JOURNAL OF MATERIALS SCIENCE 21 (1986) 4411-4418
y-Cu2(OH)aCI as precursor in the preparation of
copper (I) and (11) oxides and copper powder
O. G A R C [ A - M A R T i N E Z ,
P. M I L L A N ,
R. M. R O J A S
Instituto Qu/mica Inorg~nica "'EIh6yar'" CSIC Serrano 113, 28006 Madrid, Spain
When 7-Cu2(OH)aCI is decomposed in air or nitrogen flow, different amounts of cuprous
oxide are obtained as final product depending on both the heating rate and the ambient
atmospheres. However, the temperature of formation of cuprous oxide only appears to depend
on the partial pressure of oxygen. When thermal decomposition is carried out under dynamic
vacuum in the X-ray high-temperature diffraction chamber, using a tantalum strip as the heating element, copper is obtained as final product at a comparatively low temperature.
1. Introduction
The influence of experimental conditions on the mechanism through which thermal decomposition occurs is
well known [1, 2]; as a consequence, the properties of
the materials so obtained and the yields of the reactions are deeply modified, this being particularly
remarkable if during the decomposition processes
some volatile compounds are formed.
On the other hand, when some organometallics or
some organic salts (mainly oxalates and formates) are
thermally decomposed under suitable conditions, the
formation of the metal results [3] and this possibility
has been widely explored in order to obtain certain
metals, e.g. copper powder among others [4-11].
However, there are quite a few examples in which
from the thermal decomposition of inorganic salts,
pure copper metal is obtained as the final product
[12-14].
Previous studies on thermal decomposition of
7-Cu2(OH)3CI have been carried out by previous
authors [15-19] arriving at slightly different results
that could be explained on the basis of the different
experimental conditions used. We have considered it
worthwhile to examine systematically the decomposition reactions of 7-Cu2(OH)3CI in order to correlate the results obtained up to date, as well as to state
the influence of the experimental conditions on the
mechanisms through which copper hydroxychloride
decomposes, bearing in mind the many catalytic applications of the several products formed along the thermolysis reactions; copper (I) and (II) chlorides, oxides
and copper powder, and also considering that thermal
decomposition of this basic salt is a method that
affords a very convenient route for the preparation of
the above indicated compounds.
2. Experimental techniques
Paratacamite T-Cu2(OH)3C1 has been prepared as
described elsewhere [20]; briefly by incomplete precipitation of 0.2 M solution of CuC12"2H20 with 0.4 M
NaOH, followed by ageing at 70~ for 30 days. The
precipate was filtered off and washed with alcohol and
acetone, and kept on phosphorous pentoxide. The
0022-2461/86 $03.00 + .12 9 1986 Chapman and Hall Ltd.
chlorine and copper analyses and the X-ray diffraction
diagram [21] showed that the compound was
paratacamite.
The thermograms were recorded on a Stanton 781
Simultaneous Thermal Analysis System in still or air
flow and in nitrogen flow at several heating rates (2 to
10~ C rain-1 ). Platinum rhodium crucibles and A1203
as reference were used. A Dupont 951 thermobalance
joined to a Dupont 990 equipment was occasionally
used. The intermediates and final products were identified by X-ray diffraction and infrared spectroscopy.
Chlorine evolution, when it occurred, was qualitatively tested by the pink colour developed in a filter
paper impregnated with fluorescein and KBr solutions
[22].
The X-ray high-temperature diffraction diagrams
were obtained on an Anton PAAR H T K 10 attachment mounted on a Philips PW 1310 equipment. The
sample was deposited on a platinum sheet placed on a
tantalum strip which acts as the heating element. The
temperature was measured using a P t - P t 13% Rh
thermocouple welded on to the centre of the platinum
sheet. Vacuum (4.5 x 10-3mmHg) was accomplished by a liquid nitrogen trapped rotary pump and
it was monitored by a vacuum gauge placed in the
chamber cover. Temperature was increased in 10
degree steps and allowed to stabilize; the X-ray diagrams were then scanned or, alternatively, several
diagrams were recorded while the temperature was
held at some defined values; CuKc~, nickel-filtered
radiation was used.
3. Results
3.1. Thermal decomposition studies at low
heating rate (2 ~Cmin -1), air flow and
still air environments
Under these conditions, copper (II) hydroxychloride
dehydroxylates in one or two consecutive steps, as
can be seen respectively in the DTA and TG curves
shown in Figs la and b. The weight losses and the
temperature ranges in which they occur in addition
to the temperature of the DTA peaks are shown in
Table I.
441 1
TG
0
x
10~176 i
t
0
cooling
t-
FI~I
O
x
LU
ITG
1
1
O
cooling
W
(b)
i
500
T(*C)
1000
Figure 1 D T A and T G curves of ?-Cu2(OH)3C1 obtained at
2 ~ C m i n -I heating rate in (a) air flow, (b) still air.
