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Inorg. Phys. Theor. 1417

Published on 01 January 1968 on http://pubs.rsc.org | doi:10.1039/J19680001417
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Thermal Studies on Halides and Basic Halides of Copper(ii)

By M. C . Ball * and R. F. M. Coultard, Department of Chemistry, University of Technology, Loughborough,
Leicestershire

The thermal decomposition of the halides and basic halides of copper( 1 1 ) have been studied by a thermogravimetric
method. The hydrated chloride loses water and then halogen to give the copper(!) compound which then oxidises
to copper(1 1 ) oxide ; the bromide behaves similarly. The basic chlorides dehydroxylate, then lose halogen, while
the basic bromide loses halogen first and then water. The behaviour of the hydrated fluoride and the basic iodide
is complicated by the simultaneous loss of water and halogen as hydrogen fluoride or iodine. Activation energies for
some of the reactions have also been derived.

BASIChalides of the divalent metals have been widely
studied, and there is great confusion in the early litera-
ture.l This confusion has been reduced in recent years
by the work of Feitknecht and his co-workers,2who have
clarified the methods of preparation and crystal structures
of most of the known compounds. The first-row transi-
tion metals form two groups of compounds of general
formula M (OH)X and M2(OH),X, which have simple
structures derived from hexagonal or cubic close-packed
hydroxy and halide ions, with the metal ions in octa-
hedral sites3
Basic salts are of interest because of the variable modes
of decomposition which exist, vix., dehydroxylation
followed by loss of halogen or vice versa. Those of
copper are of particular interest because of their form-
ation during corrosion of the metal.
EXPERIMENTAL
All compounds used in the present study were prepared by
known methods with slight modifications, with the exception
of copper(I1) chloride dihydrate and copper(I1) bromide.
The identity of each preparation was confirmed by X-ray
diffraction. Copper(I1)fluoride dihydrate was prepared by
1 See J. W. Mellor, 'A Treatise on Inorganic Chemistry,'
Longmans Green, London, 1923, vol. 3, p. 178.
( a ) H. R. Oswald and W. Feitnecht, Helv. Chirn. A d a , 1961,
44, 847; ( b ) 1964, 47, 272.
W. Feitknecht, ' Essays in Co-ordination Chemistry,'
ed. W. Schneider, G. Anderegg, and R. Gut, Birkhauser Verlag,
Basel, 1964, p. 84.
the dissolution of copper(I1) carbonate in aqueous hydro-
fluoric acid; the mixture was set aside for 24 hr., and then
the precipitate was filtered off and washed with water and
ethanol (Found : Cu, 46.4. Calc. for H,CuF,O : 46.2%).,
Copper(11) chloride dihydrate was AnalaR grade material.
Copper(I1)bromide was reagent grade material. The only
hydrate known to exist is the tetrahydrate, which is reported
to dehydrate at 40°.5 Attempts to prepare this hydrate
were unsuccessful. Material which was crystallised from
water dehydrated continuously up to 120".
Copper (11) hydroxide fluoride was prepared by heating
a suspension of copper(I1)fluoride dihydrate in water under
reflux for 24 hr. ; the precipitate was filtered off and washed
with water, ethanol, and ether (Found: Cu, 63.9. Calc.
for HCuFO: Cu, 63-8y0).4
Copper(I1) hydroxide chloride was made hydrotheriiially
from a 4 : 1 mixture of copper(I1) chloride dihydrate and
copper(I1) oxide by treatment for 3 days a t 250" in a sealed
glass tube. Excess of copper(I1) chloride was removed by
washing the crystals with methanol (Found: Cu, 54.9.
Calc. for HC~CLIO:Cu, 54.75%). Attempts to prepare the
analogous bromide were unsuccessful; all experiments
produced dicopper(11) trihydroxide bromide.
Botallackite [u-Cu,(OH),Cl] was prepared by passing
carbon dioxide-free air into an aqueous solution of hydro-
chloric acid ( 0 . 1 ~ )and sodium chloride ( 2 ~ containing
)
pieces of copper foil. After ca. 48 hr. the pH rose to 5 and
C. M. Wheeler and H . H. Haendler, J . -4rner. Chem. SOC.,
1954, 76, 263.
N. S. Kurnakov and A. A. Sementschenko, 2. anorg. Chem.,
1895, 9, 337.

