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Vanadium in caustic potash
49 °
Chemical Section.
[ J. F. I.,
h o t w a t e r for its solution, its s o d i u m salt is v e r y soluble, and from its c o n c e n t r a t e d liquid separates in b e a u t i f u l red colored needles f o r m i n g bundles. T h e a m i d e of t h e acid (C6H 3 (NO2) OH. CONH=) consists of b e a u t i f u l orange-yellow colored tufts. I t m e l t s at i6oO_i6i o, a n d dissolves easily in h o t alchohol. T h e above a c c o u n t concludes m y s t u d y of the action of the vapors from nitric acid a n d arsenic-trioxide upon t h e three hydroxy-benzoic acids. T h e results briefly s u m m a r i z e d are these : W i t h ortho-oxy-benzoie acid two nitro acids were o b t a i n e d ; with meta-oxy-benzoic acid one nitro acid and a tri-nitrom e t a p r o d u c t resulted, a n d w i t h para-oxy-benzoie acid one recta-nitro acid. T h e course of the reaction in t h e s e t h r e e cases (the m-oxy-acid excepted) was not a t t e n d e d by a n y t r o u b l e s o m e i n t e r m e d i a t e products, and for this reason the m e t h o d m a y p e r h a p s become serviceable in the n i t r a t i o n of other oxyacids. CHEMICAL LABORATORY OF THE UNIV. OF PA.,
PHILADELPHIA, November I8, I889.
VANADIUM
IN C A U S T I C P O T A S H .
BY EDGAR F. SMITH,
[Read at the Staled 3[eelinA~ of the 6"/zemical SecEon, November z9, z8S9.7 T h e occurrence of v a n a d i u m in commercial caustic soda has been noticed (See B a u m g a r t e n , Zcitschrift f l i t C/lcmie, I865, 605, and Donath, Zcitsc/zrift feir Analyt. Chemic, 21, 45). As far as I am aware, it has not been observed in caustic potash, hence the following lines. W h i l e e n g a g e d in m a k i n g certain decompositions, for w h i c h I e m p l o y e d the o r d i n a r y stick potash, I was r a t h e r surprised, after s a t u r a t i n g the alkaline solutions w i t h hydrogen sulphide, a c i d u l a t i n g w i t h h y d r o c h l o r i c acid, and heating for several hours, to discover t h a t the s e p a r a t e d s u l p h u r showed a decidedly chocolate-brown color. T h i s occurred
Dec., x889.]
Chemical Sectian.
491
repeatedly. T h e q u a n t i t y of dark material was n e v e r v e r y great, y e t it was present, even in potash from alcohol. S o m e p r e l i m i n a r y e x p e r i m e n t s were m a d e which pointed to v a n a d i u m . I therefore s a t u r a t e d the w a r m a q u e o u s solution of three p o u n d s of stick p o t a s h with h y d r o g e n sulphide. H e a t was applied for several hours longer, and d u r i n g this period the liquid g r a d u a l l y a s s u m e d a yellow to deep red color. H y d r o c h l o r i c acid was added to distinct acid reaction. T h e s e p a r a t e d s u l p h u r was quite dark in color. A f t e r filtration and washing, the residue vcas dried and t r e a t e d w i t h carbon disulphide to extract the free sulphur. T h e chocolate-colored m a s s r e m a i n i n g after this t r e a t m e n t dissolved, with exception of a slight quantity, in yellow ammon i u m sulphide, from which it w a s reprecipitated b y dilute acid. A g a i n washed, t r e a t e d with carbon disulphide, and carefully ignited, there r e m a i n e d a crystalline mass. W i t h a small q u a n t i t y of this last p r o d u c t I m a d e the phosphorous b e a d t e s t - - y e l l o w , passing t h r o u g h dark to green w h e n cool. A n o t h e r special test consisted in dissolving" a portion of the ignited residue in a drop of conc. sulphuric acid, free from iron. One cc. of w a t e r was next added, and to this colorless solution from one to three drops of a dilute potassium ferrocyanide solution, w h e r e u p o n the liquid acquired a fine green coloration. This latter test Dr. Walz (American C/zemzst, vol. vi, p. 453) e m p l o y e d in d e t e c t i n g the m i n u t e q u a n t i t i e s of v a n a d i u m in A m e r i c a n magnetites. H e considers it conclusive evidence of the presence of vanadium. T h e m o s t i m p o r t a n t test, and t h a t which I applied to the r e m a i n d e r of the ignited residue, after effecting its solution in nitric acid, was to add a large piece of a m m o n i u m chloride to the ammoniacal solution. T h e m o r n i n g following, crystals of a m m o n i u m v a n a d a t e had separated. T h e s e gave the true v a n a d i u m bead, and w h e n ignited, m o i s t e n e d with pure, s t r o n g nitric acid and evaporated, left the deep redcolored residue characteristic of v a n a d i u m compounds. T h e v a n a d i u m sulphide, as first obtained, was impure, c o n s e q u e n t l y the reactions were at times masked, and it was only after eliminating some silver and iron that the r e a c t i o n s were u n q u e s t i o n a b l e .