3.2. Thermal decomposition studies at
high-heating rate (10 ~ C min -1 ); air f l o w
or still-air environments
The dehydroxylation reaction occurs, as at low heating rates, in one or two consecutive steps depending
on the environmental conditions (see Table II and
Figs 2a and b) and in both cases Cu2OC12 and CuO
were the compounds identified at 360 ~C. From this
temperature up to 462~ the evolution of chlorine
occurs and it is particularly evident when the thermograms are recorded in the 951 Dupont thermobalance
in air flow, that because of the strong smell of chlorine,
it was qualitatively recognized.
From 460 ~C up to about 650 ~C condensation of a
yellow product on the colder parts of the quartz tube
of the Dupont thermobalance is observed; a yellow
film is also formed in the upper cold part of the
Stanton equipment. The X-ray diagram of this yellow
product showed the most intense lines of anhydrous
cupric chloride [25] which rapidly transforms into the
dihydrated form [26] on standing in the open air.
When cupric oxychloride is thermally decomposed
in air, it transforms into cuprous chloride, cupric
oxide and chlorine which can react with some oxide to
yield cupric chloride [18]. Accordingly, the following
overlapping reactions can be assumed to occur in the
temperature range 360 to 465 ~C.
Cu2OC12 ~ CuC1 + CuO + 89
89
+ 89
~ 89
+ 88
CuC1 +~o2 CuO + 89
It is most probable that copper hydroxychloride
Cu(OH)C1 is formed as an intermediate when the
initial compound dehydroxylates in still air, but the
data provided by the X-ray diffraction and infrared
spectroscopy are not conclusive. The X-ray diffraction
diagrams obtained on samples heated up to 320~
show the Cuz(OH)3C1 and CuO diffraction lines and
also two shoulders at angles of 15.90~ and 32.61 ~ 20;
their interplanar spacings are those of the (1 0 0) and
(1 21) most intense lines of Cu(OH)C1 [23]. The
infrared spectrum shows features of Cu2 (OH)3C1 and
the OH stretching bands are clearly resolved.
Copper (II) oxychloride and oxide are identified on
samples heated up to 350~ [23, 24] and chlorine is
evolved between this temperature and 456 ~C; it was
tested qualitatively as indicated above; copper oxychloride decomposes and simultaneously oxidizes to
cupric oxide.
The experimental weight losses agree with those
reported by Ball and Coultard for the thermal
decomposition of ?-Cu2(OH)3CI. The main differences lie in the decomposition ranges [16].
At low heating rates the formation of cupric oxide
is almost quantitative and there is no evolution of
any copper halide. This result is in agreement with
that obtained by Kiss and Lloyd [19] at low heating
rates (3 ~C min-1), although they did not identify
the unstable intermediate C u 4 C 1 2 0 3 , a mixture of
Cu2OC12 and CuO, because the X-ray powder diagram was recorded at an inadequate temperature
(300 ~C).
441 2
CuzOClz +}~
+ 89
+ 2!C12 + 88
(1)
(2)
(3)
(4)
The calculated weight loss for the overall Reaction 4
is 12.83%, being the experimental values 11.34% and
13.33% calculated from the data obtained on thermo'grams recorded in still or air flow, respectively.
The extension and completion of the above reactions will be affected by the environmental conditions
and, consequently, some small differences between the
experimental and calculated weight losses might be
expected.
Later, the cupric chloride thus formed is evolved
and cupric oxide is the product isolated up to 1030~C,
when it transforms into cuprous oxide which melts at
1140~C with a slight weight gain caused by the picking
up of some oxygen [19]. A continuous weight loss of
the liquid sample is observed up to the final programmed temperature; this is caused by the evolution
of oxygen in the melted sample as well as by the
removal of some liquid cuprous oxide.
The experimental and theoretical weight losses calculated according to the proposed reactions are indicated in Table II. In air atmosphere, the temperature
of the reaction
CuO --* 89
+ 89
is not affected by the heating rate, as can be seen in
Tables I and II, neither is it the temperature at which
Cu20 melts, it being about 100~ lower than the
reported melting point [27], but it is in agreement with
the data of Kiss and Lloyd [19].
1037
I140
1025
1133
1042
1141
341
320
341
1027
1137
279
341
456
1040
1141
320
Tf
*Weight losses have been calculated as a percentage of the original sample.
tWeight gain calculated as a percentage of the actual sample weight.
