CopPEr electrorefining and electrowinning electro- Iytes are used in the production of approximately 9 nillion tons of metallic copper per year, 95 pet by electrorefining and 5 pet by electrowinning. The den- sities, viscosities, electrical conductivities and heat ca- pacities of these electrolytes affect the purities of the Product metal and the energies consumed by the refining and winning processes." Recent papers have reported measurements of densities, viscosities and electrical conductivities for the systems CuSO,-H,0? and CuSO,-I1,50,-H,0.! This paper extends the work tocover solutions containing copper, nickel, arsenic, iron and sulphurie acid in the ranges: ElctrorefiniogEleetrowinning Range Range Clempersture Temperature 30-70°C), 20.0°C), opp concentration 0-60 & E55 g dm “Free'H,SO, concentration 165-223'g dm? 10-165 din? Nickel conetneation O20gdm —“O4 gdm Asseniceoneeatrtion Oiogdm? Od Edm? (Ferrous) Iron concentration OS gdm? — 0-20 gdm”? All concentrations in the paper are expressed (Ta- ble) in grams dm~? of solution at 20 °C, Free sul phuric acid is defined as the amount of H,S0, added to the solution or the acid equivalent to the SO}" ions remaining after all copper, nickel and iron ate removed as CuSO, + NiSO, + FeSO, ‘The properties measured during the study are tabu= fated as raw data (Tables II to V) and they are also interpreted where possible by linear equations of the ‘ype, Property = K'Xa, « (species concentration), + br where K, a and b are constants and where [species concentration} isin g dm~? at 20 *C and ris temper- ature, |. DENSITIES 8) Experimental Densities were measured by means of 25 ml and 430ml pyenometers (Fisher Scientific, Montreal) with at least three measurements being taken for each reported. DEREK C. PRICE, formerly Researeh Avsodale, Departncal oF Mising and Metaursicl Engineering, Mal Univers Mor, teal, Canada, i now with Duval Corporation, Tucson, Az 88712. WILLIAM G: DAVENPORT is Profesor of Metallurgy, Depart en of Mining and Metallurgical Engineering, MeCil Unicel, Montes, Canad, Manuscript submited Febrony 10,1961, Densities, viscosities, electrical conductivities an copper, nickel, arsenic, iron and sulphuric acid in the concentration ranges of copper ¢lectrorefining and electrowinning clectrolytes have been measured. Equations are presented for calculating these properties as a function of electrolyte composition and temperature, ISSN 03602141811 21-0639500.2510 R METALLURGICAL TRANSACTIONS B © 1981 AMERICAN SOCIETY FOR METALS AND VOLUME 125EUACESBisfE 5ai:C2bdNICAL. THE METALLURGICAL SOCIETY OF AIME Physico-Chemical Properties of Copper Electrorefining and Electrowinning Electrolytes DEREK C. PRICE AND WILLIAM G. DAVENPORT id specific heats of solutions containing. value, The reproducibilities of the results were 0.0001 ‘gem or better. The measurements gave specifie -ravity values which were then converted t0 absolute densities from published? water density values, by Results and Discussion ‘The density results are listed in Table Il. They may be represented 20.01 g em~? by the linear equation: absolute density, g em~? = 1.022 + 10-9(1.04[As] + 224(Cul + 2371Fe] + 055(11,80,] + 2241Ni) ~ 058) m ((As}, (Cul, [Fe, [H,S0q, [NiJ; concentrations g dm-? 