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Biochimica et Biophysica Acta 1757 (2006) 871 – 875

Memoir on the decomposition of water and of the bodies that it holds in
solution by means of galvanic electricity☆
C.J.T. de Grotthuss 1
Received 16 February 2006; accepted 26 July 2006
Available online 29 July 2006

Chapter I. Action of galvanic electricity on certain bodies sation, and which takes place upon precipitation of the
dissolved in water dissolved metals by means of other metals. The ancients
would add to the name arbor that of the deity to whom the
I metal was consecrated. Hence the terms arbor Dianae, arbor
Martis, arbor Veneris, etc. Of all the phenomena arising from
Without pausing to discuss the multitude of hypotheses put galvanism, none is as beautiful or as interesting as such
forth to explain the decomposition of water by the electromotive vegetation, which gradually composes before our eyes the
apparatus, I shall present a general theory of the decomposition image of a beautiful shrub, furnished with its foliage and
of liquids by galvanic electricity, which seems to me a simple adorned with its metallic glow.
and satisfactory explanation of its effects. I was led to this
theory by the following observations. IV

II Wollaston, the famous English physicist, has already noted
that upon applying an electric current in a metal solution, the
When a current of galvanic electricity, whose intensity is metal was revived at the tip of the electrode through which the
proportional to the interval occupied by the liquid, and which negative electricity flows; but I do not know whether or not it
runs between the tips of the two conducting wires, is applied to a was also observed that this revival is likely to adopt a symmetric
saturated metallic solution, interesting phenomena are arrangement, when the action has sufficient energy and once it
observed, even to one not concerned with understanding their has lasted for some time. (See Biblioth. britan., vol. 18).
cause. At the tip of the wire in contact with the disc of zinc,
oxygen is released, while at the tip of the wire in contact with V
the disc of copper, the molecules of the dissolved metal are
resurgent and adopt a symmetric arrangement spreading in the Not all dissolved metals are decomposed by galvanic
direction of the galvanic current. electricity. From manganese nitrate I obtained gaseous bubbles
at the negative pole2 instead of a metallic deposit; and it
III seems that, when under the same circumstances the dissolved
metal has a greater affinity for oxygen than that of hydrogen
This arrangement is but an imperfect crystallisation of the for the same principle, it is solely water which undergoes
metallic molecules, perfectly similar to that known as arbori- decomposition.

The following is a translation of the paper “Mémoire sur la décomposition VI
de l’eau et des corps qu’elle tient en dissolution à l’aide de l’électricité
galvanique,” by C.J.T. de Grotthuss, Ann. Chim. (Paris) 58:54-74 (1806);
translated from the French by Régis Pomès, Structural Biology and
During the arborisation of metals at the negative pole, no gas
Biochemistry, Hospital for Sick Children, 555 University Avenue, Toronto, is seen to come out; whence I conclude either that nascent
Ontario, Canada M5G 1X8, and Department of Biochemistry, University of
Toronto. E-mail: I shall henceforth use the expression positive pole to refer to the tip of the
This memoir was printed in Rome in 1805. We thought that it would be wire connected to the disc of zinc, and the expression negative pole to denote
pleasant to find it here, and the author himself wished that it be reprinted. the tip of the wire in contact with the copper disc.

0005-2728/$ - see front matter © 2006 Elsevier B.V. All rights reserved.

