[ 379 ]

XXIII. Experimentson the Formation of Volatile , and on

the Affinities of the Phlogifticatedand light Inflammable
By W illiam Auftin, M . D.Fellow of •Colleg
ciansj communicated by Charles Biagden, R.

Read May 29, 1^87. 1 ‘

T N the former part of the year 1787* I undertook to exa-

JL mine the elaftie fluid produced upon decompofing volatile
alkali by the electric ftroke, as firft fuggefted by D r. P riest ­
ley. Some alkaline air being thus decompofed, and all its
inflammable part feparated by combuftion in glafs veflels in-t
verted in quickfilver, I obferved a confiderable remainder of
phlogifticated a ir; and after many accurate experiments was
fully Convinced, that this phlogifticated air had made a part in
the conftitution of the alkali. This difeoveryr induced me to
make a variety of fynthetical experiments o n the phlogifticated
an d lig h t inflammable airs, with the hopes o f forming volatile
alkali from its Ample elements. I n this undertaking I alfo de­
rived much affiftance from the ingenious labours of D u
P rie STle y ; who, in the courfe of his experiments, had been
repeatedly ftruck with the fmell of volatile alkali from fub*
fiancesnot fuppofed to contain it, and had pointed out Tome
important' phenomena attending its produdion. But having
acquired a more perfed knowledge of Its cdnftituent parts, I
was enabled to produce volatile alkali in a more Ample mahhef^
and more demonftrative of its elements^ than hfe had done. •
V o l . LXXVII1. E e e I was
„So r.Austin on
D
I was not apprifed, when I hnd thefe experiments ill hand,
that the firft objeft of my inquiry, the decompofition of volatile
alkali, and analyfis of its parts, had been fuccefsfully treated j
by the celebratedM. BkRTiioLLET; and that his obfervations had
appeared in R o z i e r ’ s Journal fome months before. T o him |
therefore I give up that part of the fubje<S; and (hall confine
myfelf in the following obfervations to fome experiments oti
the formation of volatile alkali, and on the affinities of the
phlogifticated and light inflammable airs, which have not, I *
believe, been hitherto taken notice of*
Firft, I endeavoured to combine the phlogifticated and hg h f ;
inflammable airs, by mixing them together in various propor­
tions in their elaftic ftate, and adding to them ftieh fubftances as ;
1 thought likely to promote their uniting and forming an alkali.
W ith this view, I threw up to the mixture of thefe airs, ma~
.rine acid air, the marine and vitriolic acids, to which I alio joined .
alkaline air. I tried the effed. of cold upon thefe mixtures,
by applying to the tubes containing them ;cloths moiftened
w ith ether. I even, paffed the ek&ric fpark repeatedly through:
them , though w ith little probability of fuceefs.. XSaftly, I
decompofed alkaline air, and tried to reunite the identical parts
which fo rm ed it by fimilar additions;, but I could hot perceive*
that in any inftance. volatile alkali was produced from its two
conftituent parts mixed together in their Ample aeriform ft ate.
Yet it is well known, that thefe two bodies unite very rea- j
dily, when they arernot in an elaftic ftate. utfoxpe&ed
appearance of volatile alkali had been obterved by Di> P r ie s t -t
ley and M r. K irw an before we were acquainted w ith its
conftitution, and by M . j H aussM/AN fince this difcovery of
M . Berth o llet . An experiment was exhibited before feve-*
xal Gentlemen at Sir J oseph B anks’s Houfe, fome years, ago,
 Formation o f Volatile Alkali*3 ^ r
in which the quantity of volatile alkali pioduced is very re*
markable. In this experiment a few ounces ot powdered tiri
are moiftened with fdme moderately ftrong nitrous acd, and
after they have flood together a:minute or two, about half an
o u n c e o f fixed alkali is mixed with them. A very pungent
fmell of volatile alkali is immediately perceived. .T h e experi­
ment fucceeds equally, if lime be ufed inilead of fixed alkali*
Any perfon, who moifiens a drachm or two of filings of zinc
with a folution of cupreous nitre* and, after they begin to a&
on each other, adds to them a little fait of tartar, will find
volatile alkali to be produced. Nitrous acid, or cupreous nitre,
mixed with iron filings, fulphur, and a little water, and kept
in a clofe vefiel for fome hours, yields a. fmell of volatile
alkali ; and if a piece of paper, ftained with a vegetable blue
fubilance, be thrown into the veflel, it will, m a (hort time, be
turned to a green colour. J In each of thefe experiments the ni­
trous acid and the water are decompofed. Dephlogifticated air
from each of them combines with the metal, and their other con-
flituent parts, the phlogiflicated air of the acid, and inflam­
mable air of the water, being difengagei at the fame inftant,
unite and form volatile alkali. Many other fimilar experi­
ments might be mentioned; but thefe are abundantly fuffi-
cient to prove, that if phlogiflicated and light inflammable air
be prefented to each other at the inftant of their feparation from
folid or liquid fubftances, and before their panicles have re­
ceded from each other, they readily combine and generate vola­
tile alkali. x
i T h at thefe two fubftances do not combine in their elaftic
i Hate, feems to be owing principally to the inflammable
: air* W hen thefe two airs combine, it feems neceflary that
; they part with a certain quantity of that fire to which they
[ owe their elafticity; and that, unlefs their attradion to each
E ee2 other
382 D r. A ustin on the
other exceed their attradlion to fire, they will not unite. Even
when they are combined in the form of volatile alkali, if heat
be applied, they immediately recede from each other, and the
alkali is decompofed. W hen they are not in an aeriform ftate
their attra&ion to each other is greater, on account of the -i
proximity of their p arts; it is then fuperior to their attra&ion
to fire, and therefore they combine ; but when their particles 1
have receded from each other, as .in the aeriform ftate, their |
attra&ion to each other is fo diminilhed by the diftance o f |
their parts, th at their attrattion to fire, which is uniform , i
prevails, and keeps them in a feparate ftate. T he fpecific gra- J
v ity o f inflammable air being eleven times left than th a to fp h lo - \
gifticated air, the diftance of its particles muft be greater than ^
