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( March 20, 1891.



cetber there seems to be very little evidence of the break-
ing op of the elements in the san as far as my experi-
ments go.

Evcte after comparing the solar spedrum with all
known elements, there are still many important lines not
accounted for. Some of these I have accounted for by
silicon, and th6re are probably many more. Of all known
substances this is the most difficult to bring out the lines
in the visible spedrum, although it has a fine ultra violet
one.' Possibly iron may account for many more, and all
the elements at a higher temperature might develop more.

Then, again, very rare elements, like scandium, vana-
dium, &c., when they have a strong speArum, may cause
strong solar lines, and thus we may look for new and even
rare dements to account for very many more. Indeed, I
find many lines accounted for by the rare elements in
gadolinite, samarskite, and fergusonite other than yttrium,
erbium, scandium, praseodymium, neodymium, lan-
thanum, and cerium, which I cannot identify yet, and
which may ht without a name. For this reason, and to
discover rare elements, I intend finally to try unknown
minerals, as my process gives me an easy method of de-
teding any new substance or analysing minerals, however
many elements they ma^ contain.

The research is much indebted to the faithful and care-
ful work of Mr. L. B. Jewell, who has aded as my assis-
tant for several years. Preliminary publications of results
will be made in the yohns Hopkins Univtrsiiy Circulars,

Among the latest results I may mention the spedro-
scopic separation Of yttrium into three components, and
the adual separation into two.



RESEARCHES ON "OIL FOR REDS»'
(ALIZARIN OIL).
. By M. 8CHBURBR.KBSTNER.

Thb sulphonic compound which is found in <*oil for
reds** may be isolated by treating this produd with a
suitable mixture of water and ether. The ether dissolves
the fatty acids which are not sulphonised (or rather de-
sulphooited by the adion of water during the washing of
the crude produd obtained on allowing sulphuric acid to
ad upon castor oil), whilst the sulphonised substance
remains in solution in the watery portion, separate from
the ethereal stratum. To isolate it the aqueous solution
is precipitated with a solution of sodium sulphate at xo**
Baumi.

On evaporating the ethereal stratum we obtam the fatty
acids, more or less polymerised, the weight of which may
be determined, whilst the precipitation of the aqueous
solution enables us to give account of the sulphonic body.
In general two preparations made under conditions which
seem identical do not always give the same results.
The **oil for reds'* obtained contains variable proportions
of the two principal produds. The fatty acids by the
«dion of the water during the washings are thus changed
to a greater or less extent, and the solubility of the oil
in water is so much the greater as these desulphonised
fatty acids are present in a smaller quantity. In fad,
they are soluble only by reason of the presence of the
sulphonised body, and they give the solution that fluor-
escence from which a solution of oil is never free.

As for the degree of polymerisation, it seems to be more
copsiderable in the substances extraded by ether than in
the soluble body. Thus the fatty acids withdrawn from
one and the same preparation, and separated in the state
of sulphonised and non-sulphonised bodies lespedively,
gave the molecular weights 402 and 472 (the molecular
weight of the normal acid is 298).

Sulphoridnoleic acid, precipitated from its watery solu-
tion by sodium sulphate, forms a syrupy hydrate without
any appearance of fluorescence when it has been freed
Irom the noorsolpbonised fatty acids by means of ethers.



It enters .into the composition of the most soluble ** oil
for reds ** to the extent of 40 to 50 per cent, the remain-
ing 50 or 60 per cent being formed of fatty acids insoluble
in water. In this calculation the accompanying water is
disregarded.

The sulpho- fatty acid in an isolated state has a com-
position approaching that of diricinosulphonic acid.

It is impossible to dehydrate it completely without
decomposing it into sulphuric acid and fatty acid. If it
is dried at a temperature not exceeding 60° its decom-
position is very slight, and it then contains 4 per cent of
sulphur.

