ISIJ International, Vol. 36 (1 996), No. 5, pp.

522-527

The Kinetics of Dissolution of Copper and lron in AqueousCupric

AmmineSolutions

Satoshl UCHIDAIchlro TAKEMURA.1)

Masanori TOKUDA2)
and K. OSSEO-ASARE3)
Institute Advanced Materials Processing. Tohoku University. Katahira, Aoba-ku. Sendai. Miyagi-ken, 980 Japan.
for
1) Toyota Motor Corporation. Toyota-cho, Toyota, Aichi-ken, 471 Japan.
2) Center for Interdisciplinary Research. Tohoku University. Katahira, Aoba-ku, Sendai. Miyagi-ken. 980 Japan.
3) The Pennsylvania State University. 202A Steidle Building. University Park. PA 16802. USA,

(Received on September29. 1995, accepted in final form on November29. 1995)

The dissoiution rate of metallic copper plate in aqueous cupric amminesolutions was studied at
0.05-1 .O CuS04concentration, 0-3 OOO
mol// rpm rotation speed and temperatures between I 0-90'C. The
dissolution rate was mainly controlled by chemical reaction at the temperature below 30'C, and by diffusion
of cu pric complex at temperatures higher than 40'C, It wasfound that the dissolution rate of copper increases
with an increase in temperature and rotation speed, while a maximumrate was observed for increasing
Cu(1 l) concentration. The effect of different anion showedsignificant results on dissolution rate of copper
and iron, and carbonate ion wasfound to prevent the corrosion of iron. The selective dissolution of copper
from iron scrap was suggested.
KEYWORDS: dissoiution; copper; kinetics; cupric amminesolution; rotation disc method; iron scrap.

industrial of this process for the scrap in

application
l. Introduction
1966.8) Many kinetic studies of dissolution reaction
Recently the recycling of iron scrap is recognized to of copper into an arnmoniacal solution were perform-
be an important issue for the near future from the point ed.9~ 17) In these studies, diluted ammonium hydroxide
of view of effective utilization of resources or an en- solution was used as a solvent, and oxygen as an oxidarit.
vironmental harmony. The copper metal mingles with The kinetic study of dissolutlon rate of copper into cupric
shredded iron scrap from mainly motors and cables of amminesolutions, In which Cu(II)/Cu(1) redox reaction
cars, and it gets difficult to reject separately by magnetic was utilized, was reported by Smith in 1973.17) The
filtration. Even O.1 wto/o of copper impurlty prevents the rotating disc method was used in his study at rotating
recyciing of the steel scrap since it spreads widely into speed from 16 to 360 rpm and temperature from 20 to
the crystal grain boundary of iron, then the resistivity 40'C. Diffusion coefficient and diffusion activation
for stretch decreases. Hence the low cost process of energy were studied electrochemically by Sedzimir with
removal of copper which is a serious impurity e]ement rotating disc method at rotating speed below 960rpm
for iron making has been demanded. For a selective and ternperature from 15 to 50'C.18)
separation of copper from iron scrap, various methods Meanwhile, the problem of steel scrap treatment has
such as chlorination method,1,2) Iow temperature de- been paid attention to in recent years, and Cu(II)/Cu(1)
struction method, slag-metal refinement method3) and redox reaction was reconsidered again for Its selective
fused aluminum bath treatment method4) has been dissolution of copper and high leaching speed. Some
proposed. Eventhough these pyrometallurgical processes researchers proposed the reaction principle for the
have advantages of a high reaction rate, facilities and removal of copper from steel scraps, or motor scraps
consumption also high and they in pilot scale.19~22) Nevertheless,
energy are prevent it
no study was found
from practical appreciation. On the other hand, hy- which gives kinetic information to enable processing for
drometallurgical treatment is attractive for its selective the removal of copper from steel scraps. For that purpose,
separation and low energy operation even though the we studied a]1 effective parameters such as temperature
reaction rate Is slower. (l0-90'C), rotation speed (0-3 OOOrpm), concentration
It is well known that ammoniacal solutions dissolve of cupric amminecompiex (0.05-1 .2 mol/1), pH(8-lO.5)

copper very well and this reaction was reported firstly and partial oxygen pressure (0-1 atm) In
a wide range
1
by Peligot in 858.5) The leaching of copper from native and tried to optimize these conditions for the selective
copper ore was examined by Benedict in 1929.6) A dissolution of copper in high concentrated cupric ammine
similar process was taken by Kennecott Copper Cor- complex solutlons.
poration in Alaska7) 1933. Yurko reported the first

