Hydrometallurgy, 21 (1988) 1-7 1

Elsevier Science Publishers B.V,, A m s t e r d a m - - P r i n t e d in T h e Netherlands

D e n s i t i e s and Viscosities of CuS04-H2SO4-H20

Solutions

J. H O T L O S a n d M. J A S K U L A
Department of Physical Chemistry and Electrochemistry, Jagellonian University, 30 060
Cracow (Poland)
(Received April 30, 1987; accepted in revised form October 26, 1987 )

ABSTRACT

Hotlos, J. and Jaskula, M., 1988. Densities a n d viscosities of CuSO4-H~SO4-H~O solutions. Hy-
drometaUurgy, 21: 1-7.

Density and kinematic viscosity data for the ternary system CuSO4-H2SO4-H~O were deter-
mined over wide ranges of concentrations (0.2M < c(:,,so, < 1.15M, 0.25M < c.~so4 < 2.5M) and
temperature (25 ° C < T < 60 ° C ). T h e results are described using empirical functions.

INTRODUCTION

Solutions containing copper sulfate and sulfuric acid are interesting princi-
pally because they have been used in industrial copper electrorefining for over
100 years and also in electroplating baths. To describe the processes occurring
in these solutions it is necessary to know a number of physico-chemical pa-
rameters, of which density and viscosity are of basic importance.
When investigating transport phenomena and thermodynamic equilibria in
CuSO4-H2S04 solutions, it became apparent that there was a lack of reliable
pertinent data valid over a wide range of component concentrations and tem-
peratures. The available literature data are dissipated and incoherent, and sys-
tematic determination of density p and kinematic viscosity u was required.

EXPERIMENTAL

Densities and viscosities were determined for 38 solutions containing CuSO4

and H2SOa at four temperatures, 25, 35, 45 and 60 ° C.
Copper sulfate pentahydrate p.a. (POCh Gliwice) additionally twice recrys-
tallized, sulfuric acid p.a. (Merck) and double distilled water were used. The
concentration of copper sulfate was varied between 0.2 and 1.15 M, and that
of sulfuric acid between 0.25 and 2.5M. The solutions were prepared in such a

0304-386X/88/$03.50 © 1988 Elsevier Science Publishers B.V.

way that their molar concentrations at 25 ° C were at the points of the planned
concentration matrix. The concentrations of the components were determined
independently by potentiometric titration with E D T A or N a O H , respectively.
Densities of the solutions were measured using 25 ml pycnometers equipped
with their own thermometers (at 25 and 35 °C) and 10 ml pycnometers (at 45
and 60 ° C ). The pycnometers were calibrated with four times distilled water at
various temperatures. The temperature was maintained within + 0.5 ° C. The
experimental deviation was + 1 k g / m 3.
Kinematic viscosities were determined with a capillary viscometer with sus-
pended level (Seidert-Deckert viscometer), calibrated with water. The efflux
time varied within the range 124.26 + 0.07 s at 25 + 0.1 °C to 66.02 _+0.05 s at
60 + 0.1 ° C. The viscometer was supported in a thermostatic water bath, the
temperature of which was maintained within 0.1°C. For each solution, two
independent sets of experiments have been made and in each 5-10 efflux times
were measured. The reproducibility of the measurements was perfect (0.1% ),
but taking into account errors which come from the temperature control in-
accuracy and from using the simplified formula (with no corrections) for vis-
cosity calculations, the error of viscosity determination was estimated to be
about 1%.

RESULTS AND DISCUSSION

Density

There are many papers devoted to determination of the density of either

CuSO4 or H2SO4 aqueous solutions. Very useful data and empirical functions
p(c,T) can be found in SShnel's paper [1].
Fewer data on densities are available for the ternary system CuSO4-H2SO4-
H20 [2-6], and only a few solutions have been examined. Recently, Price and
Davenport [7 ] have published an extensive paper devoted to determination of
density in two ranges of concentration and temperature, corresponding to so-
lutions used in electrorefining (large amounts of copper and acid, t > 50°C),
and to those used in electrowinning (a small amount of copper sulfate,
t < 40 ° C ). Important ranges of concentration and temperature still remain for
which the density has not yet been measured.
In the present work, the densities of CuSO4-H2SO4 solutions in a wide range
of concentrations and temperatures were determined systematically. The re-
sults (Table 1 ) show that the density depends on CuSO4 concentration much
more than on H2SO4 concentration, and that the dependence on temperature
is relatively small.
All the density results were described as a function of three variables:
p (X, Y,T) = ( K + L × X + M × Y) × exp (Ep/T) (1)
TABLE 1