1418
the basic salt was precipitated (Found: Cu, 59.2. Calc. for
H,ClCu,O, : CU, 59.5574). 6
Paratacamite (y-Cu,(OH),Cl) was prepared by the
hydrolysis of copper(I1) hydroxychloride with cold water
(Found: Cu, 59.3. Calc. for H,ClCu,O,: Cu, 59.557'0).2b
Atacamite [8-Cu,(OH),Cl] was a sample from Wallaroo,
South Australia, supplied by the British Museum (off B.M.
35720). Traces of goethite were removed before the
material was used.
Dicopper (11) trihydroxide bromide was prepared hydro-
thermally from moist copper(11) bromide and copper(I1)
oxide. Excess of copper(I1) bromide was removed with
methanol (Found: Cu, 49-0. Calc. €or H,BrCu,O,: Cu,
Published on 01 January 1968 on http://pubs.rsc.org | doi:10.1039/J19680001417
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J. Chem. SOC. (A), 1968
ments could be made unambiguously from differential
weight loss curves.
Thermal Decomposition.-Copper (11) chloride dihydrate
normally lost two molecules of water in a single step to
form the anhydrous material, although in one run an
inflection corresponding to the monohydrate was ob-
served a t 115". Copper(I1) chloride lost halogen at a
fairly low temperature to form copper(1) chloride which
then volatilised and oxidised. Copper(I1) bromide also
decomposed to give the copper(1) compound which then
oxidised at a higher temperature.
Copper(I1)fluoride dihydrate did not dehydrate simply

49.2y0).2b and lost water and hydrogen fluoride to produce a basic

Dicopper (11) trihydroxide iodide was prepared by heating salt. The data obtained are in agreement with those of
copper(I1) acetate hydrate (4 g . ) and potassium iodide
(1.6 g.) in water (400 ml.) a t 60" for several hours ; the solution
Wheeler and Haendler * for decomposition in the air;
was allowed to cool to room temperature after which the these authors give the following equations for the
decomposition :
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precipitate was filtered off (Found: Cu, 41.6. Calc. for

