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acetic acid, a clear solution is obtained, which, after a
short time, deposits a crystalline substance ; if quickly
separated by filtration, this produd is almost colourless,
but it decomposes when kept, becoming yellow. It was
conceivable, judging from the manner in which it was
produced, that the compound was a nitrate, formed by
the simple displacement of the hydroxylic hydrogen by
NOa, and the results of analysis were in accord with this
view ; but such a nitrate should be reconvertible into the
parent substance by treatment with, alkali,- whereas
adually it affords, as chief produd, bromoniironaphihoL
Bromobetanaphthol, in like manner, eventually yields
«i-nitrobetanaphthol, and the tri* and tetrabromo- deriva-
tives afford di- and tribroroonitrobetanaphthol ; the
bromine atom displaced by NOa by this method of treat-
ment, there can be little doubt,. is invariably that in the
«x-position.

The authors are of opinion that the intermediate com-
pounds in question are nitrobromoketo-derivatives dorres-
pondingto thedichloroketo-compoundsof Zincke,and that
their formation affords evidence that the elements of nitric
acid first become added to the bromonaphthol, thus —

Br NOa
Br



CO



OH +HONOa-




HaO.



The theory that the formation of such addition com-
pounds precedes that of nitrocompounds generally
appears to afford a satisfadory explanation of a large
number of well-known fads which hitherto have remained
unexplained. The non-produ6ion of nitro-compounds
fiom paraffins and their derivatives, except in a certain
veiy limited number of special cases, appears as the
natural consequence of the inability of paraffins to form
addition compounds. The theory affords a simple
explanation of the formation of nitro- derivatives of
phtnols on nitrating hydrocarbons, to which Ndlting has
drawn special attention in the case of toluene and
orthoxylene {BirichU, 1885, 2670 ; 1888, 3x58), for if the
addition compound lose HNOa instead of H*OH a phenol
would result, thus —

HOH OH

,/\ /S HNOa A

I I +HONOa- II I "II +"N^*-

An agent that would favour the separation of the
elements of water from the addition compound would
increase the produd*on of the nitro-compound and
diminish that of the phenol ; and, as a matter of fad, it
is known that when a mixture of nitric and sulphuric
acid is used there is less of the phenol derivative produced
than when nitric acid alone is employed. A compound
such as the addition compound of benzene with nitric acid
above represented, would obviously be unstable and prone
to undeif o oxidation ; hence it is not diffictilt to under-



stand that so large an amount of nitrous fume should be
produced even on nitraring benzene. The redodion in
the amount of such fume, and the impioveroent of the
vield of nitro-derivative effeded by adding sulphuric acid,
18 doubtless attributable to the adion already referred to
of the acid in promoting the separation of the elements of
water ; sulphuric acid must be supposed, in fad, in such
cases to ad not merely as a dehydrating agent in main-
taining the nitric acid concentrated, but to exert a specific
influence on the course of change. Lastly, the resinous
matters often formed in large amount on nitrating many
phenols are, doubtless, produds of the interadion of
several molecules of the addition compounds, or of the
keto- compounds formed from them in the first instance.

The non-produdion of resinous matters when sulpho-
acids are treated with nitric acid so as to form the
corresponding nitro-compounds by displacement of the
SO3H group by NOa, a modification which often makes
it possible to prepare nitro-compounds not obtainable by
the dirtd adion of nitric acid, is also elucidated by the
author's theory ; the addition compound formed in such
a case would very readily break up into sulphuric acid
and the nitro-derivative, thus —

:C(0H)-C(S03H) : -f HONOa - C(OH)aC(NOa)(SO.H)-

-: : C(OH)C(NOa) : -t-HOSOsH.

D18CU88IOM.

Mr. Groves said that he had been much struck, when
preparing dinitrobenzene from benzene which had bees
most carefully purified, on observing that a very appreci-
able quantity of trinitrophenol was produced ; the theory
of nitration put forward by the authors would fully account
for this.



