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Early Voltaic Batteries: an Evaluation in Modern Units

and Application to the Work of Davy and Faraday
a
Allan A. Mills
a
Department of Physics and Astronomy , University of Leicester , Leicester LE1 7RH, UK
Published online: 04 Jun 2010.

To cite this article: Allan A. Mills (2003) Early Voltaic Batteries: an Evaluation in Modern Units and Application to the Work
of Davy and Faraday, Annals of Science, 60:4, 373-398, DOI: 10.1080/00033790110117566

To link to this article: http://dx.doi.org/10.1080/00033790110117566

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 A  S, 60 (October, 2003), 373–398

Early Voltaic Batteries: an Evaluation in Modern Units and Application

to the Work of Davy and Faraday

A A. M
Department of Physics and Astronomy, University of Leicester,
Leicester LE1 7RH, UK

Received 19 June 2001. Revised paper accepted 15 November 2001

Summary
Classic voltaic batteries of the silver/zinc and copper/zinc types are the ancestors
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of today’s primary cells, and facilitated the development of many aspects of

electrical technology. Nevertheless, they appear never to have been studied and
evaluated in a quantitative manner, with results recorded in terms of volts, amps,
ohms, and watts. Research of this nature is reported here, and has been conducted
for the most part with copper/zinc cells. Log–log graphs of voltage versus load
and current, and power versus load, are presented for many electrolyte systems.
It has been shown that, although the textbook electrolyte of dilute sulphuric acid
does work, it is an order of magnitude inferior to a solution containing some
additional nitric acid. The latter diminishes the current-limiting phenomenon of
polarization, and was in fact used by Davy, Faraday, and other early investigators.
A quantitative consideration of Nicholson and Carlisle’s discovery of the electro-
lysis of water with a silver/zinc voltaic pile is followed by examination of the
electrolysis of pure water, trough batteries, and Davy’s isolation of potassium
and sodium. Every battery gives maximum power when its resistance is adjusted
(by appropriate series/parallel connections) to match the resistance of the load:
the maximum output of the ‘Great Battery’ of the Royal Institution is assessed
at no more than 3 kW. The paper concludes with a note on the recognized hazard
of long-term exposure to mercury vapour (produced by amalgamation of zinc
electrodes in batteries) and its possible relevance to the health of Michael Faraday.

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2. Some early problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2.1. Mode of operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2.2. The ‘Baghdad Battery’ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
2.3. Polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
3. Quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
3.1. Volts, amps, resistance, and power . . . . . . . . . . . . . . . . . . . . . . . . . . 376
3.2. Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
4. Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
4.1. Practical electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
4.2. Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
4.3. Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
5. Preliminary trials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
6. Cu/Zn open-circuit potentials with various electrolytes . . . . . . . . . . . . . 379
7. Cells in series: the influence of various electrolytes . . . . . . . . . . . . . . . . 379
7.1. Voltage versus load . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
7.2. Voltage versus current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
7.3. Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
8. The maximum power theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
Annals of Science ISSN 0003-3790 print/ISSN 1464-505X online © 2003 Taylor & Francis Ltd
http://www.tandf.co.uk/journals
DOI: 10.1080/00033790110117566
 374 Allan A. Mills

9. Cells in parallel: influence of electrode area . . . . . . . . . . . . . . . . . . . . . . . 383

9.1. Sulphuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
9.2. Nitro-sulphuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
9.3. Modern ‘dry’ cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
10. Some well-known early batteries and applications . . . . . . . . . . . . . . . . . 388
10.1. Nicholson and Carlisle’s voltaic pile . . . . . . . . . . . . . . . . . . . . . . . . 388
10.2. Humphry Davy: use of nitric acid in voltaic cells . . . . . . . . . . . . 389
10.3. Humphry Davy: the composition of water . . . . . . . . . . . . . . . . . . 390
10.4. Trough batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
10.5. Davy’s isolation of potassium and sodium . . . . . . . . . . . . . . . . . . 391
10.6. The Royal Institution battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
10.7. Nitric acid and load-matching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
11. Faraday and mercury poisoning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
12. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397

1. Introduction
The announcement by Volta1 in 1800 that he had succeeded in obtaining electri-
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city from a pile of pairs of silver coins and zinc discs separated by cloth moistened
with salt water generated immense world-wide interest. His ‘voltaic pile’ was widely
replicated, and research aimed at confirming the identity of ‘ordinary’ (i.e. frictional )
electricity and this new form was soon successfully under way. However, even before
the formal publication of Volta’s discovery, a lucky accident whereby the conductors
of a pile were bridged by a drop of water led to the discovery of electrolysis by
Nicholson and Carlisle.2
A desire to increase the amount of electricity generated was soon felt, and the
best pathway to achieve this appeared to be development of Volta’s second invention,
the ‘crown of cups’. The basic unit (cell ) of this arrangement was a pair of dissimilar
metals, usually copper/zinc rather than the expensive silver/zinc, immersed in brine
within a small glass vessel. A number of individual cells were then connected
sequentially in what we now term ‘series’ to form a ‘battery’. It was soon found
that dilute inorganic acids performed better than brine, dilute sulphuric acid being
most often mentioned by early reviewers such as Roget.3 This has been copied from
textbook to textbook right up to the present day, so the ‘elementary cell’ is commonly
considered to consist of ‘electrodes’ of copper and zinc immersed in dilute sulphuric
acid. It is sometimes stated to give an electromotive force (e.m.f.) of about 1 V.