C 1996 ISIJ 522

 ISIJ International. Vol. 36 (1 996). No. 5
Table l. Representative experimental conditions.
2. Experimental
The samples of metallic copper were prepared from
CuS04concentration
(NH4)2C03concentration
(mol/!)
(mol/!)
OI
O. l2.0
.O

99.90/0 copper rod of 20mm diameter, and turned into

Total dissolved nitrogen (mol//) 6.0
discs. The samples were embedded in
epoxy resin with Reaction temperature ('C) 1O90
provlsion for constant surface area for dissolution. The Rotation speed (rpm) 0-3 OOO
specimens were wet grinned with #500 to #4000 emery Po, (kg/cm2)
pH
OI
9.8
.O

papers, polished with 0.2 to O.06 pt of aluminumpowder,

cleaned with methanol, and dried successiveiy. The
ammonium carbonate and copper sulfate were of reagent 8.0
pH= 9.8
grade and used without any further purification. Water
exchanger oo
[CuS0+] = 0.2 M
was deionized by the ion after distillation. [N]T = 6M
h 6.0
The pHvalue was always kept at 9.8 in any copper sul-
a)f:~
500 rpm
o*
fate concentration by mixing ammonium carbonate and 8 X Po. = O2atm

ammoniawater. The total amount of ammoniain the o 4.

O XO I
~]
solution was also kept at 6mol/1. X~
D
The apparatus used in this experiment composedof a ~~o 20 D
~ o
simple 1Iitter glass reactor, a hot water bath, condenser, ~ X
~
D O smith
O
(1973): ~CuSOJ
= 0.3 h/L 200 rpm, 30 'C
sealing joint, digital thermometer and motor with
o
stainless steel stirring rod. The samp]e plate was placed o 20 40 60 80 1OO 120
Time (min)
on the top of the rod horizontally with silicone holder.
In the investigations the rotating disc method was Fig. l. Time dependencyof weight loss of copper at various
applied. Typical experimental procedures were as follows: temperatures.

once temperature of the solution reached the proposed 4.0

figure, it
was kept constant and the stirring rod was
immersedin the solution with a constant stirring speed. 35 o 78•C
A 70•C o; 500 rpm
o
After the reactions, the sample was taken out, washed 30 + 50•C pH= 9.8
e' x 40 •C [N]T =6 M
by water and methanol, then dried. The dissolution ,~
l::~ Q 30•C
af~ 2.S cl 20 •C Poi * 02 kg / cm~
rate was measuredfrom the change of samp]e weight by vv' e)
'1~
Or ~ 20
l*
e lO•C
analytical balance. The effects of oxygen partial pressure q)..
eeeJ)
at the interface between sample and solution were also h'~~
F;,1 l.5 o
O_ ,Q
investigated. In order to determine the effects of P0=,
~ l .O
.

7;~~ + X
mixed nitrogen and oxygen gas was introduced into the x
x
e c
solution with 100 ml/min flow rate by rotarmeter, and ;S 0.5
c e Cl
D
the solution was kept with the mixed gas for I before h OO
the reaction. The disc rotation speed was kept constant O 0.2 0.4 0.6 O8 1.O I .2 1.4
with an accuracy of ~0.50/0. Typical experimental [CuS04] (mol I l)

condition is shownin Table l. Fig. 2. Effect of Cu(II) concentration on the dissolution

rate of copper. The plane lines
were simulated by Eq.
(9) and dotted lines by Eq. (16).
3. Results

