PYRIDINE COMPLEXES OF COPPER (II)-POLYTHIONATES AND THEIR ANALYTICAL APPLICATION

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP78-04861A000400030009-7
• Release Decision: RIPPUB
• Original Classification: K
• Document Page Count: 9
• Document Creation Date: December 20, 2016
• Document Release Date: June 6, 2006
• Sequence Number: 9
• Publication Date: August 1, 1955
• Content Type: REPORT

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PYRIDINE COMPLEXES OF COPPER (II)-POLYTHIONATES
AND THEIR ANALYTICAL APPLICATION
Zettschrtft fur Anorganische Chemie 2Z (1954) 146-154
(From German)
Ay$utt 1955
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 Approved For Release 2007/10/23: CIA-RDP78-04861AO00400030009-7
PYRIDINE COMPLEXES OF COPPER (11)-POLYTHIONATES
AND THEIR ANALYTICAL APPLICATION
Zeitschrift fur Anorganische Chemie 21$ (1954) 146-154
(From German)
SUMMARY
The tetrapyridine-copper (II)-salts of tri-, tetra- and pentathionic acid are well
crystallised compounds, stable when cold, which are distinguished by crystal form and
solubility, and to some extent also by their colour (violet to blue). The most stable of
them, and at the same time the one which dissolves with greatest difficulty, is the
tetrathionate complex.
Only tri- and pentathionate are precipitated as slightly' soluble luteo compounds
by [Oo(NH3)6]C13 from the three polythionic acids; in the supernatant solution it is then
possible to precipitate [Cu(NC5H5)4]3406. Thus it is possible to obtain a good qualitative
determination of 9402 in the presence of, the other polythionic acids and thio-sulphuric
acid, which has hitherto been impossible.
Moreover, [Cu(NC5H5) 4] S406, with its Cu content of only 10.57, is suitable for the
gravimetric determination of even small amounts of copper. A method Is Indicated for
the rapid and accurate determination of amounts of copper down to 5 mg, using the normal
analysis apparatus (accuracy *,%).
Although the polythionates of various divalent heavy metals, e g. zinc, manganese,
nickel and cobalt, are fairly stable if there is no dampness in the atmosphere, it is
almost impossible to obtain stable, defined copper (II)-polythionates. Thus, v. tEINES
and CHRISTOPH [1]*, who described the preparation of numerous tetra- and penta-thionates
from heavy metals, were only able to produce the corresponding copper salts very
transitorily, as extremely unstable substances. In a work on the even more sensitive
heavy metal salts of trithionic acid MEUWSEN and HEIN ZE [2] were also unsuccessful in
obtaining from copper, in contrast to some other heavy metals, even one stable
trithionate. Even under the most careful conditions, sulphide separation occurred during
the attempt to procure its Isolation. Stabilisation of Cu3306 was only possible by
the formation of complexes; after the addition of pyridine to Its diluted, aqueous
solution, the crystalline, violet complex salt ICu(NC5H5)4]S3O6 (abbreviated to [CUPy4]SD6),
which is very stable.
The very slight solubility and low copper content of this compound led to the
investigation of its suitability for a separation and weighable form of copper.
With this object, the complex tetrathionate [CuPy4]5406, which had already been described
by CALZOLARI [3] as very slightly soluble blue needles, was again prepared and tested.
Contrary to expectations, a pentathionate with the formula [CuPy4]8506 . Zi.0 was also
obtained and, this asdistinct from.tri- and tetrathlonates, contains water of crystallisation.
The material. consists of blue flakes which dissolve without too much difficulty, remaining
stable for a few weeks but only if preserved in a cool situation.
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MOROAN and BURSTALL [4], after many fruitless experiments with the object of preparing
copper (II)-diethy1eaiiaminEpentathionate, came to the conclusion that the existence of such complex
pentathionates was not possible, on account of the effect of nitrogen bases on S5A;2. V. DEIPES
and CHRISTOPH [1] also question the possibility of obtaining these compounds, because, through the
alkalinity of nitrogeneous complex-forming substances, such as pyridine or ethylene diamine, the
pentathionate woulddedompo'se to the tetrathionate with' the separation of elemental sulphur.