2. Some early problems

2.1. Mode of operation
In the early years there was, of course, no accepted theory behind the observa-
tions. It was known that ordinary zinc dissolved in dilute sulphuric acid, the reaction
being symbolized as
Zn+H SO
ZnSO +H
2 4 4 2
It was suspected that the reaction probably occurred in steps, and that the chemical
1 Alessandro Volta ‘On the Electricity Excited by the Mere Contact of Conducting Substances of
Different Kinds’, Philosophical Transactions, 90 (1800), 403–31 (in French; English trans. in Philosophical
Magazine, 7 (1800), 289–311).
2 William Nicholson, ‘Account of the New Electrical or Galvanic Apparatus of Sig. Alex. Volta, and
Experiments Performed with the Same’, Nicholson’s Journal, 4 (1800), 179–87. W. Nicholson, A. Carlisle
and W. Cruickshank, ‘Experiments in Galvanic Electricity’, Philosophical Magazine, 7 (1800), 337–47.
3 P. M. Roget, Electricity, Galvanism and Electro-Magnetism (London, 1832).
 Early Voltaic Batteries: an Evaluation in Modern Units 375

equation merely represented their summation. This view was given greater credence
when it was found that pure zinc was not attacked by the acid unless another plate
of a more noble—and therefore unattacked—metal (such as copper, silver, or
platinum) was also placed in the solution. When connected by a wire to the zinc it
allowed a ‘charge’ to flow and the reaction could proceed, with dissolution of the
zinc and evolution of hydrogen at the noble metal electrode.4 The matter was
carefully studied, quantified and systematized by Faraday.5 For modern ideas,
reference must be made to appropriate textbooks.6
The fact that an electrode of commercial zinc in a voltaic cell slowly dissolved,
even when the cell was not in use, proved a considerable nuisance. It was ascribed
to impurities such as copper and iron setting up a multitude of tiny cells on the
surface of the metal, and was termed ‘local action’ (see note 5). This wasteful
reaction could be prevented by lifting out the electrodes,7 but then of course the cell
could not be used in an ‘on-demand’ situation. However, it was discovered that
amalgamation with mercury8 allowed only zinc to migrate through and to reach the
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interface with the ‘electrolyte’. Amalgamation did not affect the potentials and
currents generated: only the life of the cell when not being called on to generate
electricity.

2.2. The ‘Baghdad Battery’

Consideration9 of an ancient artefact that, in my view, has been mistakenly
identified as an electrochemical cell led to an attempt to operate a nominal 2.5 V
torch lamp with a five-cell Cu/Fe battery containing dilute acetic acid. The freshly
prepared series arrangement registered an open-circuit potential of 2.6 V on an
electrometer (a voltmeter of near-infinite internal resistance) but this fell to near
zero as soon as the lamp was connected across the terminals. It proved impossible
to obtain even a transient glow of the filament. Much the same result was obtained
with Cu|Zn|sulphuric acid cells. So, the textbook battery registers a satisfactory
‘standing potential’ on open circuit, but appears hardly capable of supplying suffi-
cient power to do significant work. How then could Davy10 have electrolysed fused

4 William H. Wollaston, ‘Experiments on the Chemical Production and Agency of Electricity’,

Philosophical Transactions, 91 (1801), 427–34.
5 Michael Faraday, Experimental Researches in Electricity, 2 vols (London: Quaritch, 1839).
6 Peter Atkins, The Elements of Physical Chemistry, 2nd edn (Oxford: Oxford University Press, 2001),
Chapter 9.
7 C. H. Wilkinson, ‘Description of an Improved Galvanic Trough’, Philosophical Magazine, 29
(1807), 243–44.
8 Humphry Davy, ‘On the Relations of Electrical and Chemical Changes’, Philosophical Transactions,
116 (1826), 383–422; K. T. Kemp, ‘Description of a New Kind of Galvanic Pile, and also of Another
Galvanic Apparatus in the Form of a Trough’, Edinburgh New Philosophical Journal, 6 (1828), 70–77;
Auguste de la Rive, ‘Note relative à l’action qu’exerce sur le zinc l’acide sulfurique étendu d’eau’,
Bibliothèque Universelle, Sciences et Arts, 43 (1830), 391–411; William Sturgeon, ‘On Electromagnets’,
Philosophical Magazine, 11 (1832), 194–205; K. T. Kemp, ‘Voltaic Batteries with Amalgamated Zinc’,
Sturgeon’s Annals of Electricity, 1 (1837), 81–88.
9 Allan A. Mills, ‘The Baghdad Battery’, Bulletin of the Scientific Instrument Society (68) (2001) 35–37.
10 Humphry Davy, ‘On Some New Phenomena of Chemical Changes Produced by Electricity,
Particularly the Decomposition of the Fixed Alkalies, and the Exhibition of the New Substances Which
Constitute their Bases; and on the General Nature of Alkaline Bodies’, Philosophical Transactions, 98
(1808) 1–44; idem, ‘Electrochemical Researches in the Decomposition of the Earths; with Observations
on the Metals obtained from the Alkaline Earths, and on the Amalgam Procured from Ammonia’,
Philosophical Transactions, 98 (1808), 333–70; idem, ‘On Some New Electrochemical Researches, on
Various Objects, Particularly the Metallic Bodies, from the Alkalies and Earths, and on Some Combination
of Hydrogene’, Philosophical Transactions, 100 (1810), 16–74.
 376 Allan A. Mills

sodium and potassium hydroxides to release the alkali metals, Faraday11 run the
first electric motor, or Sturgeon12 operated a powerful electromagnet?

