerogeneous nucIeaIion is oI Ihe same
Iorm wiIh IhaI oI homogeneous nucIeaIion.
2.J.2. Crowth
2.J.2.1. Mcchonism oj growth. The incorporaIion oI a soIuIe species
Io a growing crysIaI goes Ihrough a series oI sIages ¸Dirksen and King,
1991):
¸a) InIerIaciaI IransporI oI soIuIe, ¸b) adsorpIion on Ihe parIicIe
surIace, ¸c) surIace diIIusion, ¸d) inIegraIion inIo Ihe crysIaI aI a kink
siIe ¸surIace reacIion), and ¸e) desoIvaIion and waIer diIIusion away
Irom Ihe surIace.
2.J.2.2. Crowth rotc. The growIh oI a sphericaI parIicIe oI radius r is
characIerized by a rsI order and more rareIy second order ¸in Ierms
oI S) equaIion ¸SugimoIo, 1987; KandoIph and Larsen, 1971):
C÷ JrJt ÷ k
g
C
eq
S 1   9
where C is Ihe crysIaI growIh raIe ¸m s ); k is Ihe growIh consIanI
¸m moI s ) and C Ihe soIubiIiIy oI Ihe precipiIaIing soIuIe species
¸moI m ).
In conIrasI, Ihe nucIeaIion raIe ¸j) is an exponenIiaI or high power
IuncIion in Ierms oI S ¸j S ) ¸MuIIin, 199J; SohneI and Carside,
1992).
2.J.2.J. MoJcs oj growth. Depending on Ihe reIaIive magniIude oI Ihe
surIace nucIeaIion raIe vs. Ihe growIh raIe, Iwo diIIerenI modes oI
growIh arise ¸KandoIph and Larsen, 1971). The rsI one is Ihe Iayered or
mono-nucIear growIhmodewhichoccurs whenIhe raIe-IimiIing sIepis
surIace nucIeaIion; Ihe second is Ihe conIinuous or poIynucIear growIh
mode which occurs when growIh is Ihe raIe-IimiIing sIep. In indusIriaI
precipiIaIion sysIems iI is Ihe IaIIer IhaI is mosI commonIy observed.
2.J.2.4. Crowth by oggrcgotion. CrowIhuniIs, i.e. nucIei oI 0.010.1µm
aggregaIe provided IhaI coIIoid sIabiIiIy is suppressed.
The sIabiIiIy oI a coIIoid suspension due Io doubIe Iayer inIeracIion
can be described wiIh Ihe aid oI Ihe coIIoid sIabiIiIy IacIor ¸Dirksen
and King, 1991):
W ÷ o + b  
o + b
l
4
 v r  k
B
! Jrr
2
10
where
v¸r) is Ihe inIeracIion poIenIiaI energy oI Ihe Iwo doubIe Iayers
¸] m )
k is Ihe BoIIzmann consIanI ¸÷1.J8×10 ] K )
r is Ihe disIance beIween cenIers oI Iwo spheres ¸m)
o,b are Ihe parIicIe radii ¸m)
AggregaIion is Iavoured as Wdecreases, i.e. as v¸r) decreases. This is
equivaIenI Io doubIe Iayer compression. This is achieved via an increase
oI Ihe ionic sIrengIh ¸l) oI Ihe soIuIion. Speci c ion adsorpIion can have
an equaIIy posiIive eIIecI on coIIoid aggregaIion. AggregaIion is aIso
Iavoured as Ihe popuIaIion densiIy oI coIIoid increases. The phenom-
enon oI coIIoid aggregaIion due Io eIecIricaI Iorces is aIso known as
coaguIaIion. Highshear Iorces ¸agiIaIion) IendIo promoIe Ihe IormaIion
oI compacI aggregaIes. BaIch reacIors are associaIed wiIh exIensive
aggregaIion. Large parIicIes are Iess prone Io aggregaIion Ihan ne
producIs. AggregaIion is Ihe major mode oI growIh in precipiIaIion
sysIems dominaIed by homogeneous nucIeaIion. AnoIher Iype oI
aggregaIion is IhaI induced by poIymers, oIherwise caIIed occuIaIion.
NaIuraI and synIheIic macromoIecuIes have been used successIuIIy as
aggregaIion agenIs  surIacIanIs in waIer and wasIe IreaImenI
¸Cregory, 1978). Non-ionic surIacIanIs work besI aI pH , i.e. pH 89
Ior Fe¸OH) ¸IEPis Ihe pHaI whichIhe zeIa poIenIiaI is zero). The dosage
oI surIacIanI is criIicaI. For occuIaIion onIy IracIionaI coverage is
required. WiIh compIeIe coverage coIIoid sIabiIizaIion occurs insIead.
lig. 4. CrysIaIIizaIion Iree energy change as a IuncIion oI nucIei size ¸reproduced Irom
MuIIin ¸199J)).
lig. 5. VariaIion oI homogeneous nucIeaIion raIe wiIh S ¸IogIog pIoI) Ior diIIerenI vaIues
oI precipiIaIing soIid surIace energy ¸¸reproduced Irom SohneI and Carside ¸1992)).
202 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
In an unconIroIIed precipiIaIion sysIem ¸very common in baIch
precipiIaIionsysIems) whaI usuaIIyhappens is IhaI uponbuiId-upoI Ihe
soIuIe concenIraIion, S is exceeded and homogeneous nucIeaIion
occurs. AIIer some modesI moIecuIar growIhIhe nucIei aggregaIe. WiIh
Ihe progress oI Ihe precipiIaIionreacIionIhe concenIraIiondrops beIow
S and surIace nucIeaIion IoIIowed by moIecuIar growIh sIarIs
which Ieads Io cemenIing oI Ihe aggregaIes.
2.J.2.5. Porticlc morphology. The poIynucIear and Ihe aggregaIion
modes oI growIh are Ihose IhaI are mosI common ¸due Io Iack oI
supersaIuraIion conIroI) in indusIriaI precipiIaIion sysIems. As a
resuII oI Ihis Iype oI growIh Ihe produced parIicIes are poIycrysIaIIine
wiIh rough surIaces.
2.J.J. Prccipitotion rcgimcs
A pIoI oI Ihe Iinear ¸growIh) and exponenIiaI ¸homogeneous
nucIeaIion) raIe equaIions againsI saIuraIion raIio heIps Io de ne Iwo
disIincI regimes oI precipiIaIion ¸Fig. 5). Thus when SS
precipiIaIion occurs onIy on seed ¸i.e. crysIaIIiIes oI Ihe same kind) or
Ioreign soIids  Ihis is Ihe regime oI growIh-dominaIed precipiIaIion.
On Ihe oIher hand when SS homogeneous nucIeaIion
dominaIes, Ihus Ieading Io producIion oI uIIra- ne coIIoidaI pre-
cipiIaIes ¸regime oI nucIeaIion-dominaIed precipiIaIion). In hydro-
meIaIIurgy, where in generaI producIion oI weII grown precipiIaIes is
preIerred, iI is deduced Irom Ihe diagram oI Fig. 5 IhaI Ihe
precipiIaIion process wiII have Io be designed in such a way IhaI iI
wiII operaIe aI a supersaIuraIion IeveI jusI beIow S , IogeIher
wiIh recycIing oI Ihe precipiIaIe Io provide Ior Ihe necessary seed. The
use oI Ihis diagram is demonsIraIed IaIer in reIaIion Io IerrihydriIe
and scorodiIe precipiIaIion.
2.4. /ttoinmcnt oj crystollinity
The IacIors Iavouring Ihe direcI producIion oI crysIaIIine ¸as
opposed Io amorphous) compounds are high IemperaIure and Iow
supersaIuraIion. The roIe oI Ihese Iwo IacIors can be eIucidaIed by
reIerring Io Ihe mechanism oI crysIaI growIh.
2.4.1. High tcmpcroturc
EIevaIion oI IemperaIure has Ihe IoIIowing bene ciaI eIIecIs:
¸i) dehydraIion is Iavoured; ¸ii) neuIraIizaIion oI Ihe charge oI Ihe
precursor compIex is Iavoured; ¸iii) surIace diIIusion-mobiIiIy oI Ihe
adsorbed soIuIe is enhanced; and ¸iv) Ihe crysIaIIizaIion raIe ¸i.e. Ihe
reacIive incorporaIion oI soIuIe inIo crysIaI) is acceIeraIed.
DiIIerenI phases can be produced aI diIIerenI IemperaIure ranges
due Io easier desoIvaIion, e.g. IormaIion oI boehmiIe ¸ -AIOOH) aI
IemperaIures around 100 Io 120 "C as opposed Io gibbsiIe ¸ -AI¸OH) )
IhaI Iorms aI IemperaIures beIow 100 "C; or producIion oI hemi-
hydraIe oI caIcium suIphaIe near Ihe boiIing poinI oI waIer insIead oI
gypsum ¸CaSO ·2H O) which Iorms aI Iower IemperaIures ¸Li and
DemopouIos, 2005).
2.4.2. Low supcrsoturotion
Lowering oI supersaIuraIion has Ihe IoIIowing bene ciaI eIIecIs:
¸i) Ihe IormaIion oI Iarge and immobiIe poIymeric species is avoided;
¸ii) homogeneous nucIeaIion, which is responsibIe Ior Ihe producIion
oI amorphous parIicIes ¸see SIranski's ruIe in Ihe nexI secIion) and
exIensive aggregaIion Ieading Io soIuIion enIrainmenI is avoided;
¸iii) Ihe exIernaI mass IransporI process is deceIeraIed and Ihe soIidj
Iiquid inIerIace becomes Iess crowded, Ihus aIIowing Ihe surIace
inIegraIion reacIion Io proceed reIaIiveIy uninhibiIed.
