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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.
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
+ 89
~ 89
+ 88
441 2
CuzOClz +}~
+ 89
+ 2!C12 + 88
(1)
(2)
(3)
(4)
+ 89
1037
I140
1025
1133
1042
1141
341
320
341
1027
1137
279
341
456
1040
1141
320
Tf
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
4CuO + C12"~
Cu20 melts
~o2
1036
1139
322
Decomposition range:
DTA peaks (~C)
8.42
% calc.*
8.67
% found*
2Cu2(OH)3C1 ~
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
+ 88
341
~m
434
279
T~
~CuO + 89
2Cu2(OH)3 C1
362
462
647
1053
I141
279
T~
r~
T~
Decomposition range:
DTA peaks (~ C)
% calc.*
TG steps
Decomposition range:
DTA peaks (~ C)
% found*
Still air
Stages
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~'
'
I-~
Endo~-.----~Exo
"t
0
0
'
~-.
cooling~=
Endo
o. #~
--,. E xo
cooling~
&
o
o"
,,
+ 1C12 ~ 1CuCI + 88
(5)
(6)
+ +el 2 + 88
(7)
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
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
839
1231
341
434
262
T~
TGsteps
II
III
IV
V
Heating rate: 2 ~
Stages
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
89
438
637
881
1244
360
Tf
360
438
788
1227
258
T G steps
2Cu2(OH)3C1 ~
873
1227
339
434
279
Decomposition range:
DTA peaks (~ C)
6.02
34.78
4.70
12.64
% calc.*
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.
441 8
9.
10.
ll.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
Received 22 January
and accepted 10 April 1986