2.3. Polarization
The problem of the ‘pressure’ of electricity almost disappearing as soon as a
load was connected to a battery was encountered very early in the history of electro-
chemistry. It was ascribed to the film of hydrogen which was observed to form on
the silver or copper electrode of a working cell, obstructing access of reactants and
increasing cell resistance. It was also found that a failing cell which had just been
disconnected from a load could generate a potential in the reverse direction for a
brief period. The phenomenon was therefore termed ‘polarization’, and attempts to
counter it were made by adding oxidizing agents to the electrolyte, using sine and
tangent galvanometers as monitoring instruments.13
Nowadays, polarization is mostly avoided by arranging that the ion deposited
is not hydrogen, but at high discharge rates some loss of e.m.f. still occurs as a
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result of the time taken for ions to diffuse through the electrolyte. It remains an
important factor in the technical design of successful dry cells.14

3. Quantification
The history of electricity is considered in most works on the history of science,
and early cells and batteries are specifically discussed in a number of reviews.15 A
weakness is that the subject appears to be treated in a qualitative descriptive manner
based on literature and museum artefacts. Many unrecognized anomalies therefore
exist, such as those quoted above. A quantitative assessment, in modern units,
appeared to be long overdue. This necessitated the construction of working voltaic
cells and replica batteries, for obviously the few existing historical examples could
not be filled with acids.

3.1. Volts, amps, resistance, and power

The earliest experimenters16 recognized that the intensity or pressure of a flow
of electric charge must be distinguished from its overall quantity, just like the flow

11 Michael Faraday, Faraday’s Diary, ed. by Thomas Martin (London: Bell & Sons, 1932), , 50 ff
(4 September 1821 onwards); idem, Quarterly Journal of Science, 12 (1821), 186–283; idem, Experimental
Researches in Electricity, 3 vols (London: Quaritch, 1839–55), , 147–51.
12 William Sturgeon (note 8).
13 J. B. Rogers and J. Green, ‘Experiments with the Elementary Voltaic Battery’, Silliman’s Journal,
28 (1835), 33–42; C. M. S. Pouillet, ‘Mémoire sur la pile de Volta et sur la loi générale de l’intensité que
prennent les courants’, Comptes rendus de l’Académie des Sciences, Paris, 4 (1837), 267–79; E. Branly,
‘Mésure de la polarisation dans l’élément voltaique’, Comptes rendus de l’Académie des Sciences, Paris,
74 (1872), 528–31.
14 C. A. Vincent and B. Scrosati, Modern Batteries: An Introduction to Electrochemical Power Sources
(London: Arnold, 1997).
15 John Bostock, An Account of the History and Present State of Galvanism (London, 1818); P. M.
Roget (note 3); Henry Noad, Lectures on Electricity (London, 1844); F. C. Bakewell, A Manual of
Electricity, Practical and Theoretical (London: Griffin, 1859); J. J. Fahie, ‘Magnetism, Electricity and
Electromagnetism up to the Time of the Crowning Work of Michael Faraday in 1831’, Journal of the
Institute of Electrical Engineers, 69 (1931), 1331–57; J. King, ‘The Development of Electrical Technology
in the 19th Century. I: The Electrochemical Cell and the Electromagnet’ (Bulletin 228, US National
Museum, Washington, DC, 1962).
16 W. H. Wollaston for example. See note 4.
 Early Voltaic Batteries: an Evaluation in Modern Units 377

of water in a stream. Davy17 and Children18 suspected that the former varied with
the number of cells in a series-connected battery, while the latter was related to the
cumulative area of the electrodes.
Today we measure intensity (potential difference, p.d.) in ‘volts’, V, as a tribute
to Volta. The amount (or current) is measured in ‘amperes’, A, to commemorate
Ampère. It took years, however, before Ohm was able to convince the scientific
community that the ratio volts:amps was constant for a simple circuit. The constant
of proportionality is now called the ‘ohm’, V, in his honour, and is a measure of
the resistance of a circuit. Power in d.c. circuits is given by the product of
volts×amps, termed ‘watts’, W.
It is not intended to develop the history of how these units were originally
identified and measured: reference must be made to standard textbooks. None of
these units had, of course, been defined when the earliest batteries were evolving.

3.2. Electrodes
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It was recognized very early on19 that an electrochemically active couple consisted
of a combination of a comparatively noble with a relatively reactive metal. Copper,
silver, and platinum are representative of noble metals (to which electrical group
must be added graphitic carbon) while zinc was the most reactive of the metals
commonly available in the early nineteenth century. Tables of ‘standard electrode
potentials’ were later established, but are no more than a guide to possible combina-
tions. This is partly because the situation in a practical working cell is far from
standard or reversible, but also because the purity, surface conditions, and past
history of the electrodes exert a very considerable influence.

4. Apparatus
The only way to begin to understand the performance and evolution of early
batteries appeared to be to carry out experimental measurements, using modern
units, on Cu/Zn and other couples. These must be immersed in the various electro-
lytes that had been proposed. Not only should these measurements include ‘open-
circuit’ potentials, but also the voltages, currents, and work done when connected
to loads of known resistance.

4.1. Practical electrodes

$ Commercial zinc and copper sheet, 0.03 inch thick, as used for roofing.

$ Sterling silver nineteenth-century coins.

$ Graphitized carbon rod extracted from modern dry cell batteries.

4.2. Instruments
$ Digital multimeter (Black Star 3225) reading from milliamps to 10 A, and

millivolts to 10 V.

17 Humphry Davy, ‘On some Chemical Agencies of Electricity’, Philosophical Transactions, 97

(1807), 1–56.
18 J. G. Children, ‘An Account of Some Experiments, Performed with a View to Ascertain the Most
Advantageous Method of Constructing a Voltaic Apparatus, for the Purpose of Chemical Research’,
Philosophical Transactions, 99 (1809), 32–38.
19 W. H. Wollaston (note 4); Humphry Davy, ‘An Account of Some Galvanic Combinations, Formed
by the Arrangement of Singly Metallic Plates and Fluids, Analogous to the New Galvanic Apparatus of
Mr Volta’, Philosophical Transactions, 91 (1801), 397–402.
 378 Allan A. Mills

$ Electrometer (Levell TM9B) reading from microvolts to 10 V.