3.1. Effects of Temperature and Cu(II) Concentration
Figure I
shows the time dependency on the weight
loss of copper in 0.2mol/1 copper sulfate solution at
different temperatures. The higher the temperature, the
more dissolved copper. Since the increase of dissolution
amountwas proportional to time, the leaching rate was
defined as an initial slope of these lines drawn by least
square root. Similar tendency of linear relationship be-
tween reaction time and Cu(II) concentration or reac-
tion time and rotation speed was observed.
The effect of concentration of copper sulfate
dissolution rate of copper is shownin Fig. 2. Generally
speaking, the higher the concentration of copper sul-
fate, the higher the dissolution rate. However, when
the concentration is over I
mol/1, the dissolution rate
decreased sharply. This is possibly because of the for-
mation of copper oxlde. On the other hand, at tem-
peratures lower than 30'C, the effect of Cu(II) con-
centration on the dissolution rate was not observed.
Therefore, the controlling step might have changed at
the temperature around 30'C. The lines and curves are
calculated results based on mathematical models dis-
cussed later, which are in good agreement with the
experimental results.
Without Cu(II) amminecomplex in the solution, the
dissolution amount of copper is extraordinarily small
which is approximately one two hundredth of the amount
with Cu(II) amminecomplex in the solution.
A11 these dissolution rate data are plotted in terms of
Arrhenius'es equation in Fig. 3. It is evident that the
on slopes of the lines for each Cu(II) concentration changes
at the temperature around 30'C as a boundary. The
calculated apparent activation energy was summarized
in Table 2. It is confirmed that there are two different
mechanismsin the dissolution of copper. Comparedwith
the case at morethan 40'C, almost twice value wasfound
for the activation energy for the case below 30'C. In
both cases the activation energy increased slightly with
the concentration of Cu(II). The dependencyof Cu(II)
concentration on the apparent activation energy indicates

523 C 1996 ISIJ

 ISIJ International. Vol. 36 (1996), No. 5
Temperature ('C) 4,0
pH= 9,8
-5
70 50 30 lO Temperature 10 'C
P02= 0,2 kg / cm
O~}T=6 M & 30i:~
D~]T=6M
-6
+
500 rpm
Po, = 0.2 atm
O-
O~
~~
-7 pH= 9.8
O~
4) + [Cu(II)]
= I OM
~f~~{) 2.0 c [Cu(II)] = 0.8 M
v [CuSOJ=I OM X [Cu(ll)] = O.6 M
~~ -8
A [CuSOJ=08M
9 'C)
D [Cu(ll)] = 0,4 M
S
.
F~

-9
+ [CuSOJ=06M
x [CuSOJ=0,4M
~~ lO o [Cu(ll)1
= 0,2M

c [CuSOJ=0.2M ~
-lO Cl [CuSOJ=0.1M o a
o 200 40O 600 800 1OOO
-ll Rotation speed (rpm)
4.0
2.8 2.9 3O 3 1 3.2 33 3,4 35 36
lOOO/ T (1 / K) Temperature 50 'C
e)
l:~
Fig. 3. Arrhenius plot for the dissolution rate ofcopper. l~
oQ1~~ 30
,~1'
ON ~
Table 2. The apparent activation energy (kJlmol) at 500 a)._
ce eJ~ 2,0
rpm, pH=9.8, [N]T= 6 mol//, Po, =0.2 kg/ cm2. h~~
~rt =////~t
9 'o c
~tr
**.~~-
~
.