New Mithod of Preparing NitrO'Dmvativgs
udi as a Nitrating Ag0nt,**



aa. «M

and tht Uss of Nitrogen Dioxid

By Hbnry E. Armstrong and E. C. RossirBRT

Reference has been made in the foreeoing note to the
produdion from the compounds formed by the addition of
the elements of nitric acid to the bromo-derivative of
betanaphthol of nitro-derivatives of the naphthol ontr§at'
ment with alkali, a bromine atom becoming displaced by
NOa. As in this iiiteradion a bromine atom is removed
and an atom of hydrogen is added to the CO group, such
a method of treatment obviously is scarcely that best cal-
culated to effed the formation of the nttro-derivative, and,
lis a matter of fad, the nitro-derivative is not the only
produd. On treating the addition compound, however,
with sulphurous acid, a pradically theoretical yield of the
nil ro- naphthol is obtained ; this method appears to be of
general application.

The authors have been naturally led to study the adion
of nitrogen dioxide, NOai on unsaturated compounds of
various kinds, in the expcdation of obtaining addition
compounds which by loss of HNOa would pass over into
nitro-derivatives of the substances treated. They find
that such addition compounds are adually obtainable,
and that, on treatment with alkali and reducing agents,
they yield nitro-derivatives. Thus betanaphthol aftorda
as much as 75 per cent of its weight of nitro-beta-
naphthol; alphanaphthol behaves similarly. In aone
cases, the addition compound is so unstable that it spon-
taneously decomposes; thus phenol at once yields a
mixture of ortho- and para-nitrophenol. The authors
propose to study the behaviour of unsaturated compounds
generally towards nitric acid and nitrogen dioxide from
the point of view indicated in this and the previous note.

33. ** Nitrification. Part IV." By R. Warinoton.

The first sedion of the paper describes early experi-
ments, made in 1878—84, showing the existence of an
agent producing only nitrites, and the means of separating
it from soil. It was at first thought that the age of the
culture was the fador which determined the loss of the
power of producing nitrates, but this idea was negatived
by subsequent experiments. Successive cultivation in
ammoniacal solutions, made permanently alkaline with
disodium carbonate, was found to be a certain method of



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CMMlC4LMlWt,)
Jon* 19, iSgi. ) _^^_

obuiniog a purely nitrous agent. Pasture soil yielded
the nitrous agent more readily than arable soil.

The isolation and properties of the nitrous organism
are next described. The gelatinous matter which appear
nnder certain conditions at the bottom of old cultures
was in 1883 examined microscopically, and found to con.
sist of circular corpuscles imbedded in a zooglcea. In
x886 this jelly was spread on gelatin, but it yielded no
nitrifying organism. In 1889 a systemaUc attempt at the
isolation of the organism commenced. Successive culti-
vations were made in an ammonium carbonate solution,
supplied with phosphates, &c., but containing no organic
matter. A series of transparent cultures was obtained,
containing only nitf ites. These cultures were spfcad on
gelatin and agar- agar, the composition of the jelly being
made to correspond, as far as possible, with that of a
nitrifiable solution. The later cultures yielded on gelatin
one organism only, a short bacillus. This and all the
other organisms obtained by cultivation on gelatin from
nitrified solutions were seeded into both liquid and solid
media suceptible of nitrification, but without result.
Microscopical examination of the nitrified solutions
showed that cocci were abundantly present, but these
never appeared on the gelatin cultures.

The first attempts to separate the nitrous organism by
the dilution method failed. By substituting an ammo-
nium chloride solution with calcium carbonate for the
ammonium carbonate, success was obtained in Odober,
x8go, three nitrified cultures seeded with dilutions of
i/io.ooo, 1/100.000, and x/x,ooo,ooo, giving no growth on

gelatin. . . ^ j.