Densities p and kinematic viscosities u of solutions in the system CuSO4-H2SO4-H20

mcuso~ mH~s04 Densities (kg/m :~) and viscosities (m2/s)

(mol/kg) (mol/kg)
25°C 35°C 45°C 60°C

p uXIO 6 fl PX10 6 p uXIO 6 p uXIO ~

1.158 0.256 1187 1.52 1181 1.25 1175 1.03 1166 0.778
1.004 0.256 1166 1.42 1159 1.16 1155 0.938 1142 0.727
0.854 0.255 1143 1.33 1137 1.08 1133 0.891 1122 0.669
0.698 0.256 1121 1.24 1116 1.00 1110 0.825 1098 0.640
0.550 0.255 1099 1.17 1094 0.935 1087 0.779 1080 0.604
0.401 0.254 1075 1.10 1071 0.884 1064 0.730 1057 0.569
0.199 0.255 1044 1.00 1039 0.827 1036 0.674 1028 0.527
1.179 0.515 1199 1.56 1194 1.30 1188 1.04 1177 0.798
1.015 0.512 1177 1.46 1172 1.17 1166 0.972 1153 0.732
0.863 0.508 1156 1.38 1150 1.10 1143 0.908 1133 0.695
0.709 0.511 1133 1.28 1130 1.02 1124 0.843 1117 0.657
0.557 0.511 1111 1.21 1107 0.974 1099 0.793 1095 0.615
0.408 0.514 1089 1.11 1084 0.893 1080 0.737 1068 0.580
0.202 0.511 1059 1.03 1054 0.831 1052 0.688 1042 0.541
1.024 0.826 1194 1.52 1189 1.20 1184 0.978 1172 0.754
0.873 0.831 1173 1.43 1168 1.12 1163 0.923 1152 0.707
0.721 0.830 1149 1.31 1145 1.05 1139 0.866 1130 0.674
0.563 0.826 1128 1.24 1123 0.997 1116 0.819 1108 0.640
0.409 0.823 1107 1.16 1100 0.93(I 1095 0.770 1089 0.606
0.204 0.832 1078 1.07 1072 0.871 1070 0.724 1061 0.564
0.815 1.061 1175 1.38 1169 1.12 1168 0.913 1155 0713
0.901 1.324 1198 1.50 1194 1.20 1191 0.983 1174 0.764
0.732 1.320 1175 1.38 1172 1.11 1168 0.906 1153 0.704
0.576 1.328 1153 1.30 1150 1.04 1146 0.854 1133 0.665
0.421 1.316 1132 1.22 1126 0.978 1123 0.808 1111 0.632
0.208 1.330 1105 1.13 1099 0.913 1094 0.758 1084 0.580
0.908 1.828 1223 1.55 1217 1.26 1210 1.02 1196 0.794
0.741 1.836 1200 1.46 1194 1.18 1192 0.961 1177 0.746
0.593 1.860 1179 1.38 1176 1.11 1169 0.906 1160 0.708
0.427 1.820 1158 1.30 1153 1.04 1147 0.860 1134 0.673
0.212 1.839 1131 1.19 1125 0.971 1120 0.815 1108 0.615
0.764 2.383 1227 1.58 1221 1.25 1219 1.04 1200 0.796
0.596 2.362 1205 1.48 1201 1.18 1192 0.963 1181 0.744
0.442 2.396 1184 1.38 1178 1.11 1175 0.914 1159 0.716
0.217 2.370 1157 1.28 1152 1.04 1144 0.859 1131 0.656
0.613 2.813 1225 1.56 1218 1.25 1212 1.02 1199 0.794
0.441 2.793 1203 1.44 1197 1.16 1191 0.956 1178 0.743
0.219 2.792 1178 1.34 1171 1.09 1161 0.902 1156 0.709
4