Thus mainIenance oI IowS incombinaIionwiIhseedeIIecIiveIyresuIIs
in Iowering oI Ihe crysIaIIizaIion IemperaIure. WhiIe Ihe eIIecI oI
IemperaIure is weII known, IhaI oI IowsupersaIuraIion is noI. The auIhor
and co-workers have convincingIy demonsIraIed Ihe powerIuI eIIecI
supersaIuraIionconIroI has onIhe aIIainmenI oI crysIaIIiniIyinIhe caseoI
scorodiIe ¸FeAsO ·2H O) precipiIaIion rsI Irom chIoride media ¸Demo-
pouIos eI aI., 1995a) and IaIer Irom suIphaIe soIuIions ¸DropperI eI aI.,
1995; FiIippou and DemopouIos, 1997; Dabekaussen eI aI., 2001). Thus
wiIh supersaIuraIion conIroI scorodiIe was produced aI 95 "C as opposed
Io aI IeasI 150 "C required wiIhouI supersaIuraIion conIroI ¸DuIrizac and
]ambor, 1988; Swash and Monhemius, 1994).
2.5. Phosc tronsjormotion oj prccipitotcs
Many precipiIaIes Iormed are oIIen amorphous ¸due Io eiIher Iow
IemperaIure or Iack oI supersaIuraIion conIroI or boIh), and upon
ageing are converIed Io crysIaIIine compounds.
2.5.1. Stronski´s rulc
According Io SIranski's or OsIwaId SIep KuIe Ihe IeasI sIabIe phase
nucIeaIes rsI as Iong as homogeneous nucIeaIion deIermines Ihe
raIe ¸BIesa and MaIijevic, 1989). This is so because Ihe inIerIaciaI
energy requiremenIs are Iess sIringenI and as such nucIeaIion is
easier. There is no oIher sIaIemenI more Irue inprecipiIaIion reacIions
Ihan SIranski's ruIe. A good prooI oI Ihe vaIidiIy oI Ihis ruIe is Fe¸III)
hydroIysis reacIions which rsI yieId an amorphous hydroxide which
upon ageing is converIed Io progressiveIy more sIabIe crysIaIIine
phases ¸BIesa and MaIijevic, 1989):
Fe III  
aq
FeOOHH
2
Oam FeOOH or FeOOH Fe
2
O
J
11
The inIermediaIe phases are simpIy meIasIabIe modi caIions.
2.5.2. !hc Jissolutionrccrystollizotion mcchonism
As research in coIIoid chemisIry has shown ¸BIesa and MaIijevic,
1989) Ihe phase IransIormaIion reacIions in aqueous media proceed
lig. 6. De niIion oI Iwo disIincI precipiIaIion regimes wiIh Ihe aid oI Ihe raIe vs.
saIuraIion raIio curves ¸adapIed Irom DemopouIos ¸199J)).
lig. 7. DissoIuIionrecrysIaIIizaIion processes ¸adapIed Irom BIesa and MaIijevic ¸1989)).
20J C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
mainIy via Ihe dissoIuIionrecrysIaIIizaIion mechanism. According Io
Ihis mechanism ¸Fig. 7) Ihe IeasI sIabIe phase ¸A) Iorms rsI ¸as a
consequence oI SIranski's KuIe) aI a raIe K . When Ihe concenIraIion
oI Fe¸III) ¸aq) drops beIow Ihe soIubiIiIy oI A¸s), dissoIuIion oI Ihe
IaIIer sIarIs aI a raIe K . Under Ihe new Iow S environmenI creaIed,
soIid phase B Iorms ¸aI a raIe K ) which once more when Ihe
condiIions become IavourabIe dissoIves back sIowIy aI a raIe K . And
naIIy phase C Iorms ouI oI Ihe new very diIuIe and seeded aqueous
environmenI. II musI be emphasized here IhaI Ihe Iime scaIe oI Ihese
phase IransIormaIion reacIions mighI be very shorI, say minuIes Io
hours, ¸Ior exampIe in-siIu IransIormaIion oI meIasIabIe phases aI
eIevaIed IemperaIures) or very Iong, say years ¸which is Ihe case oI
mosI oI Ihe naIuraI ageing processes).
2.5.J. HyJrothcrmol convcrsion oj jcrrihyJritc
Consider as an exampIe Ihe hydroIhermaI conversion oI IerrihydriIe
¸FeOOH·xH O¸am)) Io crysIaIIine goeIhiIe ¸ -FeOOH) or hemaIiIe ¸ -
Fe O )¸NorIundChrisIensen eI aI., 1980). The amorphous phase, Ihrough
dissoIuIionrecrysIaIIizaIion in an aqueous environmenI converIs Io -
FeOOH or -Fe O depending on Ihe IemperaIure and pH ¸Fig. 8). The
reacIion sequence Ior goeIhiIe IormaIion is shown beIow:
FeOOHxH
2
Oam + JH
+ dissoIuIion
Fe
J+
+ 2 + x  H
2
O 12
Fe
J+
+ 2H
2
O
KecrysIaIIizaIion
 FeOOH+ JH
+
1J
The S-shaped kineIic curves oI Fig. 8 are IypicaI Ior nucIeaIion-
growIh Iype reacIions ¸SarraI-Mamoory eI aI., 1995).
OIher exampIes are ¸i) Ihe conversion oI IreshIy prepared
amorphous Ierric arsenaIe upon equiIibraIion in Ihe acidic region
¸pH 4) Io Ihe crysIaIIine equivaIenI ¸scorodiIe) ¸Nishimura and
Kobins, 1995; Le Berre eI aI., 2008), ¸ii) Ihe IransIormaIion oI
akageneiIe ¸ -FeOOH) Io hemaIiIe in chIoride media ¸DuIrizac and
Kiveros, 1999), and ¸iii) Ihe hydroIhermaI conversion ¸aI 220 "C) oI
jarosiIe Io hemaIiIe ¸DuIrizac, 1990).
2.5. Porticlc sizc control
For Ihe producIion oI very- ne monodispersed parIicIes, Iwo
condiIions have Io be meI: ¸1) separaIion oI homogeneous nucIeaIion
and growIh sIages via supersaIuraIion conIroI and ¸2) conIroI oI
aggregaIion via coIIoid sIabiIizaIion. According Io Ihe weII known
LaMer diagram ¸Fig. 9) ¸SugimoIo, 1987) condiIion ¸1) is meI by
causing an iniIiaI shorI-Iived homogeneous nucIeaIion evenI via Ihe
sudden ¸buI conIroIIed) increase oI supersaIuraIion above S ¸or
C according Io Ihe diagram oI Fig. 9) IoIIowed by reguIaIion oI S
¸in Ihe region: 1SS ¸or equivaIenIIy C CC where
C is Ihe equiIibrium concenIraIion). CondiIion ¸2) is meI by carrying
ouI precipiIaIion away Irom Ihe IEP and aI Iow ionic sIrengIh or by
using surIacIanI-based sIeric sIabiIizaIion.
OnIhe oIher handproducIionoI weII growncrysIaIs, whichis Ihe case
oI reIevance Io indusIriaI hydromeIaIIurgy, is achieved via thc usc oj sccJ
onJ Ihe mointcnoncc oj lowsupcrsoturotion, i.e. SS ¸see Fig. 5). II is
Ihe IaIIer condiIion, i.e. Ihe mainIenance oI Iow S IhaI has been oIIen
negIecIed in aqueous precipiIaIion process research and deveIopmenI.
2.Z. McthoJs jor thc control oj supcrsoturotion
FromIhe discussion so Iar iI has become cIear IhaI supersaIuraIion
conIroI is oI paramounI imporIance iI Ihe quaIiIy oI Ihe precipiIaIed
compound is Io be enhanced. The quesIion is however, how super-
saIuraIion can be conIroIIed in pracIice and moreover howS can
be deIecIed and avoided iI Ihe producIion oI weII grown and
crysIaIIine precipiIaIes is soughI. Some oI Ihe meIhods avaiIabIe Io
exercise supersaIuraIion conIroI are described beIow.
2.Z.1. vio pH Control
For pH-dependenI precipiIaIion reacIions, as are Ihose oI hydro-
Iysis, supersaIuraIion can be conIroIIed via proper adjusImenI-
reguIaIion oI Ihe pH oI Ihe soIuIion. One oI Ihe meIhods IhaI has
been pracIiced by coIIoid chemisIs is Ihe use oI a sIow-reIeasing base,
Iike urea. In generaI sIow neuIraIizaIion is bound Io provide
improvemenI in precipiIaIion due Io Ihe inherenI sIow supersaIura-
Iion associaIed wiIh iI. In Ihis respecI, IhereIore, CaCO and CaO
¸ignoring aI Ihis poinI any posiIive or negaIive inIerIerences Irom Ihe
IormaIion oI gypsum) wouId be expecIed Io be beIIer neuIraIizing
agenIs Ihan NaOH. This has indeed been con rmed in Ihe auIhor's
IaboraIory in Ihe cases, Ior exampIe, oI scorodiIe ¸DropperI eI aI., 1995)
and Ni¸OH) precipiIaIion ¸SisI and DemopouIos, 200J).
For IuII conIroI oI supersaIuraIion, Ihough, precise pH conIroI is
needed and Ihis can be accompIished wiIh a sIep-wise neuIraIizaIion
procedure as Ihe one deveIoped by Ihe auIhor ¸DemopouIos, 199J). This
sIep-wise neuIraIizaIion procedure ¸Fig. 10) consisIs oI Ihe IoIIowing
sIeps: FirsI Ihe soIubiIiIy curve oI Ihe compound Io be precipiIaIed is
esIabIishedinIhe IormoI C versus pHbyequiIibraIing soIids oI Ihesame
compound wiIh soIuIion aI Ihe IemperaIure oI inIeresI.
