Speciations diagrams of copper(II) in aqueous ammoniacal solutions

Full text

y ()~O"'f'taJ..J..OU~'Yta
Hydrometallurgy ~IArPAMMATA KATANOMHL
IONTQN ~ILeENOYL XAAKOY
LE YMTIKA AMMQNIAKA
~IAAYMATA
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I. rIANNOTIOYAOY, I. TIALTIAAIAPHL"
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uTToAoyi~nal TO TTOOOOTOTOUJInc:XUou TTOU6pi-
OKnai 61aAuJItvo OTO 61c:XAuJIaJIE:TIlV JIOpCPI'JoAwv
TWV TTlOavwv IOVTWV, aTT Awv Kal OUJITTAOKWV, 00-
vapTI'JOE:1TOU6uvaJIIKOUu6poyovou.
1:TIlVTTapouoa E:pyaoia aVTlJInwTTi~nal ooOTIl-
JIaTIKc:XTO TTpo6AIlJIa Tile; KaTaOKE:UI'Je; TWV 6laypaJI-
JIc:XTWVKaTaVOJII'Je; IOVTWV KaTaOKE:Uc:X~OVTae; Ta
6laypc:XJIJIaTa KaTaVOJII'Je; TWV IOVTWV 6100E:VOUe;
xaAKOU OTa aJIJIWVlaKc:X 61aMJIaTa oovapTl')OE:1 Tile;
avaAuTI~I'Je; OUYKtVTpwOIle; aJIJIwviae;.
na TIlV aVc:XTTTU(1laUTWV TWV 6IaypaJIJIc:XTWV E:AI')-
cpOlloav UTT0lJ'lloAa Ta oUJITTAoKa IOVTa, JIOVOTTU-
PIlVIKc:XKal TToAuTTUPIlVIKc:X,TTOUoxllJIaTi~oVTaI OTa
UTTOOOOTI'JJIaTa Cu2+ -NH) Kal Cu2+ -OH- aTTOTa
oTToia aTToTE:A£iTaiTO oUOTIlJIa Cu2+ -NH)- H20.
1. ElOUY(J)Yt]
H 6LOI!T)xaVLa JtaQaywYT]~ 't'U1tWI!EVWV X'UXAWl!a-
'twv XQT)OLI!01tOLELE'UQu'ta'ta al!l!WVlaXa OLaAUl!a'ta
* EpyaOttjeLO METa)J.oupyla~ EMn
OPYKTO[ n/\OYTO[/MINERAL WEALTH 116/2000
Ta OTTou6a1oTE:paOUJITTE:pc:XOJIaTa aTTo Tllv JIE:-
AtTIl TWV 6IaypaJIJIc:XTWV KaTaVOJII'Je; IOVTWV £ivai
Ta TTapaKc:XTW:
i. Ta aJIIVOoUJITTAoKa TOU 6100E:voue; xaAKOU,
Cu(NH) /+, aTToTE:Aouv TTpaKTIKc:XTie;E:TTlKpa-
TOUOE:e;Kal JIOva61Kte; JIopcpte; JIE:Tie; OTToiE:e;
aTTavTc:XTai0 xaAKOe; OTa E:Aacppwe; o(lva twe;
OTa IOXUpWe;aAKaAIKc:XaJIJIWVlaKc:X61aMJIa-
Ta.
ii. To IOVCu(NH)/+ £ivai TO oTTou6a.oTE:po IOV
OTO ouoTIlJIa Cu2+ -NH) -H20. EJICPavi~E:1E:U-
pUTaTIl TTE:pIOXI'JOTaOE:pOTIlTae; TTOUKUJIaivE:-
Tal aTTO Ta E:Aacppwe; o(lva 61aMJIaTa JIE:pH
5 twe; Ta IOXUpWe; aAKaAIKc:X61aMJIaTa JIE:
pH 14.
iii. Ta u6pO(UOuJITTAoKa TOU 6100E:voue; xaAKou
aTTaVTwvTa. OTO oUOTI"JJIaCu2+ - NH) - H20
JIOVOOTa TToM IOXUpWe;aAKaAIKc:X61aMJIa-
Ta JIE:pH JIE:yaMTE:po TOU 12 Ka. OTa apa.c:X
aJIJIwvlaKc:X 61aMJIaTa JIE:OAIKI'JooYKtVTPW-
OI"JaJIJIwviae; JIIKpOTE:plle;aTTo 0.1 M.
iv. ° xaAKOe; aTTavTc:XTai OTa aJIJIwvlaKc:X 61aM-
JIaTa JIE:Tl"Jv JIopcpl'J TWV E:AE:uOE:pwVIOVTWV
TOU, Cu2+, JIovo OTa TToAu o(lVa U6aTlKc:X61a-
MJIaTa.