-L/i~/~' ---
-----

[CuS04] ~S ~
l 0-30'C 4078'c lO tj~; -1[-~ ----~cr~~
~i ' ~4~--~
_i~'/r~~~'
O.
1 52.2 l 8.8
O.2 56.5 16,2 o
o 200 40O 600 800 1OOO
0.4
61.2 22. 1 Rotation speed (rpm)
0.6 56.8 25. l 4. o
0.8 53.9 27.4 Temperature 70 ec
1.O 54.0 28.4 &
i::.
ooE~. 30 O
O~
~2
'C~
_
/O/~
2,0
the complexity of each elemental reaction. In other words
'TJh
eJO
l:~(~~~
._fr/' Cr
this reason might be explained that transfer of species o_ 'o ~>--~
~- /~ //~
would be more difficult by the existence of hindrance at ~Sx __/~~l~
- lO D O
higher concentration of the solution. An increase of iS _~'~)~*~

viscosity of the solution might be effective. It

can be o
concluded that the main controlling step at temperatures O 200 400 600 800 1OOO
Rotation speed (rpm)
over 40'C wasthe diffusion of the Cu-arnmoniacomplex,
hence the main controlling step wasthe chemical reaction
Fig. 4 Effect of rotation speed on the dissolution rate of
copper.
at temperatures below 30'C.
3.2. Effect of Rotation Speed leaching rate of copper
was in proportion to the square
The effect of rotating
speed was studied to confirm root of rotation speed of the sample at the diffusion
whether the rate determining step of copper dissolution control condition.
is
mass transfer. The results at 10, 50 and 70'C are 3.3. Effect of pH
shownin Fig. 4.
At lO'C, in which chemical reaction maybe the rate
In this experiment, by the amount pH was adjusted
determining step, no effect of rotation speed on the
of ammoniawater. The relationship
between pH and
dissolution rate of copper was studied at O.2mol/kg
reaction rate was found. On the contrary positive re-
Cu(II) concentration, 50'C, rotation speed 500
lationship was found between the dissolution rate and rpm. The
rotation speed at 50 and 70'C. For example, the dis-
results are shown in Fig. 6. The dissolution rate has
maximum
point between pH l0.5 and 11.O and starts to
solution rate at I OOOrpm is 2.5 times bigger than that
decrease at pH higher
than 11.O. This tendency cor-
at 250rpmat 50'C. responds to the stability of cupric amminecomplex
To study the relationship between the dissolution rate
expressed by pH-log[Cu] diagram23~26) completely.
and rotation speed in more detail, measurementsunder
After the experiment, the dark brown film of CuO
higher temperature such as 90'C and higher rotation was
formed on the surface of copper sample at pH 12.
speed such as 3OOO rpm were carried out. The exper-
imental results are summarizedin Fig. 5. The Y-axis is 3.4. Effect of Anion
the dissolution rate of copper, and X-axis is the square The effect of anion on the dissolution rate of copper
root of rotation speed. It can be seen clearly that a linear wasinvestigated. The results are summarlzedin Table 3.
relationship betweenthe dissolution rate and square root As copper is separated from the steel scrap, the
of the rotation speed exists even at such a rotation speed experimental work of pure iron dissolution
was also
of 3OOO rpm. This suggests that the dissolution rate was carried out. The supply sources of
copper are CuC12,
determined by the diffusion rate of the complex. In other CuC03•Cu(OH)2and CuS04, and that of anion are
words, the chemical reaction rate is
muchfaster than the NH4Cl, (NH4)2C03and (NH4)2S04. Various experi-
diffusion In this study,
rate. it
was confirmed that the mental works have been carried out changing the

C 1996 ISIJ 524

 ISIJ International, Vol. 36 (1996). No. 5
Rotation speed (rpm)

o 500 1000 2000 3000

12
pH= 9.8
Po =0 2kg /cm2
~lf"II'~10,•J~
,D 10
~
~~
D~]T = 6M
oo~~
L~~ 8 o 90'C, [CuSOJ=0.8M
o ']~ I 70'C, [CuSOJ=0.8M
Q,~~
cseo 6 o 50'C. [CuSOJ=0.8M
h~~
l:~rl X 50'C, [CuSOJ=02M
o
.*
'o
Sx
~S\-
4
iS 2 Fig. 5.

Dissolution rate of copper square

O ve,'sus

O 10 20 30 40 50 60 root of rotation speed.