FoIIowing IhaI, supersaIuraIion curves are drawn in paraIIeI Io Ihe
soIubiIiIy curve. These supersaIuraIion curves are used Io deIermine
aIIernaIe sIep-wise neuIraIizaIion paIhs as shown in Fig. 10. SIep-wise
neuIraIizaIion invoIves neuIraIizaIion oI an acidic soIuIion oI iniIiaI
meIaI concenIraIion C and pH÷pH upIo pH . AI Ihis ¸or sIighIIyIower)
pH, seed is added and heIerogeneous precipiIaIion is iniIiaIed during
which Ihe pH is mainIained consIanI ¸or aI IeasI wiIhin Ihe
heIerogeneous precipiIaIion zone) wiIh base addiIion. When pH sIops
changing  an indicaIion IhaI precipiIaIion is more or Iess compIeIe aI
lig. 8. HydroIhermaI conversion oI amorphous IerrihydriIe  curve I corresponds Io
producIion oI a mixIure oI -FeOOH and -Fe O aI 120 "C and pH 10 whiIe curve II
corresponds Io producIion oI -Fe O aI 150 "C and pH 4.5. ¸daIa Iaken Irom NorIund
ChrisIensen eI aI. ¸1980)).
lig. 9. The LaMer diagram ¸adapIed Irom SugimoIo ¸1987)).
204 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
Ihis pH  IurIher base is added and Ihe pH is raised Io Ihe second
desIinaIion: pH and Ihe procedure is repeaIed. By IesIing various
supersaIuraIion IeveIs Ihe opIimumone is de ned Ior Ihe producIion oI
weII grown ¸and crysIaIIine iI possibIe) precipiIaIes. This semi-baIch
sIep-wise precipiIaIion procedure can be impIemenIed on a conIinuous
indusIriaI circuiI operaIionbyusinga series oI Ianks ¸reIer IoSecIionJ.1),
Ihe number oI which and Iheir respecIive operaIing ¸sIeady-sIaIe) pH
being Ihe same as Ihe sIeps and pH vaIues de ned in Fig. 10.
A criIicaI IeaIure during Ihis sIage oI invesIigaIion is Ihe
deIerminaIion oI Ihe criIicaI or oIherwise caIIed inducIion pH
¸DropperI eI aI., 1995; Dabekaussen eI aI., 2001). This pH is de ned
as Ihe pH aI which Ihe onseI oI homogeneous nucIeaIion is observed,
i.e. Ihis is Ihe pH corresponding Io S . These concepIs and
meIhods are IurIher expIained in connecIion Io Ihe descripIion oI Iwo
iron ¸III) precipiIaIion sysIems discussed in SecIion J, i.e. precipiIaIion
oI IerrihydriIe and precipiIaIion oI scorodiIe.
The approach ouIIined here may be adapIed and used in non-
hydroIyIic precipiIaIion sysIems where insIead oI sIepwise addiIion
oI base oIher precipiIaIing agenIs may be used. This is Ihe case, Ior
exampIe, oI meIaI suIphide precipiIaIion wiIh conIroIIed dosage oI
S ¸e.g. in Ihe IormoI H S). The conIroIIed addiIion oI precipiIanI as
a means oI conIroIIing supersaIuraIion has been successIuIIy
demonsIraIed in Ihe case oI high grade nickeI suIphaIe crysIaI-
IizaIion Irom spenI eIecIroIyIes wiIh isopropanoI ¸MoIdoveanu and
DemopouIos, 2002).
2.Z.2. vio mctol complcxotion onJ Jissociotion
In Ihis meIhod, which is beIIer suiIed Ior Ihe producIion oI high
vaIue compounds, Ihe meIaI Io be precipiIaIed is compIexed wiIh
sIrong compIexing agenIs Iike EDTA, NH eIc. and Ihen iI is dissociaIed
in a conIroIIed manner in order Io aIIow iIs conIroIIed reIease ¸and
Ihereby conIroIIed supersaIuraIion environmenI) and precipiIaIion. A
good exampIe oI Ihis approach is SherriII's meIhod Ior Ihe producIion
oI ne copper powders ¸SuIherIand eI aI., 1990). This meIhod consisIs
oI Ihe IoIIowing sIeps:
1: PreparaIion oI cuprous ammoniacaI soIuIion aI around 80 "C:
Cu

+ Cu NH
J
 
2+
2
2Cu NH
J
 
+
2
14
2: ConIroIIed dissociaIion oI Ihe Cu¸I)-ammine compIex by acid
addiIion:
Cu NH
J
 
+
2
+ xH
+
 1 x2  Cu NH
J
 
+
2
+ xNH
+
4
+ x2Cu
+
15
J: SponIaneous disproporIionaIion oI cuprous ions ¸simuIIa-
neousIy occurring wiIh sIep 2)
x4 2Cu
+
Cu

+ Cu
2 +
15
2.Z.J. vio Jilution
By diIuIion Ihe concenIraIion oI Ihe precipiIaIing meIaI is
eIIecIiveIy kepI Iow or equivaIenIIy Ihe supersaIuraIion IeveI is kepI
Iowand in Ihis way Ihe compIicaIions oI homogeneous nucIeaIion are
IargeIy overcome. This approach is buiII-in in Ihe operaIion oI Ihe
crysIaIIacIor  a speciaIIy designed uid bed peIIeI reacIor 
deveIoped and used in Europe Ior Ihe IreaImenI oI eI uenIs ¸Van
WeerI and Van Dijk, 199J). This reacIor, iIIusIraIed in Fig. 11, via
recircuIaIion and mixing oI Ihe IreaIed Iiquor wiIh Ihe incoming
in uenI, causes diIuIion oI Ihe meIaI concenIraIion Io a IeveI beIow
S Ihus Iavouring Ihe deposiIion oI Ihe precipiIaIed compound
on sand or seed parIicIes ¸peIIeIs).
In Ihe hydromeIaIIurgicaI indusIry Ihe goeIhiIe process deveIoped
by EZ in AusIraIia ¸Monhemius, 1980) is an exampIe where in a
pracIicaI way Ihe supersaIuraIion is conIroIIed via diIuIion. This
approach Io goeIhiIe producIion is iIIusIraIed in Fig. 12¸a). II
precipiIaIion oI goeIhiIe is aIIempIed Irom undiIuIed zinc process
soIuIions ¸IypicaI composiIion 20 gjL Fe ; T 95 "C) poorIy seIIIing
IerrihydriIe ¸paragoeIhiIe) or hydronium jarosiIe is produced
insIead. UnpubIished work done aI McCiII shows IhaI Ihere is
considerabIe room Ior opIimizaIion oI Ihe goeIhiIe process invoIving
direcI precipiIaIion Irom a Ierric suIphaIe soIuIion via diIuIion. Thus
wiIh a combinaIion oI diIuIion and neuIraIizaIion, goeIhiIe was
produced Iroma 5.5 gjL Fe suIphaIe soIuIion aI 95 "C in Ihe presence
oI seed. Iron concenIraIion was reduced Irom 5.5 Io 1 gjL in 50 min
and Ihe produced goeIhiIe conIained onIy 1.2° suIphur as suIphaIe.
2.Z.4. vio o rcJox rcoction
In Ihis meIhod, which is suiIabIe Ior precipiIaIion oI a muIIi-vaIenI
meIaI ion, i.e. Fe jFe , Mn jMn eIc, conIroIIed oxidaIion ¸or
reducIion) is used Io reguIaIe Ihe supersaIuraIion IeveI. The besI
exampIe oI Ihis approach is Ihe goeIhiIe process deveIoped by VieiIIe
MonIagne, now Umicore ¸BeIgium) ¸Monhemius, 1980). Thus upon
reducIion oI Fe by reacIion wiIh concenIraIe ¸ZnS) Ihe Ierrous
suIphaIe soIuIion ¸ 20 gjL Fe¸II)) is oxidized wiIh air aI pH J. Once
more, simiIar Io Ihe AusIraIian meIhod oI goeIhiIe producIion by
diIuIion, Ihe Fe concenIraIion is eIIecIiveIy mainIained aI Iow IeveI
¸ 2 gjL) ¸see Fig. 12 ¸b)), Ihus Ihe compIicaIions oI homogeneous
nucIeaIion are IargeIy avoided.
2.Z.5. vio o Jissolution rcoction
In Ihis meIhod Ihe meIaI Io be precipiIaIed is reIeased ¸in a
conIroIIed manner) via Ihe dissoIuIion oI a precursor compound. This
lig. 11. The crysIaIIacIor ¸reproduced Irom Van WeerI and Van Dijk ¸199J)).
lig. 10. SupersaIuraIion-conIroIIed precipiIaIion sIraIegy.
205 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
meIhod imiIaIes Ihe mechanism oI dissoIuIionrecrysIaIIizaIion
discussed in SecIion 2.5.2. This Iype oI dissoIuIion-conIroIIed
precipiIaIion process usuaIIy happens in hydromeIaIIurgy in situ
during pressure Ieaching operaIions. A good exampIe oI Ihis is
oxidaIive pressure Ieaching oI suIphides or Ihe acid pressure Ieaching
oI IaIeriIes; in connecIion wiIh Ihe IaIIer PapangeIakis and his co-
workers aI Ihe UniversiIy oI ToronIo have cIearIy demonsIraIed how
hydronium aIuniIe ¸H O)AI ¸SO ) ¸OH) Iorms via Ihe dissoIuIion oI
gibbsiIe aI 2J0 Io 270 "C ¸BIakey and PapangeIakis, 1994).