YLa 'tT)v a1tOl!axQ'UVOT) 'to'U XaAXOU am) 'ta 't'U1tWI!E-
va x'UxAWl!a'ta xa'ta 'tT)v ~aOT) 'tT)~ a1tOXaAXWOT]~
'to'U~. Ta OLaAul!a'ta 1t0'U 1tQOXU1t'to'Uv a1tO 'tT)v ~aoYJ
'tT)~ a1tOXaAXWOT)~ EXO'UV 'U"VT)AT]O'UYXEV'tQWOT)OE
xaAxo 1t0'U XWaLvE'taL o'tT)v 1tEQLOXT]'twv 130 -
47
--- ---- - - - - ---

160 gr 11 XaL E:1tL01']~ 'U'V1']A:ll O'UYXEV'tQW01'] OE af1f1w-
vLa 't1']~ 't(X~EW~ 'twv 150 gr/l. Ta OLaA:Uf1a'ta a'U't(x
xaQax't1']QL~OV'taL oav E:1tLXLvO'Uva a:1tOoA1']'ta :1t0'U
:1tQE:1tELva 'U:1too'tO'lJV :1tQoxa'tEQyaoLa :1tQLV OLa'tE-
Souv O'tO :1tEQLOaA.A.Ov.Ha va OQESEL 0 xa'taAA1']AO~
'tQO:1tO~ OLaXELQL01']~a'U't(ov 'twv a:1tOoAtl'tWV ELVaL
avayxaLo va f1EAE't1']SELmpEvo~ f1EV 1'] f10QCPtl f1E 't1']V
O:1tOLa a:1tav'twv'taL 'ta Lov'ta OLOSEVOU~ xaAxou OE
a'U'ta'ta af1f1WvLaxa OLaAUf1a'ta xaSw~ E:1tL01']~XaL 1']
xa'tavof1tl 'to'U~ o'UvaQ'ttloEL 'to'U OUVaf1LXOU'UoQoyo-
VO'U a'U'twv 'twv oLaA'Uf1a'twV.
L't1']V :1taQouoa EQyaoLa, YLVE'taL OLoALOYQacpLxtl
E:1tLOXO:1t1']01'] OAWV 'twv :1tLSaVWV O'Uf1:1tAOXWV LOV'tWV
Cu2+- OH- XaL Cu2+-NH3 :1t0'Ua:1tav'twv'taL o'ta <>La-
AUf1a'ta'to'U o'Uo'ttlf1a'tO~Cu2+- NH3 - H20 xaSw~
E:1tL01']~XaL 'tWV O'taSEQWV OX1']f1a'tLOf10U'to'U~ 0'tO'U~
25T. E:1tL01']~, avamUOOE'taL 1'] f1ESOOOAOYLa xa'ta-
OXE'Utl~'tWV OLaYQaf1f1a'twv xa'taVOf1tl~ LOV'twvll.2J XaL
xa'taOXE'Ua~ov'taL 'ta OLaYQaf1f1a'ta xa'taVOf1tl~ 'tWV
LOV'tWV<>LOSEVOU~xaAXOU OE af1f1WVLaxa OLaAUf1a'ta
o'UvaQ'ttlOEL 'to'U o'Uvaf1LXOU 'UOQoyovo'U (pH) XaL 't1']~
O'UYXEV'tQW01']~'t1']~ af1f1wvLa~ a'U'twv 'twv oLaA'Of1a-
'twv.
2. nE~LY~(UpiJ 'to'U (J\!(J'tiJ~Ul'tO~Cu2+- NH3 - HP
To ouo't1']f1a Cu2+ - NH3 - H20 a:1tO'tEAEL'taLa:1to
OVo 'U:1tOo'Uo'ttlf1a'ta, 'to 'U:1tOouo't1']f1aCu2+ - NH3
XaL 'to 'U:1tOouo't1']f1aCu2+ - OH-, :1t0'U:1tEQLYQacpOV'taL
avaA'U'tLxa :1taQaxa'tw.
2.1. IIE{}ty{}acp1j mv ovaT1j/laTo~ Cu2+ -NH3
To a'tof1o 'to'U a~w'tO'U o'to f10QLO 't1']~ af1f1WVLa~
(NH3) OLaSE'tEL Eva aou~E'Ux'tO ~EUYO~ 1']AEX'tQOVLWV
:1tQaYf1a :1t0'U xaSLo'ta 't1']V af1f1WvLa LOX'UQOO'Uf1:1tAO-
XO:1tOL1']'tLXOf1EOO OX1']f1a'tL~oV'ta~ IlEYaAo aQLSf10
O'Uf1:1tAOXWVLOV'tWV IJ.E oAa oXEMv 'ta LoV'ta f1E'taA-
AWV o'ta 'UOa'tLxa OLaAUf1a'ta.
H :1tQw't1']cpao1'] 't1']~ EQyaoLa~ amtl~ :1tEQLEAaf1oavE
OLoAwYQacpLxtl. E:1tLOXO:1t1']01']'twv O'taSEQWV 0X1']f1a'tL-
0f10U 'twv OUf1:1tAOXWVLOV'tWV[3,4,5,6,7,8J:1t0'U OX1']f1a'tL-
~ov'taL 0'tO ouo't1']f1a Cu2+ - NH3' OL o'taSEQE~ OX1']-
f1a'tLOf10U :1t0'U oQES1']xav a:1to 't1']V OLoAwYQacpLa EL-
Val OL aXOA.o'USE~:
2.2. IIE{}ty{}acp1jmv avaT1j/lam~ Cu2+-OR-
To LOV 'UOQO~ELOLO'U(OR) ELVaL 0 :1tL0 XOLVO~ O'U-
f1:1tAOXO:1tOL1']'ttl~:1t0'U a:1taV'ta'taL o'ta 'UOa'tLxa OLaAu-
f1a'ta. To LOV 'UOQO~ELOLO'UOX1']f1a'tL~ELOUf1:1tAOXa f1E-
'tQLa~ O'taSEQo't1']'ta~ f1E oAa 'ta f1E'taA.A.LXa LOV'ta
o'ta 'UOa'tLxa OLaAUf1a'ta.