a precipitate similar to 4 Wollaston. 6 ordinary device. with a magnifying glass. sulphuric acid seems capable of dissolving 3 I also obtained more or less similar results from nitromuriates of gold and gold. the When the current of galvanic electricity acts on water that vitreous fluid has an effect analogous to heat. I and the effects resume. which constantly point towards acid. whereas If the proportion of the components of the liquid is variable. If the two electrodes are switched. by testing it with prussiate of potash. and the blue part becomes electrode in contact with the disc of copper. It even seems that. de Grotthuss / Biochimica et Biophysica Acta 1757 (2006) 871–875 hydrogen combined with the oxygen of the metal oxide. whereas the pole. at the positive positive pole attracts the oxygenating principle.T. Sulfuric acid and nitric acid become were dissolved only after inducing the opposite effect. Redissolving this precipitate in muriatic imitate that of natural plants. turned the latter the source of light. VIII XII Once the shrub has reached the close vicinity of the positive pole. lead acetate and tin muriate3 nitrous and turns blue. an analogy between the decomposition of water by an electric device and XIII that operated by the voltaic pile. in which these two metals conducting wire. being infinitely slender Following a prolonged application of galvanic electricity to a in all directions. molybdic acid partly precipitates as a white powder. from nitrates of zinc. that I believe that they may be able to produce. in such a state. mercury. octahedral crystals. gave me most beautiful vegetations. it acquires a colour ever darker and it becomes oxygenated at the tip of the electrode in contact dirtier. for the tips of the metallic needles sulphate.4 Cold solutions of molybdic acid in concentrated sulphuric IX acid adopt a beautiful blue colour that disappears upon heating the solution. each may acquire the verifies that it contains a highly-oxidised oxygenated iron electric fluid of the other. and then testing it with mercuric chloride. consistently observed that oxygen and hydrogen are released It would be interesting to examine whether this gas comes partly out of together. proofs: 5 At this degree of oxygenation. Upon addition of zinc and iron. The vegetation of a gradually leads to the precipitation of a white powder coming metal obtained by means of electricity appears somehow to from the positive pole. regardless of their respective location. muriatic acid releases a large quantity of gas. It is likely that. when the two reddish hue in the region surrounding the positive pole. and negative pole attracts the oxygenated principle of the liquid.5 At the negative pole. merely turns into a greenish-white in water. the transparent. at the positive pole. by acting like an solution of iron sulphate. and appear so overladden with oxygen in the decomposition of water. and deoxygenated at the tip of the the transparent part reverts to blue. or that X action was exerted on that oxide rather than on water. effects as yet unbeknownst to VII us. the latter became blurred. That of lead takes the each part of the acid gradually reverts to its primitive state. It is remarkable that arborisation always grows from the XI negative pole to the positive one. annihilates the electric action. every time the tips of the two whereas that surrounding the negative pole. because one can hardly accept that Muriatic acid becomes so oxygenated at the positive pole hydrogen is able to strip oxygen completely off of zinc and iron that it acquires the ability to dissolve gold from the tip of the oxides.872 C.6 sulphuric acid emits a strong smell of Of all the metallic salts that I have subjected to the action sulphur while sulphur is deposited. . each other. and from iron muriate. from sulfates of as it dissolved the golden tip of the wire releasing the oxygen. The latter conclusion must be correct. if I am not mistaken. and on the ramifications of tin. decomposition of the acid. which instantly would sometimes start to oxidise while deoxidation was evident turns into a beautiful Prussian blue in that part of the liquid. from stannite of muriated potash. the resinous fluid has an effect analogous to cold. the liquor gradually becomes perfectly transparent. around the negative pole. upon decomposing water with electricity by means of an gold sulphide was formed. Here we have. the gases released by its decomposition will mix with precipitate. it stops growing. Switching the two poles around has the opposite effect: with the disc of zinc. and release oxygen upon coming into white. region surrounding that pole. whereas the action of the pile leads them to appear separately. since its foliage. Tin muriate has thus become more oxygenated at the tip of the wire that causes the release of oxygen. and cobalt. When subjected to the action of the voltaic pile. and nitric acid becomes of the electromotive apparatus. adopting a infinite number of needles. appearance of fern leaves. Here are the transparent. whereas the is either pure or charged with some soluble substance. in any case. as solvents do to certain acids. in the presence of conducting wires are very slender and very close to each other the same prussiate. One then poles are brought too close to each other. black. and that it is therefore always organised A solution of tin muriate subjected to a galvanic current in the direction of the electric current. often observed. that which I used in this experiment assumed a yellow colour platinum. copper. whereas the liquid around the negative pole turned it contact with its rays. a solution of green iron sulphate to this gold sulphate.J.