Contrary to the statements of these authors, however, when ethylene diamine or pyridine is
added to dilute solutions of entirely pure pentathionate, there is no appearance of turbidity
through the precipitation of sulphur. Thus; the addition of pyridine to the aqueous solution of
CuSO4 and K28506 results in the precipitation of the pure, complex copper pentathionate. On the
other hand, the violet crystals which were separated by adding alcohol to7a solution of CUS506
which contained ethylene diamine, were always mixtures of tetra- and pentathionates. The
substantially higher alkalinity of the aqueous solution of ethylene diamine (Kb = 8.5 . 10 5
compared with 1.7 . 10-9 for pyridine at room temperature) obviously causes partial decomposition
of the pentathionate, although no separation of sulphur can be observed.
The three pyridine complexes are insoluble in methyl alcohol, ethyl alcohol and ether;
their solubility in water decreases from the pentathionate, through the trithionate to the
tetrathionate. Apart from this the latter is also the most stable compound and at room temperature
it persists for months without decomposing.
By means of the copper-pyridine-polythionates it is possible to fill a gap Which exists
in.the qualitative analysis of the polythionic acids. While there are good indicator reactions
for the tri- and pentathionate, the reactions which are known for the tetrathionate also affect
the pentathionate equally. The presence of S406 2 can, even if only relatively small amounts of
S5062 are also present, be determined only by indirect means, i.e. by a series of quantitative
determinations; qualitative determination has hot yet been found possible [5][6]. The systematic
investigation of microcrystal precipitations by CHAMOT and BRICKENKAMP [7] particularly, likewise
brought no substantial progress In the case of tatrathioriate analysis.
Although the 'relatively easily soluble pentathionate is not suitable for indication, the
violet crystals of [CuPy4]S3o6 may possibly be used for identifying trithionic acid, assuming,
of course, the absence of certain anions. A special interest, however. attaches to the blue
needles or oblong prisms of the copper pyridine tetrathionate, because they permit direct
indication of tetrathionic acid, even in the presence of other polythionic acids and thin-sulphuric
acid. If the greater part of these disturbing Ions be eliminated beforehand as very slightly
soluble luteo compounds with [Co(NH3)6]C13, which gives no precipitate with tetrathionate, it is
possible 'to carry out the process of its identification in the remaining solution as [CuPy4]8406
without any special difficulty.
Owing to the slight solubility of this complex tetrathionate in excess solution of reagent
and its low copper content (10.60, it can also be considered for the quantitative determination
of copper. The precipitates obtained under analytical conditions exhibit 'a composition in
conformity with the formula: persistent moisture can be eliminated rapidly with alcohol and ether,
thus removing the tedious drying process at elevated temperatures. This method has been proved
successful in the case of many other weighable substances of similar composition, as has
been shown by SPACU and collaborators. We are familiar with determinations of divalent zinc,
manganese, cobalt, nickel, cadmium and copper as tetrapyridine, or dipyridenerhodanide, e. g.
[N1Py4](S(N)2 [e] or [CuPy5](SCN)2 [9], which combine accuracy with speed; their low specificity
however, is an obstacle to a wider application of these procedures.
Since, by contrast with copper, even moderately concentrated solutions of zinc, manganese,
cobalt and nickel form no sparingly soluble complex salts In pyridine and tetrathionate-containing
solution, it seemed appropriate to use [CuPy4]S4o6 for a rapid determination of copper, which
`could be applied even in the presence of these ions. Unfortunately, however, the accompanying
metals become involved to a greater or lesser degree, even in hot conditions. By adhering to
definite working conditions, it is possible to carry out only the determination of copper in the
presence of manganese; the zinc, nickel and cobalt content of the solution may amount to a
maximum of a few per cent of the amount of copper.
On the other hand the separate operation for copper determination was very satisfactory
as regards the degree of precision. Owing to its speed and very low conversion ratio (F = 0.1052),
the determination as [CuPy4]5406 may be advantageous in certain cases. Thus, amounts of copper
as low even as 5 mg can be determined accurately, to J%, using the normal analytical balance and
ordinary apparatus. It will also be possible to make accurate determinations of small quantities
of precipitated copper sulphide, after ignition and treatment with potassium.pyrosulphate, as
[CuPy4]s406, where the process of weighing as copper oxide would give most unreliable results,
owing to the quantity being too small or on account of Impurities.