the diftance of .the particles of phlogifticated air in the propor­
tion o f v ^ u to r , if the elementary particles of the two airs
be of equal magnitude ; and its effe<ft, on this account, in
diminilhing attra&ion muft be greater than that of phlogifti­
cated air, in the proportion of, or more probably as the fquares
of, thole numbers.
W hether it be admitted, that fire thus combines with other
fubftances, and is feparated from them by their mutual attrac­
tions, according to the general law, is not further material to
the prefent enquiry, than as it accounts for a circumftance
which feems to be eftablilhed by the following experim ents;
namely, that the combination of the phlogifticated and inflam­
mable airs, and the formation of volatile alkali, depends j
chiefly, if not altogether, on the approximation of the parts
of inflammable air, when phlogifticated air is prefented to
them.
Into a cylindrical glaft tube, filled w ith, and inverted in,
quickfilver, I introduced fome phlogifticated air, and after­
wards fome iron filings moiftened w ith diftilled water. By
this-!
 Formation of Volatile Alkali, 3^3
this arrangement light inflammable air,* which is given out
from water in contad with iron filings, meeting with phlo-
gifticated air. at the inftant of its extrication, combines with it,
and forms'volatile alkali. In order to d eted the minute quan­
tities of volatile alkali, which were thus generated, I fixed to
the infide of the glafs tube a fmall piece' of paper, fiained
with the rind of the blue raddifb. T h e vvegetable, (jluq was
in twenty-four hours changed to a green colour. As an addi­
tional proof of the produdion of volatile alkali, I kept in the
fame tube fome paper, which had been dipped in a folution of
cupreous nitre, expeding to fee its colour converted 'from
green to blue, by the alkali which was to be produced, .^Th^
green paper became gradually paler, and in a few days the
blue colour/(appeared. T his experiment affords a yery
fatisfadory demonftration of the formation of volatile a^k^,li. s
W ater and iron filings mixed together yield inflammable airj
but if this be given out in contad with phiogi.ftic^ted $ir, vola­
tile alkali is produced. In thefe circumftances a double attrac­
tion takes place: one part of the water is attraded by the iron;
the other is.attraded by the phlogifticated air^ and the water
feems by thefe compound affinities to be much more rapidly
decompofed, than when iron and water are mijced by themfelves.
Volatile alkali is formed in a very few fiours, i f nitrous air
be ufed inftead of the phlogifticated, all othpr circumftances re­
maining as in the former experiment. VVhen I have made, uie
of nitrous air not well freed from its acid, by which the vege­
table blue colour has been turned red, a fufficient quantity of
alkali has been generated in twenty-four hours to change, it to
a green. I f iron filings and water be expqfedj to,nitrous air
for a confiderable time, the nitrous air is, fp altered that a cin-
die burns in it w ith increafed brightnefs, as was obferved by
 r,Austin
D on the
Dr. P riestley . T his change is accounted for by the for­
mation of the alkali, which depriving the nitrous air of its phlo-
gifticated part leaves a greater proportion of dephlogifticated j
air.
This experiment alfo fucceeds in atmofpheric air, though a J
longer time is neceflary to produce a fen Able alteration in the |
colours employed as tefts of the alkali ; but the change is very
evident in a day or two. Hence we may conclude, that when- J
ever iron rufts in con ta d w ith water in the open air, or in the '
earth,1 volatile alkali is formed. Phlogifticated air is prefent ;
in all parts of the terraqueous globe, and operations are con- j
ftantly going on, by which inflammable air is feparated from j
water, and perhaps from other bodies.4 T hus we may account
for the frequent appearance o f volatile alkali in the earth, par­
ticularly where inflammable matters abound, among coals and
volcanic produdions, as alfo in animal and vegetable fubftances.
W hen iron, water, and fulphur a d upon each other in
atmofpheric air, volatile alkali is produced. T h e eudiometer j
recommended by Scheele is, for this reafon, incorred. Some
phlogifticated air difappears, and volatile alkali is formed.
This method therefore feems to have milled that great che-
mift in his analyfis of the atmofphere, and induced him to
fuppofe, that the quantity of phlogifticated air in the atmo­
fphere is only 2}times that of dephlogifticated air.
There is a combination of light inflammable a ir'w ith M i l
„'phur. forming hepatic air . It has been obferved by the cele­
brated Mr. K i r w a n , that if nitrous air be mixed with he- f
pa tic air volatile alkali will be formed. I have often repeated this
experiment, and marked the formation o f the volatile alkali by
the change of the vegetable blue to a green colour. In hepatic
air
 Formation of Volatile Alkali, 385
air the parts of inflammable air are brought nearer to each
other than they are in their Ample aeriform ftate*, an^ there-
fore the phiogifticated air of the nitrous air combines with,
them, and generates volatile alkali.
From all thefe experiments it follows, that whether phio­
gifticated air be in a ftate of purity, or mixed with dephlo-
gifticated air*, as in the atmofphere, or combined with it as in
nitrous air, it will in either cafe unite with the giavitating mat*
ter of light inflammable air, provided this fubftance be pre­
d ated to° it in a ftate of condenfation ; but. if. the circnm-
ftapces be reverfed, the fame combination does notftake place.
N o union is formed between inflammable air and the phiogifti­
cated part of nitrous air, even though marine acid be added,
which, by its attra&ion to dephlogifticated air, would cont|Ti-
bute to decompofe the nitrous air, and by its attraction to
volatile alkali would tend to unite its conftituent parts : or if
to light inflammable air we add nitrous air and iron filings,,
no combination enfues ; though it has been often obferved,
that volatile alkali is readily generated, when nitrous air is
prefented to the inflammable at the inftant of its extrication
from, water and iron*
The proportions of the phiogifticated and inflammable.airs in,
volatile alkali, as difcovered by calculation, approach very near

