Received April 7,—Read June 5, 1831.
i. On simple Voltaic Circles.
875. The great question of the
source of electricity, in the voltaic pile has engaged
the attention of so many eminent philosophers, that
a man of liberal mind and able to appreciate their
powers would probably conclude, although he might
not have studied the question, that the truth was
somewhere revealed. But if in pursuance of this
impression he were induced to enter upon the work
of collating results and conclusions, he would find
such contradictory evidence, such equilibrium of opinion,
such variation and combination of theory, as would
leave him in complete doubt respecting what he should
accept as the true interpretation of nature: he
would be forced to take upon himself the labour of
repeating and examining the facts, and then use his
own judgement on them in preference to that of others.
876. This state of the subject
must, to those who have made up their minds on the
matter, be my apology for entering upon its investigation.
The views I have taken of the definite action of electricity
in decomposing bodies (783.), and the identity of
the power so used with the power to be overcome (855.),
founded not on a mere opinion or general notion, but
on facts which, being altogether new, were to my mind
precise and conclusive, gave me, as I conceived, the
power of examining the question with advantages not
before possessed by any, and which might compensate,
on my part, for the superior clearness and extent
of intellect on theirs. Such are the considerations
which have induced me to suppose I might help in deciding
the question, and be able to render assistance in that
great service of removing doubtful knowledge.
Such knowledge is the early morning light of every
advancing science, and is essential to its development;
but the man who is engaged in dispelling that which
is deceptive in it, and revealing more clearly that
which is true, is as useful in his place, and as necessary
to the general progress of the science, as he who first
broke through the intellectual darkness, and opened
a path into knowledge before unknown to man.
877. The identity of the force
constituting the voltaic current or electrolytic agent,
with that which holds the elements of electrolytes
together (855.), or in other words with chemical affinity,
seemed to indicate that the electricity of the pile
itself was merely a mode of exertion, or exhibition,
or existence of true chemical action, or rather
of its cause; and I have consequently already said
that I agree with those who believe that the supply
of electricity is due to chemical powers (857.).
878. But the great question of
whether it is originally due to metallic contact or
to chemical action, i.e. whether it is the first
or the second which originates and determines
the current, was to me still doubtful; and the beautiful
and simple experiment with amalgamated zinc and platina,
which I have described minutely as to its results (863,
&c.), did not decide the point; for in that experiment
the chemical action does not take place without the
contact of the metals, and the metallic contact is
inefficient without the chemical action. Hence
either might be looked upon as the determining
cause of the current.
879. I thought it essential to
decide this question by the simplest possible forms
of apparatus and experiment, that no fallacy might
be inadvertently admitted. The well-known difficulty
of effecting decomposition by a single pair of plates,
except in the fluid exciting them into action (863.),
seemed to throw insurmountable obstruction in the way
of such experiments; but I remembered the easy decomposability
of the solution of iodide of potassium (316.), and
seeing no theoretical reason, if metallic contact
was not essential, why true electro-decomposition
should not be obtained without it, even in a single
circuit, I persevered and succeeded.
880. A plate of zinc, about eight
inches long and half an inch wide, was cleaned and
bent in the middle to a right angle, fi a,
Plate VI. A plate of platina, about three inches
long and half an inch wide, was fastened to a platina
wire, and the latter bent as in the figure, b.
These two pieces of metal were arranged together as
delineated, but as yet without the vessel c,
and its contents, which consisted of dilute sulphuric
acid mingled with a little nitric acid. At x
a piece of folded bibulous paper, moistened in a solution
of iodide of potassium, was placed on the zinc, and
was pressed upon by the end of the platina wire.
When under these circumstances the plates were dipped
into the acid of the vessel c, there was an
immediate effect at x, the iodide being decomposed,
and iodine appearing at the anode (663.), i.e.
against the end of the platina wire.
881. As long as the lower ends
of the plates remained in the acid the electric current
continued, and the decomposition proceeded at x.
On removing the end of the wire from place to place
on the paper, the effect was evidently very powerful;
and on placing a piece of turmeric paper between the
white paper and zinc, both papers being moistened with
the solution of iodide of potassium, alkali was evolved
at the cathode (663.) against the zinc, in
proportion to the evolution of iodine at the anode.
Hence the decomposition was perfectly polar, and decidedly
dependent upon a current of electricity passing from
the zinc through the acid to the platina in the vessel
c, and back from the platina through the solution
to the zinc at the paper x.
882. That the decomposition at
x was a true electrolytic action, due to a
current determined by the state of things in the vessel
c, and not dependent upon any mere direct chemical
action of the zinc and platina on the iodide, or even
upon any current which the solution of iodide
might by its action on those metals tend to form at
x, was shown, in the first place, by removing
the vessel c and its acid from the plates, when
all decomposition at x ceased, and in the next
by connecting the metals, either in or out of the
acid, together, when decomposition of the iodide at
x occurred, but in a reverse order; for
now alkali appeared against the end of the platina
wire, and the iodine passed to the zinc, the current
being the contrary of what it was in the former instance,
and produced directly by the difference of action
of the solution in the paper on the two metals.
The iodine of course combined with the zinc.
883. When this experiment was
made with pieces of zinc amalgamated over the whole
surface (863.), the results were obtained with equal
facility and in the same direction, even when only
dilute sulphuric acid was contained in the vessel
c (fi.). Whichsoever end of the zinc
was immersed in the acid, still the effects were the
same: so that if, for a moment, the mercury might
be supposed to supply the metallic contact, the inversion
of the amalgamated piece destroys that objection.
The use of unamalgamated zinc (880.) removes
all possibility of doubt.
884 When, in pursuance of other views
(930.), the vessel c was made to contain a
solution of caustic potash in place of acid, still
the same results occurred. Decomposition of the
iodide was effected freely, though there was no metallic
contact of dissimilar metals, and the current of electricity
was in the same direction as when acid was used
at the place of excitement.
885. Even a solution of common
salt in the glass c could produce all these
effects.
886. Having made a galvanometer
with platina wires, and introduced it into the course
of the current between the platina plate and the place
of decomposition x, it was affected, giving
indications of currents in the same direction as those
shown to exist by the chemical action.
887. If we consider these results
generally, they lead to very important conclusions.
In the first place, they prove, in the most decisive
manner, that metallic contact is not necessary
for the production of the voltaic current. In
the next place, they show a most extraordinary mutual
relation of the chemical affinities of the fluid which
excites the current, and the fluid which is
decomposed by it.
888. For the purpose of simplifying
the consideration, let us take the experiment with
amalgamated zinc. The metal so prepared exhibits
no effect until the current can pass: it at the
same time introduces no new action, but merely removes
an influence which is extraneous to those belonging
either to the production or the effect of the electric
current under investigation (1000.); an influence
also which, when present, tends only to confuse the
results.
889. Let two plates, one of amalgamated
zinc and the other of platina, be placed parallel
to each other (fi.), and introduce a drop of dilute
sulphuric acid, y, between them at one end:
there will be no sensible chemical action at that
spot unless the two plates are connected somewhere
else, as at PZ, by a body capable of conducting electricity.
If that body be a metal or certain forms of carbon,
then the current passes, and, as it circulates through
the fluid at y, decomposition ensues.
890. Then remove the acid from
y, and introduce a drop of the solution of
iodide of potassium at x (fi.). Exactly
the same set of effects occur, except that when the
metallic communication is made at PZ, the electric
current is in the opposite direction to what it was
before, as is indicated by the arrows, which show
the courses of the currents (667.).
891. Now both the solutions
used are conductors, but the conduction in them is
essentially connected with decomposition (858.) in
a certain constant order, and therefore the appearance
of the elements in certain places shows in
what direction a current has passed when the solutions
are thus employed. Moreover, we find that when
they are used at opposite ends of the plates, as in
the last two experiments (889. 890.), metallic contact
being allowed at the other extremities, the currents
are in opposite directions. We have evidently,
therefore, the power of opposing the actions of the
two fluids simultaneously to each other at the opposite
ends of the plates, using each one as a conductor for
the discharge of the current of electricity, which
the other tends to generate; in fact, substituting
them for metallic contact, and combining both experiments
into one (fi.). Under these circumstances,
there is an opposition of forces: the fluid,
which brings into play the stronger set of chemical
affinities for the zinc, (being the dilute acid,) overcomes
the force of the other, and determines the formation
and direction of the electric current; not merely
making that current pass through the weaker liquid,
but actually reversing the tendency which the elements
of the latter have in relation to the zinc and platina
if not thus counteracted, and forcing them in the
contrary direction to that they are inclined to follow,
that its own current may have free course. If
the dominant action at y be removed by making
metallic contact there, then the liquid at x
resumes its power; or if the metals be not brought
into contact at y but the affinities of the
solution there weakened, whilst those active x
are strengthened, then the latter gains the ascendency,
and the decompositions are produced in a contrary
order.
892. Before drawing a final
conclusion from this mutual dependence and state of
the chemical affinities of two distant portions of
acting fluids (916.), I will proceed to examine more
minutely the various circumstances under which the
re-action of the body suffering decomposition is rendered
evident upon the action of the body, also undergoing
decomposition, which produces the voltaic current.
893. The use of metallic contact
in a single pair of plates, and the cause of its great
superiority above contact made by other kinds of matter,
become now very evident. When an amalgamated zinc
plate is dipped into dilute sulphuric acid, the force
of chemical affinity exerted between the metal and
the fluid is not sufficiently powerful to cause sensible
action at the surfaces of contact, and occasion the
decomposition of water by the oxidation of the metal,
although it is sufficient to produce such a
condition of the electricity (or the power upon which
chemical affinity depends) as would produce a current
if there were a path open for it (916. 956.); and
that current would complete the conditions necessary,
under the circumstances, for the decomposition of
the water.
894. Now the presence of a piece
of platina touching both the zinc and the fluid to
be decomposed, opens the path required for the electricity.
Its direct communication with the zinc is effectual,
far beyond any communication made between it and that
metal, (i.e. between the platina and zinc,) by means
of decomposable conducting bodies, or, in other words,
electrolytes, as in the experiment already described
(891.); because, when they are used, the chemical
affinities between them and the zinc produce a contrary
and opposing action to that which is influential in
the dilute sulphuric acid; or if that action be but
small, still the affinity of their component parts
for each other has to be overcome, for they cannot
conduct without suffering decomposition; and this decomposition
is found experimentally to re-act back upon
the forces which in the acid tend to produce the current
(904. 910. &c.), and in numerous cases entirely to
neutralize them. Where direct contact of the zinc
and platina occurs, these obstructing forces are not
brought into action, and therefore the production
and the circulation of the electric current and the
concomitant action of decomposition are then highly
favoured.
895. It is evident, however,
that one of these opposing actions may be dismissed,
and yet an electrolyte be used for the purpose of completing
the circuit between the zinc and platina immersed
separately into the dilute acid; for if, in fi,
the platina wire be retained in metallic contact with
the zinc plate a, at x, and a division
of the platina be made elsewhere, as at s,
then the solution of iodide placed there, being in
contact with platina at both surfaces, exerts no chemical
affinities for that metal; or if it does, they are
equal on both sides. Its power, therefore, of
forming a current in opposition to that dependent upon
the action of the acid in the vessel c, is
removed, and only its resistance to decomposition
remains as the obstacle to be overcome by the affinities
exerted in the dilute sulphuric acid.
896. This becomes the condition
of a single pair of active plates where metallic
contact is allowed. In such cases, only one
set of opposing affinities are to be overcome by those
which are dominant in the vessel c; whereas,
when metallic contact is not allowed, two sets of opposing
affinities must be conquered (894.).
897. It has been considered a
difficult, and by some an impossible thing, to decompose
bodies by the current from a single pair of plates,
even when it was so powerful as to heat bars of metal
red-hot, as in the case of Hare’s calorimeter,
arranged as a single voltaic circuit, or of Wollaston’s
powerful single pair of metals. This difficulty
has arisen altogether from the antagonism of the chemical
affinity engaged in producing the current with the
chemical affinity to be overcome, and depends entirely
upon their relative intensity; for when the sum of
forces in one has a certain degree of superiority
over the sum of forces in the other, the former gain
the ascendency, determine the current, and overcome
the latter so as to make the substance exerting them
yield up its elements in perfect accordance, both
as to direction and quantity, with the course of those
which are exerting the most intense and dominant action.
898. Water has generally been
the substance, the decomposition of which has been
sought for as a chemical test of the passage of an
electric current. But I now began to perceive
a reason for its failure, and for a fact which I had
observed long before (315. 316.) with regard to the
iodide of potassium, namely, that bodies would differ
in facility of decomposition by a given electric current,
according to the condition and intensity of their
ordinary chemical affinities. This reason appeared
in their re-action upon the affinities tending
to cause the current; and it appeared probable, that
many substances might be found which could be decomposed
by the current of a single pair of zinc and platina
plates immersed in dilute sulphuric acid, although
water resisted its action. I soon found this to
be the case, and as the experiments offer new and
beautiful proofs of the direct relation and opposition
of the chemical affinities concerned in producing
and in resisting the stream of electricity, I shall
briefly describe them.
899. The arrangement of the apparatus
was as in fi. The vessel v contained
dilute sulphuric acid; Z and P are the zinc and platina
plates; a, b, and c are platina
wires; the decompositions were effected at x,
and occasionally, indeed generally, a galvanometer
was introduced into the circuit at g:
its place only is here given, the circle at g
having no reference to the size of the instrument.
Various arrangements were made at x, according
to the kind of decomposition to be effected. If
a drop of liquid was to be acted upon, the two ends
were merely dipped into it; if a solution contained
in the pores of paper was to be decomposed, one of
the extremities was connected with a platina plate
supporting the paper, whilst the other extremity rested
on the paper, e, fi: or sometimes,
as with sulphate of soda, a plate of platina sustained
two portions of paper, one of the ends of the wires
resting upon each piece, c, fi. The
darts represent the direction of the electric current
(667.).
900. Solution of iodide of
potassium, in moistened paper, being placed at
the interruption of the circuit at x, was readily
decomposed. Iodine was evolved at the anode,
and alkali at the cathode, of the decomposing
body.