L,2
Rotatlon speed (rpm)

07 80 Concentration of SO~~(mol I l)

o o
e)
0.6 o o6 OS 0,4 0,3 0.2 O,
l o 500
~
O* 6,0 rpm
Or~
O~" 0.5 0.8 pH= 9.8
t~N'
O~ 04 oo o U~]T = 6 M o~
~
i:~
Cu l'~~o 15- Po = 0.2 atm
~+_
c~' o 500 rpm
4,0
8!) ~~,,:.

06
[CuSOJ= 0,2 M
heJ) P02= O.2 atm D\l]T=
l:~fl
~~ 0.3 oo~ Cu2+ 0.2M 164 - M
2.78
O CuS04 0,2M Q
'C:)
ooe ~~j:~
Temp. 50'C rCl
~~ [SO: I= 0.6 M
~~
.-
~5 0.2
c 2,0
u_
o~'o
,n~':cLo

0.4
500 rpm
c P02O.2atm
~ O.
l e->e :sx
~5~ 0,2
E"
pH9.8
c
O o ~ Fe
85 9.0 l0.0 ~O
pH
5 Il O 11 5 12 O
o ~
o OI 0,2 0.3 O4 0.5 0.6
Fig. 6. Effect of pH on the dissolution rate of copper.
Concentration of Cl~ (mol I l)

Fig. 7. Effect of Cl and S0~- on the dissolution r'ate of Cu

Table 3. The effect of anions on the dissolution rate of cop- and Fe.
(
per x 10~ 3 kg/m2 s) at [CuS04] =0.2 mol/!, 500
,

rpm, pH=9.8, Po,=0.2 kg/cm2, [N]T= 1.92.8 Concentration of CO~-(mol / l)

mol/!.
06 O.5 0.4 O3 0.2 O.
l o
500 rpm
[NH+Cl] [(NH4)2C03] [(NH4)2S04] h
O.
8 pH= 9,8
&
i:~
oQ1;~
Cu o
---~~o----'*+~
Po = 0,2 atm
o [CUSOJ= O2M
[CuCl2] 0.80 0.8 1 0.58 ' 0,6
0.2 mol//
++ + o~
o
[N:]T= 157 - 2.20 M
+ [CO:~~ = O6M
~l:~
m~{eJ)
[Cll
[CuC03 Cu(OH)2] ' 0.75 0.60 0.60 0.4
o~ 'o
O.
I moll! F,
~SJ~
[CuS04] 0.74 O.7 1 0.47 u'
'n
0.2
0.2 mol// ~i Fe
+
+ +, + : The dissolution of Fe was observed.
o \
O OI 0.2 0.3 0.4 0.5 o6
-: The dissolution of Fe was not observed. Concentration of Cl~ (mol I l)

Fig. 8. Effect of Cl~ and C023 on the drssolutron rate of Cu

combination of the above two different kind of materials. and Fe.
The pHvalue waskept constant by adding and adjusting
the amount of ammonia. The difference of the total carbonate.27,28)
nitrogen content between the solution is about I .9-2.8; More precise experiment are carried out. Figures 7
also, the species and the total amount of anion are a and 8 shows the effect of concentration of Cl~lSO~-
little different. The accurate comparison or analysis is and Cl~/0~ - on the dissolution rate of both copper and
not possible, Nevertheless, the following two points can iron. In both cases, the higher concentration of Ci~
be made. resulted in the higher dissolution rate of copper. It
can
(1) The existence of chlorine ion promotes the dis- be seen clearly that the existence of C0~~anion makes
solution rate of copper; while the role of the sulfate improve of resistivity of corrosion of iron.
ion is just the opposite. The dissolution rate of copper
in the case of using CuC12-NH4Cl is twice
as high as 4. Discussion
that using CuS04-(NH4)S04.
4.1. Principle
(2) In the case of pure iron dissolution, the existence
of chlorine ion makes the dissolution reaction occur. Whena
copper is exposed to ammoniacal solution,
the major anodic reaction taking place is
However, when the chlorine ion and the carbonate ion
coexist, the pure iron does not seem to dissolve in the 3Cu +4NH 2[Cu(NH3)2] + + 2e~ .(1)
solution, possibly because of the formation of iron