Scie,ttific _/Votes a n d Comments.
492 The potash
impure
sulphide
weighed
about
from one-half
the
three
pounds
[J.F.I., of caustic
gramme.
CHEMICAL LABORATORY OF THE UNIV. OF PA.,
PHILADELPHIA, November 18, 1889 .
NOTES
AND
COMMENTS.
CttEMISTRY. NEW PHOTOGRAPHIC DEVELOPERS.--Eikono.g'en, introduced but a few months ago by Dr. Andresen, of Berlin, as a developing agent for dry plates and bromide paper, seems to have grown into favor with more extended tests and to justify in a high degree the expectations formed. The following are the most prominent facts of its current literature, already quite extensive. Chemically it is the sodium salt of amido-/~-naphthol-~-sulphonic acid, having the symbol SOaN a Clo H OH NH2 The formulae for its use, as well as its action, are closely analogous to those of hydroquinone. The deposit formed by it is, however, said to be finer and of a very delicate bluish-black color, thus bringing out all the ~nest details. By some hydroquinone is regarded as giving stronger negatives, all things being equal, but the eikonogen as giving better half shadows, a n d consequently better for portraiture than for landscape photography. It is said to be particularly well adapted for lantern slides and line work nega~tives; and in spectroscopic photography it seems as sensitive as pyrogallol in giving the shades of depth corresponding to variation in brightness of the ~pectral line~, knd at the same time to give a picture with blacker lines, more easily seen under the microscope. For bromide paper, according to General Brown, it is undoubtedly the developer of the future, affording warmer tones than the oxalate, and beautifully clear whites, without acid flushing, with simple rinsing with water before fixing. Whilst the appearance of the picture is slow, especially as a used developer, preferably twenty-four hours old, is preferred, the development is regular and uniform to every detail, without risk of staining ; and the same ~olution can be used for a number of prints. It is said to be unaffected in its action by variation in temperature, and therefore adapted to all climates. It is non-poisonous; does not stain the fingers; will keep over a month m i x e d ; acts so energetically that only half the exposure is required as that .with pyrogallol, and development occupies a much shorter time. The solution can be used over and over again without staining until its reducing power is exhausted. It is, on the other hand, especially adapted to development of over-exposures. With ill its excellencies it is a cheap developer, and will keep indefinitely as a dry powder. Its slight solubility, however, will prevent its use in concentrated stock solutions, as pyrogallol.
Chemical Section.
[ J. F. I.,
h o t w a t e r for its solution, its s o d i u m salt is v e r y soluble, and from its c o n c e n t r a t e d liquid separates in b e a u t i f u l red colored needles f o r m i n g bundles. T h e a m i d e of t h e acid (C6H 3 (NO2) OH. CONH=) consists of b e a u t i f u l orange-yellow colored tufts. I t m e l t s at i6oO_i6i o, a n d dissolves easily in h o t alchohol. T h e above a c c o u n t concludes m y s t u d y of the action of the vapors from nitric acid a n d arsenic-trioxide upon t h e three hydroxy-benzoic acids. T h e results briefly s u m m a r i z e d are these : W i t h ortho-oxy-benzoie acid two nitro acids were o b t a i n e d ; with meta-oxy-benzoic acid one nitro acid and a tri-nitrom e t a p r o d u c t resulted, a n d w i t h para-oxy-benzoie acid one recta-nitro acid. T h e course of the reaction in t h e s e t h r e e cases (the m-oxy-acid excepted) was not a t t e n d e d by a n y t r o u b l e s o m e i n t e r m e d i a t e products, and for this reason the m e t h o d m a y p e r h a p s become serviceable in the n i t r a t i o n of other oxyacids. CHEMICAL LABORATORY OF THE UNIV. OF PA.,
PHILADELPHIA, November I8, I889.
VANADIUM
IN C A U S T I C P O T A S H .
BY EDGAR F. SMITH,
[Read at the Staled 3[eelinA~ of the 6"/zemical SecEon, November z9, z8S9.7 T h e occurrence of v a n a d i u m in commercial caustic soda has been noticed (See B a u m g a r t e n , Zcitschrift f l i t C/lcmie, I865, 605, and Donath, Zcitsc/zrift feir Analyt. Chemic, 21, 45). As far as I am aware, it has not been observed in caustic potash, hence the following lines. W h i l e e n g a g e d in m a k i n g certain decompositions, for w h i c h I e m p l o y e d the o r d i n a r y stick potash, I was r a t h e r surprised, after s a t u r a t i n g the alkaline solutions w i t h hydrogen sulphide, a c i d u l a t i n g w i t h h y d r o c h l o r i c acid, and heating for several hours, to discover t h a t the s e p a r a t e d s u l p h u r showed a decidedly chocolate-brown color. T h i s occurred
Dec., x889.]
Chemical Sectian.