901. Protochloride of tin,
when fused and placed at x, was also readily
decomposed, yielding perchloride of tin at the anode
(779.), and tin at the cathode.
902. Fused chloride of silver,
placed at x, was also easily decomposed; chlorine
was evolved at the anode, and brilliant metallic
silver, either in films upon the surface of the liquid,
or in crystals beneath, evolved at the cathode.
903. Water acidulated with sulphuric
acid, solution of muriatic acid, solution of sulphate
of soda, fused nitre, and the fused chloride and iodide
of lead were not decomposed by this single pair of
plates, excited only by dilute sulphuric acid.
904. These experiments give abundant
proofs that a single pair of plates can electrolyze
bodies and separate their elements. They also
show in a beautiful manner the direct relation and
opposition of the chemical affinities concerned at
the two points of action. In those cases where
the sum of the opposing affinities at x was
sufficiently beneath the sum of the acting affinities
in v, decomposition took place; but in those
cases where they rose higher, decomposition was effectually
resisted and the current ceased to pass (891.).
905. It is however, evident,
that the sum of acting affinities in v may
be increased by using other fluids than dilute sulphuric
acid, in which latter case, as I believe, it is merely
the affinity of the zinc for the oxygen already combined
with hydrogen in the water that is exerted in producing
the electric current (919.): and when the affinities
are so increased, the view I am supporting leads to
the conclusion, that bodies which resisted in the
preceding experiments would then be decomposed, because
of the increased difference between their affinities
and the acting affinities thus exalted. This
expectation was fully confirmed in the following manner.
906. A little nitric acid was
added to the liquid in the vessel r, so as
to make a mixture which I shall call diluted nitro-sulphuric
acid. On repeating the experiments with this
mixture, all the substances before decomposed again
gave way, and much more readily. But, besides
that, many which before resisted electrolyzation,
now yielded up their elements. Thus, solution
of sulphate of soda, acted upon in the interstices
of litmus and turmeric paper, yielded acid at the
anode and alkali at the cathode; solution
of muriatic acid tinged by indigo yielded chlorine
at the anode and hydrogen at the cathode;
solution of nitrate of silver yielded silver at the
cathode. Again, fused nitre and the fused
iodide and chloride of lead were decomposable by the
current of this single pair of plates, though they
were not by the former (903.).
907. A solution of acetate of
lead was apparently not decomposed by this pair, nor
did water acidulated by sulphuric acid seem at first
to give way (973.).
908. The increase of intensity
or power of the current produced by a simple voltaic
circle, with the increase of the force of the chemical
action at the exciting place, is here sufficiently
evident. But in order to place it in a clearer
point of view, and to show that the decomposing effect
was not at all dependent, in the latter cases, upon
the mere capability of evolving more electricity,
experiments were made in which the quantity evolved
could be increased without variation in the intensity
of the exciting cause. Thus the experiments in
which dilute sulphuric acid was used (899.), were
repeated, using large plates of zinc and platina in
the acid; but still those bodies which resisted decomposition
before, resisted it also under these new circumstances.
Then again, where nitro-sulphuric acid was used (906.),
mere wires of platina and zinc were immersed in the
exciting acid; yet, notwithstanding this change, those
bodies were now decomposed which resisted any current
tending to be formed by the dilute sulphuric acid.
For instance, muriatic acid could not be decomposed
by a single pair of plates when immersed in dilute
sulphuric acid; nor did making the solution of sulphuric
acid strong, nor enlarging the size of the zinc and
platina plates immersed in it, increase the power;
but if to a weak sulphuric acid a very little nitric
acid was added, then the electricity evolved had power
to decompose the muriatic acid, evolving chlorine at
the anode and hydrogen at the cathode,
even when mere wires of metals were used. This
mode of increasing the intensity of the electric current,
as it excludes the effect dependent upon many pairs
of plates, or even the effect of making any one acid
stronger or weaker, is at once referable to the condition
and force of the chemical affinities which are brought
into action, and may, both in principle and practice,
be considered as perfectly distinct from any other
mode.
909. The direct reference which
is thus experimentally made in the simple voltaic
circle of the intensity of the electric current
to the intensity of the chemical action going
on at the place where the existence and direction
of the current is determined, leads to the conclusion
that by using selected bodies, as fused chlorides,
salts, solutions of acids, &c., which may act upon
the metals employed with different degrees of chemical
force; and using also metals in association with platina,
or with each other, which shall differ in the degree
of chemical action exerted between them and the exciting
fluid or electrolyte, we shall be able to obtain a
series of comparatively constant effects due to electric
currents of different intensities, which will serve
to assist in the construction of a scale competent
to supply the means of determining relative degrees
of intensity with accuracy in future researches.
910. I have already expressed
the view which I take of the decomposition in the
experimental place, as being the direct consequence
of the superior exertion at some other spot of the
same kind of power as that to be overcome, and therefore
as the result of an antagonism of forces of the same
nature (891. 904.). Those at the place of decomposition
have a re-action upon, and a power over, the exerting
or determining set proportionate to what is needful
to overcome their own power; and hence a curious result
of resistance offered by decompositions to the
original determining force, and consequently to the
current. This is well shown in the cases where
such bodies as chloride of lead, iodide of lead, and
water would not decompose with the current produced
by a single pair of zinc and platina plates in sulphuric
acid (903.), although they would with a current of
higher intensity produced by stronger chemical powers.
In such cases no sensible portion of the current passes
(967.); the action is stopped; and I am now of opinion
that in the case of the law of conduction which I
described in the Fourth Series of these Researches
(413.), the bodies which are electrolytes in the fluid
state cease to be such in the solid form, because
the attractions of the particles by which they are
retained in combination and in their relative position,
are then too powerful for the electric current.
The particles retain their places; and as decomposition
is prevented, the transmission of the electricity is
prevented also; and although a battery of many plates
may be used, yet if it be of that perfect kind which
allows of no extraneous or indirect action (1000.),
the whole of the affinities concerned in the activity
of that battery are at the same time also suspended
and counteracted.
911. But referring to the resistance
of each single case of decomposition, it would appear
that as these differ in force according to the affinities
by which the elements in the substance tend to retain
their places, they also would supply cases constituting
a series of degrees by which to measure the initial
intensities of simple voltaic or other currents of
electricity, and which, combined with the scale of
intensities determined by different degrees of acting
force (909.), would probably include a sufficient
set of differences to meet almost every important case
where a reference to intensity would be required.
912. According to the experiments
I have already had occasion to make, I find that the
following bodies are electrolytic in the order in which
I have placed them, those which are first being decomposed
by the current of lowest intensity. These currents
were always from a single pair of plates, and may
be considered as elementary voltaic forces.
Iodide of potassium (solution).
Chloride of silver (fused).
Protochloride of tin (fused).
Chloride of lead (fused).
Iodide of lead (fused).
Muriatic acid (solution).
Water, acidulated with sulphuric acid.
913. It is essential that, in
all endeavours to obtain the relative electrolytic
intensity necessary for the decomposition of different
bodies, attention should be paid to the nature of
the electrodes and the other bodies present which
may favour secondary actions (986.). If in electro-decomposition
one of the elements separated has an affinity for the
electrode, or for bodies present in the surrounding
fluid, then the affinity resisting decomposition is
in part balanced by such power, and the true place
of the electrolyte in a table of the above kind is
not obtained: thus, chlorine combines with a
positive platina electrode freely, but iodine scarcely
at all, and therefore I believe it is that the fused
chlorides stand first in the preceding Table.
Again, if in the decomposition of water not merely
sulphuric but also a little nitric acid be present,
then the water is more freely decomposed, for the hydrogen
at the cathode is not ultimately expelled,
but finds oxygen in the nitric acid, with which it
can combine to produce a secondary result; the affinities
opposing decomposition are in this way diminished,
and the elements of the water can then be separated
by a current of lower intensity.
914. Advantage may be taken of
this principle to interpolate more minute degrees
into the scale of initial intensities already referred
to (909. 911.) than is there spoken of; for by combining
the force of a current constant in its intensity,
with the use of electrodes consisting of matter, having
more or less affinity for the elements evolved from
the decomposing electrolyte, various intermediate
degrees may be obtained.
915. Returning to the consideration
of the source of electricity (878. &c.), there is
another proof of the most perfect kind that metallic
contact has nothing to do with the production
of electricity in the voltaic circuit, and further,
that electricity is only another mode of the exertion
of chemical forces. It is, the production of the
electric spark before any contact of metals
is made, and by the exertion of pure and unmixed
chemical forces. The experiment, which will
be described further on (956.), consists in obtaining
the spark upon making contact between a plate of zinc
and a plate of copper plunged into dilute sulphuric
acid. In order to make the arrangement as elementary
as possible, mercurial surfaces were dismissed, and
the contact made by a copper wire connected with the
copper plate, and then brought to touch a clean part
of the zinc plate. The electric spark appeared,
and it must of necessity have existed and passed before
the zinc and the copper were in contact.
916. In order to render more
distinct the principles which I have been endeavouring
to establish, I will restate them in their simplest
form, according to my present belief. The electricity
of the voltaic pile (856. note) is not dependent either
in its origin or its continuance upon the contact
of the metals with each other (880. 915.). It
is entirely due to chemical action (882.), and is
proportionate in its intensity to the intensity of
the affinities concerned in its production (908.);
and in its quantity to the quantity of matter which
has been chemically active during its evolution (869.).
This definite production is again one of the strongest
proofs that the electricity is of chemical origin.
917. As volta-electro-generation
is a case of mere chemical action, so volta-electro-decomposition
is simply a case of the preponderance of one set of
chemical affinities more powerful in their nature,
over another set which are less powerful: and
if the instance of two opposing sets of such forces
(891.) be considered, and their mutual relation and
dependence borne in mind, there appears no necessity
for using, in respect to such cases, any other term
than chemical affinity, (though that of electricity
may be very convenient,) or supposing any new agent
to be concerned in producing the results; for we may
consider that the powers at the two places of action
are in direct communion and balanced against each other
through the medium of the metals (891.), fi,
in a manner analogous to that in which mechanical
forces are balanced against each other by the intervention
of the lever (1031.).
918. All the facts show us that
that power commonly called chemical affinity, can
be communicated to a distance through the metals and
certain forms of carbon; that the electric current
is only another form of the forces of chemical affinity;
that its power is in proportion to the chemical affinities
producing it; that when it is deficient in force it
may be helped by calling in chemical aid, the want
in the former being made up by an equivalent of the
latter; that, in other words, the forces termed
chemical affinity and electricity are one and the same.
919. When the circumstances connected
with the production of electricity in the ordinary
voltaic circuit are examined and compared, it appears
that the source of that agent, always meaning the
electricity which circulates and completes the current
in the voltaic apparatus, and gives that apparatus
power and character (947. 996.), exists in the chemical
action which takes place directly between the metal
and the body with which it combines, and not at all
in the subsequent action of the substance so produced
with the acid present. Thus, when zinc, platina,
and dilute sulphuric acid are used, it is the union
of the zinc with the oxygen of the water which determines
the current; and though the acid is essential to the
removal of the oxide so formed, in order that another
portion of zinc may act on another portion of water,
it does not, by combination with that oxide, produce
any sensible portion of the current of electricity
which circulates; for the quantity of electricity
is dependent upon the quantity of zinc oxidized, and
in definite proportion to it: its intensity is
in proportion to the intensity of the chemical affinity
of the zinc for the oxygen under the circumstances,
and is scarcely, if at all, affected by the use of
either strong or weak acid (908.).
920. Again, if zinc, platina,
and muriatic acid are used, the electricity appears
to be dependent upon the affinity of the zinc for the
chlorine, and to be circulated in exact proportion
to the number of particles of zinc and chlorine which
unite, being in fact an equivalent to them.
921. But in considering this
oxidation, or other direct action upon the METAL itself,
as the cause and source of the electric current, it
is of the utmost importance to observe that the oxygen
or other body must be in a peculiar condition, namely,
in the state of combination; and not only so,
but limited still further to such a state of combination
and in such proportions as will constitute an electrolyte
(823.). A pair of zinc and platina plates cannot
be so arranged in oxygen gas as to produce a current
of electricity, or act as a voltaic circle, even though
the temperature may be raised so high as to cause
oxidation of the zinc far more rapidly than if the
pair of plates were plunged into dilute sulphuric acid;
for the oxygen is not part of an electrolyte, and
cannot therefore conduct the forces onwards by decomposition,
or even as metals do by itself. Or if its gaseous
state embarrass the minds of some, then liquid chlorine
may be taken. It does not excite a current of
electricity through the two plates by combining with
the zinc, for its particles cannot transfer the electricity
active at the point of combination across to the platina.
It is not a conductor of itself, like the metals;
nor is it an electrolyte, so as to be capable of conduction
during decomposition, and hence there is simple chemical
action at the spot, and no electric current.
922. It might at first be supposed
that a conducting body not electrolytic, might answer
as the third substance between the zinc and the platina;
and it is true that we have some such capable of exerting
chemical action upon the metals. They must, however,
be chosen from the metals themselves, for there are
no bodies of this kind except those substances and
charcoal. To decide the matter by experiment,
I made the following arrangement. Melted tin
was put into a glass tube bent into the form of the
letter V, fi, so as to fill the half of each
limb, and two pieces of thick platina wire, p,
w, inserted, so as to have their ends immersed
some depth in the tin: the whole was then allowed
to cool, and the ends p and w connected
with a delicate galvanometer. The part of the
tube at x was now reheated, whilst the portion
y was retained cool. The galvanometer was
immediately influenced by the thermo-electric current
produced. The heat was steadily increased at
x, until at last the tin and platina combined
there; an effect which is known to take place with
strong chemical action and high ignition; but not
the slightest additional effect occurred at the galvanometer.
No other deflection than that due to the thermo-electric
current was observable the whole time. Hence,
though a conductor, and one capable of exerting chemical
action on the tin, was used, yet, not being an electrolyte,
not the slightest effect of an electrical current could
be observed (947.).