337
322
Ibis
II
III
IV
320
306
322
T~
T~
T,
Tm
TG steps
Decomposition range:
DTA peaks (~ C)
Still air
Stages
4.22
12.86
7.50
weight
gain
3.83
13.52
6, 78
1.55t
1024
1132
310
--* 2Cu20 + O2T ~
Cu2OC12 + 2CuO + H20~" ~+
4CuO + C12"~
Cu20 melts
~o2
1036
1139
322
Decomposition range:
DTA peaks (~C)
Air flow (50 ml min- l )
[2Cu(OH)CI + 2CuO + 2H2OT] Ibis
8.42
% calc.*
8.67
% found*
2Cu2(OH)3C1 ~
TAB L E I Thermal decomposition data of Cu 2(OH)3 C1, Heating rate 2~ C rain i
1045
1140
337
341
1025
1129
275
TG steps
456
1041
1140
337
13.85
7.99
1.5t
12.50
% found*
12.86
7,50
weight
gain
12.64
% calc.*
347
438
622
1034
1126
Ibis
II
III
IV
V
356
460
631
1045
1140
337
376
479
637
1053
1145
347
337
362
462
1035
1133
279
337
4.22
5.63
16.08
6.75
1.72
8.19
--, 89
4.22
6.43
15.74
6.55
weight
gain
8.42
1045
1140
1032
1126
11
457
+ 89
CuC1 + 89
+ 89
2 + 88 2
+ 89
CuO ~- 89 2
~ 89
Cu2OCI2 + - ~ 20 23-CuO q- 89
89
+ 88 2
Cu2OCI 2 ~ CuO + CuC1 + 89 2
+ ~CuO iv, 4zCu20 + 7021, v_L* Cu20 melts
+ 88
341
~m
434
279
T~
Cu2OC12 + 2CuO + 3H2Oi" ~ +1~ /
~CuO + 89
2Cu2(OH)3 C1
362
462
647
1053
I141
* Weight losses have been calculated as a percentage of the original sample.
~Weight gain calculated as a percentage of the actual sample weight.
279
T~
r~
T~
Decomposition range:
DTA peaks (~ C)
% calc.*
TG steps
Decomposition range:
DTA peaks (~ C)
% found*
Air flow (50 ml min i )
Still air
Stages
T A B L E I I Thermal decomposition data of Cu 2(OH)3 C1. Heating rate 10~ C min - ~.
1052
1144
475
370
360
466
1033
1133
281
T~
TG steps
466
615
1052
1144
360
6.70
12.88
6.70
1.33
12.37
%found*
6.43
15.74
6.55
weight
gain
12.64
% calc.*
~F.
B'o
-:~
~h
~2
~'~
o-,,~
~a
'
I~'
E ndo ,,..-~ Exo
'
I-~
Endo~-.----~Exo
"t
0
0
'
~-.
cooling~=
Endo
o. #~
--,. E xo
cooling~
Endo .,,-- ~ Exo
&
o
o"
,,
3.3. Thermal decomposition studies in
nitrogen atmosphere at low and high
heating rates (2 and 10 ~
-1)
The thermograms recorded in nitrogen flow
(50mlmin -I) at the heating rates given above, are
shown in Figs 3a and b. The main differences between
them lie in the usual shift of the initial and final
reaction temperatures when the higher heating rate is
used, as well as in the experimental weight losses, after
dehydroxylation. Consequently, different reaction
mechanisms will rule depending on the selected heating rate.
At low heating rate, the intermediate cupric oxychloride identified at 320~ together with cupric
oxide, will decompose:
Cu20C12 --~ CuO + CuC1 + 89
Chlorine and cuprous chloride are evolved in two
consecutive steps, the latter condenses on the cold
parts of the instrument and can be easily identified;
cupric oxide is obtained at 530 ~C.
At 10~
-l, as the experimental weight loss is
considerably higher, chlorination of some cupric
oxide must be considered and the proposed reactions
are;
Cu2OC12 ---r CuO + CuCI + 89
89
+ 1C12 ~ 1CuCI + 88
Cu2OC12 --~ 23-CUC1 + 89
(5)
(6)
+ +el 2 + 88
(7)
The evolution of chlorine and cuprous chloride has
been tested, as has been the formation of cupric oxychloride and oxide as intermediates in the decomposition process, but the evolution of oxygen could not
be verified. On the other hand, cupric chloride has not
been isolated in any of the decomposition steps when
decomposition is carried out in a nitrogen atmosphere.
230 ~ C
<I
"cT]
I i20'2
9w
2400C
CuO
Cu~C12
CuO
.li
I
ClO
450~
cyo
cr~
CuO
600 ~ C
15 min
CuO
lcF
CuO
5500C
15 min
61 5~
c~2o
cTo
CuO
C ,u
CuO
Cu20
cyo
CuO
lieu
CuO
I
Cu2cl]iCuo
~,~
CTI
Cu
cyo I
CuO
I
650=C
50 min
,
15
4416
2~
3'5
21~ -",,
4's
, C_I
Evolution of 7Cu2(OH)3C1 in the X-ray hightemperature diffractionchamber.
*'~-Cu2(OH)3C1.