AI McCiII some years ago, whiIe sIudying Ihe pressure oxidaIion oI
arsenopyriIe, Ihe producIion oI weII grown scorodiIe crysIaIs was
observed ¸PapangeIakis and DemopouIos, 1990). The reacIions
invoIved were as IoIIows:
DissoIuIion:
FeAsSs + 1J4O
2
+ J2H
2
OFe
2+
150

C
+ H
J
AsO
4
aq + SO
2
4
17
OxidaIion:
2Fe
2+
+ 12O
2
+ 2H
+
2Fe
J+
+ H
2
O 18
PrecipiIaIion:
Fe
J+
+ H
J
AsO
4aq
+ 2H
2
OFeAsO
4
2H
2
O
s
+ JH
+
19
The Ieaching oI arsenopyriIe Iook pIace in a H SO medium.
AIIempIs Io precipiIaIe scorodiIe Irom a simiIar medium buI using
Ierric suIphaIe as Ihe source oI iron IaiIed Io give crysIaIIine soIids 
anoIher maniIesIaIion oI SIanski's KuIe.
AnoIher exampIe is Ihe work oI Van WeerI and DropperI ¸1994)
who sIudied Ihe conversion oI As O baghouse dusI Io crysIaIIine
scorodiIe using a HNO mediumand an auIocIave ¸1J0150 "C). When
iron was inIroduced as Fe¸NO ) saII an exIremeIy ne, diI cuII Io
IIer, scorodiIe maIeriaI was produced; however when scrap iron was
used insIead, coarse and easiIy IIerabIe scorodiIe was produced. This
was so because iron reIease was reguIaIed by Ihe dissoIuIion oI scrap,
i.e. Ihe supersaIuraIion IeveI was eIIecIiveIy kepI Iow, Ihus Iavouring
Ihe growIh oI crysIaIs.
2.8. Motrix onion onJ impurity cjjccts
The maIrix anion oI Ihe soIuIion pIus many oIher minor
consIiIuenIs oI Ihe soIuIion ¸impuriIies) may exerI signi canI eIIecIs
Io Ihe quaIiIy oI Ihe produced compound¸s).
2.8.1. Motrix onion cjjccts
¸i) The maIrix anion deIermines Ihe naIure oI Ihe precursor
compIex-cIusIer. As Ihe size, mobiIiIy and shape oI Ihe IaIIer are
imporIanI in Ihe crysIaI growIh process iI is undersIandabIe
IhaI diIIerenI crysIaI phases oI Ihe same compound may Iorm
in diIIerenI compIexing media. For exampIe, hydroIyIic pre-
cipiIaIion oI iron¸III) oxyhydroxide under ambienI pressure buI
eIevaIed ¸8090 "C) IemperaIures yieIds -FeOOH ¸goeIhiIe) in
suIphaIejniIraIe media buI -FeOOH ¸akaganeiIe) in chIoride
media.
¸ii) The maIrix anion may be incorporaIed in Ihe soIid phase due Io
incompIeIe exchange oI Ihe maIrix anion Iigand by Ihe
precipiIaIing Iigand.
ExampIe:
FeSO
+
4
+ 2OH precipiIaIing Iigand  Fe OH  
+
2
+ SO
2
4
maIrix anion Iigand  FeOOHs + H
+
+ SO
2
4
20
The above exampIe shows compIeIe exchange oI SO by OH .
In Ihe case oI incompIeIe exchange, phases Iike Fe ¸SO )
lig. 12. CoeIhiIe precipiIaIion by diIuIion ¸a) and by oxidaIion ¸b).
lig. 13. ComposiIion oI IerrihydriIe precipiIaIes produced by IasI neuIraIizaIion oI Ierric
suIphaIe soIuIions ¸J gjL Fe¸III) aI 50 "C ¸reproduced Irom Zinck ¸199J)).
205 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
¸OH) ·2H O may Iorm. The neI eIIecI is Io obIain a mixIure oI
precipiIaIes. Since Ihe Iigand exchange process is a IuncIion oI
pH, iI is noI surprising Io nd Ihe conIenI oI a precipiIaIe ¸in
maIrix anion) Io depend on Ihe precipiIaIion pH. This is
exempIi ed wiIh Ihe resuIIs oI Fig. 1J, Iaken Irom Ihe work oI
Zinck ¸199J). AI IeasI in parI, Ihe observed correIaIion oI
suIphaIe incorporaIion Io pHmay be aIIribuIed Io Ihe exisIence
oI Fe¸III)-suIphaIo compIexes ¸FeSO and Fe¸SO ) ) in Ihe acidic
region ¸FiIippou eI aI., 1995).
As, described IaIer, simiIar Io soIuIion compIexes, inner-sphere
surIace compIexes have been observed Io Iorm. In Ihis respecI,
IhereIore, Ihe incorporaIion oI SO in Ihe precipiIaIed Ierric
oxyhydroxide can be aIIribuIed in parI Io surIace compIexaIion.
The amounI Ihough oI Ihe maIrix anion incorporaIed inIo Ihe
precipiIaIed compound wiII depend noI onIy on Ihe pH or Ihe
anion concenIraIion buI on Ihe properIies oI Ihe compound ¸i.e.
amorphous vs. crysIaIIine; parIicIe size eIc.) as weII and in Ihis
respecI on Ihe way precipiIaIion is conducIed. Thus, direcI
¸wiIhouI neuIraIizaIion conIroI) precipiIaIion oI IerrihydriIe aI
pH J and 50 "C was Iound Io yieId precipiIaIes wiIh 18° SO
conIenI ¸Fig. 1J) whiIe conIroIIed precipiIaIion oI crysIaIIine a-
FeOOH in Ihe presence oI seed aI pH 2 and 95 "C was Iound Io
yieId precipiIaIes wiIh onIy J.5° SO conIenI ¸unpubIished
research). Once more Ihis is Ihe maniIesIaIion oI Ihe impor-
Iance oI supersaIuraIion conIroI in precipiIaIion processes.
¸iii) The maIrix anion inIerIeres wiIh Ihe dehydraIion process and
Ihereby wiIh Ihe crysIaIIizaIion process. Thus, producIion oI
crysIaIIine phases Irom chIoride-based soIuIions is in generaI
easier Ihan Irom suIphaIe-based soIuIions. This is so because
Ihe SO anion is highIy aquaphiIic as opposed Io Ihe CI which
is noI hydraIed ¸BaIes eI aI., 1970). This eIIecI was observed by
DemopouIos and co-workers ¸DemopouIos eI aI., 1995a;
DropperI eI aI., 1995) who Iound crysIaIIine scorodiIe Io be
produced more readiIy Irom chIoride media Ihan Irom Ihe
corresponding suIphaIe media. SimiIarIy hemaIiIe produc-
Iion Irom chIoride media can be achieved under aImospheric
pressure condiIions ¸100 "C)¸DuIrizac and Kiveros, 1999) as
opposed Io Ihe case oI hemaIiIe producIion Irom suIphaIe
media IhaI requires higher IemperaIures ¸1J0 "C) ¸ZereIIa
eI aI., 198J; Cheng, 2002).
¸iv) The maIrix anion naIIy Ihrough surIace adsorpIion mighI aIIer
Ihe growIh mode oI Ihe precipiIaIe. For exampIe, precipiIaIion
oI AI¸OH) Irom acidic suIphaIe soIuIions yieIds sphericaI
parIicIes buI Irom chIoride soIuIions yieIds rodsjneedIes
¸SugimoIo, 1987).
2.8.2. lmpurity cjjccts
Many minor soIuIion consIiIuenIs Iend Io speci caIIy chemisorb and
aIIer Ihe parIicIe morphoIogy and growIh mode oI Ihe precipiIaIe. II
shouIdbeemphasizedIhaI iI Iakes IraceamounIs oI impuriIies ¸~10 M)
Io cause signi canI eIIecIs on Ihe crysIaI IormaIionprocess ¸Dirksenand
King, 1991).
BuI in addiIion Io inIerIering wiIh Ihe crysIaI growIh process,
impuriIies Iend Io become incorporaIed inIo Ihe main precipiIaIed
phase, Ihus eIIecIing iIs composiIion and properIies ¸e.g. soIubiIiIy
sIabiIiIy, morphoIogy eIc.). LeI us now consider in more deIaiI Ihe
main mechanisms oI impuriIy incorporaIion in precipiIaIes:
¸i) Coprccipitotion as a disIricI phase; Ior exampIe Ihe coprecipiIa-
Iion oI arsenic¸V) in Ihe Iorm oI scorodiIe, FeAsO ·2H O during
Ihe removaI oI iron¸III) Irom hoI ¸95 "C) acidic suIphaIe
soIuIions as jarosiIe, NaFe ¸SO ) ¸OH) . This mechanism may
be suppressed as Iong as Ihere is a reasonabIe diIIerence in Ihe
soIubiIiIy oI Ihe Iwo coprecipiIaIed compounds. This was
demonsIraIed by DemopouIos eI aI. ¸1995a) in Ihe case oI
scorodiIejakageneiIe coprecipiIaIion Irom chIoride soIuIions.
¸ii) Substitution: In Ihis case a Ioreign consIiIuenI is subsIiIuIed in
Ihe crysIaIIine IaIIice oI Ihe precipiIaIed compound. SubsIiIu-
Iion requires good  IIing oI Ihe subsIiIuenI group in Ihe hosI
siIe and IavourabIe bond energy. We may have caIion
subsIiIuIion, such as Ca Mg CO ¸SIumm and Morgan,
1981), or anion subsIiIuIion, such as NaFe ¸SO ) ¸AsO )
¸OH) ¸H O) ¸DuIrizac and ]ambor, 1987). Vacancies or
disIorIions may be inIroduced in Ihe crysIaI due Io charge
imbaIance or non-size compaIibiIiIy beIween Ihe hosI siIe and
subsIiIuenI group, hence aIIering properIies such as soIubiIiIy.