923. From this it seems apparent
that the peculiar character and condition of an electrolyte
is essential in one part of the voltaic circuit;
and its nature being considered, good reasons appear
why it and it alone should be effectual. An electrolyte
is always a compound body: it can conduct, but
only whilst decomposing. Its conduction depends
upon its decomposition and the transmission of
its particles in directions parallel to the current;
and so intimate is this connexion, that if their transition
be stopped, the current is stopped also; if their
course be changed, its course and direction change
with them; if they proceed in one direction, it has
no power to proceed in any other than a direction
invariably dependent on them. The particles of
an electrolytic body are all so mutually connected,
are in such relation with each other through their
whole extent in the direction of the current, that
if the last is not disposed of, the first is not at
liberty to take up its place in the new combination
which the powerful affinity of the most active metal
tends to produce; and then the current itself is stopped;
for the dependencies of the current and the decomposition
are so mutual, that whichsoever be originally determined,
i.e. the motion of the particles or the motion
of the current, the other is invariable in its concomitant
production and its relation to it.
924. Consider, then, water as
an electrolyte and also as an oxidizing body.
The attraction of the zinc for the oxygen is greater,
under the circumstances, than that of the oxygen for
the hydrogen; but in combining with it, it tends to
throw into circulation a current of electricity in
a certain direction. This direction is consistent
(as is found by innumerable experiments) with the
transfer of the hydrogen from the zinc towards the
platina, and the transfer in the opposite direction
of fresh oxygen from the platina towards the zinc;
so that the current can pass in that one line,
and, whilst it passes, can consist with and favour
the renewal of the conditions upon the surface of
the zinc, which at first determined both the combination
and circulation. Hence the continuance of the
action there, and the continuation of the current.
It therefore appears quite as essential that there
should be an electrolyte in the circuit, in order that
the action may be transferred forward, in a certain
constant direction, as that there should be an
oxidizing or other body capable of acting directly
on the metal; and it also appears to be essential that
these two should merge into one, or that the principle
directly active on the metal by chemical action should
be one of the ions of the electrolyte used.
Whether the voltaic arrangement be excited by solution
of acids, or alkalies, or sulphurets, or by fused
substances (476.), this principle has always hitherto,
as far as I am aware, been an anion (943.);
and I anticipate, from a consideration of the principles
of electric action, that it must of necessity be one
of that class of bodies.
925. If the action of the sulphuric
acid used in the voltaic circuit be considered, it
will be found incompetent to produce any sensible portion
of the electricity of the current by its combination
with the oxide formed, for this simple reason, it
is deficient in a most essential condition: it
forms no part of an electrolyte, nor is it in relation
with any other body present in the solution which
will permit of the mutual transfer of the particles
and the consequent transfer of the electricity.
It is true, that as the plane at which the acid is
dissolving the oxide of zinc formed by the action
of the water, is in contact with the metal zinc, there
seems no difficulty in considering how the oxide there
could communicate an electrical state, proportionate
to its own chemical action on the acid, to the metal,
which is a conductor without decomposition. But
on the side of the acid there is no substance to complete
the circuit: the water, as water, cannot conduct
it, or at least only so small a proportion that it
is merely an incidental and almost inappreciable effect
(970.); and it cannot conduct it as an electrolyte,
because an electrolyte conducts in consequence of
the mutual relation and action of its particles;
and neither of the elements of the water, nor even
the water itself, as far as we can perceive, are ions
with respect to the sulphuric acid (848.).
926. This view of the secondary
character of the sulphuric acid as an agent in the
production of the voltaic current, is further confirmed
by the fact, that the current generated and transmitted
is directly and exactly proportional to the quantity
of water decomposed and the quantity of zinc oxidized
(868. 991.), and is the same as that required to decompose
the same quantity of water. As, therefore, the
decomposition of the water shows that the electricity
has passed by its means, there remains no other electricity
to be accounted for or to be referred to any action
other than that of the zinc and the water on each
other.
927. The general case (for it
includes the former one (924.),) of acids and bases,
may theoretically be stated in the following manner.
Let a, fi, be supposed to be a dry oxacid,
and b a dry base, in contact at c, and
in electric communication at their extremities by plates
of platina pp, and a platina wire w.
If this acid and base were fluid, and combination
took place at c, with an affinity ever so vigorous,
and capable of originating an electric current, the
current could not circulate in any important degree;
because, according to the experimental results, neither
a nor b could conduct without being decomposed,
for they are either electrolytes or else insulators,
under all circumstances, except to very feeble and
unimportant currents (970. 986.). Now the affinities
at c are not such as tend to cause the elements
either of a or b to separate, but only
such as would make the two bodies combine together
as a whole; the point of action is, therefore, insulated,
the action itself local (921. 947.), and no current
can be formed.
928. If the acid and base be
dissolved in water, then it is possible that a small
portion of the electricity due to chemical action may
be conducted by the water without decomposition (966.
984.); but the quantity will be so small as to be
utterly disproportionate to that due to the equivalents
of chemical force; will be merely incidental; and,
as it does not involve the essential principles of
the voltaic pile, it forms no part of the phenomena
at present under investigation.
929. If for the oxacid a hydracid
be substituted (927.),—as one analogous
to the muriatic, for instance,—then the
state of things changes altogether, and a current
due to the chemical action of the acid on the base
is possible. But now both the bodies act as electrolytes,
for it is only one principle of each which combine
mutually,—as, for instance, the chlorine
with the metal,—and the hydrogen of the
acid and the oxygen of the base are ready to traverse
with the chlorine of the acid and the metal of the
base in conformity with the current and according to
the general principles already so fully laid down.
930. This view of the oxidation
of the metal, or other direct chemical action
upon it, being the sole cause of the production of
the electric current in the ordinary voltaic pile,
is supported by the effects which take place when
alkaline or sulphuretted solutions (931. 943.) are
used for the electrolytic conductor instead of dilute
sulphuric acid. It was in elucidation of this
point that the experiments without metallic contact,
and with solution of alkali as the exciting fluid,
already referred to (884.), were made.
931. Advantage was then taken
of the more favourable condition offered, when metallic
contact is allowed (895.), and the experiments upon
the decomposition of bodies by a single pair of plates
(899.) were repeated, solution of caustic potassa
being employed in the vessel v, fi. in
place of dilute sulphuric acid. All the effects
occurred as before: the galvanometer was deflected;
the decompositions of the solutions of iodide of potassium,
nitrate of silver, muriatic acid, and sulphate of soda
ensued at x; and the places where the evolved
principles appeared, as well as the deflection of
the galvanometer, indicated a current in the same
direction as when acid was in the vessel v;
i.e. from the zinc through the solution to the
platina, and back by the galvanometer and substance
suffering decomposition to the zinc.
932. The similarity in the action
of either dilute sulphuric acid or potassa goes indeed
far beyond this, even to the proof of identity in
quantity as well as in direction of the
electricity produced. If a plate of amalgamated
zinc be put into a solution of potassa, it is not
sensibly acted upon; but if touched in the solution
by a plate of platina, hydrogen is evolved on the
surface of the latter metal, and the zinc is oxidized
exactly as when immersed in dilute sulphuric acid (863.).
I accordingly repeated the experiment before described
with weighed plates of zinc (864. &c.), using however
solution of potassa instead of dilute sulphuric acid.
Although the time required was much longer than when
acid was used, amounting to three hours for the oxidizement
of 7.55 grains of zinc, still I found that the hydrogen
evolved at the platina plate was the equivalent of
the metal oxidized at the surface of the zinc.
Hence the whole of the reasoning which was applicable
in the former instance applies also here, the current
being in the same direction, and its decomposing effect
in the same degree, as if acid instead of alkali had
been used (868.).
933. The proof, therefore, appears
to me complete, that the combination of the acid with
the oxide, in the former experiment, had nothing to
do with the production of the electric current; for
the same current is here produced when the action
of the acid is absent, and the reverse action of an
alkali is present. I think it cannot be supposed
for a moment, that the alkali acted chemically as
an acid to the oxide formed; on the contrary, our
general chemical knowledge leads to the conclusion,
that the ordinary metallic oxides act rather as acids
to the alkalies; yet that kind of action would tend
to give a reverse current in the present case, if any
were due to the union of the oxide of the exciting
metal with the body which combines with it. But
instead of any variation of this sort, the direction
of the electricity was constant, and its quantity also
directly proportional to the water decomposed, or
the zinc oxidized. There are reasons for believing
that acids and alkalies, when in contact with metals
upon which they cannot act directly, still have a power
of influencing their attractions for oxygen (941.);
but all the effects in these experiments prove, I
think, that it is the oxidation of the metal necessarily
dependent upon, and associated as it is with, the
electrolyzation of the water (921. 923.) that produces
the current; and that the acid or alkali merely acts
as solvents, and by removing the oxidized zinc, allows
other portions to decompose fresh water, and so continues
the evolution or determination of the current.
934. The experiments were then
varied by using solution of ammonia instead of solution
of potassa; and as it, when pure, is like water, a
bad conductor (554.), it was occasionally improved
in that power by adding sulphate of ammonia to it.
But in all the cases the results were the same as
before; decompositions of the same kind were effected,
and the electric current producing these was in the
same direction as in the experiments just described.
935. In order to put the equal
and similar action of acid and alkali to stronger
proof, arrangements were made as in fi.; the glass
vessel A contained dilute sulphuric acid, the corresponding
glass vessel B solution of potassa, PP was a
plate of platina dipping into both solutions, and ZZ
two plates of amalgamated zinc connected with a delicate
galvanometer. When these were plunged at the
same time into the two vessels, there was generally
a first feeble effect, and that in favour of the alkali,
i.e. the electric current tended to pass through
the vessels in the direction of the arrow, being the
reverse direction of that which the acid in A would
have produced alone: but the effect instantly
ceased, and the action of the plates in the vessels
was so equal, that, being contrary because of the
contrary position of the plates, no permanent current
resulted.
936. Occasionally a zinc plate
was substituted for the plate PP, and platina
plates for the plates ZZ; but this caused no difference
in the results: nor did a further change of the
middle plate to copper produce any alteration.
937. As the opposition of electro-motive
pairs of plates produces results other than those
due to the mere difference of their independent actions
(1011. 1045.), I devised another form of apparatus,
in which the action of acid and alkali might be more
directly compared. A cylindrical glass cup, about
two inches deep within, an inch in internal diameter,
and at least a quarter of an inch in thickness, was
cut down the middle into halves, fi. A broad
brass ring, larger in diameter than the cup, was supplied
with a screw at one side; so that when the two halves
of the cup were within the ring, and the screw was
made to press tightly against the glass, the cup held
any fluid put into it. Bibulous paper of different
degrees of permeability was then cut into pieces of
such a size as to be easily introduced between the
loosened halves of the cup, and served when the latter
were tightened again to form a porous division down
the middle of the cup, sufficient to keep any two
fluids on opposite sides of the paper from mingling,
except very slowly, and yet allowing them to act freely
as one electrolyte. The two spaces thus
produced I will call the cells A and B, fi.
This instrument I have found of most general application
in the investigation of the relation of fluids and
metals amongst themselves and to each other.
By combining its use with that of the galvanometer,
it is easy to ascertain the relation of one metal
with two fluids, or of two metals with one fluid,
or of two metals and two fluids upon each other.
938. Dilute sulphuric acid, sp.
g.25, was put into the cell A, and a strong
solution of caustic potassa into the cell B; they mingled
slowly through the paper, and at last a thick crust
of sulphate of potassa formed on the side of the paper
next to the alkali. A plate of clean platina was
put into each cell and connected with a delicate galvanometer,
but no electric current could be observed. Hence
the contact of acid with one platina plate,
and alkali with the other, was unable to produce a
current; nor was the combination of the acid with
the alkali more effectual (925.).
939. When one of the platina
plates was removed and a zinc plate substituted, either
amalgamated or not, a strong electric current was
produced. But, whether the zinc were in the acid
whilst the platina was in the alkali, or whether the
reverse order were chosen, the electric current was
always from the zinc through the electrolyte to the
platina, and back through the galvanometer to the
zinc, the current seeming to be strongest when the
zinc was in the alkali and the platina in the acid.
940. In these experiments, therefore,
the acid seems to have no power over the alkali, but
to be rather inferior to it in force. Hence there
is no reason to suppose that the combination of the
oxide formed with the acid around it has any direct
influence in producing the electricity evolved, the
whole of which appears to be due to the oxidation of
the metal (919.).
941. The alkali, in fact, is
superior to the acid in bringing a metal into what
is called the positive state; for if plates of the
same metal, as zinc, tin, lead, or copper, be used
both in the acid or alkali, the electric current is
from the alkali across the cell to the acid, and back
through the galvanometer to the alkali, as Sir Humphry
Davy formerly stated . This current is so
powerful, that if amalgamated zinc, or tin, or lead
be used, the metal in the acid evolves hydrogen the
moment it is placed in communication with that in
the alkali, not from any direct action of the acid
upon it, for if the contact be broken the action ceases,
but because it is powerfully negative with regard
to the metal in the alkali.
942. The superiority of alkali
is further proved by this, that if zinc and tin be
used, or tin and lead, whichsoever metal is put into
the alkali becomes positive, that in the acid being
negative. Whichsoever is in the alkali is oxidized,
whilst that in the acid remains in the metallic state,
as far as the electric current is concerned.
943. When sulphuretted solutions
are used (930.) in illustration of the assertion,
that it is the chemical action of the metal and one
of the ions of the associated electrolyte that
produces all the electricity of the voltaic circuit,
the proofs are still the same. Thus, as Sir Humphry
Davy has shown, if iron and copper be plunged into
dilute acid, the current is from the iron through
the liquid to the copper; in solution of potassa it
is in the same direction, but in solution of sulphuret
of potassa it is reversed. In the two first cases
it is oxygen which combines with the iron, in the
latter sulphur which combines with the copper, that
produces the electric current; but both of these are
ions, existing as such in the electrolyte,
which is at the same moment suffering decomposition;
and, what is more, both of these are anions,
for they leave the electrolytes at their anodes,
and act just as chlorine, iodine, or any other anion
would act which might have been previously chosen as
that which should be used to throw the voltaic circle
into activity.
