T H E J O C R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
Dec., 1 9 1 j
NOTE ON THE IDENTIFICATION OF TRIVALENT MANGANESE IN GLASS By S.
R.SCHOLES
Received July 7, 1915
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chloride. An a t t e m p t was made t o separate a n d analyze t h e product formed, b u t without success. Other ammonia derivatives were tried, a n d , in most cases, well defined compounds were obtained t h a t could be easily separated a n d analyzed. T h e method of analysis a n d procedures in making t h e compounds a r e given below. T h e analyses appear in Table I.
hIanganese, introduced as t h e dioxide, is commonly used as a decolorizer for glass, since i t imparts a violet t i n t . which effectively masks t h e green produced b y iron. T h e literature of glass is not definite regarding TABLEI--AcTIoH OF SOME ORGAHICCOMPOUNDS ON VASADIUMTETRACHLORIDE t h e particular compound of manganese responsible VANADIUM ANALYSIS for t h e color. Some of t h e best authorities, such as CALCULATEDPERCENTAGES CHLORIDE OF COMPOUND treated with K O . % V %C RN For % V %Cl % N Dralle a n d Hovestadt, regard t h e trioxide, LLIn203, ANILINE 9.06 25.09 . . . . 1 8.97 24.54 ..... 4CoHsNHz.VClr as t h e essential constituent oxide, b u t , so far as t h e DIMETHYLANILINE 1 7.97 20.7 ..... 4CsHsN(CH3)2.VClr 7.56 20.98 . . . . . writer is aware, n o definite experiments have hitherto PHEKYLHYDRAZINE 9.75 27.01 . . . . ( e x c e s s ) VClr 1 7.75 21.4 ..... 4CaHsNHNH2.VClr been described, demonstrating t h e s t a t e of oxidation in e x c e s s Z 9.80 24.1 . . . . . ........ ............... of manganese in t h e colored silicate. TOLUIDINE 1 9.03 25.25 . . . . . 4CaHaCHsNHz.VClr 8.25 22.82 9.02 9.96 C ~27.58 ~ 8.18 D i f f . portion 2 11.2 29.86 8.10 ~ C ~ H I C H ~ N H Z . V Some results, giving evidence of t h e presence of 15.4 42.6 16.8 AMMONIA 1 1 5 . 3 40.7 19.15 4NH3.VCla.4HzO 15.4 42.7 21.0 Diff. portion 2 16.15 42.2 19.1 5NHa.VClr.3HzO manganese trioxide in a glass, were obtained b y m e a n s ........ ............... Diff. Dortion 3 15.5 43.2 19.9 of t h e following experiments: METHYLAMINE1 12.6 35.6 19.8 6CH3h7H2.VCla.H20 12.9 35.7 21.1 A low-melting glass, b u t approximating t h e composi- DIPHESYLAMIKE1 11.75 30.35 . . . . . 3(CsHs)iXHz.2VCh 11.46 31.75 . . . . . tion of a commercial glass, except in manganese, was BEHZOL 26.2 54.4 . . . . . 1 29.2 53.0 . . . . . CeH4.2VCla (6 weeks) 28.7 49.7 . . . . . Shorter time 2 32.7 57.4 . . . . . CeHs.VzCls made, using: ........ .............. Shorter time 3 27.3 59.6 . . . . . s.4SD
SODA ASH
10 parts
5 parts
REDLEAD MAHGAHESE DIOXIDE 6 parts
1 part
This glass h a d a deep violet color. B y pulverizing a sample a n d treating i t with hydrofluoric acid, a pink solution was obtained, which could be decolorized b y oxalic acid a n d other reducing agents. A similar pink solution was obtained b y prolonged boiling of t h e powdered glass n-ith 30 per cent sulfuric acid. I n order t o obtain this pink solution more readily, a more soluble glass was made, using: SAND
POTASSIUX CARBOHATEMANGANESE DIOXIDE
5 parts
5 parts
1 part
F r o m this glass, b y digesting with 30 per cent sulfuric acid, a strongly colored, pink solution was obtained. It was t h o u g h t possible t h a t t h e pink color might be due t o permanganate, b u t failure t o get a colored solution b y digestion with water alone, in which this glass slowly disintegrated, showed t h e absence of permanganates. There was also a difference in color, these pink solutions possessing a less violet t i n t t h a n permanganate, for equal d e p t h of color. Manganic sulfate was t h e n prepared b y heating manganese dioxide t o partial reduction t o brown RIIn304, a n d treating this material with sulfuric acid. I n this way, a solution was made, closely resembling t h a t obtained from t h e manganese glass. Upon diluting, these solutions with several volumes of water, a light brown, flocculent precipitate appeared in both cases; also, their behavior toward oxalic acid was t h e same. These facts seem t o indicate t h e presence of trivalent manganese in t h e glass. ~IELLON IXSTITGTE OF I K D U S T R I A L RESEARCH UKIVERSITY O F PITTSBURGH,PITTSBURGH -
SOME NEW ORGANIC COMPOUNDS OF VANADIUM B y A. T.~ I Z R T AHD E S HERMANFLECK Received hlarch 23, 1915
While searching for a n organic electrolyte t o render v a n a d i u m tetrachloride a conductor of t h e electric current, t h e writer found t h a t a strong reaction took place when pyridine was mixed with vanadium t e t r a -
AKTHRACEHE 1 2 1 . 6 39.05 (Reflux condenser, 2 hours) 2 18.7 33.6 DETERMISATION
38.8
.....