20°C; # temperature °C), which shows that density is increased by all additions to the solution and decreased slightly by increasing temperature, The experimental results are in good agreement with the previous study of CuSO,-H,$0,-H,0 electrolytes? ‘The results arc also in good agreement with the ‘measurements by Claessens for Cu, Co, Mg, Na, Al, H,SO, electrolytes. The combined results of Claessens and this work may be represented by the equation: 2[Cu + Co + Fe + Na+ Ni absolute + IAs} density = 1.02 + 10-> + 3[Mg] 002g em~ + 6fAl] + 0.5(H,S0,] =06 °C. 2) 2. VISCOSITIES 4) Experimental Viscosities were determined with a standard Can- non-Fenske routine viscometer (Fisher Scientific, Montreal) using distilled water as the standard solution. ‘The precision of the results (Table III) s estimated to be 0.001 centipoise, bb) Results and Discussion, Price and Davenport have reported measurements of viscosities in the CuSO,-H,S0,-H,0 system? while ‘Claessens has examined these solutions with additions of Co, Mg, Na and Al. Also, a number of Russian workers have studied additions of Ni,” K,! Li? Na,!*Cs and Rb" and Fe and Za,” LIBRARIAN INFORMATION GENTRI P.O. BOX 585 BOKSBURG 1460‘Table L. Compositions of Synthetic Electrolytes (a) lectroreining Range ‘Table I. Densities (g cm (a) Elactrortining Solutions mn Ssiation FFemperiwe °C halon Comporion gga 20-6 Naber — Nembe TETIS,NE RI Tao vais ra ne) 3 R2 Lio “i803 RE Be te Ra ats Lise BS ne) a) Re {sor nee Ra Sonam 2 ow Rs 12033 aves eS iss ies ie RR alee es eR sl men ame) ee 1859 ry kr Meas 13815 1s ee o ms 8k 12008 ‘01 Ro ows Sie meet aa ‘on R10 3 its om 2 RR 2a 1359 mi oom SB 1 30 RD Som 0k 12150 12084 Ri @ wi o m2 1 Be 1208 190 Ru ® Ws 2» 9 2 BB Lams Ge Bs o om % 3 Rl 12599 a9 ie oR EE ‘Table |. Compositions of Synthetic ‘able I, Densities (g em) (b) Electrowinning Solutions cevinnie Renae Seaton Tempartre 7 0 Rena Number 20 30 40 0. a Sakon Componon dat 2 wi hea 0150 o10s toe Nenber___Ce HSQL =e W2 ines 10570 10068 wi > 4 Piaeanoa (ioe er vaste 1083 wi 5 OS 3 2B Wa toast vane toes Ww 5 i o's aa 8 ws 10648 ost 5 us a ° we 1.0625 1.0543 1.0839 ws on) 24s WT hte ‘0s we BOS i $b Wh Tete ian wr BS 6 i 8 ws ie 1 110 a 5 us . ° a wid 1.1283, 1.1070 we % 1 ow LIS wo BG bf Bown tee wit wi Bo a 2S wp Lo L057 oe s 165 2 U : wis as77 1.1357 Wis 3s 10 0 1 5 wis 1.2068 1.1840, wa 3 OS 3 bg Wie eet aoe tis Ms BOS 2 4 ® win L261 wie Ee i aaeemomeryaaee tie tng wr 6 4 ow Lou toot ws Ss 6 $5 as tm wD Sous i 2 8 3 wa 145s 19 wo S18 ° > 9 MH se wat sa 1g MB at tess wa S 6 2 1g “enstatizaton 13580 was Sous Ree wa 5 is ‘ i 20 The viscosities measured in the present investigation (164 values) may be represented 0.1 centipoise by the equation: — absolute viscosity (centipoise) =0.70 - 10° (46 IAS] + 83 [Cu] + 88 (Fe) + 1.6[H,S0,] + 10.0 [Ni] ~ 180 M8) 640—VOLUME 128, DECEMBER 1981 Slightly more precise equations can be developed for tlectrorefining and electrowinning electrolytes sepa- rately if this is required. ‘Viscosities of complex ionic solutions can be ex- pressed in terms of the ional concentration: re2oze 4 ‘Where C, is the concentration of ion i in gram ions per ‘dm? and Z, is the valence of ion i. The importance of this parameter is its potential applicability to industrial electrolytes which contain a great many impurities. In the present case METALLURGICAL TRANSACTIONS B zeougmS z‘Table Ii. Absolute Viscosities (centipot Electroretining Solutions Sohstion ‘Number 50 Tae 08) 1055 ors 1a vos 13, 1387 1.180 tr Nas 1345 1m 158 1483, 1a ‘Tempecature IIL Absolute Viscosities (centipolse) (o) Elactrowianing Solutions Sointon Number 20 0 @ wi 1308 ons oan w2 36 om ste ws be or? 55 wa 1306 O73 610 ws 12% cxystalization W613 0664 063 waa O76 Oat we 13 O96 oe Ws 160 oss 0730 wo 1575 oss 0703 Wil 1496 oss 0756 wo ins 0909 0776 wis 1507 os ows Wie 193 osat 789 Wis 2155 10s 0830, wis 1866 037 087 wir 6s 0865 729 wis 217 Ls 094s wis 1392 028 oes wa0 2265 119 o9T1 war ama os om wa 2s ton ala wa 24s tos