944. The following experiments
complete the series of proofs of the origin of the
electricity in the voltaic pile. A fluid amalgam
of potassium, containing not more than a hundredth
of that metal, was put into pure water, and connected,
through the galvanometer with a plate of platina in
the same water. There was immediately an electric
current from the amalgam through the electrolyte to
the platina. This must have been due to the oxidation
only of the metal, for there was neither acid nor alkali
to combine with, or in any way act on, the body produced.
945. Again, a plate of clean
lead and a plate of platina were put into pure
water. There was immediately a powerful current
produced from the lead through the fluid to the platina:
it was even intense enough to decompose solution of
the iodide of potassium when introduced into the circuit
in the form of apparatus already described (880.),
fi. Here no action of acid or alkali on
the oxide formed from the lead could supply the electricity:
it was due solely to the oxidation of the metal.
946. There is no point in electrical
science which seems to me of more importance than
the state of the metals and the electrolytic conductor
in a simple voltaic circuit before and at the
moment when metallic contact is first completed.
If clearly understood, I feel no doubt it would supply
us with a direct key to the laws under which the great
variety of voltaic excitements, direct and incidental,
occur, and open out new fields of research for our
investigation.
947. We seem to have the power
of deciding to a certain extent in numerous cases
of chemical affinity, (as of zinc with the oxygen of
water, &c. &c.) which of two modes of action of
the attractive power shall be exerted (996.).
In the one mode we can transfer the power onwards,
and make it produce elsewhere its equivalent of action
(867. 917.); in the other, it is not transferred,
but exerted wholly at the spot. The first is the
case of volta-electric excitation, the other
ordinary chemical affinity: but both are chemical
actions and due to one force or principle.
948. The general circumstances
of the former mode occur in all instances of voltaic
currents, but may be considered as in their perfect
condition, and then free from those of the second
mode, in some only of the cases; as in those of plates
of zinc and platina in solution of potassa, or of
amalgamated zinc and platina in dilute sulphuric acid.
949. Assuming it sufficiently
proved, by the preceding experiments and considerations,
that the electro-motive action depends, when zinc,
platina, and dilute sulphuric acid are used, upon
the mutual affinity of the metal zinc and the oxygen
of the water (921. 924.), it would appear that the
metal, when alone, has not power enough, under the
circumstances, to take the oxygen and expel the hydrogen
from the water; for, in fact, no such action takes
place. But it would also appear that it has power
so far to act, by its attraction for the oxygen of
the particles in contact with it, as to place the
similar forces already active between these and the
other particles of oxygen and the particles of hydrogen
in the water, in a peculiar state of tension or polarity,
and probably also at the same time to throw those
of its own particles which are in contact with the
water into a similar but opposed state. Whilst
this state is retained, no further change occurs;
but when it is relieved, by completion of the circuit,
in which case the forces determined in opposite directions,
with respect to the zinc and the electrolyte, are
found exactly competent to neutralize each other,
then a series of decompositions and recompositions
takes place amongst the particles of oxygen and hydrogen
constituting the water, between the place of contact
with the platina and the place where the zinc is active;
these intervening particles being evidently in close
dependence upon and relation to each other. The
zinc forms a direct compound with those particles
of oxygen which were, previously, in divided relation
to both it and the hydrogen: the oxide is removed
by the acid, and a fresh surface of zinc is presented
to the water, to renew and repeat the action.
950. Practically, the state of
tension is best relieved by dipping a metal which
has less attraction for oxygen than the zinc, into
the dilute acid, and making it also touch the zinc.
The force of chemical affinity, which has been influenced
or polarized in the particles of the water by the
dominant attraction of the zinc for the oxygen, is
then transferred, in a most extraordinary manner,
through the two metals, so as to re-enter upon the
circuit in the electrolytic conductor, which, unlike
the metals in that respect, cannot convey or transfer
it without suffering decomposition; or rather, probably,
it is exactly balanced and neutralized by the force
which at the same moment completes the combination
of the zinc with the oxygen of the water. The
forces, in fact, of the two particles which are acting
towards each other, and which are therefore in opposite
directions, are the origin of the two opposite forces,
or directions of force, in the current. They
are of necessity equivalent to each other. Being
transferred forward in contrary directions, they produce
what is called the voltaic current: and it seems
to me impossible to resist the idea that it must be
preceded by a state of tension in the fluid,
and between the fluid and the zinc; the first consequence
of the affinity of the zinc for the oxygen of the
water.
951. I have sought carefully
for indications of a state of tension in the electrolytic
conductor; and conceiving that it might produce something
like structure, either before or during its discharge,
I endeavoured to make this evident by polarized light.
A glass cell, seven inches long, one inch and a half
wide, and six inches deep, had two sets of platina
electrodes adapted to it, one set for the ends, and
the other for the sides. Those for the sides
were seven inches long by three inches high, and when
in the cell were separated by a little frame of wood
covered with calico; so that when made active by connexion
with a battery upon any solution in the cell, the
bubbles of gas rising from them did not obscure the
central parts of the liquid.
952. A saturated solution of
sulphate of soda was put into the cell, and the electrodes
connected with a battery of 150 pairs of 4-inch plates:
the current of electricity was conducted across the
cell so freely, that the discharge was as good as
if a wire had been used. A ray of polarized light
was then transmitted through this solution, directly
across the course of the electric current, and examined
by an analysing plate; but though it penetrated seven
inches of solution thus subject to the action of the
electricity, and though contact was sometimes made,
sometimes broken, and occasionally reversed during
the observations, not the slightest trace of action
on the ray could be perceived.
953. The large electrodes were
then removed, and others introduced which fitted the
ends of the cell. In each a slit was cut,
so as to allow the light to pass. The course
of the polarized ray was now parallel to the current,
or in the direction of its axis (517.); but still no
effect, under any circumstances of contact or disunion,
could be perceived upon it.
954. A strong solution of nitrate
of lead was employed instead of the sulphate of soda,
but no effects could be detected.
955. Thinking it possible that
the discharge of the electric forces by the successive
decompositions and recompositions of the particles
of the electrolyte might neutralize and therefore
destroy any effect which the first state of tension
could by possibility produce, I took a substance which,
being an excellent electrolyte when fluid, was a perfect
insulator when solid, namely, borate of lead, in the
form of a glass plate, and connecting the sides and
the edges of this mass with the metallic plates, sometimes
in contact with the poles of a voltaic battery, and
sometimes even with the electric machine, for the
advantage of the much higher intensity then obtained,
I passed a polarized ray across it in various directions,
as before, but could not obtain the slightest appearance
of action upon the light. Hence I conclude, that
notwithstanding the new and extraordinary state which
must be assumed by an electrolyte, either during decomposition
(when a most enormous quantity of electricity must
be traversing it), or in the state of tension which
is assumed as preceding decomposition, and which might
be supposed to be retained in the solid form of the
electrolyte, still it has no power of affecting a polarized
ray of light; for no kind of structure or tension
can in this way be rendered evident.
956. There is, however, one beautiful
experimental proof of a state of tension acquired
by the metals and the electrolyte before the electric
current is produced, and before contact of the
different metals is made (915.); in fact, at that
moment when chemical forces only are efficient as
a cause of action. I took a voltaic apparatus,
consisting of a single pair of large plates, namely,
a cylinder of amalgamated zinc, and a double cylinder
of copper. These were put into a jar containing
dilute sulphuric acid, and could at pleasure be
placed in metallic communication by a copper wire
adjusted so as to dip at the extremities into two cups
of mercury connected with the two plates.
When nitro-sulphuric acid is used,
the spark is more powerful, but
local chemical action can then commence,
and proceed without requiring
metallic contact.
957. Being thus arranged, there
was no chemical action whilst the plates were not
connected. On making the connexion a spark
was obtained, and the solution was immediately
decomposed. On breaking it, the usual spark was
obtained, and the decomposition ceased. In this
case it is evident that the first spark must have
occurred before metallic contact was made, for it
passed through an interval of air; and also that it
must have tended to pass before the electrolytic action
began; for the latter could not take place until the
current passed, and the current could not pass before
the spark appeared. Hence I think there is sufficient
proof, that as it is the zinc and water which by their
mutual action produce the electricity of this apparatus,
so these, by their first contact with each other, were
placed in a state of powerful tension (951.), which,
though it could not produce the actual decomposition
of the water, was able to make a spark of electricity
pass between the zinc and a fit discharger as soon
as the interval was rendered sufficiently small.
The experiment demonstrates the direct production
of the electric spark from pure chemical forces.
It has been universally supposed that
no spark is produced on making the contact between
a single pair of plates. I was led to expect
one from the considerations already advanced in this
paper. The wire of communication should be
short; for with a long wire, circumstances strongly
affecting the spark are introduced.
958. There are a few circumstances
connected with the production of this spark by a single
pair of plates, which should be known, to ensure success
to the experiment. When the amalgamated surfaces
of contact are quite clean and dry, the spark, on
making contact, is quite as brilliant as on breaking
it, if not even more so. When a film of oxide
or dirt was present at either mercurial surface, then
the first spark was often feeble, and often failed,
the breaking spark, however, continuing very constant
and bright. When a little water was put over
the mercury, the spark was greatly diminished in brilliancy,
but very regular both on making and breaking contact.
When the contact was made between clean platina, the
spark was also very small, but regular both ways.
The true electric spark is, in fact, very small, and
when surfaces of mercury are used, it is the combustion
of the metal which produces the greater part of the
light. The circumstances connected with the burning
of the mercury are most favourable on breaking contact;
for the act of separation exposes clean surfaces of
metal, whereas, on making contact, a thin film of oxide,
or soiling matter, often interferes. Hence the
origin of the general opinion that it is only when
the contact is broken that the spark passes.
959. With reference to the other
set of cases, namely, those of local action (947.)
in which chemical affinity being exerted causes no
transference of the power to a distance where no electric
current is produced, it is evident that forces of
the most intense kind must be active, and in some
way balanced in their activity, during such combinations;
these forces being directed so immediately and exclusively
towards each other, that no signs of the powerful electric
current they can produce become apparent, although
the same final state of things is obtained as if that
current had passed. It was Berzelius, I believe,
who considered the heat and light evolved in cases
of combustion as the consequences of this mode of
exertion of the electric powers of the combining particles.
But it will require a much more exact and extensive
knowledge of the nature of electricity, and the manner
in which it is associated with the atoms of matter,
before we can understand accurately the action of
this power in thus causing their union, or comprehend
the nature of the great difference which it presents
in the two modes of action just distinguished.
We may imagine, but such imaginations must for the
time be classed with the great mass of doubtful
knowledge (876.) which we ought rather to strive
to diminish than to increase; for the very extensive
contradictions of this knowledge by itself shows that
but a small portion of it can ultimately prove true.
960. Of the two modes of action
in which chemical affinity is exerted, it is important
to remark, that that which produces the electric current
is as definite as that which causes ordinary
chemical combination; so that in examining the production
or evolution of electricity in cases of combination
or decomposition, it will be necessary, not merely
to observe certain effects dependent upon a current
of electricity, but also their quantity:
and though it may often happen that the forces concerned
in any particular case of chemical action may be partly
exerted in one mode and partly in the other, it is
only those which are efficient in producing the current
that have any relation to voltaic action. Thus,
in the combination of oxygen and hydrogen to produce
water, electric powers to a most enormous amount are
for the time active (861. 873.); but any mode of examining
the flame which they form during energetic combination,
which has as yet been devised, has given but the feeblest
traces. These therefore may not, cannot, be taken
as evidences of the nature of the action; but are merely
incidental results, incomparably small in relation
to the forces concerned, and supplying no information
of the way in which the particles are active on each
other, or in which their forces are finally arranged.
961. That such cases of chemical
action produce no current of electricity, is
perfectly consistent with what we know of the voltaic
apparatus, in which it is essential that one of the
combining elements shall form part of, or be in direct
relation with, an electrolytic conductor (921. 923.).
That such cases produce no free electricity of
tension, and that when they are converted into
cases of voltaic action they produce a current in
which the opposite forces are so equal as to neutralize
each other, prove the equality of the forces in the
opposed acting particles of matter, and therefore
the equality of electric power in those quantities
of matter which are called electro-chemical equivalents
(824). Hence another proof of the definite nature
of electro-chemical action (783. &c.), and that chemical
affinity and electricity are forms of the same power
(917. &c.).
962. The direct reference of
the effects produced by the voltaic pile at the place
of experimental decomposition to the chemical affinities
active at the place of excitation (891. 917.), gives
a very simple and natural view of the cause why the
bodies (or ions) evolved pass in certain directions;
for it is only when they pass in those directions that
their forces can consist with and compensate (in direction
at least) the superior forces which are dominant at
the place where the action of the whole is determined.
If, for instance, in a voltaic circuit, the activity
of which is determined, by the attraction of zinc
for the oxygen of water, the zinc move from right
to left, then any other cation included in the
circuit, being part of an electrolyte, or forming
part of it at the moment, will also move from right
to left: and as the oxygen of the water, by its
natural affinity for the zinc, moves from left to right,
so any other body of the same class with it (i.e.
any other anion), under its government for
the time, will move from left to right.
963. This I may illustrate by
reference to fi, the double circle of which may
represent a complete voltaic circuit, the direction
of its forces being determined by supposing for a
moment the zinc b and the platina c
as representing plates of those metals acting upon
water, d, e, and other substances, but having
their energy exalted so as to effect several decompositions
by the use of a battery at a (989.). This
supposition may be allowed, because the action in
the battery will only consist of repetitions of what
would take place between b and c, if
they really constituted but a single pair. The
zinc b, and the oxygen d, by their mutual
affinity, tend to unite; but as the oxygen is already
in association with the hydrogen e, and has
its inherent chemical or electric powers neutralized
for the time by those of the latter, the hydrogen e
must leave the oxygen d, and advance in the
direction of the arrow head, or else the zinc b
cannot move in the same direction to unite to the oxygen
d, nor the oxygen d move in the contrary
direction to unite to the zinc b, the relation
of the similar forces of b and c,
in contrary directions, to the opposite forces
of d being the preventive. As the hydrogen
e advances, it, on coming against the platina
c, f, which forms a part of the circuit, communicates
its electric or chemical forces through it to the
next electrolyte in the circuit, fused chloride of
lead, g, h, where the chlorine must move in
conformity with the direction of the oxygen at d,
for it has to compensate the forces disturbed in its
part of the circuit by the superior influence of those
between the oxygen and zinc at d, b, aided
as they are by those of the battery a; and for
a similar reason the lead must move in the direction
pointed out by the arrow head, that it may be in right
relation to the first moving body of its own class,
namely, the zinc b. If copper intervene
in the circuit from i to k, it acts
as the platina did before; and if another electrolyte,
as the iodide of tin, occur at l, m, then the
iodine l, being an anion, must move
in conformity with the exciting anion, namely,
the oxygen d, and the cation tin m
move in correspondence with the other cations b,
e, and h, that the chemical forces may be
in equilibrium as to their direction and quantity
throughout the circuit. Should it so happen that
the anions in their circulation can combine with the
metals at the anodes of the respective electrolytes,
as would be the case at the platina f and the
copper k, then those bodies becoming parts
of electrolytes, under the influence of the current,
immediately travel; but considering their relation
to the zinc b, it is evidently impossible that
they can travel in any other direction than what will
accord with its course, and therefore can never tend
to pass otherwise than from the anode and to
the cathode.