We may give account of the composition of oil for
reds by using in succession litmus and phenolpbthalein
as indicators. The litmus turns blue as soon as the suU

f>honic compound is saturated, whilst the phenolphtha-
ein only becomes coloured much later, and then only if
the non*6ulphonised fatty acid has been saturated. Upon
these properties the author has founded an analytical
process, which by means of two simple titrations made
successively gives the proportion of the two principal ele-
ments of oils for reds. The difierence between the two
values found on making use of a standard solution of
ammonia and the indication above mentioned, shows the
quantity of ammonia which has served for the saturation
of the desulphonised acids.

Care must be taken to use always the same quantities
of water, otherwise the results will not be comparable.
This expeiiment may also be useful from a pradical point
of view, since the author has proved that the tone of the
clearing of alizarin colours depends exadly on the pre-
sence of a larger or smaller proportion of the sulphonised
compound.

The standard found with litmus corresponds to the
weight of the barium sulphate which oil for reds gives if
its sodium salt has been ignited. It is also easy to follow
the polymerisation of ricinoleic acid, measuring it by its
capacity for saturation, and making use of phenol-
pbthalein.

Normal ricinoleic acid, if treated with sulphuric acid as
castor oil is done, gives a produd like that of castor oil.
On analysing it by means of double titration the author
has found a sulphonised acid and polymerised fatty acids
in the proportion of 60 — 65 to 100 of the former.

He proposes to show ultimately that ricinoleic acid ia
easily polymerised, not merely by the adion of heat, but
by that of steam, and that it may be restored to its normal
state by the adion of soda under certain conditions.-*
Comptes Rtndus,



THE DETERMINATION OF NITRIC AND

NITROUS ACIDS IN SPRING

WATER.

By MAX ROSENFBLD.

Pyrogallic acid has not been duly appreciated as a
reagent for nitric and nitrous acids. Many experiments
have convinced the author that this reagent under certain
conditions is not inferior to any other for the detedion
of nitric acid, and that it appears especially suited for the
determination of the above acids in spring water.

For the determination of nitric acid we use a solution
of 0*5 — I grm. pyrogallic acid in xoo c.c. water.

For carrying out the readion the author pours 3 c.c. of
the water under examination into a test-glass tapering to
the bottom, and adds 6 c.c. of strong sulphuric acid, which
is poured in as rapidly as possible fiom a small test-tube,
adding carefully a drop of the pyrogallic acid solution.
The upper stratum of the liquid takes at once or in the
course of a few minutes (according to the proportion of
nitric acid present) a violet to dark brown colour. It is
advantageous, about two minutes after the addition of the
pyrogallic acid, to turn ihe liquid cirefully round, so that
the coloured stratum may occupy the space of about 6



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Fermentation Induced by the Pneumococcus.



ni



c.c. For this purpose it is well to make a mark on the ^
test-glass indicating the volume (3 c.c.) of the liquid used
for the test. If 5 milligrammes nitric acid (N2O5) per
litre be present the colour appears very distindly after
a few minutes ; with 10 milligrammes nitric acid per litre
a violet colour appears at once after shaking ; with 15
milligrammes the upper stratum appears brown either at
once or after a short time. In this manner i milligramme
of nitric acid may be deteded per litre. If there are less
than 3 milligrammes nitric acid (NaOj) per litre the colour
is perceptible only after a time, and must then be com-
pared with the colour which appears under the same cir-
cumstances in pure, distilled water. In such a
comparative determination not more than one small drop
of the reagent must be used, because pure sulphuric acid
is turned a light rose by larger quantities of pyrogallic
acid. It is further necessary to diffuse the pyrogallic acid
through the space above mentioned by careful shaking
immediately after it has been added. The difference in
the colour of both liquids is distindly perceptible with a
proportion of i milligramme nitric acid per litre, and con-
sists herein, that in the nitric acid solution the coloured
stratum becomes more intense downwards, and thus
appears to have a sharply- marked boundary. In pure
distilled water the colour becomes less intense below, and
fades away gradually.

