Aug.,
1920
T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
are formed on t h e walls of t h e storage vessels. I t is necessary t o remove these deposits a t intervals of 2 t o 3 mo., as they contain an appreciable amount of ammonium salts.
799
ume of liquid in the jar will have increased t o a liter, or more, from t h e ice introduced. After complete reduction, t h e zinc hydroxide is filtered off with suction, t h e filtrate cooled t o o o C., and sodium chloride SU M MA RY in an amount calculated t o saturate t h e volume of filThis permutit method of preparing ammonia-free t r a t e is added. A voluminous precipitate of phenylwater is applicable if distilled water is used. It has hydroxylamine is soon thrown down, which, after advantages over other methods of preparation in ease standing 1 5 min., is filtered off with suction and pressed Phenylhyof operation and production of large quantities a t mini- well between filter paper. (Caution: mum expense. The disadvantages of t h e method droxylamine is a violent skin poison. Rubber gloves a r e t h a t it gives a water of higher mineral content and should be worn and care taken of t h e face and eyes. does not remove nitrate, nitrite, or albuminoid nitrogen. Alcohol is t h e best remedial application.) The slightly damp phenylhydroxylamine is disInvestigations made t h u s far would indicate t h a t t h e solved in 500 cc. of ether and allowed t o stand over American permutit, except t h e prepared Folin permutit, will not quantitatively remove ammonia. night in a closed flask in contact with fused calcium German permutit has proved very satisfactory, and chloride. The ethereal solution is filtered through indications are t h a t t h e English permutit is equally filter paper, cooled t o o o C., and saturated with dry efficient. There is a possibility t h a t Refinite and ammonia gas, prepared by gently warming strong ammonium hydroxide and drying t h e gas evolved b y Boromite may possess similar properties. passing through one or more drying bottles packed A C K N 0 V'LE D G ME N T with broken sticks of sodium hydroxide. To t h e reThe author wishes t o express his appreciation t o sulting ethereal solution of t h e ammonium salt, 6 0 g. Prof. Edward Bartow, chief of t h e Illinois State Water of cold, freshly distilled amyl nitrite are now added all Survey Division, and t o Mr. R. E. Greenfield for their a t once. T h e vessel becomes filled with crystals of assisrance and criticism during t h e preparation of this cupferron and t h e temperature rises considerably, paper. some ether possibly boiling off (Hood). The precipit a t e is filtered a t t h e pump, washed with a little ether, NOTES ON THE PREPARATION OF CUPFERRON and spread on filter paper in a cool place t o dry. The By D. R. Kasanof cupferron thus obtained is best preserved in a wideGEKERAL CHEMICAL LABORATORIES, 25 W E S T 4 2 S T~, NEW ~ Y O R K , N Y. mouthed, glass-stoppered bottle, in which a lump of amReceived April 15, 1 9 2 0 monium carbonate is placed. This may be wrapped I n x-iew of t h e increasing importance of cupferron in filter paper and suspended by a cotton thread a t as a n analytic reagent, it is believed t h a t a slight tached with sealing wax t o t h e stopper. Amalgamated zinc dust may be used t o equal admodification of t h e method of preparation of Baudisch a n d King1 may be of assistance in securing a consis- vantage i n other similar reactions. tently good yield. The method commonly employed has its weakest link in t h e preparation of the phenylhydroxylamine, t h e yield of which varies from zero NOTE ON THE USE OF ALUNDUM FILTERING CRUCIBLES By D. T. Englis t o 7 0 per cent of t h e theory, depending on t h e quality DEPARTMENT OF CHEMISTRY, UNIVl3RSITY OF ILLINOIS, V R B kNA, ILLINOIS of t h e zinc dust employed. Poor yields are probably Received April 28, 1920 due t o a microscopic coating of zinc oxide on t h e surOne of t h e many uses of porous alundum ware is face of t h e zinc dust. The author has obtained a consistentIy good yield of phenylhydroxylamine from in filtering off cuprous oxide in t h e determination of reducing sugars. In a study made by Meade and nitrobenzene by using amalgamated zinc dust. Sixty grams of nitrobenzene are thoroughly emulsi- Harris1 on t h e determination of these sugars in cane fied by vigorous stirring in 700 cc. of water, contain- products, a very close agreement is reported between ing 30 g . of ammonium chloride, in a wide-mouthed comparative tests with Gooch and alundum crucibles, jar or a beaker of 1 . 5 t o 2 liters capacity. Eighty I n similar experiments made by t h e writer diffigrams of zinc dust are amalgamated with a 2 per culty was experienced in securing complete washing. cent solution of mercurous nitrate, acidified with a Even though t h e Sargent crucible holder was used few cc. of nitric acid. After stirring this mixture there was a tendency for t h e soluble alkali and copper for a few minutes t h e zinc dust is permitted t o settle salts t o climb t o t h e upper edge of t h e porous crucible and t h e supernatant liquid is poured off. The zinc and escape removal. Spencer's2 filtering apparatus dust is washed with water, under suction, until free would doubtless have eliminated this difficulty, b u t from acid, and may then be introduced without drying, since one of these was not a t hand it was necessary a small portion at a time, t o t h e nitrobenzene emul- t o resort t o some other method. sion. Vigorous stirring throughout is essential. The T h e procedure finally adopted was t o insert t h e temperature tends t o rise after each introduction of crucible in t h e Sargent holder, b u t with t h e flange t h e zinc dust paste and must be kept a t about 16' C. downward, as shown in t h e accompanying figure. by the introduction of chipped ice. All t h e zinc dust Washing was then carried out as completely as possishould have been added within one hour, and t h e vol1
1
THISJOURNAL, 3 ( 1 9 1 1 ) , 629.
2
THISJOURNAL, 8 ( 1 9 1 6 ) , 506. I b s d , 4 ( 1 9 1 2 ) , 614.