964. In such a circle as that
delineated, therefore, all the known anions
may be grouped within, and all the cations without.
If any number of them enter as ions into the
constitution of electrolytes, and, forming one
circuit, are simultaneously subject to one common current,
the anions must move in accordance with each other
in one direction, and the cations in the other.
Nay, more than that, equivalent portions of these bodies
must so advance in opposite directions: for the
advance of every 32.5 parts of the zinc b must
be accompanied by a motion in the opposite direction
of 8 parts of oxygen at d, of 36 parts of chlorine
at g, of 126 parts of iodine at l; and
in the same direction by electro-chemical equivalents
of hydrogen, lead, copper and tin, at e, h, k.
and m.
965. If the present paper be
accepted as a correct expression of facts, it will
still only prove a confirmation of certain general
views put forth by Sir Humphry Davy in his Bakerian
Lecture for 1806, and revised and re-stated by
him in another Bakerian Lecture, on electrical and
chemical changes, for the year 1826. His general
statement is, that “chemical and electrical
attractions were produced by the same cause, acting
in one case on particles, in the other on masses,
of matter; and that the same property, under different
modifications, was the cause of all the phenomena
exhibited by different voltaic combinations.”
This statement I believe to be true; but in admitting
and supporting it, I must guard myself from being
supposed to assent to all that is associated with it
in the two papers referred to, or as admitting the
experiments which are there quoted as decided proofs
of the truth of the principle. Had I thought them
so, there would have been no occasion for this investigation.
It may be supposed by some that I ought to go through
these papers, distinguishing what I admit from what
I reject, and giving good experimental or philosophical
reasons for the judgment in both cases. But then
I should be equally bound to review, for the same
purpose, all that has been written both for and against
the necessity of metallic contact,—for and
against the origin of voltaic electricity in chemical
action,—a duty which I may not undertake
in the present paper.
I at one time intended to introduce
here, in the form of a note, a table of reference
to the papers of the different philosophers who have
referred the origin of the electricity in the voltaic
pile to contact, or to chemical action, or to both;
but on the publication of the first volume of M.
Becquerel’s highly important and valuable Traite
de l’Electricite et du Magnétisme,
I thought it far better to refer to that work for
these references, and the views held by the authors
quoted. See pages 86, 91, 104, 110, 112, 117,
118, 120, 151, 152, 224, 227, 228, 232, 233, 252,
255, 257, 258, 290, &c.—July 3rd, 1834.
ii. On the Intensity necessary for Electrolyzation.
966. It became requisite, for
the comprehension of many of the conditions attending
voltaic action, to determine positively, if possible,
whether electrolytes could resist the action of an
electric current when beneath a certain intensity?
whether the intensity at which the current ceased to
act would be the same for all bodies? and also whether
the electrolytes thus resisting decomposition would
conduct the electric current as a metal does, after
they ceased to conduct as electrolytes, or would act
as perfect insulators?
967. It was evident from the
experiments described (904. 906.) that different bodies
were decomposed with very different facilities, and
apparently that they required for their decomposition
currents of different intensities, resisting some,
but giving way to others. But it was needful,
by very careful and express experiments, to determine
whether a current could really pass through, and yet
not decompose an electrolyte (910.).
968. An arrangement (fi.)
was made, in which two glass vessels contained the
same dilute sulphuric acid, sp. g.25.
The plate z was amalgamated zinc, in connexion,
by a platina wire a, with the platina plate
e; b was a platina wire connecting the
two platina plates PP’; c was a
platina wire connected with the platina plate P”.
On the plate e was placed a piece of paper
moistened in solution of iodide of potassium:
the wire c was so curved that its end could
be made to rest at pleasure on this paper, and show,
by the evolution of iodine there, whether a current
was passing; or, being placed in the dotted position,
it formed a direct communication with the platina
plate e, and the electricity could pass without
causing decomposition. The object was to produce
a current by the action of the acid on the amalgamated
zinc in the first vessel A; to pass it through the
acid in the second vessel B by platina electrodes,
that its power of decomposing water might, if existing,
be observed; and to verify the existence of the current
at pleasure, by decomposition at e, without
involving the continual obstruction to the current
which would arise from making the decomposition there
constant. The experiment, being arranged, was
examined and the existence of a current ascertained
by the decomposition at e; the whole was then
left with the end of the wire c resting on
the plate e, so as to form a constant metallic
communication there.
969. After several hours, the
end of the wire c was replaced on the test-paper
at e: decomposition occurred, and the
proof of a passing current was therefore complete.
The current was very feeble compared to what it had
been at the beginning of the experiment, because of
a peculiar state acquired by the metal surfaces in
the second vessel, which caused them to oppose the
passing current by a force which they possess under
these circumstances (1040.). Still it was proved,
by the decomposition, that this state of the plates
in the second vessel was not able entirely to stop
the current determined in the first, and that was all
that was needful to be ascertained in the present
inquiry.
970. This apparatus was examined
from time to time, and an electric current always
found circulating through it, until twelve days had
elapsed, during which the water in the second vessel
had been constantly subject to its action. Notwithstanding
this lengthened period, not the slightest appearance
of a bubble upon either of the plates in that vessel
occurred. From the results of the experiment,
I conclude that a current had passed, but of
so low an intensity as to fall beneath that degree
at which the elements of water, unaided by any secondary
force resulting from the capability of combination
with the matter of the electrodes, or of the liquid
surrounding them, separated from each other.
971. It may be supposed, that
the oxygen and hydrogen had been evolved in such small
quantities as to have entirely dissolved in the water,
and finally to have escaped at the surface, or to
have reunited into water. That the hydrogen can
be so dissolved was shown in the first vessel; for
after several days minute bubbles of gas gradually
appeared upon a glass rod, inserted to retain the
zinc and platina apart, and also upon the platina
plate itself, and these were hydrogen. They resulted
principally in this way:—notwithstanding
the amalgamation of the zinc, the acid exerted a little
direct action upon it, so that a small stream of hydrogen
bubbles was continually rising from its surface; a
little of this hydrogen gradually dissolved in the
dilute acid, and was in part set free against the
surfaces of the rod and the plate, according to the
well-known action of such solid bodies in solutions
of gases (623. &c.).
972. But if the gases had been
evolved in the second vessel by the decomposition
of water, and had tended to dissolve, still there would
have been every reason to expect that a few bubbles
should have appeared on the electrodes, especially
on the negative one, if it were only because of its
action as a nucleus on the solution supposed to be
formed; but none appeared even after twelve days.
973. When a few drops only of
nitric acid were added to the vessel A, fi, then
the results were altogether different. In less
than five minutes bubbles of gas appeared on the plates
P’ and P” in the second vessel. To
prove that this was the effect of the electric current
(which by trial at c was found at the same
time to be passing,) the connexion at c was
broken, the plates P’P” cleared from bubbles
and left in the acid of the vessel B, for fifteen
minutes: during that time no bubbles appeared
upon them; but on restoring the communication at c,
a minute did not elapse before gas appeared in bubbles
upon the plates. The proof, therefore, is most
full and complete, that the current excited by dilute
sulphuric acid with a little nitric acid in vessel
A, has intensity enough to overcome the chemical affinity
exerted between the oxygen and hydrogen of the water
in the vessel B, whilst that excited by dilute sulphuric
acid alone has not sufficient intensity.
974. On using a strong solution
of caustic potassa in the vessel A, to excite the
current, it was found by the decomposing effects at
e, that the current passed. But it had
not intensity enough to decompose the water in the
vessel B; for though left for fourteen days, during
the whole of which time the current was found to be
passing, still not the slightest appearance of gas
appeared on the plates P’P”, nor any other
signs of the water having suffered decomposition.
975. Sulphate of soda in solution
was then experimented with, for the purpose of ascertaining
with respect to it, whether a certain electrolytic
intensity was also required for its decomposition in
this state, in analogy with the result established
with regard to water (974). The apparatus was
arranged as in fi; P and Z are the platina and
zinc plates dipping into a solution of common salt;
a and b are platina plates connected
by wires of platina (except in the galvanometer g)
with P and Z; c is a connecting wire of platina,
the ends of which can be made to rest either on the
plates a, b, or on the papers moistened in solutions
which are placed upon them; so that the passage of
the current without decomposition, or with one or
two decompositions, was under ready command, as far
as arrangement was concerned. In order to change
the anodes and cathodes at the places
of decomposition, the form of apparatus fi, was
occasionally adopted. Here only one platina plate,
c, was used; both pieces of paper on which
decomposition was to be effected were placed upon
it, the wires from P and Z resting upon these pieces
of paper, or upon the plate c, according as
the current with or without decomposition of the solutions
was required.
976. On placing solution of iodide
of potassium in paper at one of the decomposing localities,
and solution of sulphate of soda at the other, so
that the electric current should pass through both
at once, the solution of iodide was slowly decomposed,
yielding iodine at the anode and alkali at
the cathode; but the solution of sulphate of
soda exhibited no signs of decomposition, neither
acid nor alkali being evolved from it. On placing
the wires so that the iodide alone was subject to the
action of the current (900.), it was quickly and powerfully
decomposed; but on arranging them so that the sulphate
of soda alone was subject to action, it still refused
to yield up its elements. Finally, the apparatus
was so arranged under a wet bell-glass, that it could
be left for twelve hours, the current passing during
the whole time through a solution of sulphate of soda,
retained in its place by only two thicknesses of bibulous
litmus and turmeric paper. At the end of that
time it was ascertained by the decomposition of iodide
of potassium at the second place of action, that the
current was passing and had passed for the twelve
hours, and yet no trace of acid or alkali from the
sulphate of soda appeared.
977. From these experiments it
may, I think, be concluded, that a solution of sulphate
of soda can conduct a current of electricity, which
is unable to decompose the neutral salt present; that
this salt in the state of solution, like water, requires
a certain electrolytic intensity for its decomposition;
and that the necessary intensity is much higher for
this substance than for the iodide of potassium in
a similar state of solution.
978. I then experimented on bodies
rendered decomposable by fusion, and first on chloride
of lead. The current was excited by dilute
sulphuric acid without any nitric acid between zinc
and platina plates, fi, and was then made to
traverse a little chloride of lead fused upon glass
at a, a paper moistened in solution of iodide
of potassium at b, and a galvanometer at g.
The metallic terminations at a and b
were of platina. Being thus arranged, the decomposition
at b and the deflection at g showed
that an electric current was passing, but there was
no appearance of decomposition at a, not even
after a metallic communication at b
was established. The experiment was repeated several
times, and I am led to conclude that in this case the
current has not intensity sufficient to cause the
decomposition of the chloride of lead; and further,
that, like water (974.), fused chloride of lead can
conduct an electric current having an intensity below
that required to effect decomposition.
979. Chloride of silver was
then placed at a, fi, instead of chloride
of lead. There was a very ready decomposition
of the solution of iodide of potassium at b,
and when metallic contact was made there, very considerable
deflection of the galvanometer needle at g.
Platina also appeared to be dissolved at the anode
of the fused chloride at a, and there was every
appearance of a decomposition having been effected
there.
980. A further proof of decomposition
was obtained in the following manner. The platina
wires in the fused chloride at a were brought
very near together (metallic contact having been established
at b), and left so; the deflection at the galvanometer
indicated the passage of a current, feeble in its
force, but constant. After a minute or two, however,
the needle would suddenly be violently affected, and
indicate a current as strong as if metallic contact
had taken place at a. This I actually found
to be the case, for the silver reduced by the action
of the current crystallized in long delicate spiculae,
and these at last completed the metallic communication;
and at the same time that they transmitted a more
powerful current than the fused chloride, they proved
that electro-chemical decomposition of that chloride
had been going on. Hence it appears, that the
current excited by dilute sulphuric acid between zinc
and platina, has an intensity above that required
to electrolyze the fused chloride of silver when placed
between platina electrodes, although it has not intensity
enough to decompose chloride of lead under the same
circumstances.
981. A drop of water placed
at a instead of the fused chlorides, showed
as in the former case (970.), that it could conduct
a current unable to decompose it, for decomposition
of the solution of iodide at b occurred after
some time. But its conducting power was much below
that of the fused chloride of lead (978.).
982. Fused nitre at a
conducted much better than water: I was unable
to decide with certainty whether it was electrolyzed,
but I incline to think not, for there was no discoloration
against the platina at the cathode. If
sulpho-nitric acid had been used in the exciting vessel,
both the nitre and the chloride of lead would have
suffered decomposition like the water (906.).
983. The results thus obtained
of conduction without decomposition, and the necessity
of a certain electrolytic intensity for the separation
of the ions of different electrolytes, are
immediately connected with the experiments and results
given in S 10. of the Fourth Series of these Researches
(418. 423. 444. 419.). But it will require a more
exact knowledge of the nature of intensity, both as
regards the first origin of the electric current,
and also the manner in which it may be reduced, or
lowered by the intervention of longer or shorter portions
of bad conductors, whether decomposable or not, before
their relation can be minutely and fully understood.