In carrying out the rea«^ion it is absolutely necessary
to mix the liquid to be tested with sulphuric acid exadly
in the proportions here indicated. It occurs in presence
of large quantities of nitric acid that the dark colour
which first appears disappears again on shaking. In such
a case several drops of the pyrogallic acid must be added
to the solution.

As the difference of intensity in the colour produced by
pyrogallic acid according to the quantity of the nitric
acid present, may be distindly recognised (up to the pro-
portion of 15 milligrammes per litre), and admits of a
comparison with the tones of colour obtained in the same
conditions in solutions containing a known amount of
nitric acid, this method may serve for an estimation of
the nitric acid in spring water.

If this estimation is only rough it allows us to decide
very rapidly whether a potable water contains more or
less than the permissible maximum of nitric acid.

The test-glasses in which the operation is performed
must not be previously wiped out with linen or cotton
cloths, since even small quantities of cellulose in contaA
with sulphuric acid produce the colouration of pyrogallic
acid.

The author has examined the sensitiveness of Schoen-
bein's readion, and finds that there may be founded upon
it a comparative colorimetric method for the estimation
of small quantities of nitric acid.

The reagent is a solution of 0*5 grm. pyrogallic acid in
go c.c. of water, to which are added zo c.c. ef concen*
trated siilphuric acid.

In order to perform the readion zoo c.c. of the water
in question are placed in a narrow cylinder of colourless
glass, i8»20 cm. in height, and mixed with a c.c. solu-
tion of pyrogallic acid. If the liquid contains 0*4
m.grm. nitrous acid (NaOj) per litre, the yellow colour
appears immediately ; with 0*3 m.grm. in six minutes ;
with 0*2 in about twenty-three minutes ; whilst with o'X
m.grm. nitrous acid per litre the colour appears only after
the lapse of about seven hours. The difference in the
colour is perceptible with a difference of 0*005 m.grm.
nitrous acid in 100 c.c. of water if this quantity does not
contain more than 0*05 m.grm. nitrous acid. With larger
proportions the colour, if seen from above through the
column of liquid, is too intense to allow of the difference of
colouration being distinguished. Within the above limits
. (0*01 — 0*05- m.grm. nitrous acid in- iqoc.c. of liquid) the
differences of colour remain perceptible, so that the limit
of error per litre is less than 0*1 m.grm. Pyrogallic acid
is also turned yellow by free alkalies.— Z^i^i^Ari/i^ Anah
Chimii.f vol. xxix., p. 661.



PROCEEDINGS OF SOCIETIES.

CHEMICAL SaCIRTY.
March sth^ 1891.

Dr. W. J. Russell, F.R.S., President, in the Chair.

Mr. a. W. Oxford was formally admitted a Fellow of
the Society.

Certificates were read for the first time in favour of
Messrs. William Bate, National Explosives Company,
Hayle, Cornwall ; Alexarider Lauder, University College,
Bangor, North Wales ; Cecil George Freer Tbongert
Colonial College, Hollesley Bay, Suffolk.

The following papers were read :—

14. " Crystalline Form of the Caieium Salt of Optiealty
Active Glyceric Acidy By Alprbo E. Tutton, Royal
College of Science, London.