Ano 't1']v OLoALOYQacpLa oQES1']XaV OL O'taSEQE~ oX1']-
f1a'tL0f10U OAWV 'twv :1tLSavwv f10VO:1t'UQ1']VLXWVO'U-
f1:1tAOXWVLOV'tWV[3,4.5.6.7,8] :1t0'U OX1']f1a'tL~OV'taL o'to
ouo't1']f1a Cu2+ - OR. OL O'taSEQE~ a'U'tE~ ELVaLOL
aXOA.o'USE~:
Cu2++ HP = CuOH+ + H+ *0/ = 10-75 (6)
Cu2++ 2H20 = CU(OH)20 + 2H+ *02= 10-14.8 (7)
Cu2++ 3H20 = Cu(OH)/- + 3H+ *03 = 10-271 (8)
Cu2++ 4HP = CU(OH)42-+ 4H+ *04 = 10-39.6 (9)
Ta LOV'ta OLOSEVOU~ xaAXOU, Cu2+, EXO'UV 't1']V Lxa-
VO't1']'ta va OX1']f1a'tL~OUV XaL :1tOA'U:1t'UQ1']VLXaOUf1:1tAO-
xa f1E 'ta LOV'ta 'UOQO~ELOLO'U O'ta 'UOa'tLxa OLaAUf1a-
'ta. L'UVtlSW~ 1'] O'taSEQO't1']'ta 'tWV :1tOA'U:1t'UQ1']VLXWV
O'Uf1:1tAOXWV ELVal aQXE'ta f1LXQO'tEQ1'] a:1tO a'U'ttl 'tWV
f10VO:1t'UQ1']VLXWV O'Uf1:1tAOXWV XaL YLa a'U'to 'tOY AOYO
O'UVtlSw~ 'ta :1tOA'U:1t'UQ1']VLxa OUf1:1tAOXa af1EAOUV'taL
xa'ta 't1']V X1']f1LXtl :1tEQLYQacptl 'tWV 'UOa'tLXWV 0'U0't1']-
f1a'twv XaL 't1']V xa'taOXE'Utl 'tWV OLaYQaf1f1a'twv xa-
'taVOf1tl~ 'tWV LOV'tWV ouvaQ'ttlOEL 'to'U OUVaf1LXOU
'UOQOYOVO'U 'tWV oLaA'Uf1a'twV. To O:1tO'UOaLO'tEQO :1t0-
A'U:1t'UQ1']VLXOOUf1:1tAOXO 'twv LOV'tWV OLOSEVOU~ xaA-
xou f1E 'ta LOV'ta 'UOQO~ELOLO'U ELVaL 'to Cu/OH)/+
XaL 1'] o'taSEQa oX1']f1a'tL0f10U 'to'U ELVaL 1'] axoAo'US1']:
2Cu2++ 2H 0 = Cu (OH )2+ + 2H+ *0 = 10-10.6
(10)
2 2 2 22
3. AUly~a~~a xa'tavo~iJ~ 'twv LOV'tWV bL(J6EVOtJ~
xaAxotJ (J\!va~'tiJ(JEL 'to\! b\!Va~LxotJ \!b~oyovo\! (J'to
(JtJ(J'tt)~a Cu2+ - NH3 - H20
To X1']f1LXOouo't1']f1a Cu2+ - NH3 - H20 :1tEQLYQa-
cpE'taL a:1to 'tL~ Xt)f1LXE~ E~LOWOEL~(1) - (10). L'tO
ouo'tt)f1a amo 0 OLaA'Uf1EVO~OLOSEVtl~ xaAXO~ 'U:1taQ-
XEL f1E 't1']v f10QCPtl 'tWV EAEUSEQWVLOV'tWV'to'U XaL f1E
'tt)v f10QCPtl 'tWV O'Uf1:1tAOXWVLOV'tWV 'to'U f1E NH3
(af1LVOOUf1:1tAOxa) XaL OR ('UoQo~'UOUf1:1tAOxa).
Ha 't1']v xa'taoxE'Utl 'to'U oLaYQaf1f1a'to~ xa'tavof1 tl~
'twv LOV'tWV 'to'U OLOSEVOU~ xaAxou 'U:1tO/.,OYL~OV'taL
'ta :1toooo'ta 'to'U xaSE LOV'tO~ OLOSEVOU~ xaAxou,
a:1tAOU tl O'Uf1:1tAOXO'U,o'ta O:1tOLa xa'taVEf1E'taL 0 O'U-
VOALXO~OLaA'Uf1EVO~xaAxo~ :1t0'U 'U:1taQXELo'to OLaA'U-
f1a. Ta :1toooo'ta a'U'ta ExcpQa~ov'taL W~ axoAouSW~:
OPYKTOL nAOYTOL!MINERAL WEALTH 116/2000
Cu2++ NH3 = Cu(NH3)2+ o = 104.1 (1)
/
Cu2++ 2NH = Cu(NH ) 2+ o = 107.5 (2)
3 3 2 2
Cu2+ + 3NH = Cu(NH ) 2+ o=1010.7 (3)
3 3 3 3
Cu2+ + 4NH = Cu(NH ) 2+ o=1013 (4)
3 3 4 4
Cu2+ + 5NH = Cu(NH ) 2+ o=1012.4 (5)
3 3 5 5
48

ao = [CU2+]/CUT
an = [Cu(NH3)n2+]/C~ n=I,. ..,5
a. = [Cu(OH) (2-Y)]/Cu
Ty=I,.. .,4
y y
a22= 2[Cu2(OH)/+]/CuT
(11)
(12)
(13)
(14)
3.1. Y:n:OAOYLO~O<;'toov ouyx.£v'tQwo£oov 'toov LOV'tooV
'tOUxaAxov om vbanx6 btaAvlla
Y:n:08E'tOv'ta<; O'tL 'to OL<iAU~a £i.Val X.OQ£O~EVO O£
CU(OH)2(S)' 11 ouyx.EV'tQOOOl1 'toov £A£u8£QOOv LOV'tooV
oL08£vou<; xaAx.ou o'to uOa'tLx.o a~~oovLax.o OL<iAU~a
U:n:OAOYL~£'taLa:n:o 'tllv 0'ta8£Qa 'tou YLVO~EVOUOLa-
AU'toP"'tar- 'tou Cu (OH)K =10-19.3[3.8] OUlimoo-
'1 ~ 2(s)' sp , r''t'
va ~£ 'tllv £~LOOOOl1(15):
[Cu2+] =K,; .[H+]2
Kw
o:n:ou K W £LVal 11 0'ta8£Qa au'tOOLao'taoll<; 'tOU V£-
QOu :n:ou o'tou<; 25°C £i.VaL LOll ~£ 10-14.
