Notes

1485

The results in Table 2, where Ka increases with the TOPO concentration in the organic phase, also
indicates this, the addition of TOPO favouring the formation of the highly soluble Zn(TTA)~.TOPO.
In Table 3, it may be seen that increasing the acidity of the aqueous phase, "strips" the organic phase
because the TTA becomes protonated:
Zn(TTA)2"2H20 -k 2H + ~ Zn2+ + 2HTTA + 2H20
This is further supported by the high value of Ka (28-9) in Table 4, when the aqueous phase was
distilled water.
It appears from the data of Table 4 that the effect of the various copper Cu(II) complexes is
independent of pH and that the decreasing Kd values parallels the stability of the complexes. The
least stable complexes furnish sufficient Cu z+ ions to replace the Zn2+ in the ternary complexes. The
colour change of the organic phase confirmed this reaction:
Zn~+ complextorg) + Cu2iaq) ~ Cu 2+ complextorg) + Zn~+taq)
This is in keeping with the observation of WALKERand LI,~2~that the formation constant of
Zn(TTA)~ + TOPO ~- Zn(TTA)2"TOPO
in CC14 is only 10 I/mole. Further KE16) has measured the formation constant of
Cu(TTA)2 + TOPO ~ Cu(TTA)a'TOPO
in benzene solutions and this has the much higher value of approximately 1700 1/mole.
These back-extraction studies using a labelled ternary complex are a new approach to solvent
extraction and should provide useful information.

Acknowledgement--This work was supported by the Australian Institute of Nuclear Science and
Engineeringthrough Project 65/90--(Prop. E2) and was carried out in the laboratories of the A,A.E.C.
Lucas Heights, N.S.W.
The University of Newcastle,
New South Wales,
Australia.

W . R . WALKER

Australian Atomic Energy Commission,

Lucas Heights, N.S.W.
Australia.

M. S. FARRELL

'~' C. H. KE, Duquesne University, Pittsburgh, Pa., Private communication.

J. inorg, nucl. Chem., 1966, Vol. 28, pp. 1485 to 1488. Pergamon Press Ltd. Printed in Northern Ireland

The thermal dissociation of [Co(NH3)~CO3]X type complexes

(Received 8 November 1965; in revised form 15 December 1965)
WENDLANDTet al. ~1' have previously reported the thermal dissociation of several [Co(lig)2CO3]X
(where lig is ethylenediamine, 1,2-propanediamine and 1,3-propanediamine) complexes and
[Co(NHa)4COs]NO3. Only qualitative observations were made, however, concerning their thermal
stabilities and dissociation reactions. We wish to report here a more detailed investigation concerning
the thermal dissociation of the [Co(NH3)4COa]X (where X is chloride, bromide, iodide, and nitrate)
type complexes.
~t~ W. W. WENDLANDT,T. D. GEORGEand K. V. KRISHNAMURTY,J. inorg, nucl. Chem. 21, 69 (1961).

Notes

1486

TABLE 1.--ANALYSIS OF COMPLEXES

(~) Co

(~o) NH8

Compound

Theor.

Found

Theor.