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DESCRIPTION OF EXPERIMENTS
Starting materials: K28306 was obtained according to RASCHIG [i0] by introducing
so, into a solution of Na2S203 and NaHN3 in the presence of arsenite and precipitation with
KCI. Na2S406 . 2 H2O and K2S406 were prepared according to KURTENAQ(ER and LASZLO [11] and
,KURTENACKER and FLUSS [i'''] from.S02 and Na2S203 with arsenite as catalyst. For obtaining
K23506 . 3 I120 As(III) was similarly used: as a catalyst to assist the conversion of thlo-
sulphuric acid into pentathionic acid In the method of STAMM, SEIPOLD and GOEHRfNG [13].
All the salts were quite pure after one recrystallisation.
Copper (II)-tetrapyridine pentathionate: 2.50 g (= 10.0 rmcl) Cu904 5 H2O and
5.40 g (= 15.0 mmol) K5S505 . 2 H2O are dissolved in 400;wl water. 15 ml pyridine is added
and immediately stirred vigorously; rapid separation of a blue deposit consisting of thin
crystal flakes is produced. This is separated without delay, washed with water, and after
treatment with alcohol and ether it is dried over silica gel in the evacuated desiccator.
The yield Is. about 5.0 ;g = 75% `of the theoretical
[Cu(NC5H5) 4] 5506 . 2 H2O
Calculated
Cu 9.5
S 23.8
C 35.7
H 3.6
N 8.3
Found
9.619.6
24.0,23.9
36.4
3.7
8.6
Copper (II)-tetrapyridine trithionate and copper (II) tetrapyridine tetrathionate:
By a simplification of the methods of preparation referred to [2.3], the two complex salts
can be obtained in an. analogous manner to the pentathionate. Instead of K28506 use is made
of 2.80 g (= 10.4 mmol) K23306 or 3.20 g (= 10.4 mmol) Na2S406 2 H20. The yield of
[CuPy.4]5306 is about 4.0 g = 70~, of [CuPy4]5406 about 5.7 g = 9.6% of the theoretical.
Distinction between 53062 and S406-: A micro-drop (0.01 ml) of the solution to be
tested is mixed on the object slide with an equal volume of the reagent solution
(0.85 5 CuC12 2 H2O + 8.0 g pyridine/100 ml); If ;spontaneous crystallisation does not
occur, this can be stimulated by scratching with a sharp-edged glass rod. If 53062
(x.0.02 molar) is present, rectangular, violet crystals appear. (Figure 1). Limit of
detection: .40 y 53062; limit concentration: 1:250.
In the case of the tetrathlonate (> 0.02 m) there is inn Q1iate separation of needles
or elongated prisms (Figure 2), which, In contrast to the trithionate crystals, show a pure
blue coloration. Limit of detection: 12 y S,4062; limit concentration: 1:850. With
lower concentrations down to 0.005 m scratching with a needle is necessary to produce the
crystals..
The blue crystals of the pentathiona.te (Figure 3) appear only from a fairly concentrated
solution; they have almost no significance for the identification of S5082.
Determination of 54082 together wi Lh the other polythionates and other disturbing anions:
then S4062 and tri- or pentathionate are present simultaneously, there is always formation of
peculiar growth forms of mixed crystals with a predominating tetrathionate content. For
perfect identification of S4062, therefore, the greater part of the other polythionates must
be removed, a procedure which is possible by precipitation with cobalt (III)-hexammine chloride.
A few drops of the experimental solution are gradually mixed in the pointed capillary
tube with mall amounts of extremely finely ground [Co(NH3).6]Cl3; each time the precipitation
of the luteo salts' Is. brought about by vigorous trituration with a glass rod, and the solid
reagent is added until the'solution is coloured yellow by the excess. Centrifuging is then
performed. and a drop, removed with the capillary tube; this is then-tested, by the addition of
copper chloride-pyridine reagent and seeding, for 54062. With very low concentrations, the
crystals do not appear before 5-10 minutes.
