Identification and Thermal Stability of Copper(1) Sulfate

KIMVO VANA N D FATHIHARASHI

Dc,p~rr./riic~~ll
ofMi17i1igcrncl M~/c~lhr,lp?,,
Larcrl U n i ~ . c ~ r sQ
i / t~r.r.h ~ c1 0 . Qiiehrc
Received May 10, 1972

Anhydrous Cu,SO, was prepared and its X-ray diffraction pattern was established. Differential thermal
analysis. thermogravimetric analysis, and X-ray diffraction methods were used to study the effect of heating
in different atmospheres. The formation of Cu,SO, as an intermediate in chemical processes has been discussed.
- -
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Le sulfate cuivreux anhydre a ete prepare et son spectre de diffraction de rayons-X Ctabli. L'analyse thermi-
que diffkrentielle, I'analyse thermogravimktrique et les mkthodes de diffraction de rayons->( ont i t e utilisees
pour etudier l'effet de la chaleur sous des atmosph6res diffkrentes. La formation de Cu2S0, comme interme-
diaire dans des processus chimiques a kte discutee. [Traduit par le journal]
Canadian Journal o f Chemistry. 50, 3877 (1972)

Introduction Reagent grade Cu,O was not suitable for this purpose
because it contained CuO. Therefore, CuzO was freshly
While extensive literature exists for CuSO,, prepared from Fehling's solution (5). The other method
very little is known about Cu2S04(1 ). Druce and described by Brauer(6) and involving the reduction o f c u ~ r i c
~, . ,s -
Fowles (2) r e ~ o r t e dthat c~,so., was formed
during the dissolution ofmetallic cuin hot con-
acetate by -hydrazine was not ~ o ~ v e n i e nbecause
t
obtained was extremely fine powder and was difficultto
C;,O

wash. The purity of Cu,O was ascertained by X-ray diffrac-

centrated (2). Schenck (3) tion and thermogravimetricanalysis,
from vapor pressure tIIeasurements on the sys-
For personal use only.

Cu,SO, was then prepared according to Recoura's

tem Cu,S-CuSO, at 300-500 "C the possible
formation of Cu,SO, according to the equation
Cu,SO, was identified indirectly by quenching
the samples in water and filtering; the appear-
ance of metallic copper was indication of the
presence of Cu,SO, since it disproportionates in
water according to :
H,O
Cu2S0,-Cu + CuSO,
Recent work (4) showed that Cu2S0, is formed
during the reduction of CuSO, by Hz.
2CuS0, + 2H2 + Cu2S0, + SO, + 2 H 2 0
Cuprous ion can be readily formed in aqueous
sulfate solutions (1). For example, metallic
copper dissolves in CuSO, solution in absence
of air to form Cu' ions. CuSO, solutions can
be reduced by SO, o r C O under pressure at
about 90 "C to generate Cu'. However, it is
not possible to crystallize Cu,SO, from aqueous
solutions. The present investigation was under-
taken to acquiremore information on anhydrous
cu,so,.
Experimental
Prc,parar ion nrld Irk.nrifica~ionof'Cu,SO,
The starting material for preparing Cu,SO,
method (7) by the reaction of Cu,O with dimethyl sulfate:
Cu,O + (CH3),so, + cu,so, + (CH3)20
Cu,SO, so prepared was washed with ether and dried a t
60 "C in a stream of argon for 24 h ; it was pale beige in color.
According to Recoura, this material disproportionates in
water to give metallic copper and pure cupric sulfate solution
in equimolecular amounts, thus indicating that copper
existed in the cuprous form. Because of its sensitivity to
moisture it was stored in a desiccator. Reaction of Cu with
hot concentrated H,SO, did not yield any Cu,SO, as
claimed by Druce and Fowles (2).
Since the X-ray diffraction pattern of Cu,SO, is not
described in the literature, we present it in Table 1 as ob-
tained by powder diffractometry counter method from the
sample we prepared. Two hours were needed for obtaining
a diffractogram. The diffractogram showed the presence of
CuSO,, the amount of which was estimated from thermo-
gravimetric analysis in argon to be 25% as described later.
The presence of CuSO, in the sample seems to be inherent
to the method of preparation and not due to deterioration
by exposure to the air, because a sample exposed to the air
for 10 h contained the same amount of CuSO, as a freshly
prepared sample and no metallic copper.
Sttidies on Cu,SO,
Differential thermal analysis (DTA) and thermogravimet-
ric analysis (TGA) were used to study the effect of heating
Cu,SO, in different atmospheres. The DTA instrument was
a Stanton model Standata 6-25 with stainless steel sample
holder; weight of sample was about 200 mg. The T G A
instrument was a Fisher Series 100 T G A System; weight
of sample was about 20 mg. In both instruments a continuous
gas flow was maintained, and a heating rate of 10 "C/min
is Cu,O. was used.
 VO V A N A N D H A B A S H I : ON C u ( l ) SULFATE 3873

7
TABLE1. X-ray diffraction pattern
of Cu2S04,copper target (K,,
radiation), 0 in degrees, d i n
Angstrom units, 111, refer to height
of peaks, 1. = 1.5405 A I.0 7
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0.6 I I I I
ZOO 400 600 800
T E M P E R A T U R E ,"C

FIG.I . T G A curve showing the decomposition of

Cu2S04 in argon. Heating rate 10 "C/min, gas flow 80
ml/min.
For personal use only.

