Taory. Synth. LAV, 3, lag 88, CHROMIUM(M}) ACETATE (Chromous Acetate) Ifo CxCleag. + C CaClyag. + 2NACWHO,~> Cx(CaHT0.)2 + 2NACI + 09 (Gttnae nr Haun acm xo Jaue Kusano ‘Tho procedure and apparatus deserted by Balthis and Bailar! have been modifed to eliminate vertain handling Aificukies and to give increased yields of chromium(I1) fcetate. Reduction of the ehronaiua(IT) fon is effected by using « Jones reductor. This makes i unnecessary to filter the ehromium(II) eblorde solution. "Tho reductor ay be used for « number of preparations without rep ishing the gine. The chromium(ID) chloride solution ix run from the reductor diretly into the sodium soetate solution to ensure complete use ofall the chromium(ID) salt. Transfer of the reaction slurry from the bottom ofthe reaction flask to filter makes it posible to dry completely ‘nd process the precipitate under nonoxidising conditions Procedure ‘The apparatus is oxt up as indicated in Fig. 97. The reductor®columa A has 2m. id. and in tted st B with 12cm. plug of glass wool. ‘The sine amalgam column it about 45 om. in height. ‘Tho special stopcosk C has «10 rm. id the connestion to the rection Sask D is made ‘with rubber tubing. Funnel Z is a course, inters-elase Siler, about 4 in. in diameter. The glass string tad Fis 9 located that good mixing of tho precipitate with the ashing agent, and mixing drig the dying proses are possible, ‘Nitrogen is puss through the reaction ase during the ‘entire precipitation and is. passed over the precipitate * ivy fie, Un, | Diet of Kany, wren, a, {The Gost oan ata gu be mov mines | cunoromun sozrare uo uring filtration. The nitrogen is fred from oxygen by passing it through towers fled with alkaline pyrogslol and smmoniacal eopper() chord ‘The zine is amalgamated for use in the Jones reduetor by stising a quantity of 10- to 20.uesh gine for 10 minutes in ‘solution containing 0.1 3F mereury(ID) ebloride in 1 AF ‘hydrochloric acd, ‘The sine column is washed thoroughly ‘with water and then with a small quantity of 19 eulfrie ‘cid. "The liquid level in the reductor i at all times kept above the top of the sine column, ‘Ninety grims of chromium(IT1) chloride 6-hydrate i ssolved in 120 mi of watar and 30 ml. of 2 Naulurie ‘cid, "Tho colution is poured into the reductor colutan andwo Lory. Sgate, 1059. 160 Nonaavie svxrmses the rate of dow through the column adjusted by stopeoek Geo thatthe chromium ealt solution dropping into the reac- tion fk D is bright blue in color. Ax soon as this conic tion i achieved, a filterd solution of 252 g. of sodium ‘ootata in 325 mi of water i added to the reaction fs. hough H. ‘The mixture in the reaction ask D is wired for short periods during the precipitation. ‘Whon precipitation is complete, nitrogen (or natural gu) fs passed through funnel B and stopecee C is opened, By ‘areful regulation of the nitrogen rato slight suction may ‘be applied to filter Sask J so that only aitrogen pases through the precipitate, The precipitate is washed with freshly boiled distilled water whidh i introducod at K. Drying is cared out by washing with sloohol and then ‘with ether, the last traots of ether being removed by the steam of uitrogen. Tho chromium(TT) scctte precipitate, ‘hich iss deop red powder, ust be completly dry® before texposure to the ai, aa it oxidizes very rapidly when Inost tothe deep violet chromium(II1) salt. ‘The yield is 85.0, oF 85 percent of the theoretial based om CrCl 6H0, mma Baan: Toot Berne 28 (88, 2: Pano aman "Guan Ami” Oe 2 kn “ny Sin Ines New ony 1, 40, ANHYDROUS CHROMIUM(I) CHLORIDE (Chromous Chloride) CrCl} Hes BCH, + 2H Anhydrous chromium(I1) chloride has been propared by three ecentilly diferent methods: (1) by treatment of Aeon dying pal wn fund to ncn ode pode a sl podnc emt ‘Tiny of eats Cale, oe Ane, Oni {Mechta of Treo, Cae, am, 0 Canoe Sint ANHYDROUS oMRoMTUMUD CHLORIDE 181 ‘anhydrous ehromium(IMD chloride with bydrogen at red heat;* 2 by the action of hydrogen chloride upon metalic ‘chromium'*; and (8) by the dehydration of hydrated chro ‘mium(1}) ebloride in vacu at 1807." Tho last method does not give a pure product; oxidation, hydrolysis, or both ‘cour. ‘The product of the second method is often con taminated with meta ‘The fest method i beet; partial reduction to metal may occur but ean be prevented by ‘sng a mixture of hydrogen and hydrogen ehloride.* Procedure A ‘A Vycor or silica tube, 60 em. long with s 15mm. bore, i ‘baked for I hour at 450° while a curent of dry hydrogen chloride is passed through it, The tube is cooled and the Iyidrogen ehloride is replaced by dry air. Five grams of aniydrous chromiumn (HI) eblorid! is tntroduoed into the ‘tubo and purifed by sublimation ina current of dry ehlorine for dry hydrogen chloride st 600%. The gas stream is ‘adjusted to pace at rate of 20 to 90 ml. per minute thi alo of flow providing for the formation of lrge fakes. Tron(IT) chlovide that may sppour i sublimed and caused to collect at the end of the tube. After itis removed, the Drifed chromiuum(HI2) chloride that ie deposited st the fend of the furnaoo ean be obtained, "The apparatus employed for the reduction is shown in Fig. 28. A pyrex reaction tube 2.5 X 80 em. pre- ‘viously heated fr tocus at 500, is fttod with a two-hole rubber stopper carrying an outot tube and the longer tube B, 8 mm. in diameter, for leading the gases to the closed end; this tube should slip rather easily into the rubber stopper. ‘Tho sublimed chromium(I}) chloride is spread font toward the clowd end of the reuetion tube and the Tatter is placed in an electic resistance furaaco, the tam= perature of which can bo measured with a thermocouple Dry oxjyen-feo hydrogen and hydrogen chlorde,* each at the rate of 50 ml per minute, ar pesied first into a ‘T-tube where they mix, and then le t th elosed end of the