244 
THE PHARMACEUTICAL JOURNAL AND TRANSACTIONS. [September 24,1870. 
always occur secondary reactions, wliicli have here¬ 
tofore escaped the notice of experimenters. 
Note first the action of the current upon the neu¬ 
tral sulphate of ammonia, thus:— 
so 3 nh 4 o=(so 3 +o) + (Nsg^ 
Positive Pole. Negative Pole. 
Then at the positive pole, (S0 3 -+- 0) + 3H0 
= S0 3 3H0 -f- 0,* at the negative, NH 4 = NH 3 + H. 
Beating this in mind, observe the results of my 
experiments upon the organic alkalies. 
I.-ELECTROLYSIS OF ATROPINE. 
Neutral sulphate of atropine. The reaction is 
very rapid at first, but gradually abates. The nega¬ 
tive electrode recovers the pure atropine in very fine 
crystals,—in fact, the crystals when washed, and 
dissolved in boiling water, yield a solution which 
will not give a trace of precipitate when treated with 
chloride of barium. 
At first pure oxygen only is disengaged at the po¬ 
sitive pole, but carbonic acid and carbonic oxide 
soon appear, and at the same time the fluid in the 
corresponding compartment acquires a distinct yellow 
colour. 
An analysis of the gas after twelve hours gave 
these results:— 
Volume of gas... 257 ) p i 
After the action of KH0 2 . 246 ) 2 4 — 
,, „ „ the pyrogallate.. 14 0 2 = 232 
„ „ „ ,, acid chloride.. T8 C 2 0 2 =12-2 
Which gives the composition of the gas :— 
Carbonic acid. 478 
Carbonic oxide . 475 
Oxygen . 90'66 
Nitrogen. 031t 
Secondly.—Acid sulphate of atropine. The de¬ 
composition is effected with great energy, and the 
positive solution acquires at once a fine yellow colour. 
From the start a mixture of oxygen, carbonic acid, 
and carbonic oxide is evolved. The experiment 
being arrested when the ciystals of atropine com¬ 
menced forming upon the negative electrode, the 
composition of the gas from the positive pole was 
found to be as follows:— 
After 24 hours. After 48 hours. 
C 2 0 4 . 8-3. 7-9 
0 2 . 87-9. 88-6 
C<>0 2 . 3-8. 8-9 
N. . . 0-4 
At the close of the electrolysis, the positive solu¬ 
tion had acquired a magnificent yellow colour, whilst 
the negative compartment was still colourless. But 
observe another result, still more remarkable and 
well worth attention. The positive compartment 
duiing the entire series of experiments had the cha¬ 
racteristic odour of the essential oil of almonds; on 
the other hand, the negative liquid, after treatment 
with caustic potassa, gave abundant white fumes 
upon the approach of a stick impregnated with hy¬ 
drochloric acid, showing the presence of ammoniacal 
compounds, the nature of which remain to be deter¬ 
mined by thorough study. 
These results are not without interest. They de¬ 
termine, substantially, what I have already an¬ 
* See the compilation, c New Electrolytic Researches,’ 1868. 
■f The nitrogen contained in the gas, and which appears in 
all of the succeeding analyses, is due to the presence of a 
small quantity of air which it is almost impossible to guard 
against. 
nounced in another paper, that the secondary pheno¬ 
mena at the positive pole arise from a combustion 
provoked by the oxygen; and, further, that at the 
other extremity the current has a single fundamental 
action—it decomposes a salt, an acid, into two parts, 
one basic, hydrogen or metal, which goes to the ne¬ 
gative pole, while the remaining elements are set at 
liberty at the positive pole. All the other phenomena 
are but accessories, and can only be regarded as 
resulting from the oxidation of organic substances. 
But to return to atropine. It is known from the 
studies of Pfeiffer, Kraut and Ludwig, that atropine, 
when treated with sulphiiric acid and bichromate of 
potassa, yields benzoic acid. It may be anticipated 
that this acid, or possibly the essential oil of almonds, 
may eventually become a source for the derivation of 
atropine. 
II.-ELECTROLYSIS OF BRUCINE. 
Neutral sulphate of brucine. The electrolysis of 
this salt is easily accomplished; after a few mo¬ 
ments a beautiful red halo appears around the infe¬ 
rior extremity of the positive electrode. This halo 
increases little by little until it pervades the com¬ 
partment, the contents of which eventually become 1 
blood-red. It will be observed that this coloration 
is precisely the same as results from the application 
of nitric acid to the alkaloid. 
There is no gaseous disengagement at the positive 
pole; it follows that all of the oxygen which is libe¬ 
rated is absorbed, serving to oxidize the brucine, and 
this is a demonstration that the red coloration is 
not due to the formation of any nitrogenous com¬ 
pound, but results from direct oxidation. 
Secondly.—Acid sulphate of brucine. As soon as 
the current is established the positive solution ac¬ 
quires a fine red colour; this effect is instantaneous,, 
and this experiment may be useful as a beautiful 
lecture illustration. 
The oxidation is very energetic, and the gas from 
the first contains carbonic acid. 
First gas. After 4 hours. After 24 hrs,. 
Carbonic acid.. . 
... 4-9 _ 
.. 10-6 ... 
. .. 4-4 
Carbonic oxide . 
. .. 6-6 .... 
.. 10-9 .. . 
. .. 5-8 
Oxygen -... 
... 877 .... 
.. 77-9 ... 
. .. 89-1 
Nitrogen. 
... 0-8 .... 
.. 0-6 ... 
... 0-7 
Within twenty-four hours the red coloration gives 
place to a fine yellow colour, and small crystals com¬ 
mence to appear in the still acid negative compart¬ 
ment. By the fourth day the solution is about ex¬ 
hausted, and the yield of carbonic acid and carbonic 
oxide is very small. The crystals deposited are hard 
and granular; after being washed and dissolved in 
boiling water, their solution is acid to test paper, 
and gives a precipitate with chloride of barium, 
showing that acid sulphate of brucine contaminates 
the crystals. When treated with nitric acid the 
blood-red colour appears. 
III.-ELECTROLYSIS OF STRYCHNINE. 
First.—Acid sulphate of strychnine. The saline 
solution is a poor conductor of the current, so that 
the decomposition is but slowly effected. Oxygen is 
disengaged on one side, and hydrogen on the other, 
and the negative electrode recovers the strychnine 
in confused crystalline masses. 
The positive solution assumes towards the close of 
the experiments a light yellow colour, indicating oxi¬ 
dation, an oxidation, however, which occurs within, 
circumscribed limits, and does not seem able to take- 