-0
1 960 560 660 7O
; sbo 9dO
TEMPERATURE , O C

FIG.2. DTA curve showing the decomposition of

Cu2S04 in argon. Heating rate 10 "C/min, gas flow 80
ml/min. Letters a to e indicate the temperatures at which
heating was interrupted and samples obtained were exam-
ined by X-ray diffraction (see Table 2).

steps at about 560 and 650 "C. DTA curves

Samples of CuS0,.5H20 were heated in both DTA and
TGA apparatus and the thermograms so obtained were
compared. Since the sample in DTA apparatus is in intimate
contact with the thermocouple, the temperatures at which
dehydration and decomposition take place were considered
precise enough for calibrating the TGA.
Reaction products were identified by interrupting the
heating of samples under investigation at a certain tempera-
ture and examining the residue by X-ray powder diffractom-
etry. Sulfur dioxide liberated during the tests was detected
by absorption in KI solution acidified by 1% HCI and con-
taining starch as indicator. The solution was continuously
titrated during a test by KIO, solution to maintain a con-
stant color (8).
Results and Discussion
Hcwting in Argon
The TGA thermogram presented in Fig.
shows that the first decom~ositiontakes d a c e at
about 300 "C followed by two other overiapping
shown in Fig. 2, however, revealed peaks at 400,
610, 720, and 805 "C. SO, ~ r o d u c e din this case
was first detected at 350 C. Heating was in-
terrupted at different temperatures (marked a to
(. in Fig. 2) in the DTA instrument and the
samples obtained were examined by X-ray
diffraction. The products identified by this
method are shown in Table 2. It can be con-
cluded from this information that the drifting
of the base line in the endothermic region in
DTA curve starting at about 220 "C may be
attributed to the ~ a r t i a l decom~osition of
Cu,SO, according tb
cu2so, -, Cu +cuso,
The first stage ofdecomposition then follows the
reaction
~CU,SO,-+ ~CUSO,+ 2 c u 2 0 + so2
 3874 C A N A D I A N J O U R N A L OF CHEMISTRY. VOL. 50. 1972

TABLE2. Identification of products of decomposition of TABLE3. Identification of products of decomposition of

Cu,SO, in argon by X-ray diffraction Cu,SO, in air by X-ray diffraction

Temperature Temperature
of of
Point interruption Product Point interruption Product
onDTA in DTA on DTA inDTA
curve ("c) Major Minor Trace curve ("c) Major Minor Trace

a 300 Cu,SO, CuSO, Cu rr 250 CuSO,, Cu,O - -

b 450 CuSO,, Cu,O - Cu b 350 CuSO,, CuO - -
c 650 CuO.CuSO,, Cu,O - Cu C 740 CuO.CuSO,, CuO - -
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d 740 CuO.CuSO,, CuO - Cu d 880 CuO - -

e 880 CuO - Cu

Data in Table 2 suggest that the above

reactions are followed by
4CuS0,
CuO.CuS0,
+ Cu,O
+ Cu,O
-- 3Cu0.CuS04 + SO,
4Cu0 + SO,
CuO.CuSO, -. 2Cu0 + SO, + $ 0 2
which correspond to the last three DTA peaks
in Fig. 2. The liberation of SO, in each step was
confirmed.
Hcwting in Air
For personal use only.

0.6 1 I I I I 1
200 4 00 600
T E M P E R A T U R E ,'C
8 00
Figure 3 shows the TGA curves for the
behavior of Cu,SO, when heated in air. It can
FIG.3. TGA curve; showing the behavior of Cu2S04
when heated in air. Heating rate 10 "C/min, gas flow be seen that there are two steps indicating a
100 ml/min. Letters a to d indicate the temperatures at which weight increase at 120 and 200 "C, and a loss in
heating was interrupted and samples obtained were exam- weight at 600 "C. Figure 4 shows the DTA
ined by X-ray diffraction (see Table 3). curves for the same process. It can be seen that
the first two reactions are exothermic while the
last two are endothermic. X-ray diffraction
analysis after each step (Table 3) and the
percentage change in weight conform to the
following reaction scheme

1
100 200 300 400 500 600 700 800 900
T E M P E R I T U R E .*C
These reactions can therefore be assigned to the
FIG.4. DTA curves showing the behavior of Cu2S04 DTA peaks in Fig. 4.
when heated in air. Heating rate 10 "C/min, gas flow
100 mlimin. Healing in H ,
Figure 5 shows that the change in weight
The weight change according to this equation is during reduction by Hz is gradual in the tem-
9.6% while data in Fig. 1 indicate 7.2%. The perature range 120 to 340 "C. X-ray diffraction
discrepancy between these two values is due to analysis of residues obtained when heating was
the presence of CuSO, in the sample which interrupted at 250 "C showed the presence of
remains undecomposed in the low temperature CuSO, and Cu. I t seems that reduction takes
place according to the equation
range. The amount of CuSO, in the sample can
be calculated as 25% of its weight. Cu,SO, + 2H, - 2Cu + SO, + 2H,O
 VO V A N A N D H A B A S H I : O N C u ( l ) S U L F A T E 3875

