850 Short communications

Financial support by the school of graduate studies University of Missouri - Kansas City is grate-
fully acknowledged.
Department of Chemistry DONALD A. S~UCEK
University of Missouri - Kansas City K. L. CHENG
Kansas City. Missouri 64100, U.S.A. HENRY A. DROLL

Summary-The stability constants of some non-protonated 1: 1 metal

complexes of triethylenetetraminehexa-acetic acid are reported; log
K values are Cd 19.8, Co(II) 20.4, Ni 19.9, Pb 19.5, Sm(II1) 24.3, Zn
20.1.
Zusammenfassung-Die Stabilitltskonstanten einiger nichtprotonierter
Metallkomplexe (1: 1) von Triiithylentetraminhexaessigstiure werden
mitgeteilt; die log K-Werte sind fiir Cd 19,s; Co (II) 20,4; Ni 19,9;
Pb 19,5; Sm (III) 24,3; Zn 20,l.
R&urn&--On rapporte les con&antes de stabilitb de quelques complexes
m&alliques non proton& 1: 1 de l’acide tri&hyl&net&raminehexa-
acetique; les valeurs de log K sont Cd 19,s; Co(H) 20,4; Ni 19,9;
Pb 19,5; Sm(II1) 24,3; Zn 20,l.
REFERENCES
1. R. S. Sievers and J. C. Bailar, Jr., Inorg. Chem., 1962, 1,174.
2. T. A. Bohigian and A. E. Martell, ibid., 1965,4, 1264.
3. R. Pfibil and V. Veself, Talanta, 1962,9,939.

Talmta, 1968,Vol. 15,pp. 850to 852. PergatmnPress. Printedin Northern Ireland

Improved specific separation of selenium by solvent extraction with saturated

monoketones
(Received 22 December 1967. Accepted 18 March 1968)

IN PREVIOUS paper++ we have shown that in moderately concentrated hydrochloric acid, selen-
ium(IV) reads with saturated aliphatic monoketones (acetone, ethyl methyl ketone, diethyl ketone,
isobutyl methyl ketone, etc.) to form organoselenium compounds that are soluble in chloroform.
In our earlier work we were unable to decide which was the most suitable ketone, or the best method
for complete decomposition of organoselenium compounds without loss of selenium. The aim of the
present paper is to deal with these problems.

EXPERIMENTAL
The experiments were carried out with a solution containing 100 rg of selenium per ml and labelled
with the &active isotope Ye; 1 ml of this solution had an activity of 4670 cpm. The ketones used
were distilled, and then stored in the dark. The hydrochloric acid must contain no free chlorine,
because the latter interferes with formation of the organoselenium compounds.
Choice of ketones
According to our previous work,4 the rates of interaction of selenium with various ketones do
not differ significantly (except for isobutyl methyl ketone), at the same acidity. In the present investi-
gation, attention was given to the availability of the ketones and to their behaviour during the de-
composition of the organoselenium compound. The most suitable were acetone, ethyl methyl ketone
and acetophenone.

The aqueo;s phase containing 100 ,ug of selenium and 0.025-1.0 ml of ketone was acidified to the
desired decree. diluted to 10 ml and shaken. After standing for 30 min. the organoselenium comuound
was extracyed with 10 ml of chloroform, and the activity 07 both phases was Measured. Formaiion of
the organoselenium compound begins at lower acidity with acetone or ethyl methyl ketone than
with acetophenone, but at sufficiently high acidity formation is most complete with acetophenone.
 Short comrmmications 851

Moreover, the extractability is independent of the total ethyl methyl ketone or acetophenone con-
centration whereas it is strongly dependent on acetone concentration. The influence of sulphuric
acid was examined because some types of sample are dissolved in sulphuric acid; sulphuric acid up to
2M concentration does not affect the extraction.

Decomposifion of fhe organaselenium compound

It is very difficult to-decompose the organoselenium compound completely without formation of
coloured decomuosition uroducts and loss of selenium. Manv uossibilities were studied. The best
found was the one used in the recommended procedure. Its &ciency was checked radiometrically
and no loss of selenium was found.

~omposifion of the a~efophe~ne-seienium compound

Selenium dioxide was dissolved in 7M hydrochloric acid in a separatory-funnel, then acetophenone
(mole ratio acetonhenone:selenium = 25) was added dronwise with shakine. After formation
of a white crystalline precipitate the mixture was shaken vigorously for a long crne and allowed to
stand for 2 hr. Excess of ketone was extracted into benzene and the precipitate was filtered off under
suction, washed first with chloroform, then with ethanol, and dried at room temperature. The white
needle-shaped crystals were soluble in acetophenone and chloroform. Elementary analysis corre-
sponded to the formula SeCl,(C,HO,),.