* Since thefe experiments were made*. T have found that this is not the cafe.-
The eleftric fpark decompofes hepatic air, aqd leaves a quantity, of inflammable
air equal in bulk to the hepatic air very nearly. However, as the inflammable
air leaves the fulphur upon the application o f the.ele&rical fpark, it fhould. feem,,
I that the proper matter o f ipflammable air is more difpofed to combine, with fire
S than with fulphur j which may be the reafbn why hepatic air is decpmpofbd by
nitrous air, while pure inflammable air is not affe&ed by j*,.
m ■ ’ f * : ;J ^ t o -
*86
.
D/\ Austin the
fo therefult*of M, B erthojllet ’s experiments. I f we take
the fpecific gravities of thefe airs, given in Mr. Kirwan’s ;
late publication,
ioo cubic inches contain 18 ,16 grains o f alkaline air.
— —— « 30,535 — o f phlogifticated air. 1
— IX ------ —— 2,613 — o f inflammable air.
According to M .'B erthollet alkaline air is expanded upon
decompofltiom from 1,7 to 3,3. Its fpecific gravity after de-
compofition muft therefore be leffened in the fame proportion;
and 100 cubic inches will be found to contain only 9,355
grains of alkaline air thus expanded. In w hat proportion m uft
the phlogifticated and inflammable airs be, in order to form a
mixture of this fpecific gravity ?
L et x reprefent the number of grains of phlogifticated air
in 100 cubic inches o f the mixture : then 9 * 3 5 5 -# will ex-
prefs the number of grains o f inflammable air. As the w eight 1
o f one cubic inch is to a cubic inch, fo will the weight o f
either air in the mixture be to the cubic inches of that air in
the m ixtu re; and therefore the weight of a cubic inch