$ A specially constructed resistance box containing selectable wire resistors in
the logarithmic series 1, 3, 10, 30, 100, 300 and 1000 V. These were capable
of dissipating 20 W of power.

4.3. Cells
A number of identical cells were constructed to the pattern diagrammed in
Figure 1, the polyvinyl chloride (PVC ) spacers being attached with a spot of epoxy
adhesive. Imperial units were used, to be concordant with historical cells. A colour-
coded insulated flexible wire was soldered to each electrode. For use, each pair was
placed in an individual Pyrex beaker, and a chosen electrolyte added to a depth of
2 inches.

5. Preliminary trials
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One published recipe for ‘battery acid’ stipulates concentrated sulphuric acid
diluted with 12 times its weight of water, giving a concentration of 4.6% by volume.
This solution was made by slowly stirring 230 ml of ‘Analar’ acid into 5 litres of
cold tap water, and then allowing the mixture to cool overnight to room temperature
before storing in a polythene carboy. This electrolyte was used in some prelimin-
ary trials:
$ Evolution of hydrogen. When one of the above commercial zinc electrodes was
placed in the dilute sulphuric acid, hydrogen was evolved from its surface,
while a copper electrode appeared inert. However, when the pair were joined
by a wire, or touched together beneath the surface of the electrolyte, hydrogen
evolution transferred to the copper. The zinc became coated with a finely
divided black coating of copper, and a much lower amount of hydrogen was
evolved from its surface. Present-day safety regulations concerning mercury
made trials with amalgamated zinc electrodes impracticable. (See below.)
$ Variation of p.d. with time. A freshly abraded virgin Cu/Zn pair made up as
above was connected to the digital multimeter, the latter being switched to

Figure 1. Construction and dimensions of copper/zinc electrode pairs.

 Early Voltaic Batteries: an Evaluation in Modern Units 379

indicate millivolts. The electrodes were then plunged into the standard dilute
sulphuric acid, and the p.d. from time zero was noted. An initial voltage of
1.05 V fell rapidly along a descending exponential curve, appearing to bottom
out at 0.88 V between the fifth and tenth minutes. However, this voltage was
not stable: agitation dislodged bubbles and caused it to rise temporarily. After
24 h without disturbance, when a uniform black film coated the zinc, the p.d.
appeared fairly stable at 0.96 V.
$ Series connection. Cu/Zn pairs were connected one by one in series, and the
open-circuit potential was measured in each case with the electrometer. Always
the overall p.d. was additive, and corresponded to 0.96 V per cell. This was
independent of electrode area.
$ Shared electrolyte. Placing a number of series-connected cells into a common
bath of electrolyte caused the potential to fall to close to that of a single cell.
The interior electrodes are shorted out, and only the extremities remain effect-
ive. It is therefore essential to isolate each metallic couple within its own
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watertight container of electrolyte: all historical batteries did this.

$ Other electrode pairs. Silver|zinc|H SO gave an open circuit p.d. of 1.01 V,
2 4
while carbon|zinc|H SO climbed to 1.34 V.
2 4

6. Cu/Zn open-circuit potentials with various electrolytes

A number of electrolytes were made up in tap water (Table 1). Faraday (note 5)
initially used 4.5% v/v sulphuric acid, later preferring 2.5% v/v plus 2% nitric acid.
Exact quantities of other solutes are rarely given in the older literature, so concentra-
tions of 4.6% by volume for liquids, and 4.6% by weight for solids, were employed.
The open-circuit potentials given in the final column were derived from measure-
ments on five Cu/Zn cells in series, using the circuit given below. This was judged
to give a more accurate figure, averaging out any cell-to-cell variation. It was always
higher than when a load was connected across the terminals of the battery. It
appeared to be comparatively stable and reproducible for a given assembly, but
sometimes apparently identical single cells gave slightly different numerical values.

7. Cells in series: the influence of various electrolytes

Five of the Cu/Zn couples shown in Figure 1 were secured at intervals along a
Perspex bar and connected in series. The assembly was then wired into the circuit
shown in Figure 2.
A chosen electrolyte was then added to each cell with the switch open, so that
the electrometer indicated the open-circuit p.d. of the battery. One-fifth of this
voltage is shown in Table 1. The resistance box was then set to 1000 V, the switch
closed, and both meters were read. Alternative resistors of 300, 100, 30, 10, 3, and
1 V were then inserted in this order, and the corresponding voltage and currents
noted. Periods of at least 2 min were allowed for the initially falling values to
stabilize, but reproducibility was hard to achieve. A second run (i.e. after a cell or
battery had been connected to the lowest resistance) always gave lower—but more
reproducible—results. These values were adopted for the work recorded here, the
numerical data being concisely presented as log–log plots in Figures 3–5.
 380 Allan A. Mills

Table 1. Electrolytes used.

References P.d. per Cu/Zn

Electrolyte Composition (Note numbers) couple ( V )

1 Sulphuric acid 3–5,15,20,21 0.96

2 Hydrochloric acid 22 0.82
3 Nitric acid 21–23 0.72
4 (1)+sodium dichromate 24–26 1.02
5 (1)+potassium permanganate 21 1.00
6 (1)+nitric acid 5,12,18,19,27 0.82
7 (2)+nitric acid 22 0.64
8 (1)+alum 17 0.94
9 (3)+alum 28,29 0.62
10 Alum 17 1.02
11 Potassium hydroxide 5,21 1.12
12 Citric acid — 0.92
13 Acetic acid — 1.00
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14 Sodium chloride 1,3,17,21 0.78

15 Ammonium chloride 30 0.76

Figure 2. Circuit for measuring the characteristics of various batteries.