increasing with respect to the other. whose centres of action perfectly gilded with silver or gold. it follows that the pole from which resinous simpler. britan. and I must confess that this was for me an constitute the complement of the pile in action. inasmuch as its centres of action cannot decrease with respect to one without. each the conducting wires by the action of the apparatus: thus. and the latter Given the diversity of substances deposited at the negative pole. These precipitates do not seem to me to be due to a decomposition.T. where only hydrogen manifests contact with each other. there occurs. but I presume that the acid of the salt is either destroyed or decomposed there. while all the XVII molecules of hydrogen located on the same pathway will tend towards the negative pole. C. in such a way that these seem to electrical agent. time. in such 8 a way that the former acquires the positive state. p. what befalls oxygen. it would be the negative state. judging by the infinitely small quantity of alkali generated at this location. one must ask what happens The effect of the repulsion. Thus. and which came from the metal particles torn off from galvanic current goes through a certain quantity of water. which immortalises the genius of its Let us now consider a certain quantity of water. vol. it follows that when the water molecule drogen and oxygen. although real. since has long puzzled chemists and physicists. the electrical polarity manifests itself between its the elementary molecules of water solicited by the same elementary molecules. electricity. repelling oxygen. From this. a split of their natural electricity. to consider only the attractive and electricity continuously flows will attract hydrogen while repulsive forces acting on oxygen. solution must be consistent with the theory regarding the by the same token. .e. since neither pole of the electromotive apparatus can acquire 7 See Biblioth. the glass tubes became attractive force and by a repulsive force. by acting in the same direction. The first question is whether both of the the two elements of such a molecule is solicited by a constant products evolved at the two galvanic poles originate from one force which results from the attractive force and the repulsive and the same molecule of water. so that its alkaline base becomes free. Statique chimique. The glass tubes used to hold the solutions subjected to the experiments that I have just described often ended up coated with a metallic layer which seemed molten onto the glass inside will attract oxygen and repel hydrogen. either by contact or by friction represented by o h yields its oxygen o to the vitreous fluid of of one against the other. or from two different force. Pondering this polarity suggested to me moment when one applies a current of galvanic electricity to the idea that a similar polarity might very well arise between this water. and to refrain from attributing any to the action of the poles on hydrogen. At the same illumination. determine the decomposition of the liquid.9 molecules. See Fig. to hydrogen at the location where only oxygen is seen. 216. whereas the pole with vitreous electricity 9 I am assuming that each force has the same intensity. and perhaps more accurate. 15. if not at the expense of the other. which must really be the case. and because of the reciprocal action of elementary molecules in inversely. are mutually opposed. let us assume that at the onset of the isolation of hy. Theory of the decomposition of liquids by means of galvanic electricity XVIII XV The action of each force on a water molecule located in the path of the galvanic current is inversely proportional to the The decomposition of water by the electromotive apparatus square of the distance at which it is applied. which leads to a recombination of those itself?7 that the galvanic poles repel. Fig. to whom this the distance of any given molecule located between the two phenomenon offers a delicate problem. Chapter II. each pair of discs) possesses its own negative hydrogen represented by the positive sign (+). and in the latter event. The and positive poles.8 Thus. when the the tube. However. is not significant. de Grotthuss / Biochimica et Biophysica Acta 1757 (2006) 871–875 873 XIV Upon prolonged application of galvanic current to an alkaline salt solution. is an electric magnet of which each and every of oxygen represented by the negative sign (−) and of element (i. 1. 1.J. composed inventor. the base of the latter gradually precipitates around the tip of the wire with the negative electricity. and which. when of the two component principles of water is solicited by an the tips were made of gold or of silver. each of nature of water. XVI XIX The voltaic column. all the molecules of oxygen located in the pathway of current will tend towards the positive pole..