525 O 1996 IS]J

 ISIJ International Vol, 36 (1996), No. 5
where Cu' denotes copper alloy. The reduction of dis- Dissolution rate of copper can be derived from this
solved oxygen equation.
l_ v O62AD2/3 1/6col/2(CA,o~CA,s) ...(9)
H20+ 02 + 2e 20H .(2) ' .. ""'
2 . .. . . .. . .

where, i: Current to the electrode (mol/cm2 s) ,

isthe cathodic reaction in copper-free solutions. In the A: Contact area between electrode and solution
presence of oxygen, cuprous ions are converted to cupric (crn2)
complex ions by the Reaction (3). D: Diffusion coefficient of diffusion material
(cm2/s)
2[Cu(NH3)2] + + l Dynamicviscosity of
_2 02 + H20+ 4NH3 v:
(~)
: Rotation speed of electrode (rad/s)
solution (cm2/s)

= 2[Cu(NH3)4] 2+ + 20H .. . .. . . . .
.(3) CA,o : Concentration of diffusion material
(mol/cm3)
According to the fact9) that the oxidation from cuprous
ions into cupric ions is
CA,s: Concentration of diffusion material on the
faster than that from Cu' into
electrode surface (mol/cm3).
cupric ions, and that dependency of partial
oxygen In our experiment,
pressure on the leaching rate is higher than that of stirring
it is confirmed that the dissolution
speed and temperature in copper-free solutions, the rate rate of copper is proportional to the square root of
rotation speed at the diffusion control region (above
determining step may be considered as the cathodic
reaction expressed by Eq. (2). 40'C, O. 1l .O mol/1 [CuS04]). Therefore dissolution rate
is considered to follow Eq. (9)
The cupric complex ion is reduced again at the copper where diffusion material
surface since the equilibrium corresponds to the cupric amminecomplex.

[Cu(NH3)4]2 + + Cu' 4.4. The Rate Equation at Copper Oxide Formation

= 2[Cu(NH3)2] + ..........
(4)
Region
is to the right in ammoniacalsolution.
shifted
Whenthe concentration of Cu(II) is over mol/1, the I
With continuous air (or oxygen gas) bubbling, Iarge dissolution rate decreased sharply in Fig. 2. This is
amountof Cu(II) amminecomplex is considered to work possibly because of the formation of
copper oxide. The
not only as oxidant (Eq. 4) but as electron transport formation of cupric oxide on the reaction surface due to
mediator (Eq. 3) in the Cu-NH3-H2002 system.9'17)
CuOprecipitation can be predicted by the solubility
4.2. Dissolution Rate of Copperat the Chemical Reaction constant Kc~o as follows.
Controlled Step
CuO(S)+ H20(1) Cu2+ (aq) + 20H- (aq) ..
(lO)
The equation for the dissolution of copper can be
predicted from Eqs. (1) and (4), in which the dissolution Kc~0=[Cu2+][OH-]2 ...................(ll)

rate of copper is considered to be limited by chemical FromSmith's evaluation,17) the concentration of free
reaction at the temperature below 30'C. cupric ion can be related by total cupric ion at the surface
by Eq. (12).
v = klS[NH3]'" + k2S[Cu(NH3)~+],, ............(5)

Cu~+
where, k: Rate coefficient [Cu2 +]
_ (1 2)
S: Contact area between electrode and solu- ~ ~pi[NH3]i "" . . .... ....

tion.
(pi
In the preliminary
: stability constant of cupric amminecomplex)
experiment, Reaction (3) is found
The term Cu~+ can also be related to the bulk cupric
to be very slow comparedwith Reaction (4). Therefore ion by Eq. (13).
Eq. (5) can be reduced as follows.
v=k2S[Cu(NH3)~+],* ..........(6) Cu2+ Cu~+ R ....,.....(13)
.....
kd """
Hence the rate constant can be expressed generally as
follows where Ris the reaction rate (kglcm2 , s) and
kd
= 0.62D2/3v ~ 1/6co 1/2 (14)
k=Aexp - E
.. . .... . . .