TABLE 2

Polynomial (1) coefficients, percent average (av. err.) and percent maximal (max. err.) deviation
of densities obtained experimentally and calculated using polynomial (1)

Kind of concentration used K L M av. max. err.

err. (%)
(%)
X - C u +÷ (g/l) at 25°C
Y-H.~S04 (g/l) at 25°C 841 1.95 0.48 0.14 0.50
X - C u S O 4 (mol/l) at 25°C
Y - H2S04 (mol/l) at 25°C 841 124 47 0.14 0.44
X - C u S Q ( mol/kg H20 )
Y - H2S04 (mol/kg H20 ) 846 118 39 0.19 0.62

where: p = density (kg/m 3 ), K,L,M= fitted coefficients; their values depend on

the way of expressing solution concentration (Table 2), X , Y = C u S Q and
H~SO4 concentrations (g/l) or (mol/1) or (mol/kg), T=absolute tempera-
ture, E/, = temperature coefficient; its value, Ep = 53, was found by using the
same procedure as for determining E in function (2).
Those investigating physico-chemical properties of CuSO4-H2SO4 solutions
have used different ways to express the solution concentrations. Thus com-
parison of values obtained by various authors is difficult or even impossible.
For this reason, the polynomial (1) was fitted three times to the experimental
data, concentrations being expressed in: mole/dm3, mole/kg of water, and g of
copper (or sulfuric acid) per dm 3. The resulting polynomial coefficients and
the average and maximal matching errors are shown in Table 2. The results
calculated by polynomial ( 1 ) agree very well with the data obtained by Claes-
sens et al. [4], Buzhinskaya et al. [5] and Price and Davenport [7], but they
differ a little from the values reported by Eisenberg et al. [3 ].

Viscosity

The papers quoted above, during the discussion of density of C u S O 4 - H 2 S O 4

solutions, are devoted also to determining viscosity. Additional data (for dilute
solutions) were presented by Asmus [8] and Brasher and Jones [9]. The re-
sults obtained by various authors show considerable discrepancies, especially
those of Buzhinskaya et al. [6 ] differ strongly from other results, some by more
than 10%. In their comprehensive paper, Price an Davenport [7] presented a
large number of experimentally determined viscosities and proposed an em-
pirical function V(Ccuso4, CM2so4,T) to describe them. Though this function
enables one to calculate the viscosity of a solution for various concentrations
and temperatures, the accuracy with which it describes experimental data
(within O.lcP at 20-40 ° C and 0.04cP above 50 ° C ) is unsatisfactory. Moreover,
the cited function must contain some error since it does not reproduce the
experimental data.
Beside the solutions investigated in the above-mentioned papers, there are
ranges of concentration and temperature in which the viscosities of CuSO4-
H2SO4-H20 solutions have not been measured. The present work attempted
the systematic determination of viscosity in this system.
The influence of the components concentrations on the viscosity (Table 1)
is analogous to that on the density, increase in CuSO4 concentration causing
a 3-4 times larger change in v than the corresponding increase in H2SO4 con-
centration. Contrary to the density, the influence of temperature is considerable.
Claessens [4] and Price [7] attempted to describe the dependence of vis-
cosity on concentration using "total ionic concentration", F, defined as F--- ~cizi,
assuming that CuS04 is fully dissociated and the H S O j ion is completely un-
dissociated. The proper description of the behaviour of viscosity in the inves-
tigated solutions in terms of ionic strength is much more complicated than
those proposed in [4] and [7], because in reality the H S O j ion dissociates to
a certain degree, whereas copper sulfate is not completely dissociated [10].
Undissociated species must also be taken into account.
The influence of temperature on viscosity was examined by plotting In v vs.
1/T, and it was found that in each case this relation was perfectly linear (cor-
relation coefficients > 0.999 ). This allowed the determination of values of "ac-
tivation energy" Ea; these lay within the range 15.02-16.53 k J / m o l and the
average value was 15.74 _+0.36 kJ/mol.
The E a values depend on solution composition, but considering the relatively
large error in their determination (average error estimated at 0.34 kJ/mol) it
is possible only to state that the "activation energy" tends to increase when
CuSO4 concentration increases. This agrees with the observation of Alamelu
and Suryanarayana [11] for solutions containing CuS04 and with those of
Claessens et al. [4] and Eisenberg et al. [3] for CuSO4-H2SO4 solutions.
To describe the present experimental data the following function is proposed:

