1070
C H ’ I R L E S BASKERYILLE ;\ST)M. FI. H E W N E T T .
~ , ~ . 6 - * / ’ ~ i r t i r t l z g l b r r i . ~ ~ ~ l - z . . ~ . ~ - t ~ i i rHi cj ltdl ~r igr lx~i ircr,r ~ t r l (CH,):,C,H,CH21r;(SO)S : CHC,,H,(CH,, To a strong alcoholic solution of ~.~,C7-trimethylbeiiz~l-z,4,6-triinethylbenzal hydrazone, coolcti by ice water. \vas added a few drops of concentrated hytlrochlnric acitl. To this colcl solution, which was shaken after each atltlition. i t m atltletl gradiially a coiicentrated solution of sodium nitrite. Loiig. satin-like needles separated at once aiitl increasetl in iiumber upon the ;itltlition of water. T h e successful carrying-out oi this experiment reqiiirrs the use of freshly prepared hytlrazonc. I he iiitroso derivative was filtered off, Lvashetl \vel1 n.it11 \vatut o rcniol-c the excess of sodium nitrite, and recrystallizeti iroin alcohol. The long. yellow. satin-like crystals melted ;it i I/-’. The aiialysis gave 13.09 per cent. S . C‘alculatctl. 13.00 per cent. The nitroso derivative is very soluble in chloroform, ether, lmizene, antl toluene. I t is less soluble in acetone and glacial acetic acitl. It is soluble in warm ethyl, methyl, and amyl alcohols. ant1 insoluble in water. I t is a stable coinpoiiii(1. .\‘rti,nso
),{.
t ,
V S IVEI1 S I T S OF
I\.IISNRSOl’d
[CONTRIBUTION FROM T H E C H E M I C A L LABORATORY O F THE c N I \ - E R S I T Y
O F NORTH CAROLINA.]
A R S E N I C PENTACHLORIDE. BY C H A R L E S BASKRXVII,LI.:A S D H. H . WnsrE7”r. Kecei\ecl ! > > n e ‘3, iwz.
’I‘iIi: noi~-existeiiceof arsenic pentachloride has for a long time been regarded as remarkable, especially so when the analogues of that element having atomic weights below and aboveit, phosphorus and antimony, show pentavalence toward the halogens. Hurtzig antl Geuther‘ endeavored to prepare it by treating arsenious acid with phosphorus pentachloride. l\layerhofer2 Insset1 chlorine into arsenic trichloride at - 1 0 ~ C..removing t h e cxcess of chlorine by a stream of carbon dioxide, and failed t o obtain the body. Janovsky:’ treated phosphorus pentachloride with arsenic trihydritle at o0 C. with negative results. Dumas‘ I
A I I U Cheni. . /JILarnr.. 1 1 1 , i j ~ .
9 / b i d . . 158, ’)
4
326.
X w d. chrnr. GPA.,8 , 1636 (187:). AWL.Chew. ( L i e b i p . 33. 337.
ARSENIC PENTACHLORIDE.