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a:n:o 'tllv :n:aQax.a'too £~LOOOOl1(16):
(15)
.(16)
n = 1,.. .,5
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6n £LVaL11 0'ta8£Qa oXll~a'tLO~ou 'tou x.a8£ ou-
~:n:Mx.ou LOV'tO<; o:n:oo<; au'to<; :n:£QLYQacpE'taL O'tL<;
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'toov 0'ta8£Qwv WOQQo:n:La<; 'toov av'tLOQao£oov 0Xll-
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a:n:o 'tllV £~LOOOOl1(17):
[Cu2+]
[
CU(OH)(2-Y) ]=.~ .- (17)
Y Y [H+Y
y = 1,...,4
OPYKTOr nI\OYTOI:/MINERALWEALTH116/2000
O:n:ou,
*6 £LVaL11 o'ta8£Qa OXlllLa'tLO~OU'tou x.a8£ ou-
Y
IL:n:AOXOU LOV'tO<; o:n:w<; amo<; :n:£QLYQacp£'taL 0'tL<;
£~LOWO£L<; (6) -(9).
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LOV'tO<; CuiOH)22+ OLV£'taL a:n:o 'tllV £~LOOOOl1 (18).
(18)
H OALX.~ouyx.Ev'tQOOOl1'tou OLaAu~EvoU xaAXOU,
CUT' LOOU'taL~£ 'to a8QoLoILa 'toov ouyx.£v'tQwo£oov
OAOOV 'toov LOV'tooV, a:n:Awv X.aL OU~:n:AOX.OOV, ~£ 'tL<;
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a~~oovLax.o OLaAuILa XaL £x.cpQa~£'taL a:n:o 'tllv £~L-
000011(19).
C~ = [Cu2+] + [Cu(NH3)2+] + [Cu(NH3)/+] +
+ [Cu(NH3)t] + [Cu(NH3)42+] +
+ [Cu(NH3)s 2+]+ [CuOH+] +
+ [CU(OH)20] + [CU(OH)3-1] +
+ [Cu(OH)/] + 2[Cu2(OH)/+] (19)
Av'tLx.a8LO'twV'ta<; 'tL<; ouyx.£V'tQWO£L<; 'toov OUIL:n:AO-
x.oov LOV'tooV'tou oL08£vou<; xaAx.ou, o:n:oo<;au'tE<; £i.-
Val £x.cpQao~Ev£<; ~EOOO 'toov £~wwo£oov (16), (17)
X.aL (18), o'tllV £~LOOOOl1(19) :n:QOX.U:n:'t£L11 £~LoOOOl1
(20) o'tllv o:n:oLa 11 OALX.~ouYX.EV'tQOOOl1'tou OLaAuILE-
vou xaAx.ou, CUT' £x.cpQa~E'taL oav 01JVaQ'tll0ll 'tOOV
ouyx.£V'tQWO£OOV 'toov £A£u8£QOOv LOV'tooVxaAx.ou, 'tll<;
aOLaO'ta'tll<; a~~OOVLa<; X.aL 'toov UOQoyOVO'(OV'toov 'tou
OLaAu~a'to<;.
CUT =[CU"j.[1 + t. ~ANH3]"
+t. '~Y"urr +)3,,[Cu" ].[Irr' J(20)
fLa va U:n:OAOYLO'tOUV'ta :n:oooo'ta 'tou x.a8£ LO-
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oLaAu~a'to<;.
49

3.1.1. Y.1l"OAOYLa/lO~avyxiv"C~waYJ~ ac5uiam"Cwv /lO-
~iwv a/l/lwvia~ am vc5anxo c5taAV/la
H a!!!!WVLa W~ aOeEVTJ~ 1']t...EX'tQOA:lJ't1']~'UcpLo'ta'taL
oL<xo'taa1'] o'to 'UOa'tLxo OLat...'U!!a ov!!cpwva !!E 't1']V
naQaxa'tw X1']!!LXTJE!;LOW01'].
(21)
H o'taeEQa OLao'ta01']~ 't1']~ a!!!!WVLa~, Kb, 0'tO'U~
25°C ELVaLKb=1.8xlO'S [3.8].Ano 't1']VExcpQa01']'t1']~
O'taeEQa~ OLao'ta01']~ 't1']~ a!!!!WVLa~ 'UnOt...OYL~E'taL 1']
O'UYXEV'tQW01'] 'tWV LOV'tWV a!!!!WVLO'U !!EOW 't1']~ E!;L-
OWOEW~ (22).