[Co(NH3)6Icl3 is also the means of removing the disturbing ions r, 52082 and 52032.
The iodide would later give the Insoluble Cu_ with the reagent. In a moderate concentration
(> 0.1 m) dlthionate with CuC12 and pyridine would produce a precipitate similar to the 53062
which would make it more difficult to recognise the [CuPy4]5406 crystals. Special care must
be taken to ensure that thiosulphate is completely eliminated as regards its use as a luteo
salt because, in accordance with .
3 520 + 2 Cu 2 -. Cu28203 + 54062.
it would give, with the reagent solution, exactly the substance to be determined, 54062
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With the precipitation of fairly large amounts of luteo salts the solution loses some
5406 2, so that the sensitivity given for the separate determination of tetrathionate is not quite
achieved. In tests with 0402 m 54082 solutions the determination was still quite successful, even
with the 20-fold molar excess of the acids mentioned, especially too, the pentathionic acid;
corresponding blank determinations always produced negative results. C1_1 Br , NC,'80-2 have
no effect on the determination and similarly, ammonium salt up to a 0.5 molar concentration does
not influence the sensitivity at all.
?Separate determination of copper: For quantitative precipitation of copper a concentration
of about I g tetrathionate and 4 ml pyridine in 100 ml precipitation volume is sufficient.
An excess is not harmful. In a still solution the complex salt is only precipitated slowly;
by stirring either more 'or less vigorously it is possible to produce at will either fine or
coarse crystals. In all cases the deposit is very readily filterable and washable and does not
adhere to the glass-wall. The method was checked by means of a CuS04 solution with a content of
exactly 1 mg Cu/ml, the titration standard of which was verified electro-gravimetrically. Cu
determinations as [CuPy4]5406 were carried out as follows:
The neutral, or very weakly acid solution, which should contain 15-50 m,3 Cu, Is diluted
to about 80 ml, mixed with pyridine to a dark blae coloration first, and then with another 4 ml.
More strongly acid solutions are first almost neutralized with NaOH. On the addition of I g
sodium or potassium tetrathionate (dissolved in a few ml water) the precipitate appears either at
once or - in the case of small amounts of copper after stirring.. After some minutes, complete
precipitation of. the complex salt will be effected, by stirring with a glass rod and then, when
the supernatant solution is no longereblue in colour, cooling is carried out by standing for half
an hour in ice-cold water; with frequent vigorous stirring. The solution Is then filtered at
a pump on an A 2 porcelain filter crucible or a 1 0 4 glass filter crucible. For transferring
the remainder of the precipitate into the crucible,, the filtrate. is used, or if this is not
permissible, a similarly cooled solution of equal reagent-concentration (= 1 g tetrathionate
+ 4 ml pyridine/100' ml).- The outside of the crucible Is well wiped and the precipitate is dried
by washing three times at the pump with 1-2 ml absolute alcohol to which pyridine has been added
in the amount a ml to 100 ml. Each time, the suction is stopped, . and the alcohol allowed to
run down the whole crucible wall by means of a thin glass rod, and is then pumped off. There
follow 5-10 washings (according to the amount of precipitate) with a micro-wash-bottle using
small portions of absolute ether, containing pyridine (100 ml ether +. 15 drops of, pyridine).
The crucible is then rinsed again outside and evacuated in a desiccator charged with silica gel.
After 10-15-minutes weighing is carried out. F = 0.1052, log F = 0.02188 1.. Time required:
1 determination takes about 60 minutes, 4 determinations about 90 minutes including the cleansing
and weighing of the empty crucible.
According to the analyses shown in Table 1; the method gives accurate results over a wide
range, for equal additions of reagent and equal volumes of precipitate; with very low concentrations,
however, the values come out too low. Accurate determination of copper is possible, however, as
soon as work Is carried out with the same reagent concentration in smaller volumes. If, for
example, a solution containing only about 20 ml is precipitated with 1 ml pyridine and 0.25 g
tetrathionate, then, if the procedure is followed without other modification, very accurate values
are obtained, down to S mg copper. With still smaller copper contents the method becomes uncertain
once more but, of course, on account of weighing errors the limit of application of ordinary
analytical balances has then almost been reached. In Table 2 are shown the values for a series
of determinations which, on account of the small volumes and amounts of precipitate, can be
carried out particularly quickly. In this case single weighed amounts of pure CUSO4 . 5 H20,
measured out in the measuring flask, were analysed.