H,Cu,IO,: Cu, 41*75%).?
The thermograms were recorded on a Stanton Automatic
2CuF2,2H,0 ---t Cu(OH),,3CuF2 + H F + 3H,O
Thermobalance, Model TR-01, which has a maximum
operating temperature of about 950". The OS12 attach-
Cu(OH),,3CuF2+ CuO + CuF, + H F + H,O (sic)
ment was also used, which allowed the temperature to be They also state that ' the nature of the decompositions
measured a t the base of the sample crucible. Heating rates depends on the presence or absence of air. In the pres-
were 0-6'/min., 1.2"/min., and 4.O0/min. For comparison ence of air, copper(I1) oxide is the final product and no
purposes the middle rate was used. Sample weights were well defined steps in the reaction series can be observed.'
100 mg, f 10 mg. throughout. Air, dried over calcium The present work indicates that the first stage @ven
chloride and phosphorus pentoxide, was passed through above can be observed, but that the second stage pro-
the furnace a t 50 ml./min.
ceeds in a single step to give copper(@ oxide as the
RESULTS AND DISCUSSION
product.
The results of the T.G.A. runs are shown in Table 1. The observed weight losses given in Table 1 for the
The identity of the final product of all runs was con- basic salts have been interpreted according to the follow-
firmed by X-ray diffraction. The reactions postulated ing equations :
8Cu(OH)F+
TABLE1
in
Cu(OH),,3CuF2 + 4CuO + 2H,O + 2HF (1)
position weight (yo) Reaction occurring followed by the indeterminate decomposition of the
Compound -range Obs. Calc. or end product -
CuF,, 2H,O 152-250' 26-3 26.9 Loss of HF and H,O second basic salt mentioned above.
320-485 21.0 20.9 CUO
CuC1,,2H20 70-200 21.0 21.2 LOSSOf HZO 2Cu(OH)Cl--+ CuO,CuCl, H,O + (2)
365-570
570-700
20.5 20.9 LOSS
23*0* 10.7 CUO
of C1,
cuo,cuc1, +
qo,--t 2 c u o c1, +
CuBr, 187-305
425-630
35.0 35.7 Loss of Br,
28.0 28.5 CUO ZCu,(OH),Cl --w 3CuO,CuCl, + 3H,O (3)
Cu(0H)F 280-320
320-350
9.5 9.55 Loss of HF and H,O
10.9 10.54 CUO
SCuO,CuCl, +
40, .--t 4CuO C1, +
Cu (OH)CI 225-340 7.5 7.8 LOSSof HZO
380-830 38.0* 23.7 CUO Each stage in this decomposition gives approximately
a-Cu,(OH) ,C1 310-470 12.8 12.6 LOSSof H 2 0 the same loss in weight (12.6y0 and 12.9y0 respectively).
(Botall ackit e) 480-9507 11.3 12.9 CUO
y-Cu,( OH),Cl 268-450 12.8 12.6 LOSS of H,O The order of decomposition given was determined by
(Paratacamite) 450-820 12.9 12.9 CUO qualitative examination with tests for water vapour
~-CU,( OH),C1 260-435 12.8 12.6 LOSSof H 2 0 and chlorine.
(Atacamite) 450-770 12.8 12.9 CUO
,
Cu (OH),Br 260-360
370-435
27.5 27.8 Loss of Br,
10.8 10.3 CUO
2Cu,(OH),Br +
40, +3Cu(OH),,CuO + Br, (4)
Cu2(0H)31 160-225
225-400
26-3 26-7 Loss of H,O and I,
20.7 21.2 CUO
3Cu(OH),,CuO +4CuO 3H,O +
* Evidence for volatilisation of material. t Reaction not 4Cu,(OH),I +
complete at furnace maximum.
2CuI +
2[Cu(OH),,2CuO] I, + + 4H20 (5)
in the Table are those which fit the observed losses in 2CuI + 0,- 2cuo I, +
weight. In some cases, particularly among the basic
salts, reactions tended to overlap slightly, but assign-
2[Cu(OH),,2CuO] --+6CuO 2H,O +
Y. Iitaka, s. Locchi, and H. R. Oswald, HeZv. Chim. Acta, 7 0. V. Dubskq, E. Tesafik, and A. Okac, CoZZ. Czech. Chem.
Comm., 1930, 2, 266.
1961, 44, 2095.

Inorg. Phys. Theor.
The decomposition of the basic iodide is obviously
more complicated than that of the chloride or bromide.
The observed losses in weight (26.3% and 20.7%) are
both much less than those expected for loss of all the
iodine in a single step, either as iodine (41.7%) or hydro-
gen iodide (42.0); removal of water gives losses of be-
tween 5-97; and 8.85% depending on the reaction.
The equations given above are those which fit the
observed losses best. Qualitative experiments could
not separate the evolution of halogen and water-vapour.
No attempt has been made in the above equations to
formulate the reaction intermediates as mixtures of
Published on 01 January 1968 on http://pubs.rsc.org | doi:10.1039/J19680001417
View Article Online
1419
or incomplete reaction. In addition, the reactions
involving the basic iodide are obviously complex and,
in the absence of other information a t present, this
data has not been included. With these exceptions,
runs were made using each of the three heating rates
and with approximately equal sample weights of ca.
100 mg. The activation energies derived are shown in
Table 2, together with the heats of reaction where these
can be c a l ~ u l a t e d . ~
Variation of the heating rate had no
apparent effect on the derived activation energies. All
of the decompositions, with one exception, gave linear
log K 8s. 1/T plots when Dave and Chopra's ' first-order '