The nitrous organism thus obtained oxidises ammonia
to nitrous acid, and has no eifea on nitrites. It produces
nitrous acid in solutions of asparagine. milk, urine, and
urea. Grown in broth containing calcium nitrate, it does
not reduce the nitrate to nitrite. It produces no turbidity
or visible change when grown in broth or in any of the
other solutions named. .* . / ,

The nitrous organism requires no organic matter lor
iU nutrition; it is apparently capable of assimilating
carbon from acid carbonates. The presence of either
calcium or sodium acid carbonate distindly favours nitri-
fication; neutral sodium carbonate greatly hinders
nitrification. The proof that carbon is assimilated from
carbonates has been furnished by Winogradsky. The
energy that is required for the decomposition of a car-
bonate is apparently furnished by the oxidation of ammo-
nU on nitrogenous organic matter. Calcium acetate
(0-25 grm. per litre) favours nitrification when only the
nitrous organism is present. .

The nitrous organism occurs as nearly circular cor-
puscles, varying from minute points up to nearly x'o /a m
diameter ; these circular organisms stain deeply. It also
occurs as oval cocci, the length frequently exceeding i-o/*,
the ends occasionally more or less truncated.

The remainder of the paper deals with the nitric
organism. Results obtained in 1880-81 revealed the
existence of an organism which energetically converted
nitrites into nitrates, but was apparently unable to oxidise
ammonia. In 1886 and 1890 attempts were made to
separate the aftive organism from the x88i cultures by
growths on gelatin and potato ; none of the organisms
thus separated had any power of oxidising either ammo-
nia or nitrites. Recent results show that the nitric
organism develops freely in inorganic solutions containing
potassium nitrite, phopphates. &c., especially if super-
carbonates are present. Monosodium carbonate, x— 4
grms. per litre, exerted a very favourable influence, 6 grms.
a retarding influence. Disodium carbonate greatly hinders

The nitric organism produces neither nitrites nor
nitrates in ammoniacal soluiions. even when carbonic
acid or monosodium carbonate, or calcium acetate is
supplied. In tne absence of ammonia it energetically
converts nitrites into nitrates ; the presence of ammonia
18 apparently a great hindrance to its adion.



297



An attempt to isolate the nitric organism by the dilution
method failed, but apparently only one other organism (a
stout bacillus growing on gelatin) was present in some of
the cultures obtained. The stained preparations from
these cultures contained an abundance of the minute
circular organisms observed in pure cultures of the
nitrous organism ; the form of the two organisms is thus
apparently similar.

The nitrification performed by soil thus appears to be
the work of two organisms, one of which oxidises ammo-
nia to nitrite, while the other oxidises nitrite to nitrate.
The first organism is easily separated from the second
by successive cultivations in solution of ammonium car-
bonate. The second is (probably) separated as easily
from the first by successive cultivations in solution of
potassium nitrite containing monosodium carbonate.

The paper was illustrated by micro-photographs, show-
ing the nitrous organism as developed in ammoniacal
solutions, milk, and broth ; and the nitric organism grown
in a solution of nitrite. The photographs were executed
by A. Pringle, Bsq., and Dr. Bousfield.
Discussion.

Prof. Thomson, referring to the method of cultivation
on gelatinised silica described by Mr. >yarington, said
that the account given of the method reminded him of an
observation made so far back as 1875 ; a solution of silica
which he had prepared by dialysis had solidified, and he
noticed, after a time, that a growth of what he thought
was an ordinary mould had appeared on the surface;
there could have been nothing present besides the silica,
except traces of mineral salts.

Dr. MuNRO said that he was glad to see that his con-
tention that organic matter was aAually prejudicial to the
growth of the nitrifying organism was now proved.
Referring to the conclusion that two organisms were
concerned, one of which converted the ammonia into
nitrite, the other extending the oxidation to nitrate, be
asked how those cases in which only nitrates were found
were to be explained ; it very rarely happened, for in-
stance, that in well-waters the ammonia was converted
into nitrate with intervention of nitrite. Perhaps two
organisms were present, which did their work simulta-
neously.

Mr. Warinoton, in reply, said that the two organisms
would have no difficulty in ading together in very weak
solutions of ammonia.



CHEMICAL



NOTICES FROM
SOURCES.