Thus, Ior exampIe, scorodiIe produced Irom suIphaIe media
Iends Io conIain up Io 4° SO . This mode oI impuriIy
incorporaIion is Ihe mosI diI cuII Io avoid. One possibIe way
oI avoiding caIion subsIiIuIion is compIexing oI Ihe IroubIe-
some caIion and changing Ihus iIs size and charge. One such
exampIe is Ihe compIexaIion oI Cd ¸a very Ioxic eIemenI) wiIh
CI Io Iorm CdCI and Ihus avoid iIs incorporaIion in gypsum,
CaSO 2H O ¸MarIynovich, 1994).
¸iii) The oIher major mechanismoI impuriIy upIake is via oJsorption/
surjocc complcxotion. Due Io iIs wide occurrence Ihis mode oI
impuriIy upIake is discussed separaIeIy in Ihe IoIIowing secIion.
2.9. lmpurity uptokc by oJsorption
2.9.1. Surjocc complcxotion rcoctions
SoIid surIaces are never smooIh and chemicaIIy homogeneous.
SurIace heIerogeneiIy is a IacI oI IiIe and noIhing is more Irue Ihan Ior
soIids precipiIaIed ouI oI soIuIion. LeI us examine in Ihis respecI Ihe
surIace oI an oxide ¸Dzombak and MoreI, 1990). Due Io incompIeIe
coordinaIion oI Ihe surIace speci c anion and caIion siIes deveIop
on iI. The non-IuIIy coordinaIed caIions are hydraIed and Ihis is
IoIIowed by surIace hydroIysis which gives rise Io a hydroxyIaIed
surIace: jXOHE. This hydroxyIaIed surIace is IurIher hydraIed and
evenIuaIIy is engaged in reacIions wiIh soIuIe species which enIer Ihe
eIecIricaI doubIe Iayer.
This group oI reacIions is caIIed surIace compIexaIion reacIions
¸Dzombak and MoreI, 1990; Davis and Hayes, 1985). These reacIions
are considered anaIogous Io Ihe IormaIion oI soIuIion compIexes. The
IoIIowing discussion wiII Iocus on surIace reacIions occurring on
oxides. CaIion or anion surIace compIexaIion are Ihe Iwo mosI
imporIanI Iypes oI surIace reacIions invoIved in impuriIy upIake:
CaIion compIexaIion
XOH

+ M
2+
XOM
+
+ H
+
21
Anion compIexaIion
XOH

+ A
J
+ H
+
XA
2
+ H
2
O 22
SurIace compIexaIion oI caIions by hydrous oxides invokes Ihe
IormaIion oI covaIenI bonds wiIh surIace oxygen ¸or hydroxyI)
anions and Ihe reIease oI proIons Irom Ihe surIace. Speci c
sorpIion oI anions on hydrous oxides occurs via Iigand exchange
reacIions in which hydroxyI surIace groups are repIaced by Ihe
sorbing ions. In addiIion Io Ihese surIace compIexaIion reacIions
simpIe surIace ion-associaIion reacIions Ieading Io Ihe IormaIion
oI ion-pairs via eIecIrosIaIic aIIracIion Iorces may occur. However,
due Io Ihe weakness oI Ihe eIecIrosIaIic Iorces invoIved in Ihese
reacIions Ihe reIenIion oI impuriIies is weak, hence washing is
eIIecIive in removing Ihe IaIIer. This is noI Ihe case wiIh Ihe
inner-sphere-Iorming surIace compIexaIion reacIions ¸reacIions
¸21) and ¸22)). The reIenIion oI impuriIies by Ihe IaIIer reacIions
is governed by pH. This is cIearIy maniIesIed in Ihe generaI
adsorpIion equiIibrium curves iIIusIraIed in Fig. 14.
207 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
2.9.2. lmpurity uptokc
An exIensive compiIaIion oI caIion¸Pb , Zn , Cd , Hg , Cu , Ag ,
Ni , Co , Cr , Ca , Sr , and Ba ) and anion ¸PO , AsO , VO ,
H AsO , H BO , SO , SeO , S O , and CrO ) adsorpIion isoIherms on
hydrous Ierric oxides can be Iound in Surjocc Complcxotion MoJclling
¸ChapIers 5 and 7) ¸Dzombak and MoreI, 1990). Here onIy some
seIecIed adsorpIion daIa are presenIed.
2.9.2.1. Cotion sorption. Some IypicaI caIion adsorpIion daIa on
hydrous Ierric oxide are pIoIIed in Fig. 15 ¸Benjamin and Leckie, 1981).
As can be seen Ihe adsorpIion isoIherms move Iowards higher pH ¸Ior
Ihe same caIion) as Ihe concenIraIion oI Ihe caIion increases.
LeI us expIain why Ihis happens by anaIyzing Ihe reIevanI surIace
compIexaIion equaIion
K ÷ M
2+
 
ads
H
+
 M
2+
 
aq
1   2J
where concenIraIions are Iaken equaI Io acIiviIies, |M | is
equivaIenI Io jXOM , and is Ihe IracIion oI surIace IhaI is covered.
Considering nowIhe disIribuIion coeI cienI D, where D÷|M | j
|M | , Eq. ¸2J) can be wriIIen in Ihe IoIIowing IogariIhmic Iorm:
D÷ K +  1    H
+
24
For Ihe iso-disIribuIion poinI, i.e. 50° caIion adsorbed, D÷1 ¸Ior
which Iog D÷0) and Ihe IasI equaIion is reduced Io
 H
+
50
÷ K +  1   25
where |H | is Ihe |H | corresponding Io D÷1.
For IowmeIaI ion concenIraIionwe have Iowcoverage, i.e. ¸1 )
is higher Ihan ¸1 ) , where Ihe IaIIer corresponds Io high meIaI
ion concenIraIion.
By wriIing Ihe Iog |H | equaIion Ior Iow and high concenIra-
Iions and subIracIing we obIain
 H
+
50high
 H
+
50Iow
÷  1  
high
 1  
Iow
25
Since ¸1 ) j¸1 ) 1 we geI, Iog |H | Iog |H | or
pH pH .
II is cIear, IhereIore, why wiIh increased meIaI ion concenIraIion
Ihe adsorpIion isoIherms move Io higher pH. By IoIIowing exacIIy Ihe
same Iype oI anaIysis iI can be shown why Ihe adsorpIion isoIherm
moves Io Iower pH when Ihe amounI oI sorbenI, i.e. Ihe amounI oI
hydrous Ierric oxide is increased.
On Ihe oIher hand, since Ior each surIace reacIion Ihere exisIs a
characIerisIic adsorpIion equiIibriumconsIanI ¸re ecIing Ihe sIabiIiIy
oI Ihe surIace compIex), iI becomes obvious as Io why we have Ihe
diIIerenI caIion adsorpIion curves. In generaI high vaIence caIions
adsorb aI Iower pH Ihan Iow vaIence caIions. The chemicaI naIure oI
Ihe hydrous oxide subsIraIe seems Io have a raIher modesI eIIecI on
Ihe adsorpIion disIribuIion curves. Thus, Ior exampIe Ihe order oI
adsorpIion wiIh increasing pH Ior Ihe caIions Pb , Cu , and Cd on
amorphous siIica ¸SIummand Morgan, 1981) is Ihe same wiIh IhaI on
hydrous Ierric oxide ¸Benjamin and Leckie, 1981).
2.9.2.2. /nion sorption. TypicaI sorpIion daIa oI As¸V) on hydrous
Ierric oxide are pIoIIedinFig. 15. The posiIionoI Ihe adsorpIionisoIherm
lig. 14. TypicaI equiIibrium curves Ior caIion and anion sorpIion on hydrous iron oxide.
Arrows indicaIe direcIion oI increasing sorbaIejsorbenI raIio ¸reproduced Irom
Dzombak and MoreI ¸1990)).
lig. 15. CaIion adsorpIion equiIibria on hydrous Ierric oxide; condiIions: 10 M Fe , .5 H
10 M MeT ¸reproduced Irom Benjamin and Leckie ¸1981)).
lig. 16. AdsorpIion oI As¸V) on hyrous Ierric oxide; |Fe|j|As| ÷15; condiIions: 5×10 M
Fe , J.J4×10 M As ¸reproduced Irom Dzombak and MoreI ¸1990)).
208 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
depends on Ihe moIar raIio |sorbenI|j|sorbaIe|. Thus wiIh increasing
anion concenIraIion Ihe anion adsorpIion isoIherm shiIIs Io Iower
pH  Ihe opposiIe oI whaI happens wiIh Ihe caIion adsorpIion
isoIherms. On Ihe oIher hand wiIh increasing concenIraIion oI sorbenI,
i.e. hydrous ironoxidesubsIraIe, IheadsorpIionisoIhermshiIIs Iohigher
pH.
The removaI oI arsenic by adsorpIion on hydrous Ierric oxide or
IerrihydriIe has been sIudied by Kobins eI aI. ¸1988). Their removaI
curves are Ihe mirror images oI Ihe adsorpIion curves. AI Ihe high pH
region Ihe adsorpIion curves move Io higher pHwiIh increasing moIar
FejAs raIio because in reaIiIy Ihe amounI oI sorbenI ¸i.e. Fe¸OH) )
increases and Ihis resuIIs in a pH shiII. LeI us consider Ihe surIace
compIexaIion reacIion,
XOH

+ HAsO
2
4
+ H
+
XHAsO
4
+ H
2
O 27
K ÷ As
ads
 As
aq
H
+
1   28
D÷ As
ads
 As
aq
29
By simiIar anaIysis as done Ior Ihe caIion sorpIion sysIem we geI
pH
50
÷ K +  1   J0
Thus, as 1 increases, i.e. as Ihe amounI oI sorbenI increases pH
increases i.e. Ihe adsorpIion curves shiII Io higher pH and hence Ihe
enhanced sIabiIiIy oI arsenic in an exIended pH region.