CirHia.2(CiaHo.VzCls) 18.8 32.5
.....
CirHo.VzClj
22.4
O F V A S A D I U h I A N D C H L O R I N E IPi ORGANIC COMPOUNDS
One-half t o I gram of t h e substance is well mixed with finely powdered. chloride-free quicklime a n d transferred t o a combustion t u b e a b o u t 5 0 or 6 0 cm. long a n d I . j cm. in diameter. T h e t u b e is heated in a combustion furnace for from 2 t o j hours, depending upon t h e ease with which t h e substance decomposes. T h e contents of t h e t u b e are transferred t o a beaker with about 300 cc. of water a n d nitric acid added t o dissolve t h e lime. After filtering t h e solution a n d heating t o boiling, silver nitrate is added t o precipitate t h e chlorine. T h e silver chloride is filtered off, washed, dried a n d weighed. T h e filtrate is neutralized with ammonia, made slightly acid with acetic a n d lead acetate added t o precipitate t h e vanadium as l e a d vanadate. This is filtered off, washed with water, dissolved in w a r m dilute nitrlc acid, a n d evaporated t o white fumes with I O cc. concentrated sulfuric acid. After cooling a n d diluting with water, t h e lead sulfate is filtered off a n d t h e filtrate received in a 500 cc. flask a n d water added t o make a volume of 300 cc. Sulfur dioxide gas is passed into t h e solution until i t smells strongly of sulfur dioxide. A few pieces of vitrified tile are added t o prevent bumping a n d t h e flask boiled until t h e excess of sulfur d oxide gas is driven off: this requires about 15 minutes of vigorous boiling. T h e solution is t i t r a t e d hot with N / 2 0 potassium permanganate t o a faint pink end point. It is again reduced a n d retitrated. T h e permanganate m a y be standardized against pure ammonium vanadate or iron wire. ACTION O F VARIOUS COMPOUNDS O S VANADIUX TETRACHLORIDE
ANLIKE-A
freshly prepared benzol solution of vanadium tetrachloride is treated with a n excess of recently distilled aniline dissolved i n benzol. A black
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THE JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
drecipitate is formed. This is filtered o f f and washed with benzo’ t o remove t h e excess of aniline. The benzol is allowed t o evaporate spontaneously or in a Vacuum desiccator. The compound so obtained is a black powder unaltered b y exposure t o dry air a n d practically insoluble in water, b u t suffering a slight decomposition. DIMETHYLANILINE-Abenzol solution of dimethylaniline was treated with a freshly prepared solution of vanadium tetrachloride in benzol. A green precipitate or tar-like substance separated out on standing a n d adhered t o t h e sides of t h e vessel. By adding absolute ether t o t h e mixture, this separation was more complete as t h e compound appeared t o be insoluble in ether. By shaking the mixture, most of t h e substance could be made t o adhere t o t h e sides of t h e vessel a n d t h e main portion of the liquid poured off. After rinsing t h e product a couple of times with ether, it was dissolved in alcohol a n d transferred t o a beaker where t h e alcohol was allowed t o evaporate spontaneously in a warm place. PHENYLHYDRAZINE-it7hen a freshly prepared benzol solution of vanadium tetrachloride is added t o a solution of phenylhydrazine in benzol, a compound is formed. If t h e phenylhydrazine is in decided excess, t h e mixture is violet colored. B y t h e addition of more vanadium tetrachloride, it takes on a darker hue. The precipitate was filtered off using suction, a n d washed with benzol. TOLUIDINE-A solution of vanadium tetrachloride in carbon tetrachloride was treated with a solution of toluidine in t h e same solvent, a n d a black precipit a t e resembling t h e aniline compound mas obtained. This precipitate was filtered off, washed with benzol a n d dried in a vacuum desiccator. The analysis does not correspond with either of t h e formulae given in Table I, due, no doubt, t o t h e compounds, a s prepared, being insufficiently washed free f r o m excess of vanadium tetrachloride. The compound containing t h e higher percentage of chlorine a n d vanadium showed a marked tendency t o absorb moisture f r o m t h e air