(7)
RT Equations (1 1) to (14) give

From the experimental results, the order of reaction n

2+
CuO R
was nearly Oand the apparent activation energy was - kd
about 53 kJ/mol. Kc~0= [OH]2 .............(15)

fii[NH3]i
4.3. Rate of Copper at Diffusion Controlled
Dissolution i=1
Step
Rearrangement of these three equations gives the
Levich29) introduced the electrode reaction rate for the
following expression for the dissolution rate of
flow system by the rotating disk electrode as follows: copper
with CuOformation on the reaction surface.
i=0.62D2/3v~ 1/6col/2(CA,o~ CA,s) """"""(8)

C 1996 ISIJ 526

 ISIJ Internationai, Vo[, 36 (1996). No. 5
7) E. J. Duggan: Trans. AIME, 106 (1933), 547.
R::=kd(Cu2+_Kcuo
~[OH-]2
pi [NH3] i
(16)
8)
9)
W. J. Yurko: Met.
J.
Soc. Conf, 49 (1966), 55.
Halpern: J. Electrochem. Soc., 100 (1953), 421.
l O) J. Fisher and J. Halpern: J, Elecn'ochem. Soc., 103 (1956), 282.
This equation predicts that dissolution rate will l l) J. Halpern: J. Met.,
9(1957), 280.
decrease with increasing pHor decreasing free ammonia l 2) J. Halpern, H. Milants and D.
R Wiles: J. E!ect,'oche,n. Soc.,
106 (1959), 647.
in the region of CuOformation.
13) R. W. Lane and H. J. McDonald: J. Am. Chem.Soc'., 68 (1946),
All the calculated rate curves from Eqs. (9) and (16)
l699 .

were fitted in Fig. 2. They showedgood agreement with l4) B. C. Y. Lu and W. F. Graydon: J. Am. Soc., 77 (1955), 6136.
experimental data. 15) S. Uchida and I. Nakayama:J. Soc. Chenl. Ind., Japan (Suppl.),
36 (1933), 635, as reported in Diffusion and Heat Transfer in
Chemical Kinetics, by V. A. Frank-Kamenetskii. Plenum Press,
5. Summary NewYork, (1969).
Dissolution experiment of copper into cupric ammine 16) E. Yamazaki: TohokuImperial University, Sendai, Japan, Science

solutions
Reports. Pllysics. Chemist,y. Asl,'on., 9
(1920), 169, as reported
was carried out and following results were in Diffusion and Heat Transfer in Chemical Kinetics, by V. A.
obtained. Frank-Kamenetskii. PlenumPress, NewYork, (1969).
Under the condition of rotation speed 500 rpm,
(1) 17) K. A. Smith, G, W. Lower and W. A. Hockings: Int. Symp. on
Po. O.2kg/cm2 and pH 9.8, the rate determining is Hydrometallurgy, ed, by D. J. I. Evans and R. S. Shoemaker,
(1973), 265.
chemical reaction step at temperature from 10 to 30'C
and masstransfer is the one at more than 30'C.
18) J. Sedzimir and M. Bujanska: Hycl,'on7etcd!u,'gy, 3 (1978), 233.
l 9) H. Majima, S. Nigo, T. Hirato, Y. Awakura and M. Iwai:
(2) It
was found that, amongvarious factors that S/7igen-to-So.-ai, 109 (1993), 191 .

affect the dissolution rate, the rotation speed was the 20) S, Nigo, H. Majima, T. Hirato, Y. Awakura and M. Iwai:
Shigen-to-Sozai, 109 (1993), 337.
most important. Themaximum dissolution rate of copper
21) S. Uchida, R. Suzuki, Y. Umetsuand M. Tokuda: Proc. Book
obtained in this study was I .O x 10 ~ 2 (kg/cm2 s) at 90'C,
.

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527 C 1996 ISIJ