The sIabiIizing eIIecI oI caIions ¸Iike Cu ) on arsenic removaI by
high FejAs precipiIaIion reporIed by Harris and MoneIIe ¸1988) and
EmeII and Khoe ¸1994) is posIuIaIed Io be due Io surIace charge
neuIraIizaIion, i.e. jHAsO  CuOH .
2.9.J. Surjocc prccipitotion
The surIace compIexaIion reacIions IhaI were discussed above may
Iead Io surIace precipiIaIion iI Ihe sorbing ions ¸anions or caIions) are
presenI aI high concenIraIions ¸Dzombak and MoreI, 1990). WhaI
disIinguishes surIace precipiIaIion Irom surIace compIexaIion is Ihe
IacI IhaI in Ihe Iormer case we have Ihe IormaIion oI a new surIace
phase diIIerenI Irom Ihe subsIraIe phase ¸e.g. IormaIion oI Cu¸OH)
Iayer on a Fe¸OH) precipiIaIe). In oIher words wiIh increasing
concenIraIion oI sorbingprecipiIaIing ions, we have a conIinuum
Irom ¸i) pure adsorpIion ¸÷surIace compIexaIion) Io ¸ii) surIace
precipiIaIion Io ¸iii) buIk precipiIaIion ¸÷coprecipiIaIion). This is Ihe
case Ior exampIe oI arsenaIe adsorpIion on IerrihydriIe IromreIaIiveIy
concenIraIed soIuIions and Ihe conversion oI Ihe surIace compIexed
arsenaIe Io Ierric arsenaIe surIace precipiIaIe over Iime ¸]ia eI aI.,
2005, 2007).The surIace precipiIaIion mechanism is prevaIenI in
hydroIyIic precipiIaIion sysIems invoIving muIIi-meIaI ion soIuIions.
Aconsequence oI adsorpIion occurring in co-precipiIaIion sysIems
is Ihe removaI oI a caIion or anion aI a IeveI beIowIhe soIubiIiIy oI Ihe
compound in which iI is a consIiIuenI. Thus iI has been deIermined in
our IaboraIory ¸unpubIished research) IhaI Ihe soIubiIiIy oI Cu ,
when Ihe IaIIer is precipiIaIed as hydroxide by neuIraIizaIion, is
signi canIIy Iower when iI is co-precipiIaIed wiIh Fe ¸Fe¸OH) ) Ihan
iI iI is precipiIaIed aIone. The reIevanI daIa are shown in TabIe 1.
2.9.4. lmpurity uptokc control
AdsorpIive incorporaIion oI impuriIies during precipiIaIion can be
greaIIy suppressed via Ihe IoIIowing measures: a) by reducing Ihe
speci c surIace area via Ihe growIh oI Iarge and smooIh parIicIes; b) by
enhancing Ihe crysIaIIiniIy oI Ihe precipiIaIe ¸a) and ¸b) are achieved
by keeping Ihe saIuraIion raIio, S, beIow S ; c) by suppressing
aggregaIion which is responsibIe Ior soIuIion upIake; d) by modiIying
Ihe pHor pXoI Ihe soIuIion and Ihereby changing Ihe characIer oI Ihe
IroubIesome impuriIy species ¸e.g. Zn vs ZnSO ¸aq) and Ihe
characIer oI Ihe surIace charge; e) by compIexing Ihe IroubIesome
caIion ¸e.g. Cd vs. CdCI ); I) by using ionic surIacIanIs which compeIe
wiIh impuriIies Ior preIerenIiaI adsorpIion; g) by empIoying recycIing
Tablc 1
SoIubiIiIies oI Cu¸OH) in diIuIe suIphaIe soIuIions aI 25 "C ¸iniIiaI concenIraIions 10 M
CuSO ; 10 M Fe ¸SO ) )
pH SoIuIion copper concenIraIion ¸mgjL)
CuSO jaIone CuSO jFe ¸SO )
5.98 JJ.55 ¸J0.18) J.47
5.42 4.21 ¸4.4J) 0.81
5.8
5.87 ¸0.55) 0.11
7.02 0.J5 ¸0.28) 0.05
7.25 0.12 ¸0.09)
7.59 0.10 0.02
8.28 0.05 0.005
´ Numbers in ¸) denoIe soIubiIiIies caIcuIaIed according Io Baes and Mesmer ¸1985).
Tablc 2
ImpuriIy removaI by Ierric hydroxide precipiIaIionadsorpIion ¸pH 4.5, 75 "C) ¸daIa
Iaken Irom DuIrizac ¸199J))
EIemenI ¸ppm) Impure weak acid Ieach Puri ed neuIraI Ieach
Ce 1 0.1
As 0.2 0.02
Sb 1 0.1
Se  0.01
lig. 17. FormaIion oI IocaI supersaIuraIion pockeI in a poorIy mixed reacIor.
lig. 18. The mixed suspension cIassi ed producI removaI crysIaIIizer ¸MSCPK).
209 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
oI Ihe precipiIaIe, ¸Ior exampIe a reducIion oI Ihe SO conIenI oI
amorphous FeOOH Irom 9° down Io 4° was achieved upon recycIing
20 Iimes Ihe precipiIaIes ¸Zinck, 199J) and naIIy h) by puriIying Ihe
soIuIion. The above can prove very useIuI in indusIriaI precipiIaIion
appIicaIions where a precipiIaIe Iree oI impuriIies is soughI, as iI is Ior
exampIe Ihe case oI producing high grade nickeI suIphaIe Irom de-
copperized eIecIroIyIe ¸MoIdoveanu and DemopouIos, 2002) or cIean
gypsum Irom zinc pIanI wasIe waIers ¸Verbaan eI aI., 1999).
On Ihe oIher hand, when impuriIy upIake via surIace adsorpIion is
soughI, Ihen producIion oI an amorphous precipiIaIe, Iike Ierric
hydroxide ¸IerrihydriIe), is Ihe ideaI impuriIy scavenger-carrier. This is
Ihe case oI impuriIy removaI during neuIraI Ieaching in zinc circuiIs 
reIer Io daIa in TabIe 2 ¸DuIrizac, 199J). II is worIhy Io noIe IhaI aII
impuriIies IisIed are suspecIed Io be in Ihe Iorm oI anions hence Iheir
adsorpIion is Iavoured in acidic soIuIions ¸pH 44.5) as predicIed by
Ihe adsorpIion isoIherms oI Fig. 15.
2.10. Dcsign oj prccipitotion rcoctors
Mixing oI reagenIs and agiIaIion regime are very imporIanI in
precipiIaIion. II is imperaIive Io ensure uniIorm mixing in order Io
avoid IocaI supersaIuraIion pockeIs ¸Fig. 17). On Ihe oIher hand
agiIaIion speed has Io be opIimized as iI seems Io acI in Iwo opposing
ways. FirsI, as iI was menIioned in SecIion 2.J.2 shear Iorces heIp Io
prepare compacI aggregaIes; on Ihe oIher hand excessive agiIaIion
mighI Iead Io scaIing probIems due Io Iavouring oI conIacI nucIeaIion.
ConIacI nucIeaIion invoIves Ihe pIasIering oI Iresh homogeneousIy
nucIeaIed coIIoidaI parIicIes on Ihe reacIor's waIIs.
The raIe oI conIacI nucIeaIion ¸j) is a IuncIion oI Ihe IoIIowing
IacIors ¸Dirksen and King, 1991):
j kM
!
rpm  
2 4
S
1 2
J1
where
M! is Ihe mass concenIraIion oI soIids ¸kg m )
rpm is Ihe agiIaIion speed ¸rev min )
S is Ihe saIuraIion raIio
k is Ihe reacIor size and geomeIry IacIor ¸dimensionIess)
lig. 19. The Ihree aIIernaIive neuIraIizaIion paIhs IoIIowed Io eIIecI hydroIyIic
precipiIaIion oI Fe¸III) hydroxide.
lig. 20. The eIIecI oI recycIing on Ierric hydroxide densi caIion Ior ¸A) simpIe
neuIraIizaIion wiIh NaOH; Ior ¸B) neuIraIizaIion wiIh NaOH and supersaIuraIion
conIroI; and Ior ¸C) neuIraIizaIion wiIh Iime and supersaIuraIion conIroI ¸reproduced
Irom DemopouIos eI aI. ¸1995b)).
lig. 21. ParIicIe size disIribuIion oI Ihe iron hydroxide soIids produced via neuIraIizaIion
paIh II ¸see Fig. 19).
lig. 22. SEM phoIo oI Ihe Ierric hydroxide produced via sIaged-neuIraIizaIion and
recycIing ¸NeuIraIizaIion paIh III in Fig. 19) ¸reproduced Irom DemopouIos eI aI. ¸1995b)).
210 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
II is evidenI IromIhis equaIionIhaI high sIurry densiIyand excessive
agiIaIion speed aII conIribuIe Io conIacI nucIeaIion or in oIher words Io
scaIingjwaII pIaIing. On Ihe oIher hand, since Ihe exponenI oI S is much
Iower Ihan Ihe corresponding one Ior homogeneous nucIeaIion
¸IypicaIIy ranging Irom 5 Io 12) Ihe IaIIer is expecIed Io dominaIe aI
high IeveIs oI supersaIuraIion.