of phlogifticated air, or which is the fame, *30535 fhall be

to i , as # is to - L — which muft be the number o f cubic
■ >3°535 ,
inches of phlogifticated air in 100 cubic inches of the m ixture;
and the weight of a cubic inch o f inflammable air, that is,

or ,02613 : 1 :: 9> 355 “ * : the cut)ic inches

of inflammable air in 100 cubic inches of the mixture. . T h u s
we have an expreffion for the cubic inches of each air 5 thefe
two quantities taken together are equal to 160 cubic inches ‘by
feppofition. W e have then,
■4 *

>3°S35 I
 Formation of Volatile M a l i 3°7
* , 9’355~“y = ioo ;
?3°535 T »026i3
, 2,85654925 ^ 3 ^ 5 3 5 ;g 3 0 .5 3 5 s
T >02613
,0 2 6 1 3 # + 2,85654925 —>3053.5 ^7955 >
,27922 #-2,05866970
# = 7,373 the number of grains of
phlogifticated air in 100 cubic inches, or in 9,355 grains o f
the m ixture; and 9 , 3 5 5 ' 7-373 = ‘ >98* . g r a i n s o f inflam-
m ableair. , , . . . X A.i
N ow 7,373 : 1,982 •••• 121 V32 ; the quantity of phlogifti­
cated air is to that of inflammable, as 121 to 32; ‘ '
According to M. B e r t h o l l e t ’ s experiments, the quantity
o f phlogifticated is to that o f inflammable atr, as 1 : 29.
T h is is not very wide o f calculation. I f we confider the great
difficulty of obtaining thefe fpecific gravities with exaanels,
we m ull be pleafed to find fo near a concurrence, and place
more confidence in experiments on the fpecific gravities and
combinations of aeriform bodies, than has generally been given
i them. M. B e r t h o l l e t ’ s experiments come within TV o f
calculation; and this difference will be diminilhed by two-
; thirds, if we take the fpecific gravities of the phlogifticated
| and inflammable airs in the proportion of u to 1, as he has
| done, inftead of Mr. K i r w a n ’s proportion, which I have fol-
I lowed in this calculation.

•SUS*
-

Vou LXXVIH. F