K
[NH;] =l. [NH3]' [H+]
Kw (22)
HOt...LXTJ(avat...'U'tLXTJ) O'UYXEV'tQW01'] a!!!!WVLa~, NT'
ELVaL 'to aeQOLO!!a Ot...wv 'tWV !!OQCPWV !!E 'tL~ onOLE~
1']a!!!!WVLaanav'ta'taL o'to OLat...'U!!aXaL OLVE'taLano
't1']v E!;LOW01'] (23).
5 .
NT =[NH3]+[NH;]+ I.[Cu(NH3)~+] (23)
n=1
ME o'UVo'Uao!!o 'tWV E!;LOWOEWV(15), (16), (22)
XaL (23) nQoxvn'tEL 1'] E!;LOW01'](24), ano 't1']V onOLa
'Unot...oYL~E'taL 1'] O'UYXEV'tQW01']'twv aOLao'ta'twv !!O-
QLWVa!!!!WVLa~ o'UVaQ'tTJOEL't1']~ O'UYXEV'tQW01']~'twv
'UoQoyovo'(ov'twv XaL 't1']~ Ot...LXTJ~O'UYXEV'tQW01']~a!!-
!!WVLa~ 0'tO 'UOa'tLxo oLat...'U!!a.
~~p .[H+]2 -[~I~n '[NH3r]
w
Kb +
+-.[NH3].[H ]+[NH3]-NT =0
Kw (24)
H E!;LOW01'](24) ELVaL nE!!Jt'to'U oae!!OV W~ nQo~
't1']V O'UYXEV'tQW01']'twv aOLao'ta'twv !!OQLWV a!!!!w-
vLa~ XaL 1'] mLt...'UOTJ't1']~ !!EOW 1']t...EX'tQOVLXOV'Unot...o-
YLO'tTJ !!E 't1']v OOTJeELa xa'tat...t...1']t...wv !!ae1']!!a'tLxwv
nQoYQa!!!!a'twv (nx mathcad, mathematica) OLVEL
nEv'tE t...VOEL~EX 'tWV onoLwV nav'ta OL 'tEOOEQEL~
ELVaLaQV1']'tLXE~XaL aJtOQQLn'tOV'taL XaL 1'] !!La eE'tL-
XTJ XaL YLVE'taL anOOEX'tTJ.
3.2. E:n:U.\JofJ 'to\J :n:(?ool..1)Jl.a'to;
o nQoooLOQLO!!O~ 'twv :n:oooo'twv 'to'U xaeE LOV'tO~
!!E 'ta onoLa 0 oLat...'U!!EVO~xat...xo~ 'UnaQXEL 0'tO OLa-
t...'U!!a YLVE'taL ov!!cpwva !!E 'tOY at...yoQL8!!0 no'U nEQL-
YQacpE'taL o'to OXTJ!!a 1.
50
()pta~l6s 6EOOfl£VooV TOU 1tpof3AlwaTOs
NT. Ksl" Kin K". Ii,,, 'Ii" '1hz
KaOopl(}'fl6e; Tlfl~e;
0uYK£VTpoomle; uopoyov0l6vTWV
1:1ti),uml !:~I(}'W(}'1le; (24) KUl 1tpO(}'6LOpta~ll)e;
TIle; GUYK£VTpwmle; [N II, I
1:1t1AUml E~IG([)GT]S(15) Kat 1tpO(},OLOpta~ll)S
TllS (}'UYK£VTPoo(}'11S[Cu2+1
I:1Ii/,uml E~I(}'wmlS ( I q) Kat 1tp006LOPl0~ll)(
Tlls 0UYKt.VTpwmlS ICu(NH1)" 2'1
1:1ti),uml E~I(}'([)(}'1le;(17) Ka11tpO(},OlUpl(J~ll)S
Tlls 0uYK£VTp(OmlC; [Cu(OH) (2'»)J
E1tlAUml E~IGW(}'11C; (20) Kat 1tPUGOLUPl(}'fl6C;
TllS 0UYK{:VTPW(}'11C; TOU OAlKOl) XUAKOlJ. Cu I
I:1t1AUml E~l(J(U(},E([)V( I 1) - ( 14) KUl
1tpOG6LOplG~l6e; TooV1t0GOGTWVU". u", U \. Un
~XE6lCl(}'fl6C; oLUypaflfl<lTooV KUTavo~111e; Tel)V
l<')VTWV OLGOEVOl)C; xaAKOlJ GUVUPT1l(}'El TOU
6uva~llKou u6poy6vou <no 6l<lAUflU
~XHMA 1: AAyofJLellO~En{}..v01J~TWV EgLOwoEwv LOOfJ-
fJonia~ TWVLOVTWVTaV t5toeEvov~ XaA"ov
OEv()an"d ()WAvlla-ra allllwvia~.
FIGURE 1: Algorithm for the solution of equations
at the equilibrium of Copper(II) ions in
aqueous ammoniacal solution.
2:v!!cpwva I-lE a'U'to 'tOy at...YOQLe!!O, 'ta noooo'ta
'to'U xaeE LOV'tO~ 'to'U OLOeEVOV~ xat...xov o'ta onoLa
ELVaL xa'taVE!!1']!!EVO~ 0 O'UVOA.LXO~OLaA.'U!!EVO~xaA.-
XO~ no'U 'UnaQXELo'to OLaA.'U!!aExcpQa~ov'taL o'UvaQ-
'tTJOEL OVo !!E'taot...1']'twv. 't1']~ O'UYXEV'tQW01']~ 't1']~ O'U-
VOA.LXa oLat...'U!!EV1']~ a!!!!WVLa~ NT XaL 'to'U pH 'to'U
OLaA.V!!a'to~.