Found

[Co(NHa)4COs]NOs'I'2H20
[Co(NHa)4COs]C1
[Co(NHa)4CO3]Br
[Co(NHs)4CO3]I

22.8
26.4
22"0
18"7

22.3
26.0
21 "7
18"7

26.3
30.6
25"5
21"6

26.9
29.5
24"8
20"3

EXPERIMENTAL

Complexes. The complexes were prepared from [Co(NHs)4COs]NOs'0"5 H~O, which was prepared by the method described by SCHLESSINGERc2~. Treatment of the latter compound with a solution
of K X gave the [Co(NH3)4CO3]X type complexes. The compounds were analysed for ammonia by
the Kjeldahl method and for cobalt by ignition to C%O4. Results of the analyses are given in Table 1.
Apparatus. The general thermoanalytical instruments employed have been described previously. TM
The simultaneous magnetic susceptibility-TGA apparatus has previously been described. ~4~ A
heating rate of 5C min -~ was employed using a static air atmosphere in the furnace.
Mass spectrometric studies were carried out using the apparatus previously described, tS~
Analysis of dissociation products. The tube furnace and analysis assembly have been described
previously. ~6~ The samples were pyrolysed in a dynamic nitrogen atmosphere at a heating rate of
9C min -~. The evolved ammonia was collected in a 4 ~o boric acid solution and titrated with standard
hydrochloric acid. The evolved carbon dioxide was collected in a tarred " U " tube containing Ascarite.
RESULTS

AND DISCUSSION

The mass-loss curves of the [Co(NHs)4CO3]X complexes are given in Figs. 1 and 2.
Except for the compound, [Co(NH,)4COa]NOs'0"5 H~O, the initial mass-loss was due to the total
disruption of the compound. For the above compound, the first mass-loss was caused by the evolution
of water, followed by the dissociation of the anhydrous compound. The initial dissociation reaction
for all of the anhydrous compounds began in the 100-200C temperature region. No intermediate
species were detectable in the curves.
Concomitant with the dissociation reaction, reduction of the cobalt(III) central metal ion to
cobalt(II) took place. This is illustrated by the percent reduction curves of cobalt(III), also given
in Figs. 1 and 2. These curves were calculated from the equations previously given, t4~ Except for
[Co(NH8)4CO8]I, the rate of cobalt(III) reduction appeared to be similar to the mass-loss, much like
the bebaviour observed in the thermal dissociation of [Co(NH3)8]C13.'4,7~ The cobalt(III) ion is probably reduced as a result of an electron transfer from an ammonia ligand, such as has been previously
postulated for the [Co(NH3)6]C13 complex, c8~ However, as in the case of other complexes containing
iodide ion in the ionization sphere, cg~ electron transfer probably occurs from the iodide ion to the
cobalt(III) ion in [Co(NH3)4CO3]I. This may account for the erratic behaviour observed in the reduction curve.
Mass spectrometer data indicated the presence of the expected carbon dioxide, ammonia and
water, as well as small amounts of nitrogen and nitrogen(II) oxide in the dissociation products. If
any nitrogen(I) oxide was present, its peak was masked by the carbon dioxide peak (m/e = 44).
I~) G. SCHLESSINGER,Inorganic Syntheses (Edited by E. G. ROCHOW) (Vol. VI) p. 173, McGraw-Hill,
N.Y. (1960).
in) W. W. WENDLANDT, Thermal Methods of Analysis, Interscience- Wiley, N.Y. (1964).
,47 E. L. SIMMONSand W. W. WENDLANDT, submitted for publication.
is) W. W. WENDLANDTand T. M. SOUTHERN,Analytica chim. Acta 32, 405 (1965).
t6) T. M. SOUTHERN, J. R. WILLIAMSand W. W. WENDLANDT,J. inorff, nucl. Chem. 28, 1411 (1966).
m E. L. SIMMONSand W. W. WENDLANDT, submitted for publication.
la~ N. TANAKAand M. NANJO, Bull. chem. Soc. Japan 37, 1330 (1964).
tg~ W. W. WENDLANOTand J. P. SMrrn, Or. inorg, nucl. Chem. 25, 843 (1963).

Notes

1487

,,

50

5O

t'Z
W
t)
n,.*
bJ
O.

I00

" ~ ~ - -

I00

200

IOO

3oo

IOO

I
200

I
300

TEMP. C

FiG. 1 . - - M a s s - l o s s a n d per cent c o b a l t ( I l l ) reduced curves. ( A ) [Co(NH3)~COs]CI;

m a s s - l o s s - - - per cent c o b a l t ( I l l ) reduced.

@
II
II
t

I t
I
I

50

I
I

FZ
w

n~
w
[3.