491
repeatedly. T h e q u a n t i t y of dark material was n e v e r v e r y great, y e t it was present, even in potash from alcohol. S o m e p r e l i m i n a r y e x p e r i m e n t s were m a d e which pointed to v a n a d i u m . I therefore s a t u r a t e d the w a r m a q u e o u s solution of three p o u n d s of stick p o t a s h with h y d r o g e n sulphide. H e a t was applied for several hours longer, and d u r i n g this period the liquid g r a d u a l l y a s s u m e d a yellow to deep red color. H y d r o c h l o r i c acid was added to distinct acid reaction. T h e s e p a r a t e d s u l p h u r was quite dark in color. A f t e r filtration and washing, the residue vcas dried and t r e a t e d w i t h carbon disulphide to extract the free sulphur. T h e chocolate-colored m a s s r e m a i n i n g after this t r e a t m e n t dissolved, with exception of a slight quantity, in yellow ammon i u m sulphide, from which it w a s reprecipitated b y dilute acid. A g a i n washed, t r e a t e d with carbon disulphide, and carefully ignited, there r e m a i n e d a crystalline mass. W i t h a small q u a n t i t y of this last p r o d u c t I m a d e the phosphorous b e a d t e s t - - y e l l o w , passing t h r o u g h dark to green w h e n cool. A n o t h e r special test consisted in dissolving" a portion of the ignited residue in a drop of conc. sulphuric acid, free from iron. One cc. of w a t e r was next added, and to this colorless solution from one to three drops of a dilute potassium ferrocyanide solution, w h e r e u p o n the liquid acquired a fine green coloration. This latter test Dr. Walz (American C/zemzst, vol. vi, p. 453) e m p l o y e d in d e t e c t i n g the m i n u t e q u a n t i t i e s of v a n a d i u m in A m e r i c a n magnetites. H e considers it conclusive evidence of the presence of vanadium. T h e m o s t i m p o r t a n t test, and t h a t which I applied to the r e m a i n d e r of the ignited residue, after effecting its solution in nitric acid, was to add a large piece of a m m o n i u m chloride to the ammoniacal solution. T h e m o r n i n g following, crystals of a m m o n i u m v a n a d a t e had separated. T h e s e gave the true v a n a d i u m bead, and w h e n ignited, m o i s t e n e d with pure, s t r o n g nitric acid and evaporated, left the deep redcolored residue characteristic of v a n a d i u m compounds. T h e v a n a d i u m sulphide, as first obtained, was impure, c o n s e q u e n t l y the reactions were at times masked, and it was only after eliminating some silver and iron that the r e a c t i o n s were u n q u e s t i o n a b l e .
Scie,ttific _/Votes a n d Comments.
492 The potash
impure
sulphide
weighed
about
from one-half
the
three
pounds
[J.F.I., of caustic
gramme.
CHEMICAL LABORATORY OF THE UNIV. OF PA.,
PHILADELPHIA, November 18, 1889 .
NOTES
AND
COMMENTS.
CttEMISTRY. NEW PHOTOGRAPHIC DEVELOPERS.--Eikono.g'en, introduced but a few months ago by Dr. Andresen, of Berlin, as a developing agent for dry plates and bromide paper, seems to have grown into favor with more extended tests and to justify in a high degree the expectations formed. The following are the most prominent facts of its current literature, already quite extensive. Chemically it is the sodium salt of amido-/~-naphthol-~-sulphonic acid, having the symbol SOaN a Clo H OH NH2 The formulae for its use, as well as its action, are closely analogous to those of hydroquinone. The deposit formed by it is, however, said to be finer and of a very delicate bluish-black color, thus bringing out all the ~nest details. By some hydroquinone is regarded as giving stronger negatives, all things being equal, but the eikonogen as giving better half shadows, a n d consequently better for portraiture than for landscape photography. It is said to be particularly well adapted for lantern slides and line work nega~tives; and in spectroscopic photography it seems as sensitive as pyrogallol in giving the shades of depth corresponding to variation in brightness of the ~pectral line~, knd at the same time to give a picture with blacker lines, more easily seen under the microscope. For bromide paper, according to General Brown, it is undoubtedly the developer of the future, affording warmer tones than the oxalate, and beautifully clear whites, without acid flushing, with simple rinsing with water before fixing. Whilst the appearance of the picture is slow, especially as a used developer, preferably twenty-four hours old, is preferred, the development is regular and uniform to every detail, without risk of staining ; and the same ~olution can be used for a number of prints. It is said to be unaffected in its action by variation in temperature, and therefore adapted to all climates. It is non-poisonous; does not stain the fingers; will keep over a month m i x e d ; acts so energetically that only half the exposure is required as that .with pyrogallol, and development occupies a much shorter time. The solution can be used over and over again without staining until its reducing power is exhausted. It is, on the other hand, especially adapted to development of over-exposures. With ill its excellencies it is a cheap developer, and will keep indefinitely as a dry powder. Its slight solubility, however, will prevent its use in concentrated stock solutions, as pyrogallol.