2:'ta OXTJ!!a'ta2 - 5 OLVOV'taL'ta oLaYQa!!!!a'ta
xa'tavo!!TJ~ 'twv LOV'tWV OLOeEVOV~xaA.xov o'UvaQ'tTJ-
Oft 'to'U o'Uva!!LXOV 'UoQoyovo'U OE oLacpoQE'tLXTJ~ O'U-
OPYKTOr. n/\OYTO[/MINERAL WEALTH 116/2000

24 6 8 10 12 14
pH
LXHMA 2a: ,1uiY{Japp,a "a-ravop:rk TWVLOVTWVc5t08EvoVt;XaA"OV ovva{JTiJoELTOVbvvaflL"ov vb{J0Yovov
OEaflflwvw"O c5tcXAvflaflE OVy"iVT{JWOTJOAL"iJt;btaAVfliVTJt;aflflwviat; O.lM
FIGURE 2a: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing
0.1Mtotal ammonia versus pH.
lJ
CU(OH)2
Cu(OH)"'
6 8 In 12 14
pH
LXHMA 26: ,1uiY{Jaflfla "a-ravofliJt; TWV LOVTWVc5w8Evovt; XaA"ov ovva{JTiJoEL -rov c5vvaflL"ov vc5{J0Yovov
OE aflflwvw"O c5uiAvfla flE OVy"iVT{JWOTJ OAL"iJt;c5wAVfliVTJt; aflflwviat; O.lM
FIGURE 2b: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing
0.1Mtotal ammonia versus pH.
YXEV'tQWOt]<;al-.II.lWvLaxCLbLat..Uj..lam. H Ot..LXi)OUYXE-
v'tQwot] bLat..Uj..lEvt]<;aj..lj..lWvLa<;o'ta bLat..Uj..la'ta au'tCL
XUj..laLVE1aL roto a.1M EW<; 6M.
OL Jtt..t]QOCPOQLE<;Jtou JtQoxuJt'tOuv roto 'ta bLa-
YQCLj..lj..la'ta au'tCL EXOUV JtOLO'tLXO XaL OXL JtOOO'tLXO
xaQax'ti)Qa bLO'tL xa'tCL 'tt]V xa'taoxEui) 'tou<; bEV
EXOUV t..t]cpeEi. uJto'\jJt] OL EVEQYO'tt]'tE<; 'tWV LOV'tWV
at..t..CLOL OUYXEV'tQOOOEL<;'tou<;. TIaQot..a. au'tCL t] XQt]-
OPYKTOI: nAOYTOL!MINERAL WEALTH 116/2000 51
\,0
0,9
O,S
0.7
0
...
.6 0,6
'0
b n,s
0
g0,4
c::
0,3
0.2
0,\
o.n
0
QS
Q45
Q4
5
0Q3
...
5
'0 Q
...
0
0,2
0
c::
0,\:'1
0.1
),
0,05 I
2H-
0
4
0 2

h
Cu(NH,f
-I
Cu(OH),
246 8 10 12 14
pH
~XHMA 3a: L1uiY{.JaI1P,axaT:avol1:il~ iWV toV'Z"wvb£OeEVOV~xaAxov ovva{.JiiJoEt iOV bvval,UXOV vb{.J0Yovov
OE al1P,wvtaxO btaAVj1-a j1-EOVYXEVi{.JWOTjOAtXiJ~ btaAVj1-EVTJ~aj1-j1-wvia~ O.6M
FIGURE 3a: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing
.O.6M total ammonia versus pH.
CU(OH)211
)1
ClI2(OH)2 -
Cu(OH)'
246 8 10 12 14
pH
~XHMA 36: L1taY{.Jaj1-j1-aXaiaVOj1-iJ~ iWV toV'Z"wv btoeEvov~ XaAxov avva{.JiiJoEt 'fOV bvvaj1-txov vb{.J0Yovov
OE aj1-j1-wvta"o btaAVj1-a j1-EOVYXEV'Z"{.JWOTjOAt"iJ~ btaAVj1-EVTJ~aj1-j1-wvia~ O.6M
FIGURE 3b: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing
O.6M total ammonia versus pH.
OLl!otTJta a'Ut.wv trov OLaYQal!l!<ltrov, TJ 03to'UOaLO-
tTJta to'U~ 'X.aLTJa;LOnLotia to'U~ 3taQaI!Evo'Uv 3tOA:U
I!EY<lAE~OLotLI!a~ 3taQE:Xo'UvEu'X.oAaI!ia EL'X.ovaYLa
tTJv 3tEQLO?Ctl Ota8EQOtTJta~ to'U 'X.<l8E O'UI!3tAO'X.O'U
LOVtO~ OtO 'UOatL'X.o OL<lA'Ul!a XroQi~ va a3taLtELtaL 0
3tELQal!atL'X.o~ 3tQOOOLOQLOI!O~to'U~ I!EOc.o avaA'UtL-
52 OPYKTO[ nAOYTO[/MINERAL WEALTH 116/2000
1,0
0,9
0,8
0,7
0
t: 0,6
'0
'0
b0,5
0
t) 0,4
0,3
0,2
0,1
0,0 °
0,035
0.D3
0,025
0
I-
;;..
'0 0,02
'0
l-
t)
g0,015
0
t::
0,01
0,005
0
()

246 & 10 ]2 14
pH
LXHMA 4u: ,1uiy{!upp,a 'Xamvo/liJr; TWV LOVTWVbLo8EVOVr;XaA'Xov avva{!TiJoEL TOV c5VVa/lL'Xovvc5{!oyovov
'OE a/l/lWVLa'Xo c5uiAv/la /lE OVY'XEVT{!WO"lOAL'XiJr;c5LaAV/lEV'Yfr;a/l/lwviar; 1M.