FOREIGN



NoTB.^AU degrees of temperature are Centifrede unless otherwise
expressed

Comptis Ritidus Hebdomadains dis Siancts di VAcadtmU
dis Scisncis. Vol. cxii.. No. aa, June i, 1891.
Calorimetric Reaearchea on Huroic Acid derived
from Sugar.— MM. Benhelot and Andi6.— The result of
these researches is that humic acid is a polybasic acid
capable of losing one part of its water of hydration by
mere desiccation, and even in the midst of water at
ordinary temperatures in virtue of true dissociation. In
this state it combines with three equivalents ofpotassa,
forming insoluble salts; the first is monobasic, very stable,
formed with the liberation of -|-x8 cal., f #., comparable to
that ot the solid alkaline salts formed by the most power-
ful mineral acids. The two equivalents of base which
then unite to the first salt form a tnbasic salt equally in-
soluble, but liberate much less heat. These humic matters,
comparable to those of the soil, undergo thus, under the
infiucnce of a base, phenomena of hydraiion ; then, by the
inverse adion of acids, eifeds of spontaneous hydration
by dissociaiiun— a scries ot effeds in virtue of which



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•steroal eoergiet abonld be eontinaaUy iatrodaced in the
e«M!(^ i%lSfbM'4ttbib|)lfiMI "d^Mi^'HIit^^eMMi^ of
ntf^tt *Ve^etftti6n. Hiitnic add Is forttttd htmftugttn
^tM the libeffttton of hcfat, but this liberation expends
otily a |>oiti6ti of the thermit excess of these carbo*
hydriites overrarboo and "water capable of being formed
bv total destmAion. Hence it results that bunnc aoid
would bb eqaally formed from carbon and water with
absorption of heat, f.«., that it contains an excess of
energy capaMe of' being expiintded in the course of the
con^etuttve ttanifbrmattbns which are effeded either by
purely chensical adions or with the concoune of microbian
agents.

petrmDination of the Molecular Weight at the
Critical Point.^P. A. Guye.— A purely mathematical
paper not susceptible of useful abridgment.

Detedlion and Sepairation of the Platinum Metalt,
and in Particular of Palladium and Rhodium, in
Pretence oftli^ CommoQ Metalt.— A. Joly and B.
Leidi6«— (See p. 292).

On the Specifle Heats of Some Solutiont.— W.
Timofeiew. — The authpr gives his results in the form of
atahle. -. .

On the Oxidation- ProduAt of Uric Acids. — C.
Matignon. — A themso-chemical stddy of allaatoine,
alloxane, and alloxanthine. <<^-

On the Use of Ammonium Selenite for the Diag-
nosis of the Alkaloids. — A.- J. Fetrefa'a da £ilm.—
(See p. agi).



MEETINGS FO^THE WEEK.

Wbdnbsday, 24tb.— Geological, 8.

— Society of Ant, 4. (AnciversAry).
Thursday. 25th.— CbemicAl, 8L BxtraordiMiry General Meeting.

R09 al Soctoty C^lub, 6,jo. ^(Annivenary).

FaiDAY, 26th.— Royal Inttttutiop, g. (Faraday Commemoration Lec«

ture). Prof, Dewar. F.R.S.

— Phyaical, 3. *• The ConttnidHon of Non-IndoAive

Rcuitaticet." by Prof. W. B. Ayrton, F.R.S., and
Mr. T. Matter. ** The Influence of Surface-Loading
on the Flexure of Bearoa.^by Mr. C. A. Otrua-Witaon.
•*On Pocket Elearometen,** by Mr. C. V. Soya,
F.R.S. **On EleAriBcatinn dna to th* GonuA of
Gases with Liquid*/' by Mr. J. Enright, B.Sc,



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Jond 3(^1891. I



Ntw Departure in Matte StnelHng.



299



THE CHEMICAL NEWS.



Vol. LXIII., No. 1648.



ON A

NEW DEPARTURE IN MATTE SMELTING

FOR COPPER AND SILVER IN

REVERBERATORY FURNACES.