v(x,y,T) /m2s-l= lO-11X (AO+AI x x + A 2 x y

+A3xx2+A4XxXy+A5xy2)Xexp(E/RT) (2)

where x is CuS04 molality (mol/kg H20), y is the H 2 S O 4 molality, and T is

absolute temperature.
The values of the coefficients AO-A5 and the value of E (which has the
physical meaning of activation energy) were determined in the following way:
( 1 ) the value of E, was assumed, and for all experimental data the value of the
expression v/exp (E/RT) was calculated,
(2) using the multiple regression method, the coefficients AO-A5 in eqn. (2)
were evaluated,
(3) the average error of approximation was computed,
(4) changing the assumed value of E, operations 1-3 were repeated in cycles
and the value of average error of approximation was examined.
The dependence of average error of approximation on the assumed value E had
a distinct minimum, which afforded the optimum value of "activation energy"
in C u S Q and H2SO4 solutions in the investigated range of concentration and
temperature. This value, 16.28 kJ/mol, agrees with the value obtained by av-
eraging E a for all 38 solutions.
Using the optimum value of E = 16.28 kJ/mol, the AO-A5 coefficients were
computed and had the following values:
A0--164 A 3 = 3 2
A I = 48 A 4 = 2
A 2 = 13 A 5 = 3

where the kinematic viscosity v is expressed in m2/s.

The experimental values and those calculated from the polynomial differed
by less than 2.5%, whereas the average matching error was 0.86%0.
Using the polynomial (2), the viscosity values for the compositions and tem-
peratures investigated by the other cited authors were calculated. Good agree-
ment was obtained with the results reported by Claessens et al. [4] and Arvia
et al. [6]; Price's and Davenport's data [7] were somewhat lower at lower
temperatures and somewhat higher at higher temperatures. Greater discrep-
ancies were observed for the data of Eisenberg et al. [3] (which were ques-
tioned by Price and Davenport) and for those of Buzhinskaya et al. [5] which,
as was previously mentioned, differed considerably from all the other reported
values.

ACKNOWLEDGEMENTS

The study was supported by a grant within a research programme 03.08 co-
ordinated by the Institute of Inorganic Chemistry and Metallurgy of Rare Ele-
ments in Wroc|aw.

REFERENCES

1 SShnel, O. and Novotny, P., 1985. Density of Aqueous Solutions of Inorganic Substances.
Academia, Prague, pp. 102, 296-298.
2 Holler, H.D. and Peffer, E.L., J. Amer. Chem. Soc., 38 (1916) 1021-1029.
3 Eisenberg, M., Tobias, C.W. and Wilke, C.R., J. Electrochem. Soc., 103{7) (1956) 413-416.
4 Claessens, P. Feneau, Cl. and Breckpot, R., Bull. Soc. Chim. Belges, 77 (1968) 213-236.
 5 Buzhinskaya, A.V., Kandyba, L.L., Kondrashova, P.S. and Migina, A.I., Zh. Prikl. Khim
(Leningrad), 47(7) (1974) 1486-1490.
6 Arvia, A.J., Bazan, J.C. and Carozza, J.S.W., Electrochem. Acta, 11 (1966) 881-889.
7 Price, D.C. and Davenport, W.G., Metall. Trans. B, 11B (1) (1980) 159-163.
8 Asmus, E., Ann. Physik, 36 (1939) 166-182.
9 Brasher, D.M. and Jones, F.R., Trans. Faraday Soc., 42 (1946) 773-779.
10 Freeman, R.W. and Tavlarides, L.L., J. Inorg. Nucl. Chem., 43 (10) (1981) 2467-2469.
11 Alamelu,S. and Suryanarayana, C.V., Acta Chim. Acad. Sci. Hung., 21 (1959) 333-341.