a n d become tar-like, also due, probably, t o a n excess of uncombined vanadium tetrachloride. ANMOXIA-A current of ammonia gas was generated b y heating ammonium hydroxide a n d passing t h e evolved gas through a drying tower containing solid caustic potash. This gas was passed into a benzol solution of vanadium tetrachloride a n d a precipitate formed. When saturated with ammonia, t h e precipitate was filtered off a n d washed with benzol. I t was t h e n dried i n t h e air a n d analyzed. Portions I , z a n d 3 were m a d e a t different times. T h e compound is practically insoluble in water b u t decomposes on heating or on standing in water. hIinera1 acids decompose it with t h e formation of a bluish green solution. When heated alone in a closed t u b e , water is driven off a n d ammonium chloride sublimes a n d deposits on the cooler portions of t h e tube. T h e residue obtained after driving off all t h e volatile matter is black in color and earthy in appearance, a n d when analyzed was found t o contain 63.0 j per cent vanadium,
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showing i t t o be composed principally of vanadium tetroxide. B y continued heating in t h e air i t oxidizes t o t h e pentoxide. SIETHYLAMIXE--1ethylamine was prepared by heating a 33 per cent solution a n d passing t h e evolved gas through a drying tower containing solid potassium hydroxide. The gas was bubbled through a filtered solution of vanadium tetrachloride in gasoline a n d a yellow precipitate formed. D I P H E & ’ Y L A M I S B - ~ ~ carbon tetrachloride solution of vanadium tetrachloride was added t o a n excess of a solution of diphenylamine in carbon tetrachloride. An indigo-blue precipitate was formed which, when dried, was grass-green. BENZOL--When vanadium tetrachloride is added t o benzol, t h e mixture has a slightly darker color t h a n vanadium tetrachloride alone. If t h e mixture is allowed t o stand some time, a precipitate settles out a n d hydrochloric acid is formed a t t h e same time. By pouring off the excess of benzol solution, filtering a n d washing with benzol, a purple colored compound is obtained which is unacted upon by dry air. By heating in a test tube, brownish vapors were given off. When added t o water, it dissolves, with hissing, forming a brown colored solution. The compound was analyzed by dissolving in dilute nitric acid a n d proceeding in t h e manner previously described. Portion I was obtained after a mixture of benzol a n d vanadium tetrachloride had stood for about six weeks. Portions z and 3 were obtained b y allowing t h e action t o continue a shorter time. ANTHRACENE-( I ) When a solution of vanadium tetrachloride in carbon tetrachloride was mixed with a solution of anthracene in t h e same solvent, a black precipitate was immediately formed a n d hydrochloric acid given off. ( 2 ) Another portion was prepared by mixing a carbon tetrachloride solution of vanadium tetrachloride with a solution of anthracene a n d heating under a reflux condenser for two hours. CHEMICAL LABORATORY COLORADO SCHOOL OF MINES,GOLDEN
T H E COMPOSITION OF FROZEN ORANGES AND LEMONS’ By H. D. Y O U N C ~
Received June 21, 1915
There is very little information, so far as the-author has been able t o find with t h e limited library facilities a t his command, as t o t h e effect of freezing temperatures on t h e composition of citrus fruits. Whenever a freeze occurs in one of t h e citrus districts and t h e injured fruits begin t o appear on t h e market, t h e daily press contains dispatches as t o t h e findings of health officers in t h e larger cities, b u t very little, if a n y , records are t o be found in t h e scientific journals. Following a very severe freeze in January,’ 1913, in Southern California, a large amount of work was done 1 Paper No. 9, Citrus Experiment Station, College of Agriculture, University of California, Riverside, Califotnia. 2 Grateful acknowledgment is made t o Mr C. 0. Smith a n d Mr: E. E. Thomas, University of California, and Miss Alpha Rasor, Winthrop College, Rock Hill, South Carolina, for their assistance.
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