984. In the case of water, the
experiments I have as yet made, appear to show, that,
when the electric current is reduced in intensity below
the point required for decomposition, then the degree
of conduction is the same whether sulphuric acid,
or any other of the many bodies which can affect its
transferring power as an electrolyte, are present or
not. Or, in other words, that the necessary electrolytic
intensity for water is the same whether it be pure,
or rendered a better conductor by the addition of these
substances; and that for currents of less intensity
than this, the water, whether pure or acidulated,
has equal conducting power. An apparatus, fi, was arranged with dilute sulphuric acid in the
vessel A, and pure distilled water in the vessel B.
By the decomposition at c, it appeared as if
water was a better conductor than dilute sulphuric
acid for a current of such low intensity as to cause
no decomposition. I am inclined, however, to
attribute this apparent superiority of water to variations
in that peculiar condition of the platina electrodes
which is referred to further on in this Series (1040.),
and which is assumed, as far as I can judge, to a
greater degree in dilute sulphuric acid than in pure
water. The power therefore, of acids, alkalies,
salts, and other bodies in solution, to increase conducting
power, appears to hold good only in those cases where
the electrolyte subject to the current suffers decomposition,
and loses all influence when the current transmitted
has too low an intensity to affect chemical change.
It is probable that the ordinary conducting power
of an electrolyte in the solid state (419.) is the
same as that which it possesses in the fluid state
for currents, the tension of which is beneath the
due electrolytic intensity.
985. Currents of electricity,
produced by less than eight or ten series of voltaic
elements, can be reduced to that intensity at which
water can conduct them without suffering decomposition,
by causing them to pass through three or four vessels
in which water shall be successively interposed between
platina surfaces. The principles of interference
upon which this effect depends, will be described
hereafter (1009. 1018.), but the effect may be useful
in obtaining currents of standard intensity, and is
probably applicable to batteries of any number of pairs
of plates.
986. As there appears every reason
to expect that all electrolytes will be found subject
to the law which requires an electric current of a
certain intensity for their decomposition, but that
they will differ from each other in the degree of
intensity required, it will be desirable hereafter
to arrange them in a table, in the order of their electrolytic
intensities. Investigations on this point must,
however, be very much extended, and include many more
bodies than have been here mentioned before such a
table can be constructed. It will be especially
needful in such experiments, to describe the nature
of the electrodes used, or, if possible, to select
such as, like platina or plumbago in certain cases,
shall have no power of assisting the separation of
the ions to be evolved (913).
987. Of the two modes in which
bodies can transmit the electric forces, namely, that
which is so characteristically exhibited by the metals,
and usually called conduction, and that in which it
is accompanied by decomposition, the first appears
common to all bodies, although it occurs with almost
infinite degrees of difference; the second is at present
distinctive of the electrolytes. It is, however,
just possible that it may hereafter be extended to
the metals; for their power of conducting without
decomposition may, perhaps justly, be ascribed to their
requiring a very high electrolytic intensity for their
decomposition.
987-1/2. The establishment of
the principle that a certain electrolytic intensity
is necessary before decomposition can be effected,
is of great importance to all those considerations
which arise regarding the probable effects of weak
currents, such for instance as those produced by natural
thermo-electricity, or natural voltaic arrangements
in the earth. For to produce an effect of decomposition
or of combination, a current must not only exist,
but have a certain intensity before it can overcome
the quiescent affinities opposed to it, otherwise
it will be conducted, producing no permanent chemical
effects. On the other hand, the principles are
also now evident by which an opposing action can be
so weakened by the juxtaposition of bodies not having
quite affinity enough to cause direct action between
them (913.), that a very weak current shall be able
to raise the sum of actions sufficiently high, and
cause chemical changes to occur.
988. In concluding this division
on the intensity necessary for electrolyzation,
I cannot resist pointing out the following remarkable
conclusion in relation to intensity generally.
It would appear that when a voltaic current is produced,
having a certain intensity, dependent upon the strength
of the chemical affinities by which that current is
excited (916.), it can decompose a particular electrolyte
without relation to the quantity of electricity passed,
the intensity deciding whether the electrolyte
shall give way or not. If that conclusion be confirmed,
then we may arrange circumstances so that the same
quantity of electricity may pass in the same
time, in at the same surface, into the same
decomposing body in the same state, and yet, differing
in intensity, will decompose in one case and in
the other not:—for taking a source of
too low an intensity to decompose, and ascertaining
the quantity passed in a given time, it is easy to
take another source having a sufficient intensity,
and reducing the quantity of electricity from it by
the intervention of bad conductors to the same proportion
as the former current, and then all the conditions
will be fulfilled which are required to produce the
result described.
iii. On associated Voltaic Circles,
or the Voltaic Battery.
989. Passing from the consideration
of single circles (875. &c.) to their association
in the voltaic battery, it is a very evident consequence,
that if matters are so arranged that two sets of affinities,
in place of being opposed to each other as in fig. 76. (880. 891.), are made to act in conformity,
then, instead of either interfering with the other,
it will rather assist it. This is simply the
case of two voltaic pairs of metals arranged so as
to form one circuit. In such arrangements the
activity of the whole is known to be increased, and
when ten, or a hundred, or any larger number of such
alternations are placed in conformable association
with each other, the power of the whole becomes proportionally
exalted, and we obtain that magnificent instrument
of philosophic research, the voltaic battery.
990. But it is evident from the
principles of definite action already laid down, that
the quantity of electricity in the current cannot
be increased with the increase of the quantity
of metal oxidized and dissolved at each new place
of chemical action. A single pair of zinc and
platina plates throws as much electricity into the
form of a current, by the oxidation of 32.5 grains
of the zinc (868.) as would be circulated by the same
alteration of a thousand times that quantity, or nearly
five pounds of metal oxidized at the surface of the
zinc plates of a thousand pairs placed in regular
battery order. For it is evident, that the electricity
which passes across the acid from the zinc to the
platina in the first cell, and which has been associated
with, or even evolved by, the decomposition of a definite
portion of water in that cell, cannot pass from the
zinc to the platina across the acid in the second
cell, without the decomposition of the same quantity
of water there, and the oxidation of the same quantity
of zinc by it (924. 949.). The same result recurs
in every other cell; the electro-chemical equivalent
of water must be decomposed in each, before the current
can pass through it; for the quantity of electricity
passed and the quantity of electrolyte decomposed,
must be the equivalents of each other.
The action in each cell, therefore, is not to increase
the quantity set in motion in any one cell, but to
aid in urging forward that quantity, the passing of
which is consistent with the oxidation of its own zinc;
and in this way it exalts that peculiar property of
the current which we endeavour to express by the term
intensity, without increasing the quantity
beyond that which is proportionate to the quantity
of zinc oxidized in any single cell of the series.
991. To prove this, I arranged
ten pairs of amalgamated zinc and platina plates with
dilute sulphuric acid in the form of a battery.
On completing the circuit, all the pairs acted and
evolved gas at the surfaces of the platina. This
was collected and found to be alike in quantity for
each plate; and the quantity of hydrogen evolved at
any one platina plate was in the same proportion to
the quantity of metal dissolved from any one zinc
plate, as was given in the experiment with a single
pair (864. &c.). It was therefore certain, that,
just as much electricity and no more had passed through
the series of ten pair of plates as had passed through,
or would have been put into motion by, any single
pair, notwithstanding that ten times the quantity
of zinc had been consumed.
992. This truth has been proved
also long ago in another way, by the action of the
evolved current on a magnetic needle; the deflecting
power of one pair of plates in a battery being equal
to the deflecting power of the whole, provided the
wires used be sufficiently large to carry the current
of the single pair freely; but the cause of
this equality of action could not be understood whilst
the definite action and evolution of electricity (783.
869.) remained unknown.
993. The superior decomposing
power of a battery over a single pair of plates is
rendered evident in two ways. Electrolytes held
together by an affinity so strong as to resist the
action of the current from a single pair, yield up
their elements to the current excited by many pairs;
and that body which is decomposed by the action of
one or of few pairs of metals, &c., is resolved into
its ions the more readily as it is acted upon
by electricity urged forward by many alternations.
994. Both these effects are,
I think, easily understood. Whatever intensity
may be, (and that must of course depend upon the nature
of electricity, whether it consist of a fluid or fluids,
or of vibrations of an ether, or any other kind or
condition of matter,) there seems to be no difficulty
in comprehending that the degree of intensity
at which a current of electricity is evolved by a
first voltaic element, shall be increased when that
current is subjected to the action of a second voltaic
element, acting in conformity and possessing equal
powers with the first: and as the decompositions
are merely opposed actions, but exactly of the same
kind as those which generate the current (917.), it
seems to be a natural consequence, that the affinity
which can resist the force of a single decomposing
action may be unable to oppose the energies of many
decomposing actions, operating conjointly, as in the
voltaic battery.
995. That a body which can give
way to a current of feeble intensity, should give
way more freely to one of stronger force, and yet involve
no contradiction to the law of definite electrolytic
action, is perfectly consistent. All the facts
and also the theory I have ventured to put forth,
tend to show that the act of decomposition opposes
a certain force to the passage of the electric current;
and, that this obstruction should be overcome more
or less readily, in proportion to the greater or less
intensity of the decomposing current, is in perfect
consistency with all our notions of the electric agent.
996. I have elsewhere (947.)
distinguished the chemical action of zinc and dilute
sulphuric acid into two portions; that which, acting
effectually on the zinc, evolves hydrogen at once
upon its surface, and that which, producing an arrangement
of the chemical forces throughout the electrolyte
present, (in this case water,) tends to take oxygen
from it, but cannot do so unless the electric current
consequent thereon can have free passage, and the
hydrogen be delivered elsewhere than against the zinc.
The electric current depends altogether upon the second
of these; but when the current can pass, by favouring
the electrolytic action it tends to diminish the former
and increase the latter portion.
997. It is evident, therefore,
that when ordinary zinc is used in a voltaic arrangement,
there is an enormous waste of that power which it is
the object to throw into the form of an electric current;
a consequence which is put in its strongest point
of view when it is considered that three ounces and
a half of zinc, properly oxidized, can circulate enough
electricity to decompose nearly one ounce of water,
and cause the evolution of about 2100 cubic inches
of hydrogen gas. This loss of power not only
takes place during the time the electrodes of the battery
are in communication, being then proportionate to
the quantity of hydrogen evolved against the surface
of any one of the zinc plates, but includes also all
the chemical action which goes on when the extremities
of the pile are not in communication.
998. This loss is far greater
with ordinary zinc than with the pure metal, as M.
De la Rive has shown. The cause is, that when
ordinary zinc is acted upon by dilute sulphuric acid,
portions of copper, lead, cadmium, or other metals
which it may contain, are set free upon its surface;
and these, being in contact with the zinc, form small
but very active voltaic circles, which cause great
destruction of the zinc and evolution of hydrogen,
apparently upon the zinc surface, but really upon the
surface of these incidental metals. In the same
proportion as they serve to discharge or convey the
electricity back to the zinc, do they diminish its
power of producing an electric current which shall
extend to a greater distance across the acid, and
be discharged only through the copper or platina plate
which is associated with it for the purpose of forming
a voltaic apparatus.
Quarterly Journal of Science, 1831,
; or Bibliothèque
Universelle, 1830, .
999. All these evils are removed
by the employment of an amalgam of zinc in the manner
recommended by Mr. Kemp, or the use of the amalgamated
zinc plates of Mr. Sturgeon (863.), who has himself
suggested and objected to their application in galvanic
batteries; for he says, “Were it not on account
of the brittleness and other inconveniences occasioned
by the incorporation of the mercury with the zinc,
amalgamation of the zinc surfaces in galvanic batteries
would become an important improvement; for the metal
would last much longer, and remain bright for a considerable
time, even for several successive hours; essential
considerations in the employment of this apparatus.”
Jameson’s Edinburgh Journal,
October 1828.
Recent Experimental Researches, , &c. Mr. Sturgeon is of course unaware of
the definite production of electricity by chemical
action, and is in fact quoting the experiment as
the strongest argument against the chemical
theory of galvanism.
1000. Zinc so prepared, even
though impure, does not sensibly decompose the water
of dilute sulphuric acid, but still has such affinity
for the oxygen, that the moment a metal which, like
copper or platina, has little or no affinity, touches
it in the acid, action ensues, and a powerful and
abundant electric current is produced. It is probable
that the mercury acts by bringing the surface, in
consequence of its fluidity, into one uniform condition,
and preventing those differences in character between
one spot and another which are necessary for the formation
of the minute voltaic circuits referred to (998.).
If any difference does exist at the first moment,
with regard to the proportion of zinc and mercury,
at one spot on the surface, as compared with
another, that spot having the least mercury is first
acted on, and, by solution of the zinc, is soon placed
in the same condition as the other parts, and the
whole plate rendered superficially uniform. One
part cannot, therefore, act as a discharger to another;
and hence all the chemical power upon the water
at its surface is in that equable condition (949.),
which, though it tends to produce an electric current
through the liquid to another plate of metal which
can act as a discharger (950.), presents no irregularities
by which any one part, having weaker affinities for
oxygen, can act as a discharger to another. Two
excellent and important consequences follow upon this
state of the metal. The first is, that the
full equivalent of electricity is obtained for
the oxidation of a certain quantity of zinc; the second,
that a battery constructed with the zinc so prepared,
and charged with dilute sulphuric acid, is active
only whilst the electrodes are connected, and ceases
to act or be acted upon by the acid the instant the
communication is broken.
1001. I have had a small battery
of ten pairs of plates thus constructed, and am convinced
that arrangements of this kind will be very important,
especially in the development and illustration of the
philosophical principles of the instrument. The
metals I have used are amalgamated zinc and platina,
connected together by being soldered to platina wires,
the whole apparatus having the form of the couronne
des tasses. The liquid used was dilute sulphuric
acid of sp. g.25. No action took place
upon the metals except when the electrodes were in
communication, and then the action upon the zinc was
only in proportion to the decomposition in the experimental
cell; for when the current was retarded there, it was
retarded also in the battery, and no waste of the
powers of the metal was incurred.
1002. In consequence of this
circumstance, the acid in the cells remained active
for a very much longer time than usual. In fact,
time did not tend to lower it in any sensible degree:
for whilst the metal was preserved to be acted upon
at the proper moment, the acid also was preserved almost
at its first strength. Hence a constancy of action
far beyond what can be obtained by the use of common
zinc.