20 Robert Hare, ‘Calorimotor’, Silliman’s Journal, 1 (1818), 413–23.

21 James P. Joule, ‘On the Intermittent Character of the Voltaic Current in Certain Cases of
Electrolysis; and on the Intensities of Various Voltaic Arrangements’, Philosophical Magazine, 24
(1844), 106–15.
22 J. B. Rogers and J. Green (note 13).
23 William Cruickshank, ‘Description of Mr Pepys’ Large Galvanic Apparatus’, Philosophical
Magazine, 15 (1803), 94–96.
24 Robert Bunsen, ‘Ueber die Anwendung der Kohle zur Volta’schen Batterie’, Annalen der Physik,
54 (1841), 417–20.
25 R. Warrington, ‘On the Employment of Chromic Acid as an Agent in Voltaic Arrangements’,
Philosophical Magazine, 20 (1842), 393–95.
26 J. C. Poggendorff, ‘Uber die mit Chromsäure konstruirten galvanischen Ketten’, Annalen der Physik,
57 (1842), 101–11.
27 J. G. Children, ‘An Account of Some Experiments with a Large Voltaic Battery’, Philosophical
Transactions, 105 (1815), 363–74.
28 H. Davy (note 10, 1808).
29 H. Davy (note 10, 1810).
30 W. Cruickshank, ‘Additional Remark on Galvanic Electricity’, Nicholson’s Journal, 4 (1801),
254–64.
 Early Voltaic Batteries: an Evaluation in Modern Units 381

7.1. Voltage versus load

The variation of voltage of the five-cell Cu/Zn batteries with external load is
shown in Figure 3. The following can be observed.
(a) Potentials always dropped as soon as a load was connected, the degree of
diminution increasing as the load resistance decreased.
(b) Three families of curves may be distinguished. In terms of decreasing e.m.f.
we have the following: electrolytes 3–7, strong mineral acids, either them-
selves oxidizing or with oxidizing additives; electrolytes 1 and 2, dilute
sulphuric and hydrochloric acids; electrolytes 8–15, organic acids, salts, bases.
(c) The oxidizing electrolytes 3–7 are able to remove nascent hydrogen by
oxidizing it to water (see note 5) so can act as depolarizers to remove or
diminish the film on the copper electrode. These electrolytes therefore exhibit
comparatively good voltage versus load characteristics at all loads. A mixture
of sulphuric and nitric acids discovered empirically by Davy (see note 19; he
referred to the second component as ‘nitrous’ acid) was especially favoured
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by early electricians.
(d) Dilute sulphuric (1) and hydrochloric acid (2) are comparable electrolytes.
Their curves tend to be an order of magnitude below those of the oxidizing

Figure 3. Voltage versus load behaviour of a five-cell Cu/Zn battery filled with various
electrolytes identified in Table 1.
 382 Allan A. Mills

mixtures, presumably being dependent on diffusion and aerial oxidation for

depolarization.
(e) Organic acids and bases may show a reasonable open-circuit potential, but
voltage falls rapidly even when resistances as high as 1000 V are connected
across the electrodes. The curves tend to be two orders of magnitude inferior
to oxidizing strong acids.
(f ) Alum (10) shows anomalous behaviour, holding up rather better than most
salts. Perhaps this is why it was sometimes used by Davy (see notes 17, 28,
and 29) but it was found here that adding it to sulphuric or nitric acids
always reduced their performance. (Curves omitted for clarity.)
(g) The salts sodium chloride (14) and ammonium chloride (15) are extremely
poor electrolytes with the Cu/Zn couple. Nevertheless, their potential does
not fall completely to zero, so they could be (and were) used with high-
resistance loads and/or sensitive detectors. (A frog’s leg is a remarkably
sensitive detector.) Corrosion currents can be important in the degradation
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of structures built of more than one metal, especially in the marine environ-
ment. Thus, Davy’s idea of fixing zinc plates in contact with the copper
sheathing of wooden ships certainly protected the copper against dissolution
as cupric ions—but had the unfortunate result of then allowing barnacle
larvae to settle and flourish.

7.2. Voltage versus current

Figure 4 summarizes the voltage versus current behaviour of the five-cell Cu/Zn
battery with various electrolytes. It will be seen that the disturbing effect of varying
polarization makes these parameters far from proportional, one reason why Ohm
had so much difficulty getting his relationship accepted. Three families of curves are
again apparent, with oxidizing strong acids much the best.

7.3. Power
Power supplied is often the most important criterion, and milliwatts versus load
are plotted on log–log axes in Figure 5. As would be expected, the oxidizing strong
acids are much the best, the five-cell sulphuric acid/sodium dichromate battery
peaking with some 2 W into a 3–10 V external load. Nitric acid alone, or its mixture
with sulphuric acid (‘nitro-sulphuric acid’), is, however, satisfactory, and much more
pleasant to use. Pure dilute sulphuric and hydrochloric acids work, but tend to be
an order of magnitude less efficient. Other electrolytes are four orders of magnitude
inferior, and are typified by sodium chloride in Figure 6.