APPLICATIONS
Determination of selenium in copper concentrate
Add 15 ml of cont. hydrochloric acid to 0.2-2 g of sample (depending on the selenium content).
Heat on a water-bath until the evolution of hydrogen sulphide ceases, cool slightly and add 5 ml of
cont. nitric acid; heat on a sand-bath at 200” and evaporate to a moist residue; dissolve the latter in
3-4 ml of cont. hy~~~oric acid and evaporate again, repeating this twice more to remove the nitric
acid and to dehydrate the silicic acid. Do not evaporate to dryness or heat the residue for long, lest
selenium should partially volatilize. Filter off the silicic acid on a medium porosity filter and wash it
with 7-8 M hydrochloric acid. Collect the filtrate in a 50-ml volumetric flask and dilute to volume
with the same acid. Place 10 or 20 ml of the solution in a senaratorv-funnel. add 0,015 ml of aceto-
phenone, shake the mixture, let it stand for 30 min. and exiract f&t with i0 ml and then 5 ml of
chloroform (3-min shaking). Combine the extracts in another separatory-funnel and wash with
3 nil of water for 30 sec. Transfer the extract to a 25-ml volumetric flask and evaporate the chloro-
form on a boiling water-bath. Add 1 ml of cont. sulphuric acid and 3-4 drops of cont. nitric acid
to the dry residue and heat for 20-30 min on a sand-bath at 200”. Cool the solution, add 1 ml of
water and heat again to remove nitric acid and oxides of nitrogen, repeating this if the solution is not
completely colourless. Dilute with water, cool to room temperature, and add 1 ml of 0.5 % gelatine
solution, 1 m.l of cont. hydrochloric acid, O-5 ml of 1% bismuth nitrate solution and 1 ml of 25%
tin(I1) chloride solution. Shake the mixture, dilute to the mark, let stand at 20” for 40 min, and meas-
ure the absorbance at 430 rnp against a reagent blank, in 5-cm cells. Prepare a calibration curve
covering the range 5-25 pg of selenium.
When the method was applied to a copper concentrate the selenium content was found to be 91
ppm, standard deviation 3 ppm (IO results). Standard addition experiments showed complete
recovery of selenium.

Defermination of selenium in telIurium

Dissolve l-5 g of teliurium (depending on the selenium content) in 10 ml of aqua regia, on a
sand-bath, and evaporate almost to dryness. Take up the moist residue in 10 ml of 8M hydrochloric
acid, add 05 g of urea and evaporate again. Take up the residue in 8M hydrochloric acid and trans-
fer the solution to a 50-ml volumetric flask. Add 0.015 ml of acetophenone to an aliquot of this
solution, and after 30 min extract with 15 ml of chloroform. Wash the organic phase with 4 ml of
water, shaking for 30 set, tilter through a paper moistened with chloroform, and determine the selen-
ium as for copper concentrates. This method gives the possibility of determining selenium in tellurium
of high purity (99-9-99-999x).

Institute of General and Inorganic Chemistry N. JORDANOV

Bulgarian Academy of Sciences
Sofa, Bulgaria
High Pedagogical Institute L. FUTEKOV
Plovdiv, Bulgaria
852 Short communications

Smnmary-Acetophenone is the most suitable ketone for extraction

of selenium into chloroform. Methods are given for determination
of selenium in copper concentrates and metallic tellurium.
R~~~L’~toph~one est la c&one la plus appropri&e pour
l’extraction du sel&&un en chloroforme. On dorrne des methodes
pour le dosage du s&nium dans des concentrats de cuivre et dans le
tellurium m&allique
Zusannnenfassnng-Zur Extraktion von Selen in Chloroform ist
Aceto-phenon das geeignetste Keton. Es werden Vorschriften zur
Selenbeetimmung in Kupf~kon~n~aten und in metallischem Tellur
angegeben. - -
REFERENCES
1. N. Jordanov and L. Futekov, Tulanru, 1965,12,371.
2. Idem, ibid., 1966,13, 163.
3. L. Futekov and N. Jordanov, ibid., 1966,13,763.
4. N. Jordanov and L. Futekov, Zzv.Inst.po Obshcha Neorg. Khim. Bulgar. Akad. Nauk, 1966,4,25.

Talanta, 1968, Vol. 15. pp. 852 to 855. Pergamon Press. Printed in Northern Ireland

New chromogens of the ferroin-type-II

Pyrido and pyridy1 derivatives of phenaximeand q~ox~ine

(Receiued 25 January 1968. Accepted 2 March 1968)

IN CONNECTION with further studies in the preparation of sensitive and selective chromogens of the
ferroin type,’ Pfeiffer and Case* recently synthesized a variety of phenazine and quinoxaline deriv-
atives. The quinoxaline derivatives have in common a 2-pyridyl group, and the phenaxines a
pyrido[Z,3-a] group. Since the donor-atom groups of the former have greater flexibility than those
of the latter, a comparative study of the chromogenic properties of the two types is of interest. It
should reveal which is more conducive to chelation, flexibility or rigidity. Also, certain of the new
derivatives possess two ferroin-type groups, each free to act independently of the other. The possibility
that these compounds might form chelation polymers with metal ions also merits investigation.
Hence, a study of the reactions of the new compounds with iron(H) and copper(I) has been made.
The compounds are identified below by name and structure. They will be referred to by the roman
numeral assigned to each.
~uinoxaiine deri~oti~es
2-(2Pyridyl)quinoxaline (I) 2-(2-~idyl)pyrido~3,2-h]quinox~~e (II)

2-(2-Pyridyl)dipyrido[2,3-f3’,2’-hlquinoxalme 2,3-bis(2-Pyridyl)pyrido[2,3-flquinoxaline (IV)

(m)