oie wre “cystlizaion” 768d 1208 T= 2M aso, + 2M y+ Mo, + 8M pe + BM yy 65) , moles of i dm~), as is plotted against viscosity in 1. It can be seen that there are good correlations for both the present experimental results and the results of previous studies, in spite of the very large range of compositions being considered. It appears to be an tacellent method of representing wide ranges of elec trolyte data METALLURGICAL TRANSACTIONS B 1s : 3 a i Ge <0 oe 2 fe PS ost +, & o ¢ ° 7% © = Fi. I—Viscoses of copper eiecrotes as a function of ional concentration (Eq. (4). Good apremeat between the present and previous work isshowa. Present Work; Price De Claesens; © Gorbachev"; @ Kocherov" A Pomoto" 3. ELECTRICAL CONDUCTIVITIES ) Experimental Electrical conductivities were measured with a Tacussel (Lyon, France) conductivity meter type CD 6NG in combination with a type CMO4 G/R high conductivity cell. The cell was calibrated with an N KCl solution, the conductivity of this solution being calculated from extrapolations of the results of Jones and Prendergast” as reported in a previous paper.? The precision of the calculated values (Table IV) is esti- ‘mated to be + 1/2 pet of the measured value. by Results and Discussion The electrical conductivities ofthe experimental electrorefining solutions may be represented +5 pet by the equation: 1 conductivity (Giemen em) = 32+ 109 x (13 IAs] + 73 [Cu] + 45[Fe} = 5.6 [H.S0] + 9.6 [NiJ~ 14.61) (6) Conductvities ofelectrowinning solutions are not well described by linear equations like Eq, [6]. They are best interpreted directly from the data tabulated in Table IV. VOLUME 128, DECEMBER 1981—641Table IV. Electrical Conductiities (stemen m1 (a) irorefining Solutions, Solution Tempers Number i RI 047 Ossi 0395 R2 osm 0653 oes RS 0630 0740 O768 Ra om 0804 089 RS os os1s 0603 RG 0381 ots oer RT bees oni RS 0586 oan RS 503 ose Rio Osse 0? RU oss 0603 Ri 00s 067 RI oso os6i Ria 047s sai RIS 0320 0605 RIG 0386 0.66 Tobi Solution Number wi wa wa wa ws we wi we ws wio wit we wa wis wis wis wir wis wis w20 wat wn was wae Considerable data on the conductivity of electrore- fining solutions exist inthe literature, the most extensive being due to Kern and Chang"* and Skowronski and Reinoso."” In addition, Claessens" has examined the effects of Al, Co, Mg and Na on CuSO,H,80, solu- tions, These results plus those of the present work may be summarized for electrorefining solutions + 10 pet by the equation (62VOLUME 128, DECEMBER 1981 1 [Co] 4 2[A5 + Me] + 31a] 1 +9{Cu) 33.2 + 10-4 + I [Ni) + 12[Fe] ~ 6{HS04 1S m conductivity (siemen em=}) Itean be seen that with the exception of Fe, the coefficients in Eq. [7] are similar to those of the present work in Eq, (6) 4, SPECIFIC HEAT a) Experimental Specific heats were mensured by the method of cooling deseribed by Noakes" Firsly, water was placed ina thin copper beaker and was allowed to coal Inan airfilled calorimeter surrounded by a mixture of iceand water, The cooling path was measured as a function of time by means of chromel-alumel thermo- couple linked to a potentiometer and chart recorder. The procedure was then repented forthe electrolytes. The liquids were sired in all cases by a loweapeed eller, the heating effects of which had been pre- viously determined, The specific heat ofa solution was calculated from the times in which the solution and water fell from & specified temperature toa second specified tempera- {ure, usualy through a fall of 10 °C. The equation used for the calculation was: Patton + Cysuine *™*SSsoiner — Orca TAS # C, TBSSapuinr Danes where Brig 814 Baye re the respective