By W. BETTBL, Metillurgitt and Chemist.

In Odkober last, owiog to the imelting arraogements at
the Willows Mine being unsatisfaaory, I was asked by
the managing direAor of the Company to take this
department under my supervision, a handsome bonus
beinK promised if I were successful. This, in the
dire^ors' opinion, I have now earned.

The absence of sulphur in our ores and fluxes (except
in trifling amounts), and the presence of antimony
exceeding the percentage of copper in the ores to be
emelted, the copper existing as azurite and malachite —
average 4 per cent copper wet, and 40 ozs. silver per ton
(2240 Ibs^— the bulk of the ore being hydrated oxide of
iron and antimonious compounds — made the problem of
matte produdion one of difficulty ai first sight.

Other difficulties I bad to contend with. Bad coal,
containing from x8 to 40 per cent ash, gave little heat in
the furnace and much trouble (with the clinker) in the
grate ; huge accretions forming in that part of the grate
level with the bridge. 1 found that it was the pradice of
the furnacemen, once every twelve hours, to pour water
into the grate through holes in the roof, to cool the
clinker, which was then removed by steel bars and sledge
hammers; the furnace in this manner being cooled to
such an extent that fully four hours were lost every day.

This led me to devise a method of burning this poor
coal to advantage, at the same time preventing the for-
mation of the huge masses of clinker which retarded
operations. This accomplished, as will be seen from the
context, there still remained one more difficulty.

When I took charge, although the furnace had been
rurming five months, only about 4000 lbs. matte was
obtained : opinion being divided as to whether the copper
and silver went into the slags, or were, in some way,
volatilised. My opinion, that the matte would be found
in and beneath the furnace bottom, received no credence,
and it was with the greatest difficulty that I persuaded
the management to let me ** flow out " the furnace and
alter another one (not then started) in order to carry out
my arrangements with forced draught, then to excavate
the bottom, &c., from the cooled furnace (there being no
vault), and rebuild on an improved plan.

It was then found that the matte had penetrated four
feet six inches below the furnace bottom, mto every con-
ceivable crack and crevice, lumps of matte three or four
inches in diameter, with cons of charcoal, being formed
here and there. For a time these appearances puzzled
us, until in the soil, or •• veldt," outside were found large
roots, similar in shape to the lumps of matte. The roots
had been carbonised and matte had flowed round the
carbonised residue, assuming the shape of the original
roots. Further, about four inches of each ** bottom *' was
loose sand, proving that the temperature obtained in
*• smelting in '* the bottoms and during the subsequent
five months* smelting had been insufficient for ordinary
operations. . . ^

About 60 tons of matenal, containmg about x8 tons
matte, was obtained in the excavation— every joint of the
brickwork below the slag-line being a conduit for the
conveyance of matte to the foundation. I had, therefore,
to arrange a process for cooling the lower part of furnace



bottom, sides, and bridge by vaults and brick tubei,
working under a forced draught with moist air. When
the furnace was ready, I decided to melt the sand bottom
in successive layers with a material that would cause its
cohesion and impart a slight fusibility under intense heat
to produce a bottom almost impervious to molten matte.
Then, for the protedion of the sides I found a substance
to replace the *'daagga" — a "mending" composed of
mud and sand in some quartz, from abandoned workings,
which I had crushed and mixed with yellow clay. This
stood fairly well.

Drawing upon my experience In furnace-work at (i)
Middlesborough-on-Tees, where I was in pradice as a
metallurgical chemist and public analyst for six years *
at (2) The Sheffield Smelting Company's Establishment
(Gold, Silver, Platinum Metals, Lead, and Copper-Smell*
ing, &c.. Refining Works), and a similar establishment I
had charge of in Birmingham, where, between the two, I
had seven years' experience in silver, &c., smelting, and
the advantage of an intimate acquaintance with Uie re«
dudion of all classes of ores of gold, silver, copper, &c. ;



Online LibraryArnold BennettChemical news and journal of industrial science → online text (page 82 of 88)