I00

I
I OO

I
2OO

0(

I
300

I
I00
TEMP.

200

I
:300

FI~. 2 . - - M a s s - l o s s a n d per cent c o b a l t ( I l l ) reduced curves. ( A ) [Co(NH3)4CO3]I;

(B) [Co(NH3)~CO3]NOa.0-5 H~O; - m a s s - l o s s - - - per cent c o b a l t ( I I D reduced.

1488

Notes
TABLE 2 . - - R E A C T I O N

Co2OX2
moles/2 moles Co
Theor.
Found

Compound
[Co(NHa)~CO3]CI
[Co(NH3)4COs]Br

1
I

1"01
1'01

STOICHIOMETRY DATA ta~

NH3
moles/mole Co
Theor.
Found
3"66
3"66

CO2
mole/mole Co
Theor.
Found

3"68
3'46

1
1

0-90
0"97

~"~ Mole ratios based upon Equation (1).

From the reaction stoichiometry studies, as summarized in Table 2, the dissociation reaction obeys
the equation:

6[CofNH3),COs]X(s) --~ 3Co2OX2(s) q- Nz(g) -k 6CO~(g) -k 22NH3(g) q- 3H20(g)

(1)

The exact nature of the solid residue, Co~OX2, is not known. From the mass-loss curve, this is the
indicated stoicheiometry; on heating the compound to 500C in air, Co804 is formed. No consistent
stoichiometry results could be obtained for the nitrate or iodide complexes. For the former,
2.5-2-7 moles of ammonia and one mole of carbon dioxide, per mole of complex were found. For
the latter, 3"3 moles of ammonia and 0'58--0.62 moles of carbon dioxide, per mole of complex were
observed, as well as iodine vapour.

Acknowledgment--The support of this work by the United States Air Force, Office of Scientific
Research, through Grant No. 23-63, is gratefully acknowledged.

Department of Chemistry,
Texas Technological College,
Lubbock, Texas

W . W . WENDLANDT
J . H . WOODLOCK

J. inorg, nucl. Chem., 1966, Vol. 28, pp. 1488 to 1489. Pergamon Press Ltd. Printed in Northern Ireland

Dilanthanide molybdates and tungstates Ln2MOe

(Received 26 January 1966)
BORCHARDTtll has recently described tungstates of the lanthanides Ln~WOs. The present note
describes the analogous molybdates Ln2MoO8 and the structures of these compounds.
Materials were prepared by firing intimate mixtures of MoO3 or WO3 and Ln203 at 1000 or
1300C respectively. X-ray diagrams were obtained on a Philips diffractometer using copper
radiation.
Table 1 presents a survey of the results, including those for the analogous bismuth compounds
reported earlier. ~2~
We were able to determine the structure types of these compounds from the X-ray powder data.
The structure of LazMoO6 has been described by SmL~N and LUNDBORGJ8) The structure of the
series LnzWO6 (Ln = Ho-Lu, Y) can be deduced from the La2MoOe structure by a monoclinic
distortion. X-ray powder patterns of this series look like that of La2MoO6, but a number of reflections
are split. All reflections except some weak ones could be indexed on a monoclinic cell, which is
twice as large as that of La~MoO~: La2MoOs is tetragonal with a = 4.09 and c = 15-99 .~, Y2WOe,
for example, is monoclinic with a = 5"50, b = 5'34, c = 15.15/~ and fl -----88"3.
The powder patterns of the series Ln2WO6 (Ln = Pr-Dy) and Ln~MoO6 (Ln = Sm-Lu, Y)
differ from that of LazMoOs, but resemble that of BizNbOsF. t4) They were indexed using a cell
~1~H. J. BORCHARDT,J. chem. Phys. 39, 504 (1963).
c~ G. BLASSE,J. inorg, nucl. Chem. 28, 1124 (1966).
ts~ L. G. SILL~Nand K. LUNDBORG,Z. Anorg. allg. Chem. 252, 2 (1943).