1071
thought he had arsenic pentachloride, but Capitaine' proved it to b e a mixture of As,O, and AsC1,. Weber having prepared SbCl,PCl,, Cronander2 sought its analogue AsCl,PCl,, but only .obtained AsC1,PClz. Marignac3 obtained AsF, as a double fluoride of potassium. Sloane4 prepared AsIj and endeavored to secure the pentachloride by saturating arsenic trichloride with chlorine at -23" C. at ordinary pressure and obtained the ratio As : C1: : I :4.447. There was a gradual decrease in the ratio up to 24" C. when it became I :4.08, then there was an abrupt change rapidly approaching I :3. Such observations made the existence of As,Cl, quite conceivable. Baeyer's pentahalogen compounds of arsenic in which one to four chlorine atoms have been replaced by alkyl radicals and Michaelis'5 work with phenyl residues are well known. Recently the pentavalent organic arsenic compounds have become much augmented by the extensive work of Michaelis.o The procedure of Sloane' offered encouragement, provided the reaction should be carried out at a lower temperature. Chemically pure arsenic trichloride was prepared and redistilled from concentrated sulphuric acid and its purity determined by analysis. About 5 cc. of the liquid were placed in a dry test-tube buried in solid carbon dioxide loosely packed in a Dewar bulb and dry chlorine led in. The crystalline trichloride (m. p. -18" C.) assumed a greenish yellow color and became liquid, which grew in bulk. Bessons showed that arsenic trichloride saturated with chlorine at zero does not solidify at -30" C. Davy also showed that it does not freeze at -29" C. when well saturated with chlorine. After a few minutes, the time varying with different experiments, the stream of gas was cut off and the excess of liquid chlorine removed by fractional distillation. Chlorine boils at -33.6" C. We verified this by completely boiling away several cubic centimeters of chlorine at -33" C. in other experiments. As a safeguard we allowed the temperature to rise to -31" C. 1 J o u r . Pharm., 2 5 . 524. Rer. d . chem. GPS.,3 , 1466 (1873). 3 A n n . Chem. (Liebig). 145, 249.
2
4 3
Chem. News, 4 6 , 194 (1881). Ber. d . chem. Ges.. 8 , 1316and 9,1566. ( L i e b i g ) , 3 2 0 , 271 (1902).
6 A m . Chem. 7 Loc. c i f .
Combf. vend.. 109, 940.
A K S E N I C PENT A C H L(1 K I D E .
1072
'l'he liquid was cooled again to -3j" C. and samples were removed as the temperature rose by means of a small pipette chilled to the temperature of the refrigerating agent. These samples in one experiment were placed directly in water; in another it was deemed better to place them i n a dilute sodium hydroxide solution. 111the former case immediate solution occurred with those portions removed at temperatures below -2j' C., while at those higher a \vhite precipitate, evidently of arsenious oxide, formed, increasing i n amount with elevation of temperature. The orthoarsenic acid \\-as determined as magnesium pyroarsenate and chlorine as silver chloride. T h e filtrate from the magnesium ammonium arsenate in the former was tested for the presence of arsenious compounds. S o n e were found up to -25' C . . when arsenious acid was found in traces increasing in amount with rise of teniperature, T h e r a t i o hetween arsenic as arscriic acid, and chloritic, was I :j 01' :IsC'l~. --It-2j" C. the ratio rose to I :6. The loss of chlorine x i i ( 1 consequent return to the trivalent condition bccame more and 1111)rc marlied, the higher the temperature. I he following analytical results werc obtained for tivo teinperaturw i n one experiment : , \
'Tcmptrature. oc
-35 -25
.41tiouiit lakeii.
Clrloriire foutid. Per cent.
796 0.26675 0. I
69.93 73.21
'I'heoretical.
70.26
....
Katio obtained. 4 s : c1. 1
4.93
I
: 5.75
.\rsenic pentachloricle is readily soluble in carbon disulphide absolute ether cooled to -30° C. From the latter, when chilletl several degrees, it crystallizes in yellow prisms. I t loses cliloriiie when heatctl above -28" C. O n exposure to the air it f ~ u n e s ,evolving hytlrochloric acid vapor and as the temperature riws forms crystals, most likely of the trichloride, which melt soc)ii to the liquid state. X special preparation was made and sealetl in a tube. 'I'he greenish-yellow liquid when cooled to - -.3So or -40" C. iwe had no thermometer for determining this acciirately) formed beautiful yellow crystals. 11 is iiot regartletl necessar? to give our several unsuccessful l)rc.liminary experimciits to secure the hocly for analysis. Suffice i t t o say that placing the body in a pipette or weighing-bottle a t tlic. tcmpcratiire of the air brought aboitt its immediate decomposition to the original trichloride, chlorine being evolved. aiitl
I ~ s I \ E H S I T Y OF N O R T I ! C A H O I . I N A ,
April 15.1902