BaIch reacIors are characIerized by variabIe supersaIuraIion envir-
onmenI. In Ihis respecI Ihen baIch reacIors are noI good Irom Ihe
sIandpoinI oI supersaIuraIion conIroI. To avoid Ihis inherenI de ciency
oI Ihe baIchreacIor, Ihe precipiIanI wiII have Io be added in a conIroIIed
manner Io ensure consIanI S ¸semi-baIch con guraIion). This ¸Ior
exampIe) is Ihe approach Iaken in deveIoping Ihe sIep-wise neuIraIiza-
Iion procedure Ior supersaIuraIion conIroI discussed in SecIion 2.7.1.
ConIinuous sIirred Iank reacIors ¸CSTK), on Ihe oIher hand, oIIer a
sIabIe supersaIuraIion and seeded environmenI due Io Iheir sIeady-
sIaIe operaIion. We can disIinguish Iwo Iypes oI conIinuous precipiIa-
IionreacIors, Ihe Mixed Suspension Mixed ProducI KemovaI CrysIaIIizer
¸MSMPK) and Ihe Mixed Suspension CIassi ed ProducI KemovaI
CrysIaIIizer ¸MSCPK) ¸Fig. 18). The rsI one is noIhing eIse buI Ihe
IamiIiar CSTK-Iype reacIor. This reacIor ingeneraI resuIIs in ne parIicIes
oI wide size disIribuIion ¸due Io iIs inherenI residence Iime disIribuIion
IuncIion) and as such, whiIe iI is easy Io operaIe, iI IaiIs neverIheIess Io
produce dense and weII grown precipiIaIes. However Ihe MSCPK-Iype
reacIor eIIecIiveIy operaIes insuchawayIhaI IheIiquidandsoIid phases
have diIIerenI mean residence Iimes. The soIuIion ows conIinuousIy
andraIher IasI whiIeIhe soIids eiIher are removedperiodicaIIyaI a much
sIower raIe or are recycIed. In Ihis way Ihe soIids spend much Ionger
Iimeinside Ihe reacIor Ihus aIIowingIor Iheir growIhandcrysIaIIizaIion.
OperaIion naIIy oI a series oI CSTKs wiIh soIids recycIing and
disIribuIed addiIion oI Ihe precipiIanI as described IaIer in Fig. 24
appears Io be Ihe besI con guraIion Ior a hydromeIaIIurgicaI precipiIa-
Iionprocess seekingIoproducecIeanandweII grownprecipiIaIedsoIids.
3. Casc studics
J.1. Prccipitotion oj lc¦lll) ¦oxy)hyJroxiJcs
HydroIyIic precipiIaIion is one oI Ihe mosI imporIanI groups oI
precipiIaIion reacIions. Prior Io Ihe IormaIion oI Ihe hydroxide soIid
Ihe meIaI ions undergo parIiaI hydroIysis and IormsoIubIe hydroIysed
species. These hydroIysed species under high supersaIuraIion
undergo poIymerisaIion and evenIuaIIy condensaIion via parIiaI Ioss
oI Iheir soIvaIion waIer. Due Io Ihe ease wiIh which high vaIenI
caIions hydroIyse and poIymerize, Ihe producIs oI Iheir hydroIyIic
precipiIaIion reacIions are highIy amorphous. MeIicuIous conIroI oI S
aI very IowvaIues is necessary Io overcome Ihis Iendency oI meIaI ion
hydroIyIic poIymerizaIion. These phenomena are Io be iIIusIraIed by
lig. 23. ParIicIe size disIribuIion oI Ihe iron hydroxide soIids produced via sIaged
neuIraIizaIion ¸neuIraIizaIion paIh III ¸in Fig. 19)).
lig. 24. ConIinuous sIaged-neuIraIizaIion process circuiI ¸reproduced Irom DemopouIos eI aI. ¸1995b)).
lig. 25. The soIubiIiIy curves oI scorodiIe and akageneiIe and Ihe Iwo domains oI
precipiIaIion ¸reproduced Irom DemopouIos eI aI. ¸1995a).
211 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
reIerring Io Ihe mosI common meIaI ion hydroIysis sysIem: IhaI oI Fe
¸III). For an exIensive reviewoI Ihe hydroIyIic chemisIry oI caIions Ihe
reader is reIerred Io Baes and Mesmer ¸1985). For Ihe speci c sysIem
oI Fe¸III) hydroIysis exIensive reviews have been pubIished among
oIhers by FIynn ¸1984) and DuIrizac ¸1979).
Acid rock ¸mine) drainage soIuIions conIain iron¸III) suIphaIe and
severaI oIher base meIaI suIphaIes. NeuIraIizaIion oI Ihe eI uenIs
wiIh Iime is Ihe sIandard IreaImenI meIhod used around Ihe worId.
The probIemwiIh Ihis meIhod, as pracIised Ioday, is IhaI iI produces a
Iarge voIume oI amorphous sIudge, which is characIerized by poor
seIIIing properIies and IowsoIids conIenI, ¸5° wiIhouI recycIing and
1020° wiIh recycIing).
To demonsIraIe Ihe superioriIy oI Ihe supersaIuraIion-conIroIIed
approach Io Ihe IreaImenI oI such acidic eI uenIs, an exIensive series
oI IaboraIory IesIs has been perIormed, deIaiIs oI which are described
eIsewhere ¸Zinck, 199J; DemopouIos eI aI., 1995b). In Ihis work
synIheIic H SO jFe ¸SO ) conIaining eI uenIs ¸pH 2.5; 1000 mg jL
Fe , 5000 mg jL SO ) were neuIraIized wiIh NaOH aI 50 "C IoIIowing
Ihree diIIerenI neuIraIizaIion procedures. NaOH was used insIead oI
Iime since iI was our aim rsI Io undersIand Ihe crysIaIIizaIion oI
Ierric hydroxide ¸Ihe acIuaI producI was 2-Iine IerrihydriIe ¸]ambor
and DuIrizac, 1998)) and Ior IhaI Ihe IormaIion oI gypsum had Io be
avoided.
The rsI procedure invoIved direcI convenIionaI neuIraIizaIion in a
singIe sIep Io naI pH 9. This is depicIed in Fig. 19 as neuIraIizaIion
paIh I. SoIuIion was agiIaIed aI IhaI pH Ior 4 hours. The produced
sIudge ¸IerrihydriIe) was Iound Io be IoIaIIy amorphous wiIh Iow
soIids conIenI ¸5°) and poor seIIIing raIe ¸2 mjh). This approach Io
neuIraIizaIion and Ihe obIained resuIIs correspond Io Ihe mosI
common way neuIraIizaIion is pracIised in indusIry.
The second neuIraIizaIion approach IesIed corresponds Io Ihe High
DensiIy SIudge Process ¸HDS), i.e. iI invoIved sIudge recycIing and a
reIaIiveIy sIow neuIraIizaIion raIe ¸neuIraIizaIion paIh II  Fig. 19) buI
noI sIricI supersaIuraIion conIroI. AI Ihe end oI each IesI 90° oI Ihe
precipiIaIe was recycIed as seed Ior Ihe nexI IesI. The duraIion oI each
IesI ¸during which pH was graduaIIy increased) was abouI 4 h.
KecycIing was Iound Io signi canIIy improve Ihe sIudge quaIiIy,
yieIding a soIids conIenI oI 25 Io J0° aIIer 15 recycIes ¸Fig. 20  curve
A). In Ierms oI seIIIing, Ihe producI was sIighIIy beIIer Ihan IhaI
produced in Ihe rsI experimenI wiIh IypicaI seIIIing raIes varying
beIween 2 and 4 mjh. Size disIribuIion anaIysis ¸Fig. 21) reveaIed IhaI
precipiIaIion occurred under boIh homogeneous nucIeaIion-con-
IroIIed and growIh-conIroIIed regimes ¸see Fig. 5  SecIion 2.J.J)
due Io Iack oI precise supersaIuraIion conIroI.
FinaIIy neuIraIizaIion was eIIecIed in a sIep-wise Iashion ¸neu-
IraIizaIion paIh III. Fig. 19) as described in SecIion 2.7.1 ¸see Fig. 10).
Once more sIudge recycIing as in Ihe HDS meIhod was empIoyed and
Ihe IoIaI duraIion oI each IesI was again 4 h. This crysIaIIizaIion
IreaImenI proved indeed Ihe besI approach in yieIding high densiIy
Ierric hydroxide sIudges. The sIudge consisIed oI disIincI parIicIes
¸Fig. 22) wiIh uniIorm and coarse parIicIe size disIribuIion ¸Fig. 2J)
¸20 µm average parIicIe size) and a 55° soIids densiIy aIIer onIy 8
recycIes ¸Fig. 20 curve B). Moreover Ihe sIudge exhibiIed J Io 5 Iimes
IasIer seIIIing raIe ¸12 mjh).
lig. 27. SEMphoIos oI gypsumproducedwiIh¸Iop) andwiIhouI seed¸boIIom) byconIroIIed
neuIraIizaIion aI Iow S IeveI ¸reproduced Irom OmeIon ¸1998) and Verbaan ¸2000)).
lig. 26. SEM phoIos oI scorodiIe deposiIed on gypsum ¸reproduced Irom Singhania eI aI. ¸2005)).
212 C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
Having proved IhaI supersaIuraIion conIroI resuIIs in Ihe
producIion oI super dense and compacI sIudges iI was decided
nexI Io repeaI Ihe sIep-wise neuIraIizaIionjrecycIing experimenI
¸under Ihe same condiIions as beIore) buI now using sIaked Iime
insIead oI NaOH. NoI onIy did Ihis series oI IesIs con rm Ihe
eIIecIiveness oI Ihe supersaIuraIion-conIroIIed approach buI iI
provided even more dense sIudges wiIh soIids conIenI as high as
57° aIIer 10 recycIes ¸Fig. 20  curve C). The sIudge generaIed
consisIed oI disIincI phases: gypsum ¸55.5°) and IerrihydriIe
¸JJ.5°). No unreacIed Iime was deIecIed in Ihe sIudge which is an
indicaIor oI Ihe inherenI high eI ciency oI Iime uIiIizaIion
associaIed wiIh Ihis supersaIuraIion-conIroIIed neuIraIizaIion
procedure.