The presence of alkali salts has no effect on the accuracy of the determination; in the
analyses in Table 1, up to 3 g KC1 or KH SO4 was added in some cases before precipitation. On
the other hand, interference is caused by complex-forming substances such as NH 3, tartrate, etc.,
which combine with Cu+2' to form stable complex ions. Ammonium salt also, even in moderate
concentration, Interferes in the quantitative separation of copper. For example, with the
addition of 1 g NH4C1/100 ml the Cu-value came out too low by 1.0?'-, with the addition of 2 g
.NH4C1, 3.2.
Separation of copper from manganese: Coprecipitation of manganese can be prevented to
a high degree by precipitating the greater part of the copper in the presence of an approximately
equal amount of' tetrathionate and only tnen adding an excess. Purer precipitates are also
obtained if, in addition, to free pyridine, a little pyridinium salt is also added. The procedure
is as follows:
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The neutral solution, which should be about 80 ml, is mixed first with 5 ml approximately
normal HCl or I g KH8J4, then with 6 ml pyridine. 1 g tetrathionate is dissolved in 10 ml water
and at first only 2 ml is taken for analysis. After allowing it to stand for a short time a
precipitate is brought down by stirring and then the remaining 8 ml is added in small quantities
during the course of some minutes; while this is happening the precipitate is agitated each
time by vigorous stirring. It is then put into ice and the procedure which follows is the
same as that for the separate determination of copper (Control analyses; Table 3).
When more than 5-10% of cobalt, nickel and especially zinc Is present the values for
the copper become too high; smaller amounts of the above foreign metals, on the other handy
hardly have any effect on the determination as [Cu(NC5HS) 4] 5406.
REFERENCES
[i] 0.v. IEINES and E. CHRISTOPH. Z. anorg. alig. Chem. = (1933) 209.
[2] A. MEUWSEN and G. HEINZE. Z. anorg. alig. Chem. 02 (1952) 86.
[3] F. CALZOLARI. Atti Accad. naz. Lincei "A (1915) 921
[4] G. T. MORGAN and F.H. BURSTALL. J. Clem. Soc. (London) (1) 1927, 1268.
[5] A. KURTENAC ER. Analytical Chemistry of the Oxygen Acids of Sulphur.
Stuttgart, 1938, p. 139.
[8]
Handbook of Analytical Chemistry Part II, Qualitative methods of analysis,
Berlin and Heidelberis 1948, p. 84.
[7] E.M. CHAMOT and R.W. BRICKENKAMP. Mikrochemie t,,g (1935) 121.
[a] G. SPACU and J. DICK. Z. analyt. Chem. 7A (1927) 492.
[9] G. SPACU and J. DICK. Z. analyt. Chem. U (1927) 185.
[10] F. RASCHIG. Sulphur and Nitrogen Studies, 1924, p.295.
[11] A. KURTENACKER and G. LASZLO. Z. anorg. allg. Chem. = (1936) 359.
[12] A. KURTENACKER and W. FLUSS. Z. anorg. alig. Chem. 2L0 (1933) 128.
[13] H. STAMM, 0. SEIPOLD and M. GOEHRING. Z. anorg. allg. Chem. 24_7 (1941) 277.
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EXP. NO.
STANDARD
WEIGHED
COPPER/mg.