Figure 4
4~
258
320
419
834
1228
l
242
302
392
806
1227
Tm
Decomposition range:
D T A p e a k s (~
335
423
785
1227
244
423
530
836
1244
355
Tf
6.78
27.42
5.75
5.19?
12.50
%found*
111
~Cu20 + 88
Cu20 melts
3CuO + CuCI + ~C121"---* 3CuO + CuCII" --,
2Cu2(OH)3C l 1_~ Cu2OC12 + 2CuO + 3H20 ~ --r
839
1231
341
434
262
T~
TGsteps
*Weight losses have been calculated as a percentage of the original sample.
tWeight gain calculated as a percentage of the actual sample weight.
II
III
IV
V
Heating rate: 2 ~
Stages
T A B L E I I I Thermal decomposition data of Cu2(OH)3C1 in nitrogen flow (50 ml min -1)
23.2
5.62
8.28
12.64
% calc.*
788
1224
300
399
255
884
1228
374
466
300
Tr
88
+ 88
--, 89
+ so2t ~
-I- 88
+ 88
+ 88
Cu20 melts
4.92
35.52
4.92
6.96 t
12.56
% found*
t + 88 T --,
~CuO + ~CuClt
Cu2OC12 --* 3CuC1 + 89
89
438
637
881
1244
360
Tf
Cu2OC12 + 2CuO + 3H20 ~
360
438
788
1227
258
T G steps
--, ~CuO + ~CuC1 + 88
2Cu2(OH)3C1 ~
873
1227
339
434
279
Heatmg rate: I0 ~Cmin -~
Decomposition range:
DTA peaks (~ C)
6.02
34.78
4.70
12.64
% calc.*
Cupric oxide transforms into cuprous oxide
between 785 and 836 ~ C or 796 and 881 ~C, depending
on the heating rate, and melts in both cases, at
1227~ C. In nitrogen flow, melting is not accompanied
by any mass increase, but once cuprous chloride is
liquid the continuous weight loss observed when the
thermograms were obtained in air, also occurs in
nitrogen, and it is especially pronounced at the low
heating rate.
The most outstanding result obtained when the
decomposition is carried out in a nitrogen atmosphere
refers to the comparatively low temperature at which
cupric oxide transforms into cuprous oxide. On the
other hand, this oxide melts at the usually reported
temperature (1223 ~C), that is higher than the values
obtained for the melting temperature in air. The
slightly different results reported in the literature can
be explained in terms of the experimental conditions
used by the different authors and in fact, the overlapping of some of the reactions indicated above cannot be rejected. Nevertheless, the obtention of the
decomposition products formed during the thermolysis of 7-Cu2 (OH)3 C1 can be considerably improved if
the experimental conditions are very carefully chosen.
tantalum has a non-passive role in the reaction. The
characteristics and properties of the metal and of the
oxides formed in the decomposition reactions are
being studied.
Acknowledgements
The authors thank the Department of Crystallography of the Instituto Rocasolano, for the use of the
X-ray high-temperature diffraction chamber.
References
1.
2.
3.
4.
5.
6.
7.
8.
3.4. X-ray high-temperature diffraction
studies
When ])-Cu2(OH)3C1 is decomposed under a dynamic
vacuum of 4.5 x 10 3mmHg in the X-ray hightemperature diffraction chamber, it transforms in the
way shown in Fig. 4.
The X-ray diffraction lines of copper oxychloride
have never been observed, but those of cuprous
chloride are clearly seen in the diagrams recorded
between 230 and 350~
If copper oxychloride is
formed, it will rapidly decompose, and cupric oxide is
the only product observed at 450 ~ C.
Cuprous oxide begins to appear at about 550~ C and
from this temperature up to 615~ its characteristic
diffraction lines progressively increase; it is the main
component of the mixture C u 2 0 - C u O - C u existing at
615~
Later the temperature was held at 650 ~C and several
X-ray diagrams were scanned every 5min; after
50 min the X-ray diagram was that of pure copper
[28], which was the final product.
In order to prepare some larger amounts of copper
powder, different specimens, placed in a platinum
boat, were heated in a furnace under the same vacuum
conditions previously used; all the attempts were
unsuccesful, the final products were copper (I) or (II)
oxides depending on the limit temperatures.
A new experiment was then performed in the hightemperature chamber, but on this occasion a platinum
strip was used as the heating element. The evolution of
the compound was markedly different. The salt began
to decompose at about the same temperature (240 ~ C)
and between 480 and 680~ the X-ray diagram was
that of cupric oxide. Cuprous oxide was not formed
until the 680 ~C was reached and it was obtained as a
pure compound from 780 up to 925 ~ C; copper could
never be obtained.
From these experimental data it is inferred that
441 8
9.
10.
ll.
12.
13.
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15.
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18.
19.
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Received 22 January
and accepted 10 April 1986