times for the solution and water to fall the same amount of temper~ ature, The same container and the same volume of water and solutions were used forall experiments, The results are listed in Table V. b) RESULTS AND DISCUSSION The specific heats of both electrorefining and electro- winning solutions may be represented +0.2J g-!C-! by the equation: absolute specific Booch Beg PSS = 4.06 — 10-9 (6.710) + 1.7 (H,S0) + 6.7 [Fe] + 42 [Ni] - 139 io} Arsenic was found to have no signifiant effect within the precision of the present results and analysis. No previous work on heat capacities has been found in the literature but the present results can be compared with those of CuSO,-H,0 and H,S0,-H,0" solutions as, has been done in Fig. 2. As ean be seen there isa good agreement in spite of the huge variations in solution composition. METALLURGICAL TRANSACTIONS B NyTable V. Spocitic Heats (4 g-1 °C (a) ctroretining Solutions. 3a 35 Ba 35 36 36 33 35 34 35 36 34 34 3a ba 34 36 33 33 34 34 a3 34 33 38 35 33 33 ba 33 3a 3a 33 33 as 32 32 Fe 33 33 34 22 32 ul Table V. Specitic Heats (J ¢* °C) (0) Eiectrowinning Solutions “Temperature Range “C Be is se oo _ em mene a3~«< St BS eye 393k daa 37003738 wio 360037 3B aa wi sleet s0ee sel 37h a6) wie 3603888 wis 350033 SBS wir 36037 3k aga wis M433 RSS wat Se eos ea wa ee ee ee eh Ma toe Fig. 2—Speife heats of electrowinning lectolyes as compared to those of CuSO, H,0 and H,S0,-H,0 Solutions.” Decreasing the ‘proportion of HO inthe solution is shown to enuse a decreate i ‘pesfc het METALLURGICAL TRANSACTIONS B GENERAL DISCUSSION AND CONCLUSIONS ‘The equations developed in this work show that the ‘metals in copper electrolytes behave in a consistent ‘manner, e. they all: 1) increase density and viscosity; 2) decrease conductivity and specific heat. Density and viscosity are increased by the addition of large, high molecular weight metal cations and SO; anions to the solution while conductivity is decreased by the presence ‘of large metal cations in place of small, mobile H* cations. Heat capacity per unit volume appears to ‘remain relatively constant but since the addition of ‘metal sulphates increases density, specific heat per unit mass of solution decreases, Sulphuric acid additions affect density, viscosity and specific heat in a similar manner to metal sulphate additions. However, sulphuric acid increases electrical ‘conductivity rather than decreasing it because it sup- plies highly mobile H* cations to the solutions As would be expected, inczeases in temperature increase electrical conductivity and fluidity due to increased mobility of the ions. Density and heat capac- ity are only minimally affected, ‘The actual quantitative effects which sulphuric aci metals and temperature have on the electrolyte prop- erties do not appear to be predictable—resort must be made to experimental data and empirical equations, REFERENCES 1. D.C: Price and W.G. Davenport: Metal Trans B, 1980, ol 11B, pp. 15968. 2. D.C Price H. Larsson ané W. . Davenport: Nowe J. de ‘Cami, 1980, sel 4 pp. 7-9. 3, Viscosity of Elecrahier and Related Proprt, The International Encylopedia of Pyscel Chemis and Chemical Phys, 9.3, Pergamon Pres, Oxfor, 1965 ‘Univesté de Lown, 1967 5: P,Chaesens CL Fenent and R Breckpot: Bull. Soc, Chem. Belgs, 1988, ol, 71, pp 212-21 6. V.I'Kocharey, Me Rondrateva and AL. Levin: Ten ‘Meal, 1968, v0.7, pp. 29-20. 7. A.V, Pomosov and GN. Prshvityna; fe, ¥ysth, Ucn Zane 1964, vo. 7, p. 45-50 8. S.¥-Gorbachev and R. M. Vaenin: Zh, Fz, Khim, 1954, vol. 28 pp. 135-46. 9. S°V. Grbacher and RM. 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