This paper presents the results of a complete crys-
tallographical investigation of the calcium salt,
Ca(C3H504)2,2HaO, of the optically adive (dextro-
rotatory) form of glyceric acid described (TraHs,^ 1891, p.
96) by Frankland and Frew. The crystals belong to
the monodinic system, and are hemibedcal, tb^ forma
JTii]' and {oii)^ being only developed at ihe right-
hand extremity of the symmetry axis, attd the 'forms
I III I and {211} At the left extremity. The bemi-
hedrism is also manifested by a difference in the prism
faces of the form { ixo| , those apon the right side of the
symmetry plane being much more brilliant than those
upon the left side. The ratio of the axes is aibic*
1*4469: 1:06694. A complete table of angles is given,
the result of the measurement of a dozen crystals. The
optic axial plane is perpendicular to the symmetry plane,
and the first median line is nearly perpendicular to the
basal plane. The true angle of the optic axes is aVaLi »
34* 56'. aVaNa=35*' 28', aVaTc-sO"* i6'. The meaa
refraaive index fi is i'4496, 1*4521, and i'4545 ^or lithium,
sodium, and thallium light respeAively. The sign of
double refradion is positive. The calcium salt of this
dextrorotatory glyceric acid must therefore be added to
the list of optically adive substances whose crystals are
also hemihedral, a list which includes all the hitherto
well investigated cases.

15. <* Fermentations Induced by the Pneumococcus of
Friedldnder.'* By Percy F. Frankland, Ph.D., B.Sc.»
(London), Arthur Stanley, and Wm . Frew.

That this well known micro organism is capable of
inducing fermentative changes in suitable solutions of
glucose and cane-sugar was first pointed out by Brie{[er,
Zeit. /, Physiol, Chem,, vol. viii., p. 30<^33'^ *nd vol. ix«,
1—7). The authors have confirmed these observations of
Brieger*s, and have further found that the organism
ferments maltose, milk-sugar, raffinose, dextrin, aqd
mannitol, but that, like the bacillus ethaceticus, it does
not attack dulcitol. They have made a special study of
the fermentations of glucose and mannitol, determining
quantitatively the proportions in which the several pro-
dudls are formed. These produds are in each case ethyl
alcohol, acetic acid, generally accompanied by a little
formic acid and a trace of succinic acid, carbon dioxide,
and hydrogen. Both the glucose and mannitol were in
all cases only partially fermented, and the decomposition
of the glucose was especially incomplete, glucose being
apparently less readily attacked by the organism than
mannitol and cane-sugar. The fermentation was not
rendered more complete bv furnishing the organism with
a more abundant supply of nitrogenous food. . ^.

In the first instance, fermentations were conduced on
60 grms. of glucose 4md .mannitol respedively, with th«
following rcsulta:—



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136



ChlorO" and Brofno-iUrivatives 0/ Naphthoic &c.



f CaiyicAL News,
t March 90, 1891.



I.

Ormi.
glncoM.


I.

Grmi.
nuuinitol*


III.

Grmt*

nuuinilo}


05897


4-xx


5-06


1*6578


2-9921


3-1617



Ethyl alcohol . •• ••

Volatile acids calcu-|

lated at acetic acid]

The produds of the mannitol fennentations are not
only qualitatively similar to those obtained in the
fermentation of the same substance by the Bacillus
sthaceticus, but the relative proportions in which they are
formed are almost identical, the ratio corresponding
closely to the molecular proportions

aCaHs-OHtCHaCOOH.

In the subseqoect experiments, in which the volume
and composition of the evolved gases were determined,
only la grms. of mannitol were employed ; in this case
also veiy similar ratios were obtained, although a period
of two years had elapsed since the above fermentation
bad been carried on.

The following results of analysis show the composition
of the gas evolved in a fermentation with xa grms.
mannitol, after the air in the apparatus had been
displaced : —

i6UidAy. asrddsy. S4thdAy. 4iitdA7. Avenge.

COt .. 5x77 6x'a9 6618 65-47 6x*x8

O2 •• 0*09 0-15 o*aa 0*09 o*x4

Ha .. 4797 38-26 33-47 34*i9 38*47

Na .. 0-X7 0-30 I-X3 o*a5 0*21

100*00 100-00 loo'oo 100-00 100-00

The lower proportion of carbon dioxide in the earlier
part of the fermentation is doubtless due to the liquid
saturating itself with the gas, and the excess at the end
to the slow decomposition of the calcium bicarbonate
formed in the first instance. The average composition of
the gas may be taken to be 6 volumes or molecules of
carbon dioxide to 4 volumes or molecules of hydrogen.
Taking into account the adual volume of gas given off,
the several produds are in very close accord with the
molecular proportions ; 9CaH60 : 4CaH402 : laCOa : 8Ha,
derived from 6 mol. props, of mannitol, a mol. props, of
carbon dioxide being formed by the adion of the acetic
acid on the added calcium carbonate.

