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216 INORGANIC S Y N T H E S E S
Procedure
A. HEXAMMINECOBALT(II1) CHLORIDE
4COc12 + 4NH4Cl+ 20NH3 + 0 2 +
4[Co(NH3)6]Cl, + 2HzO
Two hundred and forty grams (1 mol) of cobalt(I1)
chloride 6-hydrate and 160 g. (3 mols) of ammonium
chloride are added to 200 ml. of water. The mixture is
shaken until most of the salts are dissolved. Then 4 g. of
activated decolorizing charcoal* and 500 ml. of concen-
trated ammonia are added. Air is bubbled vigorously
* In order to obtain a rapid reaction, care must be exercised in the choice
of this catalyst. Charcoal from the center of a package has been found t.o
be much more effective than that from the top.
218 INORGANIC SYNTHESES
B. HEXAMMINECOBALT(II1) NITRATE
1. 4Co(NO3)2 + 4NH4NO3 + 20NH3 +
4[Co(NH3)6I(NO3)3+ 2Hz0
0 2 -+
C. 'HEXAMMINECOBALT(II1) BROMIDE
+
CoC03 2HBr -+ CoBrz HzO 4- COz +
+ +
2CoBrz 2NH4Br 10NH3 H202 -+ +
2[Co(NH3)JBr3 + 2Hz0.
Twenty-four grams (0.20 mol) of cobalt carbonate* is
added slowly to 100 ml. of 45 per cent hydrobromic
acid (0.80 mol). To the solution, 2 g. of activated char-
coal and 120 ml. of concentrated ammonia (1.6 mols of
NH3) are added. The precipitate of cobalt(I1) salt that
appears is disrega.rded, and 40 ml. of 30 per cent hydrogen
peroxide (0.40 mol) is added slowly while the solution is
stirred. When the vigorous effervescence has ceased, the
main part of the cobalt(I1) precipitate has been converted
into the desired product. To complete the equilibrium
adjustment, the mixture is heated for 5 min. on a steam
bath and then left standing for 55 hr. The salt-carbon
mixture is filtered, washed with a little cold water, and
treated with 900 to 1000 ml. of water containing sufficient
* A cobalt determination must be made on the cobalt carbonate used if a::
accurate check on the yield of the complex salt is desired.
220 INORGANIC SYNTHESES
D. HEXAMMINECOBALT(II1) OXALATE
+
~ [ C O ( N H ~ ) ~ 3Na2C2O4
]C~~ +
4H20
[ C ~ ( N H ~ ) ~ I Z ( C Z ~6NaC1+
~)~.~HZ~
Hexamminecobalt(II1) oxalate is prepared by adding a
soluble oxalate t o a solution of the ch10ride.l~ The salt
dried at 96" contains four mols of water. This precipita-
tion is a quant,itative method for determining the amount
of hexamminecobalt(II1) ion in a mixture.
Properties
The hexamminecobalt(II1) salts are obtained as reddish-
brown crystals, orange-yellow when finely divided. The
solubilities in water in mols per liter at 20" are: chloride,
0.26; nitrate, 0.052; sulfate, 0.020; oxalate (18"), 0.00069;
bromide (18"), 0.04. In liquid ammonia at -80" the
chloride forms a 6-ammoniate of the formula
[CO(NH3)6]Cl3*6NH3.
The oxalate is soluble in oxalic acid solution. A great
many double salts are formed. A detailed discussion of the
properties and formation of other salts appears in Gmelin.16
References
1. FREMY:Ann. chim.phys., 131 36, 257 (1852).
2. JORGENSEN:2. anorg. Chem., 17, 455 (1898).
3. LA^ and LARSON: J. Am. Chem. SOC.,42, 2025 (1920).
4. MORGAN and MAINSMITH: ibid., 121, 1970 (1922).
TRIS(ETHYLENEDIA,VLINE)COBALT(NI)CHLORIDE 22 1
5. J . prakt.
JORGENSEN: Chem., [2] 23, 229 (1881).
6. RIILLs: Phil. Mag.; [4] 36, 245 (1868).
7. B ~ u N Ann.,
: 142, 52 (1867).
8. JACOBSEN: Overs. Danske Sclsk. Forh., 1899, 564.
9. Ref. 2, p. 457.
10. BILTZ:Z. anorg. Chem., 83, 178, (1914).
11. BILTZand BILTZ:(trans. by Hall and Blanchaid): “Laboratory Methods
of Inorganic Chemistry,” p. 175, John Wiley & Sons, Inc., New York,
1909.
12. Ref. 8, p. 575.
13. Ref. 10, p. 177.
14. BJERRUM:“Metal Ammine Formation in Aqueous Solution,” p. 241,
P. Haase and Son, Copenhagen, 1041.
15. SORENSEN:dissertation, p. 64, Copenhagen.
16. GMELIN: “Handbuch der anorganischen Chemic,” No. 58 B (Kobalt-
ammine), pp. 46-72, Verlag Chemie G.m.b.H., Eerlin, 1930.
Procedure
Sixty-one grams of 30 per cent ethylenediamine is partly
neutralized with 17 ml. of 6 N hydrochloric acid and the
* UrGversity of Illinois, Urbana, Ill.
t The Ohio State University, Columbus, Ohio: deceased,