oxide plus halide or hydroxide, e.g. CuO,CuCI, as
+
CuO CuCl,, since the chlorine in this intermediate
is lost in a single step rather than two stages as for
copper(I1) chloride itself.
Kinetic Studies.-The method of Dave and Chopras
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equation was used. The exception, copper hydroxide
chloride, required the use of a ' second-order ' equation
to produce a linear relationship. The concept of ' reac-
tion order in solid-state reactions has little theoretical
justification, since many reactions are diffusion or

was used to treat the experimental thermogravinietric nucleation controlled, and the concept of ' order ' takes
no account of either of these; it is only used here to
TABLE 2 follow the original authors' terminology.
Heating Activation energy The activation energies in Table 2 are much larger
rate (kcal./mole) than those heats of reaction which could be calculated;
Reaction ("lmin.) Average
this could indicate that the rate-controlling step was
Dehydration of CuC1,,2H20 0-6
1-2
4.0
:f
13.1
} 13.4 not chemical reaction but some other process such as
diffusion or nucleation. However, dynamic methods
Dehalogenation of CuCl, * 0.6 such as thermogravimetric or differential thermal
1.2
4.0 36.9 analysis often give higher activation energies than iso-
Dehalogenation of CuBr, t 0.6 thermal studies and it is for this reason that doubts have
1.2 28.5 been cast on the derivation of such energies. A convinc-
4.0 28.0 ing explanation of these high values has been given by
Oxidation of CuBr $ 0.6
1.2
4.0
40.2
32.6
45.2
} 41.0
Ingraham,lo in terms of the formation of highly energetic
intermediates by the rapid flow of heat into the sample
Dehydroxylation of Cu(0H)CI 0.6 under dynamic heating conditions. The formation of
1.2 54.0 these intermediates raises the activation energy over
4-0 53.8 that required for the comparable isothermal reaction.
Dehydroxylation of Cu,(OH) ,C1 0.6
1.2
4.0
::::}
70.6
70.0
Which of these situations holds for the compounds in
the present study, viz. diffusion or nucleation control vs.
Dehalogenation of Cu,(OH),Br 0.6
1.2
4.0
43.1
50.2
49-2
} 47.5
the formation of energetic intermediates, can only be
decided by relatively lengthy isothermal studies.
Although relatively few direct comparison can be made,
Dehydroxylation of Cu,(OH),Br 0.6
1.2
4.0
:;::}
56.5
59.0 it would appear that the stability of the various halides
decreases in the order F > C1 > Br > I and that the
* Heats of reaction (kcal./mole): * 17.0, t 8-3, 2 12.4. activation energies follow the same order. Srivastava
and Secco found a similar order of stability in the
curves. This involves calculation of rate constants from cadmium hydroxide halides,ll but a reverse order for
the differential weight loss us. temperature curve, from the zinc compounds.12
which normal log k vs. 1/T plots give the activation
energies for the reaction. [7/1311 Rcceiued, October llth, 19671
Not all of the reactions studied were suitable for this 10 T. R. Ingraham, Proceedings 1st Toronto Symposium on
kinetic treatment, due either to volatilisation of material, Thermal Analysis 1965,' ed. H . G. Mca4die, Chemical Institute of
Canada, p. 81.
* N. G. Dave and S. K. Chopra, 2. p h y s . Chem. (Frankjztrt), 11 0. K. Srivastava and E. A. Secco, Canad. J . Chenz., 1967,
1966, 48, 17. 45, 1375.
0. Kubaschewski, E. LI. Evans, and C. B. Alcock, ' Metal- l a 0. K. Srivastava and E . A. Secco, Canad. J . Chent., 1967,
lurgical Thermochemistry,' Pergamon, Oxford, 4th edn., 1967. 45, 579, 585.