FIGURE 4a: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing 1M
total ammonia versus pH.
LXi ~!"lA 46: ,1Lay{!a/l/la 'XaTaVO/liJr; TWV LOVTWV bLo8EVOVr; xaA'Xov avva{!TiJoEt TOV c5vva/lt'Xov vc5{!Oyovov
OE a/l/lWVLa'Xo c5LaAV/la /lE OVYXEVT{!WO"l OAt'XiJr; bLaAV/lEV'Yfr; a/l/lwviar; 1M
FIGURE 4b: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing 1M
total ammonia versus pH.
XWV ItESOOWV nou EcpOOOV U1t(xQXouv ELVaL ouv~Sw~
oanaV'IlQE~ XaL anaL'tmJv 't'llv unaQs'll ESELOLXEUltE-
vwv OUOXEUWV.
4. I;\Jf13tEQaa,...a'ta .
~ultCPwva ItE 'ta oLaYQaltlta'ta xa'tavolt~~ LOV'tWV,
o xaAxo~ anav'ta'taL ItE 't'llV ltoQCP~'twv EAEUSEQWV
OPYKTO[ nI\OYTO[/MINERAL WEALTH 116/2000 53
1,0
0,l)
O,X
0,7
0
f- 0,6
..
'0
' 0,5
0
g0,4
t::
0,3
0,2
0, I
0,0 °
0,014
0,012
0,01
0
f-
...
;£ 0,00& I
'+ . II
'0 ClI2(OH)2- CU(OH)2
f-
g 0,006
0
t::
0,004
0,002 1+
CuOH
°°24 6 & 10 ]2 14
pH

24 6 10 14
12
8
pH
~XHMA. Sa: L1~ay~app,a xawvo/liJ~ TWV~oVrwv &O(JEVOV~xaAxov ovva~TiJoE~ TOV bvva/l~xOV vbl':IOYovov
. OE a/l/lwv~axo b~aAV/la /lE OVYXiVT~WOTJ OA~XiJ~btaAV/liVTJ~ a/l/lwvia~ 6M
FIGURE Sa:.Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing 6M
.total ammonia versus pH
Cu(OHh 0
268 10 1412
4
pH
~XHMA 56: L1~ay~a/l/la xawvo/liJ~ TWV~OVTWV&O(JEVOV~xaAxov ovva~TiJoE~ TOV bvva/l~XOV vb~oyovov
OE a/l/lwv~axo &aAV/la /lE OVyxiVT~WOTJ OA~XiJ~&aAv/liVTJ~ a/l/lwvia~ 6M .
FIGURE 5b: Speciation diagram of Copper(II) ions in aqueous ammoniacal solution containing 6M
total ammonia versus pH
54 OPYKTO[ nI\OYTO[/MINERAL WEALTH 116/2000
1,0
0,9
0,8
0,7
0
!: 0,6
'0
-
.0,5
0
g04
c: '
0,3
0,2
0,1
0,0
0
0,007
0,006
0,005
0
...
. 0004
- ,
'0
...
.g 0,003
0
c:
0,002
0,001
00

lOWCWV'to\!, CU2+, !AOVOO1:a 1tOA:UO~LVa \!Oa'tlXa
OlaA:U!Aa1:a.H 1t£QloX1)o't1']V01tOLa £1tlxQa'tEL 'to lOV
CU2+ Xal a1tO't£A£L 1tQaX'tlXa 't1']V!AOVaOlx1)!AOQcp~
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a\!~aV£l a1to 0.1 o£ 6M 1'] 1t£QLOX~o'tae£Qo't1']w~
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OE pH !AlXQo't£Qo'to\! 2.
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O\!YXEV'tQW01'] 't1']~ OWA\!!AEV1']~ a!A!AWvLa~, NT' o'to
OlaAwa.
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'tl!AWV pH a1to 2-8 !A£ 'tao1'] !AE'taXLV1']01']~'t1']~
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't£QO o~lva Ol~AU!AaW xaew~ 1'] NT a\!~aV£l
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1tO'tE O'to OlaA\!!Aa Xal £!AcpaVL~E'tal O't1']V 1t£-
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'ta 1t£QLOOO't£QO o~LVa OlaAU!Aa'ta xaew~ 1'] NT
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'tl!AWV pH ano 6-12 !A£ 'tao1'] !AE'taXLV1']01']~'t1']~
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lOV o't1']v 1t£QLOX~ 'twv O\!OE't£QWV olaAwa'twv
!A£pH 6-8.
iv. To lOVCu(NH3)t ELVal'to 01t0\!Oalo't£QolOV
o'to ouo't1']!AaCu2+ - NH3 - Hp. E!AcpavL~£l
£'UQuw't1']1t£QLOX~owe£Qo't1']'ta~ 1t0\! X\!!AaLv£-
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ELVal 1tQax'tlxa 'to !AOVaOlxolOV o't1']v 1t£QLOX~
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!Aa'ta !A£ OAlX~ O\!YXEV'tQW01']OlaA\!!AEv1']~a!A-
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'tl!Awv pH a1to 8-14 !A£'tao1'] !A£WXLV1']01']~'t1']~
1t£QLOX~~o'tae£Qo't1']W~ 1tQo~ 'ta 1t£QLOOO't£QO
OPYKTOr nI\OYTOr/MINERAL WEALTH 116/2000
aAxaAlxa OlaAU!Aaw xaew~ 1']NT a\!~aVEl a1to
0.1 O£ 6M. To lOV a'U'to a1tox'ta O\!V£XW~a\!-
~avo!A£V1']01t0\!Oalo't1']'ta o'to ouo't1']!Aa Cu2+ -
NH3 - HP xaew~ 1'] OAlX~ O\!YXEV'tQW01']'t1']~
OlaA\!!AEV1']~a!A!AWVLa~,NT' a\!~aVE'tal a1to 0.1
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OlaAU!AaW !A£ oAlX1) O\!YXEV'tQW01']a!A!AWVLa~
!A£yaAu't£Q1']~ano 6M YLVE'tal Xal 'to £1tlxQa-
'touv lOV o'to OlaA\!!Aa.