By plotting out the volumes of evolved gas on a
diagram, in which the ordinates represent the volumes in
cubic centimetres, and the abscissae the time of fermenta-
tion in days from the date of inoculation, the authors
obtain a curve for which the equation is—

. e-73'-

X — 0*0061 + ooo574<«

x6. " Tk0 Volumttric Estimation of Ttllurium, Part
II." By B. Brauner. Ph.D.

The author finds that although a solution of iodide in
potassium iodide ads on alkaline tellurates in accordance
with the equation

NaaTeOs+Ia+aNaOH - NaaTe04+aNaI + HaO,

the adion is verv slow and incomplete at the ordinary
temperature, so that heat must be applied for its com-
pletion. On acidification the excess of iodine is set free,
but it has hitherto been found impossible to exaaiy
determine the end of readion by titration with thio-
sulphate.

The titration of solutions of tellurium dioxide in chlor-
hydric acid with permanganate is found to be imprac-
ticable, as varying quantities of chlorine are evolved
during the process.

When a solution of tellurium dioxide in sulphuric acid
is titrated with permanganate, the following interchange
occurs :—
aKMn04+4HgS04+4TeO«=KaS04 f

+ Mnt(S04)s +4H.O +4Te05.



In order to destroy the manganic salt which is formed«
eithcc decinormal ferrous sulphate or oxalic acid is
added until decolorisation takes place, after which per-
manganate is added in slight excess. After subtracting
the volume of permanganate corresponding to the ferrous
salt or to oxauic acid from the total of permanganate
added, the quantity of tellurium dioxide is calculated frooa
the volume of permanganate necessary for its oxidation,
as if the following adion had taken place : —

2KMn04+3HaS04+5Te02»KaS04+

+aMnS04+3HaO+5Te03.
Owinp; to the evolution of some oxygen, the quantity of
tellurium dioxide found is greater by i per cent than that
calculated from the equation.

In alkaline solution the change which takes place is
that indicated by the equation

aKMu04+3TeOa » KaO + aMnOa +3TeOs.
After addition of an excess of sulphuric acid oxalic acid
is used for re-titration in the manner previously stated,
but the results are 0*35 per cent too high. The results
obtained by both methods are accurate when the correc-
tions mentioned are applied.

17. <* ChlorO' and Bromo-dirivativts of Naphthol and
Napkthylamin$y By Hbnry £. Armstrong and B. C.

ROSSITBR.

This communication is a continuation of one published
in the Proc, Chtm, Soe, in 1889.

1 : 4'Diehloro fi naphthol. — A better jrield of this com-
pound than is obtained by Zincke*s method appears to re-
sult from the gradual interadion of chloro-^ naphthol and
sulphu^l chloride at ordinary temperatures, about 30 per
cent of the chloro- being converted into the dichloro-
compound. The mixture obtaintd on steam-distilling the
crude product is sulphonated, and the mixture of salts
resulting from the dired neutralisation of the acid solution
with potassium carbonate is extraded with boiling alcohol,
which dissolves the dichloro- but not the monochloro-
sulphonate. The dichloronapbthol is recovered by heating
the sulphonate with dilute sulphuric acid at azo*.