1003. Another excellent consequence
was the renewal, during the interval of rest, between
two experiments of the first and most efficient state.
When an amalgamated zinc and a platina plate, immersed
in dilute sulphuric acid, are first connected, the
current is very powerful, but instantly sinks very
much in force, and in some cases actually falls to
only an eighth or a tenth of that first produced (1036.).
This is due to the acid which is in contact with the
zinc becoming neutralized by the oxide formed; the
continued quick oxidation of the metal being thus prevented.
With ordinary zinc, the evolution of gas at its surface
tends to mingle all the liquid together, and thus
bring fresh acid against the metal, by which the oxide
formed there can be removed. With the amalgamated
zinc battery, at every cessation of the current, the
saline solution against the zinc is gradually diffused
amongst the rest of the liquid; and upon the renewal
of contact at the electrodes, the zinc plates are
found most favourably circumstanced for the production
of a ready and powerful current.
1004. It might at first be imagined
that amalgamated zinc would be much inferior in force
to common zinc, because, of the lowering of its energy,
which the mercury might be supposed to occasion over
the whole of its surface; but this is not the case.
When the electric currents of two pairs of platina
and zinc plates were opposed, the difference being
that one of the zincs was amalgamated and the
other not, the current from the amalgamated zinc was
most powerful, although no gas was evolved against
it, and much was evolved at the surface of the unamalgamated
metal. Again, as Davy has shown, if amalgamated
and unamalgamated zinc be put in contact, and dipped
into dilute sulphuric acid, or other exciting fluids,
the former is positive to the latter, i.e. the
current passes from the amalgamated zinc, through
the fluid, to the unprepared zinc. This he accounts
for by supposing that “there is not any inherent
and specific property in each metal which gives it
the electrical character, but that it depends upon
its peculiar state—on that form of aggregation
which fits it for chemical change.”
Philosophical Transactions, 1826,
.
1005. The superiority of the
amalgamated zinc is not, however, due to any such
cause, but is a very simple consequence of the state
of the fluid in contact with it; for as the unprepared
zinc acts directly and alone upon the fluid, whilst
that which is amalgamated does not, the former (by
the oxide it produces) quickly neutralizes the acid
in contact with its surface, so that the progress
of oxidation is retarded, whilst at the surface of
the amalgamated zinc, any oxide formed is instantly
removed by the free acid present, and the clean metallic
surface is always ready to act with full energy upon
the water. Hence its superiority (1037.). 1006.
The progress of improvement in the voltaic battery
and its applications, is evidently in the contrary
direction at present to what it was a few years ago;
for in place of increasing the number of plates, the
strength of acid, and the extent altogether of the
instrument, the change is rather towards its first
state of simplicity, but with a far more intimate
knowledge and application of the principles which govern
its force and action. Effects of decomposition
can now be obtained with ten pairs of plates (417.),
which required five hundred or a thousand pairs for
their production in the first instance. The capability
of decomposing fused chlorides, iodides, and other
compounds, according to the law before established
(380. &c.), and the opportunity of collecting certain
of the products, without any loss, by the use of apparatus
of the nature of those already described (789. 814.
&c.), render it probable that the voltaic battery
may become a useful and even economical manufacturing
instrument; for theory evidently indicates that an
equivalent of a rare substance may be obtained at
the expense of three or four equivalents of a very
common body, namely, zinc: and practice seems
thus far to justify the expectation. In this
point of view I think it very likely that plates of
platina or silver may be used instead of plates of
copper with advantage, and that then the evil arising
occasionally from solution of the copper, and its
precipitation on the zinc, (by which the electromotive
power of the zinc is so much injured,) will be avoided
(1047.).
iv. On the Resistance of an Electrolyte
to Electrolytic Action, and on Interpositions.
1007. I have already illustrated,
in the simplest possible form of experiment (891.
910.), the resistance established at the place of
decomposition to the force active at the exciting place.
I purpose examining the effects of this resistance
more generally; but it is rather with reference to
their practical interference with the action and phenomena
of the voltaic battery, than with any intention at
this time to offer a strict and philosophical account
of their nature. Their general and principal
cause is the resistance of the chemical affinities
to be overcome; but there are numerous other circumstances
which have a joint influence with these forces (1034.
1040. &c.), each of which would require a minute examination
before a correct account of the whole could be given.
1008. As it will be convenient
to describe the experiments in a form different to
that in which they were made, both forms shall first
be explained. Plates of platina, copper, zinc,
and other metals, about three quarters of an inch
wide and three inches long, were associated together
in pairs by means of platina wires to which they were
soldered, fi, the plates of one pair being either
alike or different, as might be required. These
were arranged in glasses, fi, so as to form Volta’s
crown of cups. The acid or fluid in the cups
never covered the whole of any plate; and occasionally
small glass rods were put into the cups, between the
plates, to prevent their contact. Single plates
were used to terminate the series and complete the
connexion with a galvanometer, or with a decomposing
apparatus (899. 968. &c.), or both. Now if fi be examined and compared with fi, the latter
may be admitted as representing the former in its
simplest condition; for the cups i, ii, and iii of
the former, with their contents, are represented by
the cells i, ii, and iii of the latter, and the metal
plates Z and P of the former by the similar plates
represented Z and P in the latter. The only difference,
in fact, between the apparatus, fi, and the trough
represented fi, is that twice the quantity of
surface of contact between the metal and acid is allowed
in the first to what would occur in the second.
1009. When the extreme plates
of the arrangement just described, fi, are connected
metallically through the galvanometer g, then
the whole represents a battery consisting of two pairs
of zinc and platina plates urging a current forward,
which has, however, to decompose water unassisted
by any direct chemical affinity before it can be transmitted
across the cell iii, and therefore before it can circulate.
This decomposition of water, which is opposed to the
passage of the current, may, as a matter of convenience,
be considered as taking place either against the surfaces
of the two platina plates which constitute the electrodes
in the cell in, or against the two surfaces of that
platina plate which separates the cells ii and iii,
fi, from each other. It is evident that if
that plate were away, the battery would consist of
two pairs of plates and two cells, arranged in the
most favourable position for the production of a current.
The platina plate therefore, which being introduced
as at x, has oxygen evolved at one surface
and hydrogen at the other (that is, if the decomposing
current passes), may be considered as the cause of
any obstruction arising from the decomposition of
water by the electrolytic action of the current; and
I have usually called it the interposed plate.
1010. In order to simplify the
conditions, dilute sulphuric acid was first used in
all the cells, and platina for the interposed plates;
for then the initial intensity of the current which
tends to be formed is constant, being due to the power
which zinc has of decomposing water; and the opposing
force of decomposition is also constant, the elements
of the water being unassisted in their separation
at the interposed plates by any affinity or secondary
action at the electrodes (744.), arising either from
the nature of the plate itself or the surrounding fluid.
1011. When only one voltaic pair
of zinc and platina plates was used, the current of
electricity was entirely stopped to all practical purposes
by interposing one platina plate, fi, i.e.
by requiring of the current that it should decompose
water, and evolve both its elements, before it should
pass. This consequence is in perfect accordance
with the views before given (910. 917. 973.).
For as the whole result depends upon the opposition
of forces at the places of electric excitement and
electro-decomposition, and as water is the substance
to be decomposed at both before the current can move,
it is not to be expected that the zinc should have
such powerful attraction for the oxygen, as not only
to be able to take it from its associated hydrogen,
but leave such a surplus of force as, passing to the
second place of decomposition, should be there able
to effect a second separation of the elements of water.
Such an effect would require that the force of attraction
between zinc and oxygen should under the circumstances
be at least twice as great as the force of attraction
between the oxygen and hydrogen.
1012. When two pairs of zinc
and platina exciting plates were used, the current
was also practically stopped by one interposed platina
plate, fi. There was a very feeble effect
of a current at first, but it ceased almost immediately.
It will be referred to, with many other similar effects,
hereafter (1017.).
1013. Three pairs of zinc and
platina plates, fi, were able to produce a current
which could pass an interposed platina plate, and effect
the electrolyzation of water in cell iv. The
current was evident, both by the continued deflection
of the galvanometer, and the production of bubbles
of oxygen and hydrogen at the electrodes in cell iv.
Hence the accumulated surplus force of three plates
of zinc, which are active in decomposing water, is
more than equal, when added together, to the force
with which oxygen and hydrogen are combined in water,
and is sufficient to cause the separation of these
elements from each other.
1014. The three pairs of zinc
and platina plates were now opposed by two intervening
platina plates, fi. In this case the current
was stopped.
1015. Four pairs of zinc and
platina plates were also neutralized by two interposed
platina plates, fi.
1016. Five pairs of zinc and
platina, with two interposed platina plates, fi, gave a feeble current; there was permanent deflection
at the galvanometer, and decomposition in the cells
vi and vii. But the current was very feeble;
very much less than when all the intermediate plates
were removed and the two extreme ones only retained:
for when they were placed six inches asunder in one
cell, they gave a powerful current. Hence five
exciting pairs, with two interposed obstructing plates,
do not give a current at all comparable to that of
a single unobstructed pair.
1017. I have already said that
a very feeble current passed when the series
included one interposed platina and two pairs of zinc
and platina plates (1012.). A similarly feeble
current passed in every case, and even when only one
exciting pair and four intervening platina plates were
used, fi, a current passed which could be detected
at x, both by chemical action on the solution
of iodide of potassium, and by the galvanometer.
This current I believe to be due to electricity reduced
in intensity below the point requisite for the decomposition
of water (970. 984.); for water can conduct electricity
of such low intensity by the same kind of power which
it possesses in common with metals and charcoal, though
it cannot conduct electricity of higher intensity
without suffering decomposition, and then opposing
a new force consequent thereon. With an electric
current of, or under this intensity, it is probable
that increasing the number of interposed platina plates
would not involve an increased difficulty of conduction.
1018. In order to obtain an idea
of the additional interfering power of each added
platina plate, six voltaic pairs and four intervening
platinas were arranged as in fi; a very
feeble current then passed (985. 1017.). When
one of the platinas was removed so that three
intervened, a current somewhat stronger passed.
With two intervening platinas a still stronger
current passed; and with only one intervening platina
a very fair current was obtained. But the effect
of the successive plates, taken in the order of their
interposition, was very different, as might be expected;
for the first retarded the current more powerfully
than the second, and the second more than the third.
1019. In these experiments both
amalgamated and unamalgamated zinc were used, but
the results generally were the same.
1020. The effects of retardation
just described were altered altogether when changes
were made in the nature of the liquid used between
the plates, either in what may be called the exciting
or the retarding cells. Thus, retaining
the exciting force the same, by still using pure dilute
sulphuric acid for that purpose, if a little nitric
acid were added to the liquid in the retarding
cells, then the transmission of the current was very
much facilitated. For instance, in the experiment
with one pair of exciting plates and one intervening
plate (1011.), fi, when a few drops of nitric
acid were added to the contents of cell ii, then the
current of electricity passed with considerable strength
(though it soon fell from other causes (1036; 1040.),)
and the same increased effect was produced by the
nitric acid when many interposed plates were used.
1021. This seems to be a consequence
of the diminution of the difficulty of decomposing
water when its hydrogen, instead of being absolutely
expelled, as in the former cases, is transferred to
the oxygen of the nitric acid, producing a secondary
result at the cathode (752.); for in accordance
with the chemical views of the electric current and
its action already advanced (913.), the water, instead
of opposing a resistance to decomposition equal to
the full amount of the force of mutual attraction
between its oxygen and hydrogen, has that force counteracted
in part, and therefore diminished by the attraction
of the hydrogen at the cathode for the oxygen
of the nitric acid which surrounds it, and with which
it ultimately combines instead of being evolved in
its free state.
1022. When a little nitric acid
was put into the exciting cells, then again the circumstances
favouring the transmission of the current were strengthened,
for the intensity of the current itself was
increased by the addition (906.). When therefore
a little nitric acid was added to both the exciting
and the retarding cells, the current of electricity
passed with very considerable freedom.
1023. When dilute muriatic acid
was used, it produced and transmitted a current more
easily than pure dilute sulphuric acid, but not so
readily as dilute nitric acid. As muriatic acid
appears to be decomposed more freely than water (765.),
and as the affinity of zinc for chlorine is very powerful,
it might be expected to produce a current more intense
than that from the use of dilute sulphuric acid; and
also to transmit it more freely by undergoing decomposition
at a lower intensity (912.).
1024. In relation to the effect
of these interpositions, it is necessary to state
that they do not appear to be at all dependent upon
the size of the electrodes, or their distance from
each other in the acid, except that when a current
can pass, changes in these facilitate or retard
its passage. For on repeating the experiment
with one intervening and one pair of exciting plates
(1011.), fi, and in place of the interposed plate
P using sometimes a mere wire, and sometimes very
large plates (1008.), and also changing the terminal
exciting plates Z and P, so that they were sometimes
wires only and at others of great size, still the results
were the same as those already obtained.
1025. In illustration of the
effect of distance, an experiment like that described
with two exciting pairs and one intervening plate (1012.),
fi, was arranged so that the distance between
the plates in the third cell could be increased to
six or eight inches, or diminished to the thickness
of a piece of intervening bibulous paper. Still
the result was the same in both cases, the effect
not being sensibly greater, when the plates were merely
separated by the paper, than when a great way apart;
so that the principal opposition to the current in
this case does not depend upon the quantity
of intervening electrolytic conductor, but on the relation
of its elements to the intensity of the current,
or to the chemical nature of the electrodes and the
surrounding fluids.
1026. When the acid was sulphuric
acid, increasing its strength in any of the
cells, caused no change in the effects; it did not
produce a more intense current in the exciting cells
(908.), or cause the current produced to traverse
the decomposing cells more freely. But if to very
weak sulphuric acid a few drops of nitric acid were
added, then either one or other of those effects could
be produced; and, as might be expected in a case like
this, where the exciting or conducting action bore
a direct reference to the acid itself, increasing
the strength of this (the nitric acid), also increased
its powers.
1027. The nature of the interposed
plate was now varied to show its relation to the
phenomena either of excitation or retardation, and
amalgamated zinc was first substituted for platina.