Ta \!OQo~\!OU!A1tAOXa'to\! OlOe£VOU~xaAxou a1ta-
V'twv'tal o'to ouo't1']!Aa Cu2+ - NH3 - H20 !AOVOo'ta
1tOAULOX\!QW~aAxaAlxa OlaAU!AaW !A£pH !A£yaAu-
't£Qo 'to\! 12 Xal o'ta aQala a!A!AWVlaXaOlaAu!Aa'ta
!A£ oAlx1) O\!YXEV'tQW01'] a!A!AWVLa~ !AlXQo't£Q1']~ a1to
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YXEV'tQW01']o'to ouo't1']!Aa Cu2+ - NH3 - H20
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1t'tEl !A£ 't1']v 1t£QLOX1)o'tae£QO't1']'ta~ 'tWV a!ALVO-
O\!!A1tAOXWV'to\! xaAXOU 'ta 01tOLa '\!1t£QlOXUO\!V
a1tOA\!'ta.
ii. To CU(OH)20 £!AcpavL~E'talo't1']v 1t£QlOX1)'tl!AWV
pH 11 EW~ 14 Xal a1tav'tawl O£ !A£yaA1']a\!-
YXEV'tQW01']o'to ouo't1']l!a Cu2+ - NH3 - H20
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'tl!!WV pH ano 12 EW~ 14 Xal anav'tawl O£
!!£yaA1']O\!YXEV'tQW01']o'to ouo't1']!!a Cu2+ - NH3
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'tl!!WV pH a1to 12 EW~ 14 Xal ELVal'to £1tlxQa-
'touv lOV o'to ouo't1']!!a Cu2+ - NH3 - H20 o'ta
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't1']'ta 'to'\! a\!~aV£l !!£ au~1']o1'] 't1']~ oAlX1)~ a\!-
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O£ a\!'to 'to lOV O£V ~£1t£Qva 1tO'tE 'to 0.7% 'to\!
oAlxa OlaAWEVO\! xaAXOU.
55

BIBAIOrPAcJ>IA
1. e. IT XATZHIQANNOY, llotOTLu1jAWIAvo1]UaL
X1]J,tLu1jIoo~~o1ria,A81jva, 1976, pp. 107-109.
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ABSTRACT
SPECIATION DIAGRAMS OF COPPER (II) IONS
IN AQUEOUS AMMONIACAL SOLUTIONS
Dr. D. Panias, M. Kokolakis,I. Giannopoulou,
I. Paspaliaris.
Copper(II) aqueous ammoniacal solutions .are
commonly used as etchants in printed circuit board
industry. The spent ammoniacal etching solutions
resulting from the ammoniacal etching process have a
high content in copper and also in ammonia. This
liquor is classified as hazardous material and has to
be treated before it is disposed to the environment.
Speciation diagrams of copper(lI) ions in aqueous
ammoniacal solutions are very important. They offer
us information about the composition of solution
determining the percent amount of each copper(lI)
bearing ion, simple or complex, relative to the total
copper(lI) content of the solution as a function of the
solution pH. This a very crucial information when
the management of the spent ammoniacal etching
solutions are under consideration.
In this paper, speciation diagrams of copper(lI) ions
in aqueous ammoniacal solutions are developed for
several analytical concentrations of ammonia in solution
varying between O.IM to 6M. In developing these
diagrams, the Cuz+-NH3 and Cu2+ -OH- subsystems
have been taken into consideration.
The Cuz+-NH3 system consists of five complex ions
having the general formula Cu(NH3)nz+,where n is an
integer varied between 1 to 5.
* National Technical University of Athens, Laboratory of Metallurgy
Manuscript received from:
- the authors on 1.3.99
- the Review Committee on 24.6.99
56
I
--
The Cuz+- OH- system consists of four mononuclear
complex ions having the general formula Cu(OH) (Z-y),
y
where y is an integer varied between 1 to 4, and one
polynuclear complex ion having the formula
CUz(OH)/+. - - -
The most important conclusions that can be drawn
by this work are the following:
a. All complex ions of Cu(II) with ammonia
predominate in slightly acid to high base solutions.
More accurately, copper(II) exists wholly as
Cu(NH3)n2+in ammoniacal solutions with pH
varied between 2 to 13.
b. Cu(NH3)/+ is the most important ion having a
broad stability area extented from pH 5 to pH
14. Practically, this ion in the only copper(lI)
bearing ion in ammoniacal solutions with pH
varied between 8 to 11.
c. The hydroxo complexes of copper(lI) are not
important in ammoniacal solutions. Among them,
Cu(OH)t and Cu(OH)t are the most important.
Their stability area is located in strong alkaline
solutions with pH 12 to 14 and their percent
amount in solution increases as the analytical
concentration of ammonia decreases.
d. Uncomplexed copper(lI) ions, Cu2+,exist only in
high acid solutions.
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