8. The maximum power theorem

It was soon observed that a particular arrangement of batteries best suited a
given load. Thus, in 1831, Henry31 reported that the pull of an electromagnet could
be increased by winding more turns of wire upon it—but only up to a certain limit.
After that point, either the additional turns had to be connected in parallel with
those already present, or a battery with more pairs of plates had to be utilized.
According to King (note 15) the existence of an optimum match was first clearly
31 Joseph Henry, ‘On the Application of the Principle of the Galvanic Multiplier to Electromagnetic
Apparatus, and also to the Development of Great Magnetic Power in Soft Iron, with a Small Galvanic
Element’, American Journal of Science, 19 (1831), 400–08.
 Early Voltaic Batteries: an Evaluation in Modern Units 383
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Figure 4. Voltage versus current characteristics of five-cell Cu/Zn battery with electrolytes
1–15, omitting 8 and 9.

recognized by Jacobi in 1844. Now known as the maximum power theorem,32 it

states that the power dissipated in an external load is greatest when its resistance is
equal to that of the cell, battery, or other source of e.m.f.
Figure 5 indicates that the effective electrolytes 1–5, when used in this particular
size of Cu/Zn battery, give maximum power with loads of a few ohms. Nitro-
sulphuric acid (6) was exceptional in peaking off the graph at about 0.5 V. These
values for internal cell resistance are in general agreement with those deduced by
application of Kirchhoff ’s laws.33

9. Cells in parallel: influence of electrode area

The simplest voltaic cells contain rectangular copper and zinc electrodes of
identical size, disposed parallel to one another and separated by a narrow gap
0.25–0.5 inches wide.34 There is, however, no a priori reason why this should be the
optimum arrangement: early researchers simply copied Volta, who in turn was
(unconsciously?) influenced by his pile of discs. In the course of time dissimilar
32 G. R. Noakes, A Textbook of Electricity and Magnetism (London: Macmillan, 1948), pp. 147–48.
33 Ibid., pp. 141–46.
34 F. C. Bakewell (note 15).
 384 Allan A. Mills
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Figure 5. Power versus external load characteristics for a five-cell Cu/Zn battery with electro-
lytes 1–7.

dimensions and other dispositions were considered,35,36 but the classic system of
parallel electrodes of identical size stood the test of practicality and economy.
The wide-ranging curiosity of William Wollaston did, however, cause him to
question the contribution of the side of the zinc facing away from the copper. He
suggested placing a second copper anode, electrically connected to the first, on the
far side of the zinc.37 The latter would therefore be suspended between two copper
anodes, care being taken that an electrolyte-filled gap was maintained around all
three electrodes. Subsequent workers tried this ‘double-copper’ arrangement, and
reported apparent improvements in performance (notes 5 and 37).
Quantitative investigations of these area-related parameters were made with new
supplies of the 0.03-inch zinc and copper sheet used in the ‘series’ investigations
above. The metals were abraded with medium-grade alumina paper, and then
guillotined into strips 14 inches long by 1, 2, 4, and 6 inches wide. Flexible insulated
wires were soldered to a narrow edge of each. The electrodes were then assembled
into the following configurations using 0.25-inch PVC spacers and nylon screws:
35 J. B. Rogers and J. Green (note 13).
36 C. Binks, ‘On Some of the Phaenomena and Laws of Action of Voltaic Electricity, and on the
Construction of Voltaic Batteries’, Philosophical Magazine, 11 (1837), 68–89.
37 J. G. Children (note 27).
 Early Voltaic Batteries: an Evaluation in Modern Units 385
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Figure 6. Power versus external load for a five-cell Cu/Zn battery with a sodium chloride
electrolyte (14).

(a) simple Cu–Zn pairs;

(b) ‘double-copper’ assemblies, Cu–Zn–Cu;
(c) Cu–Zn pairs, but with the outside face of the zinc covered with waterproof
self-adhesive vinyl sheet.
Each assembly was clamped vertically in an individual glass measuring cylinder, and
an electrolyte added to give an immersed depth of 12 inches. Two electrolytes were
chosen from Table 1: dilute sulphuric acid (1) and nitro-sulphuric acid (6). The
circuit diagrammed in Figure 2 was then used to measure e.m.f. and current at
various loads.

9.1. Sulphuric acid

The numerical results are again too numerous to quote, but are summarized in
Figure 7. The susceptibility of this electrolyte to current-dependent polarization gave
a rather complex picture, but the following were found.
(a) The greater the area (as would also be obtained by connecting identical
single cells in parallel ), the better the e.m.f. (and so current) holds up as the
load resistance decreases.
(b) A ‘double-coppered’ zinc strip is nearly equivalent in performance to a
‘single-copper’ cell of twice its width (e.g. a 2-inch ‘double copper’ cell
approximates a 4-inch ‘single copper’ cell ).
(c) Covering the far face of the zinc electrode in a ‘single-copper’ cell with an
insulating film produces only a slightly deleterious effect.
 386 Allan A. Mills
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Figure 7. Voltage versus load for Cu|Zn|H SO cells of constant length (12 inches) but
2 4
various widths, showing the influence of surface area: curve a, 6-inch double copper;
curve b, 6-inch single and 4-inch double copper; curve c, 4-inch single copper; curve
d, 2-inch double copper; curve e, 1-inch single copper.

It does then appear that Wollaston’s speculation was correct: the far face of the zinc
contributes only a little (estimated at 10%) to the current-holding capacity of the
simple cell. ‘Double coppers’ greatly improve performance. Nevertheless, the fact
that a black film appears on both faces of the zinc in the elementary cell shows that
copper ions do reach the distal face.

9.2. Nitro-sulphuric acid

This oxidizing electrolyte gives a simpler picture (Figure 8). Elimination of
polarization at the lower current levels results in a horizontal line of constant voltage

Figure 8. Voltage versus load for Cu/Zn electrodes of constant length (12 inches) but varying
width immersed in nitro-sulphuric acid (6): curve a, 4-inch single and 2-inch double
copper; curve b, 1-inch double copper; curve c, 1-inch single copper. Also shows the
behaviour of modern dry cells.
 Early Voltaic Batteries: an Evaluation in Modern Units 387

(820 mV ) for both ‘single’ and ‘double’ electrodes of all widths. However, when the
external load is less than 30 V and the current taken exceeds some 50 mA, the e.m.f.
delivered by the 1 inch × 12 inch single electrodes begins to fall. The wider and
doubled arrangements maintain the potential for the greater currents passed by 10 V
loads, up to about 150 mA with 4-inch ‘double coppers’. Figures 9 and 10 show
how power continues to be delivered into still lower external resistance loads
(10–1 V), but the e.m.f. can drop to as low as 600 mV.
The advantages of increased area and ‘double coppers’ in maintaining the voltage
are again illustrated. Of course, larger (and thicker) zincs also last longer when the
cell or battery is delivering a given power.