RELATIVE
SOLUTION
AMOUNT
CALCULATED
FOUND
ERROR
[ CUPY4] S406
N
ml
Mg
1
100.00
953.2
100.00
100.24
+ 0.2
2
100.00
953.3
100.00
100.26
+ 0.3
3
50.00
475.1
50.00
49.97
- 0.1
4
50.00
475.4
50.00
50.00
-
5
50.00
473.9
50.00
49.84
- 0.3
6
50.00
475.3
50600
49.99
-
7
25.00
236.8
25.00
24.90
- 0.4
8
26.00
237.2
25.00
24.95
- 0.2
9
25.00
237.7
25.00
25.00
-
10
25.00
237.9
25.00
25.02
+ 0.1
11
25.00
237.6
25.00
24.99
-
12
25.00
238.2
25,00
25.05
+ 0.2
13
20.00
190.9
20.00
20.08
+ 0.4
14
20.00
190.7
20.00
20.06
+ 0.3
15
20.00
190.7
20.00
20.06
+ 0.3
16
20.00
190.9
20.00
20.08
+ 0.4
17
20.00
190.9
20.00
20.08
+ 0.4
18
20.00
190.5
20.00
20.03
+ 0.2
19
15.00
142.2
15.00
14.95
- 0.3
20
15.00
142.5
15.00
14.99
- 0.1
21
15.00
142.1
15.00
1404
- 0.4
22
15.00
142.5
15.00
14.99
- 0.1
23
15.00
142.5
15.00
14.99
- 0.1
24
15.00
142.1
15.00
14.94
- 0.4
EXP.NO,
WEIGHT OF
WEIGHT OF
COPPER/mg.
RELATIVE
CuSO4 . 5 aq
LCuPY4J 5406
CALCULATED
FOUND
ERROR
Mg
mg
%
25
237.8
114.7
12.10
12.06
- 0.3
26
237.6
115.1
12.10
12.10
-
27
237.8.
114.8
12.10
12.07
- 0.3
28
237.5
114.7
12.10
12.06
- 0.3
29
172.5
83.9
8.78
8.82
+ 0.5
30
172.5
83.7
8.78
8.80
+ 0.2
31
147.4.
71.2
7.50
7.49
- 0.1
32
147.4 .
71.3
7.50
7.50
-
33
147.4 .
71.4
7.50
7.51
+ 0.1
34
147.4 .
71.2
7.50
7.49
- 0.1
35
122.9 .
59.1
6.26
6.22
- 0.6
36
122.9 .
59.5
6.26
6.26
-
37
122.9 .
59.2
6.26
6.23
- 0.5
38
104.1 .
50.5
5.30
5.31
+ 0.2
39
104.1 .
60.5
5.30
5.31
+ 0.2
40
104.1 .
50.5
5.30
5.31
+ 0.2
41
104.1 .
50.4
5.30
5.30
-
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EXP.NO. STANDARD
SOLUTION
FOREIG WEIGHT OF
METAL [CuPy4]S4O6
mg mg
25.00
25.00
25.00
26.00
25.00
25.00
25.00
25.00
50.00
50.00
10.0
25.0
25.0
25.0
25.0
35.0
50.0
50.0
25.0
50.0
237.9
237.7
238.0
237.5
238.6
238.7
238.1
238.7
476.4
476.0
52
53
54
55
56
2 5.00
25.00
25.00
25.00
25.00
1.0
2.0
3.0
4.0
5.0
238.8
238.3
237.7
238.1
239.2
57
58
59
80
61
25.00
25.00
25.00
25.00
25,00
1.0
2.0
3.0
4.0'
5.0
23 7.4
237.1
237.8
239.6
240.3
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
50.00
50.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.02
25.00
25.03
2 4.98
25.09
25.10
25.04
25.10
50.10
50.06
24.90
25.06
25.00
25.04
25* 16
24.97
24.94
25,01
2 5.20
25.27
RELATIVE
ERROR
+ 0.1
- 0.1
+ 0.4
+ 0.4
+ 0.2
+ 0.4
+ 0.2
+0.1
- 0.4
+ 0.2
+ 0.2
+ 0.6
- 0.1
- 0.2
+ 0.8
+ 1.1
62
25.00
1.0
238.1 1 25.00
25.04
+ 0.2
63
25.00
2.0
239.1 1 25.00
25.15
+ 0.6
64
25.00
3.0
241.1 25.00
25.36
+ 1.4
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If .
Fig.l: Crystals of [CiPy4]SP6
(Magnified x 60)
Fig.2: Crystals of [CuPy4]S4O6
(Magnified x 60)
F1g.3: Crystals of [CuPy4]SSD6
2 H2O (Magnified x 60)
Approved For Release 2007/10/23: CIA-RDP78-04861A000400030009-7