The impIemenIaIion oI Ihe newIy deveIoped sIaged-neuIraIizaIion
process on a conIinuousIy operaIing indusIriaI circuiI is described in
Fig. 24. The number oI Ianks and Ihe operaIing pH in each Iank has
been deIermined Ior a speci c eI uenI according Io Ihe neuIraIizaIion
procedure described in Fig. 10.
J.2. Crystollizotion oj scoroJitc
The producIion oI scorodiIe ¸crysIaIIine Ierric arsenaIe dihydraIe)
is advocaIed as Ihe preIerred rouIe oI immobiIizing arsenic Irom
arsenic-rich meIaIIurgicaI eI uenIs and dusIs ¸DemopouIos eI aI.,
1994; Swash and Monhemius, 1998; Harris, 2000; Kiveros eI aI.,
2001; DemopouIos, 2005). One meIhod oI producIion is auIocIave
precipiIaIion aI IemperaIures above 150"C ¸Swash and Monhemius,
1994, 1998). This approach is in agreemenI wiIh Ihe sIaIemenI made
earIier IhaI eIevaIed IemperaIure Iavours Ihe aIIainmenI oI crysIaI-
IiniIy. The oIher avenue Ior producing crysIaIIine scorodiIe, i.e. Ihe
mainIenance oI Iow S, was expIored by Ihe auIhor and co-workers
rsI Irom chIoride media ¸DemopouIos eI aI., 1995a) and subse-
quenIIy Irom suIphaIe media ¸DropperI eI aI., 1995; FiIippou and
DemopouIos, 1997; Dabekaussen eI aI., 2001; Wang eI aI., 2000;
DemopouIos eI aI., 200J; Singhania eI aI., 2005, 2005). To Ihis end
Ihe conIroIIed-supersaIuraIion procedure oI Fig. 10 combined wiIh
Ihe use oI seed, described in SecIion 2.7.1 was empIoyed aI
IemperaIures beIow 100"C. More speci caIIy crysIaIIine scorodiIe
was produced rsI aI 80 "C Io 95 "C Irom chIoride media
¸DemopouIos eI aI., 1995a). FaiIure Io conIroI SS ÷8) resuIIed
in producIion oI amorphous Ierric arsenaIe. In oIher words Ihe
mainIenance oI Iow S eIIecIiveIy reduced Ihe crysIaIIizaIion
IemperaIure Irom 150 "C Io 100"C.
The crysIaIIizaIion oI scorodiIe Irom suIphaIe media aI 8595 "C
proved successIuI as weII when Ihe conIroIIed-supersaIuraIion
procedure was appIied, buI Ihere were some key diIIerences
beIween Ihe Iwo sysIems. The criIicaI supersaIuraIion associaIed
wiIh Ihe onseI oI homogeneous nucIeaIion ¸i.e. S ) was Iound
Io be aI IeasI 70, i.e. 10 Iimes higher Ihan IhaI Ior Ihe chIoride
sysIem. EquaIIy surprising was Ihe diIIerence in behaviour when
scorodiIe is crysIaIIized Irom soIuIions ¸chIoride vs suIphaIe) wiIh
high Fe¸III)jAs¸V) moIar raIio. Thus in Ihe case oI Ihe chIoride
sysIem ¸Li and DemopouIos, 2005) iI was possibIe by appIying
sIricI supersaIuraIion conIroI Io precipiIaIe sequenIiaIIy scorodiIe
¸aI pH 1.5) IoIIowed by akageneiIe ¸ -FeOOH)¸aI pH 1.5) ¸reIer Io
Fig. 25) Irom FejAs ÷4 soIuIions. However, Ihe suIphaIe sysIem
does noI behave in Ihe same manner. In Ihe IaIIer case Ihe presence
oI excess iron, i.e. aI FejAs 2, iI was Iound Io signi canIIy reIard
Ihe crysIaIIizaIion oI scorodiIe  Ihis mosI IikeIy being Ihe
maniIesIaIion oI Ihe diIIerence in iron compIexaIion prior Io
precipiIaIion ¸Singhania eI aI., 2005).
FinaIIy, oI inIeresI Io underIine here, is IhaI under proper
supersaIuraIion conIroI iI is possibIe Io grow scorodiIe noI onIy on
scorodiIe seed buI as weII on oIher Iypes oI soIids Iike hemaIiIe and
gypsum. The deposiIion oI scorodiIe on gypsumis iIIusIraIed wiIh Ihe
SEM phoIo oI Fig. 25.
J.J. Crystollizotion oj gypsum
FormaIion oI gypsumand precipiIaIion is omnipresenI in a varieIy
oI hydromeIaIIurgicaI processes, being more prevaIenI in neuIraIiza-
IionwiIhIime or IimesIone oI suIphuric acid-basedprocess soIuIions 
as done Ior exampIe aI Ihe Iijima Zinc Ke nery in ]apan ¸Yamada eI aI.,
1998) or Ior acidic wasIe waIers ¸Verbaan eI aI., 1999). In Ihe conIexI oI
Ihe IaIIer case we have sIudied Ihe crysIaIIizaIion oI gypsumwiIh Ihe
purpose oI producing high densiIy and cIean gypsum ¸OmeIon, 1998;
Verbaan, 2000). This research has Iocused on eIaboraIing a neuIraIiza-
Iion Iechnique IhaI promoIes Ihe producIion oI weII grown and cIean
gypsummaIeriaI via conIroIIedsupersaIuraIion¸achievedvia Ihe sIep-
wise eIevaIion oI pHreIer Io SecIion 2.7.1) and producI recycIing. An
imporIanI nding oI Ihis work was IhaI, in addiIion Io conIroIIing
supersaIuraIion and recycIing, Ihe choice oI sIarIing seed maIeriaI is
criIicaI. Thus, simpIe recycIing oI IreshIy prepared gypsum maIeriaI
proved ineIIecIive even when aII oIher conIroIs were appIied. II was
onIy wiIh Ihe use oI synIheIic or naIuraIIy occurring gypsum as seed
maIeriaI ¸OmeIon, 1998) IhaI gypsum wiIh Ihe desired properIies
couId be produced. The characIerisIic diIIerences in gypsummorphoI-
ogy obIained by using no seed or synIheIic seed can be appreciaIed by
examining Ihe SEM phoIos oI Fig. 27. The unseeded sysIem produced
gypsum exhibiIing Ihe so-caIIed roseIIe morphoIogy characIerized
by high speci c surIace area and Ihus prone Io high impuriIy upIake
and poor seIIIing behaviour. The maIeriaI produced by simpIe
recycIing oI Ihe IreshIy ¸homogeneousIy) prepared seed was very
ne in size IhaI again gave poor seIIIing behaviour. However, Ihe
maIeriaI produced wiIh good quaIiIy seed ¸synIheIic gypsum) and
under conIroIIed ¸Iow) supersaIuraIion environmenI proved Io be
superior Io Ihe oIher ones.
The in uence oI seeding under supersaIuraIion conIroI on impuriIy
upIake is exempIi ed wiIh Ihe daIa oI Fig. 28 ¸Verbaan, 2000). II can be
cIearIy seen IhaI up Io one order oI magniIude Iower impuriIy upIake
occurs when neuIraIizaIion is conducIed in such a way Iavouring Ihe
producIion oI smooIh and Iarge gypsum crysIaIs ¸Fig. 27a) ¸reIer Io
SecIion 2.9.4).
4. Concluding rcmarks
By Iar supersaIuraIionis Ihe mosI imporIanI parameIer IhaI conIroIs
Ihe properIies ¸parIicIe size, morphoIogy, crysIaIIiniIy and cIeanIiness)
oI a compound produced via aqueous precipiIaIion. II wouId noI be an
exaggeraIion Io sIaIe IhaI as Iong as supersaIuraIion is conIroIIed, iI is
aImosI cerIain IhaI a producI oI superior quaIiIy wiII be obIained.
lig. 28. ImpuriIy upIake during gypsum crysIaIIizaIion aI pH 4 as a IuncIion oI seeding
¸CondiIions 1 gjL caIion concenIraIion, excepI Na was 10 gjL, 50 gjL seed, 50 gjL CaO,
10 gjL, H SO ¸reproduced Irom Verbaan ¸2000)).
21J C.P. Dcmopoulos / HyJromctollurgy 95 ¦2009) 199214
DeveIopmenI oI supersaIuraIion-conIroIIed aqueous precipiIaIion
meIhods is expecIed Io grow in Ihe near IuIure boIh in Ihe area oI
producIion oI advanced maIeriaIs such as nanosized powders ¸Li and
DemopouIos, 2008) buI aIso in Ihe area oI indusIriaI hydromeIaIIurgy
and IreaImenI oI eI uenIs Irom chemicaI and meIaIIurgicaI opera-
Iions. A soIid undersIanding oI crysIaIIizaIion Iheory is a prerequisiIe
Io successIuI deveIopmenI and impIemenIaIion oI advanced pre-
cipiIaIion IechnoIogy.
Acknowlcdgcmcnt
The auIhor is indebIed Io aII pasI and currenI sIudenIs and
research associaIes oI his, who Ihrough Iheir hard work and ingenuiIy
conIribuIed Io Ihe work reviewed in Ihis arIicIe.
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