9.3. Modern ‘dry’ cells

These consist of a graphitic carbon rod surrounded by a concentric cylinder of
zinc foil. The annular gap is filled with an immobilized moist electrolyte containing
complex zinc–ammonium ions. For comparison with the early cells, ‘Duracell’ brand
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cells of various sizes were tested. (It is common to refer to single cells as ‘batteries’
nowadays.)
Results for a new D-size cell (the largest commonly available) and the tiny AAA
cell (which had been in storage for many months) have been added to Figure 8. It
will be seen that, as before, the larger the physical size the better the e.m.f. stands
up under conditions of increasing current drain. Storage resulted in a general
depression of the e.m.f. available.

Figure 9. Current versus voltage for Cu/Zn electrodes of various widths immersed 12 inches
in nitro-sulphuric acid (6): curve a, 2-inch double copper; curve b, 2-inch single
copper; curve c, 1-inch double copper; curve d, 1-inch single copper.
 388 Allan A. Mills
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Figure 10. Power versus load for Cu/Zn electrodes of various widths immersed 12 inches in
nitro-sulphuric acid (6): curve a, 2-inch double copper; curve b, 2-inch single copper;
curve c, 1-inch double copper; curve d, 1-inch single copper.

10. Some well-known early batteries and applications

Conventional historians (historians of events) cannot travel back in time to
investigate their subjects firsthand, or alter their environment, so are necessarily
greatly dependent on documentary evidence. Historians of science are potentially
more favourably placed: scientific experiments should (by definition) be repeatable
by anyone at any time, with identical results. Regrettably, this valuable additional
mode of investigation is rarely practised. Some classic experiments in the history of
electrochemistry will now be examined, applying the data gained in the above
experimental sections to supplement the information given in well-known biographies
and reviews.

10.1. Nicholson and Carlisle’s voltaic pile

Very soon after learning of Volta’s work, the surgeon Anthony Carlisle observed
the evolution of minute bubbles of gas around an iron wire placed on one plate of
a voltaic pile when a drop of water was used to improve the connection. This pile
consisted of 36 sterling silver half-crowns separated by corresponding 1.25-inch
diameter discs of zinc and pasteboard, the latter moistened with saline. William
Nicholson suspected the gas to be hydrogen (from its smell ).
Together, Nicholson and Carlisle38 pursued this chance observation with
improved apparatus. This incorporated brass wires inserted through corks closing
the ends of a 0.5-inch glass tube filled with water. The tips of the wires were
positioned about 1.75 inches apart. A fine stream of bubbles was observed to rise
from the wire connected to the silver termination of the pile, while the other brass
38 See note 2.
 Early Voltaic Batteries: an Evaluation in Modern Units 389

wire became tarnished and oxidized. The evolved gas was confirmed to be hydrogen
by its inflammability. Repetition with platinum wires gave gaseous oxygen in addition
to the hydrogen previously observed.
A quantitative experiment was then conducted with a freshly assembled pile
containing 68 Ag/Zn pairs connected to platinum electrodes in water. This time,
however, arrangements were made to collect both the evolved gases. The authors
state that the hydrogen released over a period of 13 h displaced 142 grains of water,
equivalent to a volume of 9.2 ml at room temperature.
These observations prove that the currently common idea that the voltaic pile is
incapable of work is not entirely true. I found the open-circuit potential between a
Victorian (1894) half-crown and a freshly abraded zinc plate, when separated by
cloth moistened with 5% saline, to be initially 1.00 V. I also found that a minimum
potential of 3.0 V (from a modern power pack) was required to produce visible
evolution of gases from platinum wires positioned about 1 mm apart in a brightly
illuminated drop of tap water. (This figure is higher than might be expected because
of the phenomenon of overvoltage when a gaseous product is involved.) So, although
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the 36 or 68 V open-circuit potentials expected from the Nicholson and Carlisle piles
must have dropped when the electrolysis apparatus was connected across their
terminal plates (terminals), it must still have exceeded 3 V.
It is possible to estimate the average current flowing from the data given by the
experimenters. First, from the gas laws, 9.2 ml of hydrogen at room temperature (say
17 °C ) correspond to 8.7 ml at 0 °C. Now, hydrogen has a density of 0.0899 g/litre
at standard temperature and pressure (STP), so 8.7 ml must weigh 0.78 mg. Faraday’s
law states that 1.00 g of hydrogen is released by the passage of 96 500 C (ampere
seconds), so 0.78 mg of the gas is liberated by 75.3 C. Thirteen hours contain 46 800 s,
so the average current flowing was 1.6 mA. The total resistance of the circuit (pile
plus water drop) would have to have exceeded 1875 V. The measurements reported
above confirm that these figures are feasible for a freshly assembled pile of comparat-
ively large silver and zinc discs connected to a high-resistance load. Because of
corrosion and drying-up, such a pile is not expected to remain active for more than
a few days. The indefatigable Wollaston reported in a letter to a friend39 that an
extensive pile of silver and zinc discs was not necessary to accomplish the electrolysis
of water. He claimed that three (or even two) shillings were sufficient. This would not
be expected from my measurements above, and I have been unable to confirm his
extreme claim. A five-coin pile gave an open-circuit potential of 4.8 V on the electro-
meter, but when connected to two 0.3 mm platinum wires dipping into a drop of
water the e.m.f. fell to 3.7 V. A current of 0.3 mA flowed, and after a minute or two
it was possible to see tiny bubbles adhering to the platinum wires. There can be no
doubt that the prompt discovery of the electrolysis of water was facilitated by the
fact that its gaseous decomposition products are readily visible at the microgram level.