On employing one voltaic pair and one interposed zinc
plate, fi, there was as powerful a current,
apparently, as if the interposed zinc plate was away.
Hydrogen was evolved against P in cell ii, and against
the side of the second zinc in cell i; but no gas
appeared against the side of the zinc in cell ii, nor
against the zinc in cell i.
1028. On interposing two amalgamated
zinc plates, fi, instead of one, there was still
a powerful current, but interference had taken place.
On using three intermediate zinc plates, fi,
there was still further retardation, though a good
current of electricity passed.
1029. Considering the retardation
as due to the inaction of the amalgamated zinc upon
the dilute acid, in consequence of the slight though
general effect of diminished chemical power produced
by the mercury on the surface, and viewing this inaction
as the circumstance which rendered it necessary that
each plate should have its tendency to decompose water
assisted slightly by the electric current, it was
expected that plates of the metal in the unamalgamated
state would probably not require such assistance, and
would offer no sensible impediment to the passing of
the current. This expectation was fully realized
in the use of two and three interposed unamalgamated
plates. The electric current passed through them
as freely as if there had been no such plates in the
way. They offered no obstacle, because they could
decompose water without the current; and the latter
had only to give direction to a part of the forces,
which would have been active whether it had passed
or not.
1030. Interposed plates of copper
were then employed. These seemed at first to
occasion no obstruction, but after a few minutes the
current almost entirely ceased. This effect appears
due to the surfaces taking up that peculiar condition
(1010.) by which they tend to produce a reverse current;
for when one or more of the plates were turned round,
which could easily be effected with the couronne
des tasses form of experiment, fi, then the
current was powerfully renewed for a few moments, and
then again ceased. Plates of platina and copper,
arranged as a voltaic pile with dilute sulphuric acid,
could not form a voltaic trough competent to act for
more than a few minutes, because of this peculiar
counteracting effect.
1031. All these effects of retardation,
exhibited by decomposition against surfaces for which
the evolved elements have more or less affinity, or
are altogether deficient in attraction, show generally,
though beautifully, the chemical relations and source
of the current, and also the balanced state of the
affinities at the places of excitation and decomposition.
In this way they add to the mass of evidence in favour
of the identity of the two; for they demonstrate,
as it were, the antagonism of the chemical powers
at the electromotive part with the chemical powers
at the interposed parts; they show that the first
are producing electric effects, and the second
opposing them; they bring the two into direct
relation; they prove that either can determine the
other, thus making what appears to be cause and effect
convertible, and thereby demonstrating that both chemical
and electrical action are merely two exhibitions of
one single agent or power (916. &c.).
1032. It is quite evident, that
as water and other electrolytes can conduct electricity
without suffering decomposition (986.), when the electricity
is of sufficiently low intensity, it may not be asserted
as absolutely true in all cases, that whenever electricity
passes through an electrolyte, it produces a definite
effect of decomposition. But the quantity of
electricity which can pass in a given time through
an electrolyte without causing decomposition, is so
small as to bear no comparison to that required in
a case of very moderate decomposition, and with electricity
above the intensity required for electrolyzation, I
have found no sensible departure as yet from the law
of definite electrolytic action developed in
the preceding series of these Researches (783. &c.).
1033. I cannot dismiss this division
of the present Paper without making a reference to
the important experiments of M. Aug. De la Rive
on the effects of interposed plates. As I
have had occasion to consider such plates merely as
giving rise to new decompositions, and in that way
only causing obstruction to the passage of the electric
current, I was freed from the necessity of considering
the peculiar effects described by that philosopher.
I was the more willing to avoid for the present touching
upon these, as I must at the same time have entered
into the views of Sir Humphry Davy upon the same subject
and also those of Marianini and Hitter, which
are connected with it.
v. General Remarks on the active Voltaic Battery.
1034. When the ordinary voltaic
battery is brought into action, its very activity
produces certain effects, which re-act upon it, and
cause serious deterioration of its power. These
render it an exceedingly inconstant instrument as
to the quantity of effect which it is capable
of producing. They are already, in part, known
and understood; but as their importance, and that
of certain other coincident results, will be more evident
by reference to the principles and experiments already
stated and described, I have thought it would be useful,
in this investigation of the voltaic pile, to notice
them briefly here.
1035. When the battery is in
action, it causes such substances to be formed and
arranged in contact with the plates as very much weaken
its power, or even tend to produce a counter current.
They are considered by Sir Humphry Davy as sufficient
to account for the phenomena of Ritter’s secondary
piles, and also for the effects observed by M.A.
De la Rive with interposed platina plates.
1036. I have already referred
to this consequence (1003.), as capable, in some cases,
of lowering the force of the current to one-eighth
or one-tenth of what it was at the first moment, and
have met with instances in which its interference
was very great. In an experiment in which one
voltaic pair and one interposed platina plate were
used with dilute sulphuric acid in the cells fi, the wires of communication were so arranged, that
the end of that marked 3 could be placed at pleasure
upon paper moistened in the solution of iodide of
potassium at x, or directly upon the platina
plate there. If, after an interval during which
the circuit had not been complete, the wire 3 were
placed upon the paper, there was evidence of a current,
decomposition ensued, and the galvanometer was affected.
If the wire 3 were made to touch the metal of p,
a comparatively strong sudden current was produced,
affecting the galvanometer, but lasting only for a
moment; the effect at the galvanometer ceased, and
if the wire 3 were placed on the paper at x,
no signs of decomposition occurred. On raising
the wire 3, and breaking the circuit altogether for
a while, the apparatus resumed its first power, requiring,
however, from five to ten minutes for this purpose;
and then, as before, on making contact between 3 and
p, there was again a momentary current, and
immediately all the effects apparently ceased.
1037. This effect I was ultimately
able to refer to the state of the film of fluid in
contact with the zinc plate in cell i. The acid
of that film is instantly neutralized by the oxide
formed; the oxidation of the zinc cannot, of course,
go on with the same facility as before; and the chemical
action being thus interrupted, the voltaic action diminishes
with it. The time of the rest was required for
the diffusion of the liquid, and its replacement by
other acid. From the serious influence of this
cause in experiments with single pairs of plates of
different metals, in which I was at one time engaged,
and the extreme care required to avoid it, I cannot
help feeling a strong suspicion that it interferes
more frequently and extensively than experimenters
are aware of, and therefore direct their attention
to it.
1038. In considering the effect
in delicate experiments of this source of irregularity
of action, in the voltaic apparatus, it must be remembered
that it is only that very small portion of matter which
is directly in contact with the oxidizable metal which
has to be considered with reference to the change
of its nature; and this portion is not very readily
displaced from its position upon the surface of the
metal (582. 605.), especially if that metal be rough
and irregular. In illustration of this effect,
I will quote a remarkable experiment. A burnished
platina plate (569.) was put into hot strong sulphuric
acid for an instant only: it was then put into
distilled water, moved about in it, taken out, and
wiped dry: it was put into a second portion of
distilled water, moved about in it, and again wiped:
it was put into a third portion of distilled water,
in which it was moved about for nearly eight seconds;
it was then, without wiping, put into a fourth portion
of distilled water, where it was allowed to remain
five minutes. The two latter portions of water
were then tested for sulphuric acid; the third gave
no sensible appearance of that substance, but the
fourth gave indications which were not merely evident,
but abundant for the circumstances under which it
had been introduced. The result sufficiently
shows with what difficulty that portion of the substance
which is in contact with the metal leaves it;
and as the contact of the fluid formed against the
plate in the voltaic circuit must be as intimate and
as perfect as possible, it is easy to see how quickly
and greatly it must vary from the general fluid in
the cells, and how influential in diminishing the
force of the battery this effect must be.
1039. In the ordinary voltaic
pile, the influence of this effect will occur in all
variety of degrees. The extremities of a trough
of twenty pairs of plates of Wollaston’s construction
were connected with the volta-electrometer, fi. (711.), of the Seventh Series of these Researches,
and after five minutes the number of bubbles of gas
issuing from the extremity of the tube, in consequence
of the decomposition of the water, noted. Without
moving the plates, the acid between the copper and
zinc was agitated by the introduction of a feather.
The bubbles were immediately evolved more rapidly,
above twice the number being produced in the same
portion of time as before. In this instance it
is very evident that agitation by a feather must have
been a very imperfect mode of restoring the acid in
the cells against the plates towards its first equal
condition; and yet imperfect as the means were, they
more than doubled the power of the battery. The
first effect of a battery which is known to
be so superior to the degree of action which the battery
can sustain, is almost entirely due to the favourable
condition of the acid in contact with the plates.
1040. A second cause of
diminution in the force of the voltaic battery, consequent
upon its own action, is that extraordinary state of
the surfaces of the metals (969.) which was first
described, I believe, by Ritter, to which he refers
the powers of his secondary piles, and which has been
so well experimented upon by Marianini, and also by
A. De la Rive. If the apparatus, fi. (1096.),
be left in action for an hour or two, with the wire
3 in contact with the plate p, so as to allow
a free passage for the current, then, though the contact
be broken for ten or twelve minutes, still, upon its
renewal, only a feeble current will pass, not at all
equal in force to what might be expected. Further,
if P^ and P^ be connected by a metal wire, a
powerful momentary current will pass from P^ to
P^ through the acid, and therefore in the reverse
direction to that produced by the action of the zinc
in the arrangement; and after this has happened, the
general current can pass through the whole of the system
as at first, but by its passage again restores the
plates P^ and P^ into the former opposing condition.
This, generally, is the fact described by Ritter,
Marianini, and De la Rive. It has great opposing
influence on the action of a pile, especially if the
latter consist of but a small number of alternations,
and has to pass its current through many interpositions.
It varies with the solution in which the interposed
plates are immersed, with the intensity of the current,
the strength of the pile, the time of action, and
especially with accidental discharges of the plates
by inadvertent contacts or reversions of the plates
during experiments, and must be carefully watched
in every endeavour to trace the source, strength,
and variations of the voltaic current. Its effect
was avoided in the experiments already described (1036.
&c.), by making contact between the plates P^ and
P^ before the effect dependent upon the state of
the solution in contact with the zinc plate was observed,
and by other precautions.
1041. When an apparatus like
fi. (1017.) with several platina plates was used,
being connected with a battery able to force a current
through them, the power which they acquired, of producing
a reversed current, was very considerable.
1042. Weak and exhausted charges
should never be used at the same time with strong
and fresh ones in the different cells of a trough,
or the different troughs of a battery: the fluid
in all the cells should be alike, else the plates
in the weaker cells, in place of assisting, retard
the passage of the electricity generated in, and transmitted
across, the stronger cells. Each zinc plate so
circumstanced has to be assisted in decomposing power
before the whole current can pass between it and the
liquid. So, that, if in a battery of fifty pairs
of plates, ten of the cells contain a weaker charge
than the others, it is as if ten decomposing plates
were opposed to the transit of the current of forty
pairs of generating plates (1031.). Hence a serious
loss of force, and hence the reason why, if the ten
pairs of plates were removed, the remaining forty
pairs would be much more powerful than the whole fifty.
1043. Five similar troughs, of
ten pairs of plates each, were prepared, four of them
with a good uniform charge of acid, and the fifth with
the partially neutralized acid of a used battery.
Being arranged in right order, and connected with
a volta-electrometer (711.), the whole fifty
pairs of plates yielded 1.1 cubic inch of oxygen and
hydrogen in one minute: but on moving one of
the connecting wires so that only the four well-charged
troughs should be included in the circuit, they produced
with the same volta-electrometer 8.4 cubical
inches of gas in the same time. Nearly seven-eighths
of the power of the four troughs had been lost, therefore,
by their association with the fifth trough.
1044. The same battery of fifty
pairs of plates, after being thus used, was connected
with a volta-electrometer (711.), so that by quickly
shifting the wires of communication, the current of
the whole of the battery, or of any portion of it,
could be made to pass through the instrument for given
portions of time in succession. The whole of the
battery evolved 0.9 of a cubic inch of oxygen and
hydrogen in half a minute; the forty plates evolved
4.6 cubic inches in the same time; the whole then evolved
1 cubic inch in the half-minute; the ten weakly charged
evolved 0.4 of a cubic inch in the time given:
and finally the whole evolved 1.15 cubic inch in the
standard time. The order of the observations was
that given: the results sufficiently show the
extremely injurious effect produced by the mixture
of strong and weak charges in the same battery.
The gradual increase in the action
of the whole fifty pairs of plates was due to the
elevation of temperature in the weakly charged trough
by the passage of the current, in consequence of which
the exciting energies of the fluid within were increased.
1045. In the same manner associations
of strong and weak pairs of plates should be
carefully avoided. A pair of copper and platina
plates arranged in accordance with a pair of
zinc and platina plates in dilute sulphuric acid,
were found to stop the action of the latter, or even
of two pairs of the latter, as effectually almost
as an interposed plate of platina (1011.), or as if
the copper itself had been platina. It, in fact,
became an interposed decomposing plate, and therefore
a retarding instead of an assisting pair.
1046. The reversal, by
accident or otherwise, of the plates in a battery
has an exceedingly injurious effect. It is not
merely the counteraction of the current which the
reversed plates can produce, but their effect also
in retarding even as indifferent plates, and requiring
decomposition to be effected upon their surface, in
accordance with the course of the current,
before the latter can pass. They oppose the current,
therefore, in the first place, as interposed platina
plates would do (1011-1018.); and to this they add
a force of opposition as counter-voltaic plates.
I find that, in a series of four pairs of zinc and
platina plates in dilute sulphuric acid, if one pair
be reversed, it very nearly neutralizes the power of
the whole.
1047. There are many other causes
of reaction, retardation, and irregularity in the
voltaic battery. Amongst them is the not unusual
one of precipitation of copper upon the zinc in the
cells, the injurious effect of which has before been
adverted to (1006.). But their interest is not
perhaps sufficient to justify any increase of the length
of this paper, which is rather intended to be an investigation
of the theory of the voltaic pile than a particular
account of its practical application.
For further practical results relating
to these points of the
philosophy of the voltaic battery, see
Series X. S 17.
1163.—1160.—De.
Royal Institution, March 31st,
1834.