elements of water will continue until the water is completely decomposed. and oxygen is part of the composition of all the acids whose nature gaseous hydrogen was released by tips b and d. Morichini. throughout this operation. whereas the vegetations After my apparatus had remained in constant operation for previously described formed at tips b and d. the mind conceives how molecules n and p 11 Tincture of turnsole [Translator's note: litmus]. that if it were possible to apply a galvanic current in water such (c) Even if the component principles of water could not be that it follows a perfectly circular line. The same thing occurs. and that of a to the action of the electromotive device.J. I noticed the polarity at base at the negative pole. (a) The proportion of hydrogen cannot increase in water located in the vicinity of the positive pole. obtained oxygen at tips a and c. and the when the vessels contained lead acetate dissolved in water. I latter from the presence of hydrogen. whereas oxygen is repelled by alternatively. is immediately rehydrogenated by the arrival of molecule X. and The theory of water decomposition that I have just presented this succession of decomposition and recombination of the leads to the following consequences. when subjected to a galvanic current. but neither oxygenation. thereby regenerating the body that had at first been of another molecule of oxygen o′ whose hydrogen h′ decomposed. while ammonia]. since hydrogen is will exchange their composing principles reciprocally and constantly attracted to it. Thus. 2. XXI XXIII Having exposed the liquids contained in two or more vessels The production of an acid at the positive pole. but these effects may be explained by the action of nascent oxygen and hydrogen on the colouring 10 I communicated my memoir to M. the electrical polarity still manifested itself clearly. for. See Section IX. turns red around the positive pole. See Fig.12 See Section IX. according to between the liquids contained in each vessel. only the water away from it.874 C. is known to us. hydrogenation. relatively to water molecule Q P which. nor alkalinity would be observed in any of its water. parts. if one imagines this same wire to be infinitely small. subjected to the effect of galvanic action. recombines with r. oxygenation is impossible in the water decomposed. also support the proposed theory. would still remain acidity. all the water molecules of combined into any proportion other than that which the liquid located in this circle would be decomposed and constitutes water. but in the opposite direction. Tips a and c gave him gaseous oxygen. whence. the former must result from oxygenation. whereas all those located at intermediate positions surrounding the negative pole. the latter would still be decomposed as recomposed at once: whence it follows that this water. etc. which was length of wire b c as much as I could. This talented chemist told me matter. whereas hydrogen tries to move It is clear that. as it XXII yields its hydrogen Q to the resinous fluid of the − wire. cloths moistened with a sodium muriate solution were After I brought the vessels closer together and shortened the covered here and there with a saline efflorescence. since the XX oxygen of the whole liquid traversed by galvanic current tends towards that point. 12 that he obtained a similar result upon examining the gases released when the Hydrogen is a constituent part of volatile alkali [Translator's note: aqueous vessels contain only water. .11 in water subjected to galvanic the ends of the metallic wires used to establish a connection electricity. and are not sufficient to deduce acidity and alkalinity. From this I deduce it. its hydrogen h is at once reoxygenated by the arrival would unite. and reverts to blue upon switching the respective position of the two poles. molecules located at the tip of the conducting wires will be (b) By the same token. the + wire. without changing their nature.10 days. de Grotthuss / Biochimica et Biophysica Acta 1757 (2006) 871–875 Fig. although described. 2. the analogy.T.

13 After exposing from the air. such as is found in the elementary If we knew of any substance other than oxygen that could be molecules of water traversed by galvanic current. rather than mixing with the acts in secret. occupied one half of the tube and had.J. such as. in electricity. then evidently prove that the decomposition of water by means electric polarity takes place among the elements of the oxide. but even though it The admirable simplicity of the law to which this phenom- has been decomposed either by this reaction or by the electric enon is subjected is also observed. de Grotthuss / Biochimica et Biophysica Acta 1757 (2006) 871–875 875 nothing but soda bound to carbonic acid that it had absorbed solution. In metallic solutions. and whose molecules: an opinion generally accepted. An analogous result would that they are solicited by the same forces. provided experiment with respect to the latter. metallic particles which it holds in solution. must also provoked by the positive pole. lead acetate and copper nitrate. one cannot help but recognise one of the most other. with the other powerful agents of the grand operations of nature. are subjected to a mutual exchange of their elements. and consistent with metal is deposited at the negative pole. Acid reacts with these the theory which I dare submit to the scrutiny of scholars. Nature can neither create nor destroy. although it is widespread in the universe. law of the universe. 13 This condition is easily fulfilled if one uses two solutions of different colours. C. when one considers the wonderful effects of I filled a bent tube with two different metallic solutions. and plunging the negative pole successively into one and into XXIV the other. for example. but all XXV bodies. to our astonishment. the pole remained coated with the revived metal of the solution in which it was plunged. and. we could repeat the above result in the elementary molecules of all other liquids. often such a way that each one of them. in the power. which. revival occurs nevertheless. without exception. . The polar arrangement. of galvanic electricity occurs in relation to two different whose oxygen is transferred to the positive pole. the two liquids thus arranged to the action of galvanic current.T. since the number of bodies never increases nor decreases. a single contact point in the middle.