X : 4 *. ^'-Trichloro-fi-naphthoL — The oily by-produA
obtained in preparing a large quantity of trichloro-i9-
ketonenaphthalene, when allowed to stand during many
months, was found to slowly give off hydrogen chloride
and to become partially solid ; the solid was freed from
oil by washing with acetic acid and was re-crystallised
f^om this solvent. The substance thus obtained proved
to be a trichloro -^-naphthol, and as it yields x : a : 3-
chlorophthalic acid on oxidation, and is reduced by
sodium amalgam to x : 4-dichloro jSnaphthol, it is most
probably the x : 4 : 4'*modification. It crystallises in short
soft needles melting at 157— 158*"; its acetyl derivative
melts at Ia9^

ChlorO'fi-naphtholsulphonic Acid. — x-Chloro-, 1:3-1 '^^^
X :4-dichloro-, and 1:3:4'- and i : 4 : 4'4-trichloro-/3-
naphthol are all sulphonated with the greatest care, each
yielding a derivative of x : 3'- (Schaefer's) fi naphtholsul*
phonic acid, proof that this is the case being afforded by
the formation of this acid from each of the chloro-acids on
redudion. This result is noteworthy inasmuch as 3' : i«
dibromo- and bromochloro-/3- naphthol — in which the
position occupied by the sulpho-group in Schaefer*s acid
is occupied by bromine — are distmdly less readily sul-
phonated than any of the chloronaphthols referred to ;
and it is a matter of interest also that neither is a deriva-
tive of the Weinburg /3-acid, isomeric with Schaefer's
formed from them ; hence it would seem that a j3-sulphonic
acid only results when the i3-3'-position is free, viz., that
which is symmetrically situated relatively to the /B-OH
group.

X : i*'Dihromo and Bromochloro-p-naphthol. — In the
previous communication it was stated, that on brominating
either bromo- or chloro-^- naphthol, the bromine is intro-
duced into the second nucleus. To determine the position
taken up by the bromine, the bromochloronaphtnol was



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distilled with PCI5 ; i : 2 : 3'-trichloronaphtha1ene was one
of the produAs obtained, and it would seem therefore that
it occupies the position 3'-. As both dibromo- and
bromochloronaphthol afford 1:3: 4-bromophthalic acid
on oxidation, this conclusion may be regarded as estab-
lished. Independent confirmation of this result is afforded
by the observation that chloro /3-acenaphthylide is con-
verted by bromine almost quantitatively into a bromo-
chloracenaphthalide (m.p. 2x6°), which affords a bromo*
chloronaphthylamine (m. p. 119**) and a bromochloro-
naphthalene (m.p. t^f) in which the bromine atom
occapies the ^- 3'-position ; also by Clauses recent state-
ment that when brominated bromo-iB-acenaphthalide in
like manner yields z : 3'-dibromo-i3-naphthylamine {jf. pr,
Chem),

The conclusion thus arrived at, however, is in opposi-
tion to that to be deduced from Smith and Meldola*s
statement, that tetrabromo-/3-napbthol, when oxidised,
yields the broroophthalic acid whose anhydride melts at
134", f.#., the 1:2: 3-acid. The authors have, therefore,
studied the adion of bromine in excesss on jS.naphthoI.
They find that, contrary to Smith's statement, the pre-
paration of tetrabromonaphthol is attended with very
considerable difficulty, the product chiefly consisting of
tribromonaphthol ; the separation of this latter by crys-
tallisation is difficult, but is easily accomplished by
acetylating the crude produA and re-crystallising the
acetate from benzene and from acetic acid. The acetate
Cfystallises in long fine needles melting at 184% and is
very easily hydrolysed. Tribron^onaphthol melts at 155 —
X56** ; 00 oxidation with alkaline permanganate it yields
2:3: 4-bromophthalic acid. The authors are still engaged
in investigating this compound and the other produds of
the adion of bromine in excess on /3-naphthol.

Action of Nitric Acid and of Oxidising Agents on
ChlorO' ana Bromonaphthols. — Nearly all the chloro- and
bromo - derivatives of ^ - naphthol yield charaderistic
quinone derivatives when submitted to the adion of nitric
acid ; in most cases the formation of these is preceded by
that of an unstable intermediate compound, the deter-
mination of whose composition presents great difficulties.



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