These three reactions proceed simultaneously

until all Cu2S04 is reduced to Cu. DTA curves
did not yield any significant data because the
heat liberated or absorbed is the sum of the
above reactions.
Hccrtirzg in CO
Figure 6 shows the TGA curve for reduction
by CO. In the temperature range 200 to 400 OC
the behavior is the same as in the case when
heating in argon. At 400 "C, X-ray diffraction
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revealed the presence of CuSO, and C u 2 0 ,

i.c., the following reaction takes place
3Cu,SO, + 2cus0, + 2 c u , o + SO,
0.4 I I I Above 400 "C, CuSO, is reduced in two steps,
100 200 3 00 400 namely to C u 2 0 then to Cu as follows (4)
T E M P E R A T U R E ,"C

FIG. 5. TGA curves showing the reduction ofCu2S0, by

H,. Heating rate 10 "C/min, gas flow 360 ml/min.
2CuS0,
3Cu,O
+ 3CO
+ 3CO -
-t Cu,O + 2S0,
6Cu + 3C0,
+ 3C02

I I I I I
Conclusions
Anhydrous Cu,SO, can be readily prepared in
about 75% purity by the action of dimethyl
For personal use only.

sulfate on Cu,O; the remaining 25% is CuSO,.

The material is fairly stable in dry air at room
temperature but decomposes rapidly in presence
of moisture or on heating. In air or in H,,
decomposition starts at 120 OC while in argon
or in CO decomposition takes place at 200 OC. I t
is doubtful that Cu2S04can exist above 300 "C
under any circumstances.

The financial support of the National Research Council

of Canada is gratefully acknowledged.

0.4 1 I I I 1. Gmelin. Handbuch der anorganischen Chemie. Vol. 60.

2 00 400 600 8 00 Kupfer. Part B. Weinheim. 1958. pp. 487-551.
TEMPERATURE ,OC
2. J. G. F. D ~ u c and
s G . FOWLES. Chem. News, 137. 385
FIG. 6. TGA curves showing the reduction of Cu,SO, (1928).
by CO. Heating rate 10 "C/min, gas flow 100 ml/min. 3. R. SCHENCK. Z. Elektrochem. 43,438 (1937).
4. F . HADASHI,K. VO VAN, and R. DUGDALE.T O be
published.
5. J. W. MBLLOR. Comprehensive treatise on inorganic
and the H2° liberated reacts with the and theoretical chemistry. Vol. 3. Longman, London.
remaining Cu2S04 to form Cu and CuSO, 1928. p. 120.
6. G . BRAUER. Handbook of preparative inorganic chem-
H20
istry. Academic Press, New York. 1965. p. 101 1.
cu,so,- CuSO, + Cu 7. A. RECOURA.C. R. 148, 1105 (1909).
CuSO, is then reduced to Cu2S0, 8 Annual book of ASTM standards, Part 32. American
Society for Testing and Materials. Easton, Md., U.S.A.
2CuS04 + 2H, -t Cu,S04 + SO, + 2H,O 1971. p. 839.
 This article has been cited by:

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2. J.H.A. Kiel, W. Prins, W.P.M. van Swaaij. 1992. Performance of silica-supported copper oxide sorbents for SOx/NOx-removal
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3. H. J. Berthold, J. Born. 1987. �ber Kupfer(I)-sulfat Cu2SO4. Darstellung und thermische Eigenschaften. Zeitschrift f�r
anorganische und allgemeine Chemie 550:7, 7-15. [Crossref]
4. Peter Bukovec. 1987. Thermal analysis in inorganic chemistry: progress report. Thermochimica Acta 110, 383-387. [Crossref]
5. Henryk Debirski, Jadwiga Walcznk. 1985. Thermal decomposition of copper /I/ sulfate. Thermochimica Acta 92, 677-680.
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6. S. Guy, C.P. Broadbent. 1983. Formation of copper(I) sulphate during cupric chloride leaching on a complex Cu/Zn/Pb ore.
Hydrometallurgy 11:3, 277-288. [Crossref]
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 105.195.12.26 on 01/24/19

7. N. Jacinto, M. Nagamori, H. Y. Sohn. 1982. Dry method preparation and melting point of Cu2SO4. Metallurgical Transactions
B 13:3, 515-517. [Crossref]
8. . References 289-321. [Crossref]
9. Kim Vo Van, Fathi Habashi. 1974. Kinetics of reduction of solid copper sulphate by hydrogen and carbon monoxide. The Canadian
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11. Fathi Habashi, Raymond Dugdale. 1973. The reduction of copper sulfate and its application in hydrometallurgy. Metallurgical
Transactions 4:5, 1429-1430. [Crossref]
For personal use only.