10.2. Humphry Davy: use of nitric acid in voltaic cells

The invention of the voltaic pile led Humphry Davy to begin his brilliant
researches in electrochemistry.40 In particular, his initial studies led him to emphasize
39 William H. Wollaston. Letter to Henry Hasted, 6 June 1800. Quoted by M. C. Usselman,
‘Wollaston’s Microtechniques for the Electrolysis of Water and Electrochemical Incandescence’, in
Electrochemistry, Past and Present, ACS Symposium 390, ed. by J. T. Stock and M. V. Orna (American
Chemical Society, 1988), Chapter 2, pp. 20–31.
40 Harold Hartley, Humphry Davy (London: Nelson, 1966); Science and the Sons of Genius: Studies
on Humphry Davy, ed. by Sophie Forgan (London: Science Reviews Ltd, 1980); David Knight, Humphry
Davy: Science and Power (Cambridge: Cambridge University Press, 1992).
 390 Allan A. Mills

the importance of oxidation of the zinc (a pile would not work if isolated from the
air) and to discover the improved performance consequent on moistening the porous
barriers with dilute nitric acid.41 Although he was later to modify his theoretical
views,42 this is doubtless why he incorporated this oxidizing reagent in electrolytes
for batteries, with the order-of-magnitude improvement quantified above.

10.3. Humphry Davy: the composition of water

Davy was puzzled by the traces of alkali left on evaporation of water that had
been extensively electrolysed to yield hydrogen and oxygen. He believed that pure
water consisted solely of these gases in combination, so hypothesized that the solids
must have come from the glass still used to purify the water, or the vessels employed
to contain it. He therefore constructed a silver still and (realizing the possibility of
contamination by spray generated by bursting bubbles) operated it in film-boiling
mode. When the resulting very pure water was subjected to electrolysis it gave
hydrogen and oxygen in the expected ratios, and complete evaporation left no
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solid residue.43 Knight (see note 40) has pointed out the anomaly that really pure
water would have such a low conductivity that the experiment should not have
worked. That it did was almost certainly due to the dissolution of atmospheric
carbon dioxide giving carbonic acid in solution. (It is ‘equilibrium water’, not
‘conductivity water’.)

10.4. Trough batteries

An early form of battery was described in 1801 by Davy and Cruickshank (see
notes 19 and 30). It consisted of a wooden trough with grooved sides, into which
were slid 10–40 plates of copper (or silver) and zinc soldered back to back and
connected in series. The assembly was made watertight and acid resistant with pitch,
and electrolyte added to each cell.
In 1807 Wilkinson (note 7) proposed the improvement of using wooden partitions
to create individual compartments, so that the appropriately supported electrodes
could be raised when out of use. The dimensions of these plates varied from 1D inches
× 1D inches to 12 inches × 12 inches (notes 40 and 41) or even 48 inches ×
24 inches in Children’s huge battery referenced in note 27. Various electrolytes were
used in the early years (see Table 1) but an aqueous mixture of sulphuric and nitric
acids had proved itself generally superior by 1809. A simplified diagram of such a
trough has become the standard symbol for a battery, and is used as such in Figure 2.
When moulded gutta-percha became available, ten-cell troughs containing
4-inch-square electrodes became popular on account of their durability and reduced
weight. Such batteries were used, for example, by Faraday (Figure 11).
A working replica of a ten-cell trough battery was set up by making a wooden
trough to hold ten rectangular polythene vessels. Each contained a pair of 4-inch-
square copper and zinc electrodes (Figure 12). It was first filled with nitro-sulphuric
acid (electrolyte 6) and tested against external loads diminishing logarithmically
from 1000 to 0.5 V in the procedure detailed above. The electrolyte became very
hot. As usual, the second series of results, obtained after the battery had once
delivered its maximum power, was preferred. The procedure was then repeated with

41 See the reference to Davy in note 19.

42 Colin A. Russell, ‘The Electrochemical Theory of Sir Humphry Davy’, Annals of Science, 15
(1959), 1–25.
43 See the reference to Davy in note 17.
 Early Voltaic Batteries: an Evaluation in Modern Units 391
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Figure 11. ‘Faraday mystifies Daniell with a slick demonstration of the 3-cup trick.’ Note the
plunge battery in the background. From an untitled and undated calotype positive in the
possession of the Royal Institution. It must date from before 1845, when Daniell died.
Source: TRI99023 Portrait photograph of Michael Faraday (1791–1867) and John
Frederic Daniell (1790–1845) (photo). The Royal Institution, London, UK/
Bridgeman Art Library.

dilute sulphuric acid (electrolyte 1) in the cells. With this, they became merely warm.
In both cases, an unpleasant fine mist was generated by the bursting bubbles of
hydrogen. Results are displayed in Figures 13–15. They confirm that nitro-sulphuric
acid is much superior to sulphuric acid alone, the former enabling the battery to
maintain 8.0 V out to 50 mA, and 7.8 V with a current of 100 mA. The maximum
power delivered was 15 W into a 0.5 V load, when the battery delivered 8.3 A at
1.8 V. A similar amount of energy was dissipated in the electrolyte as heat. The
sulphuric acid electrolyte gave a maximum power of only 1.6 W into a 1 V load,
represented by a current of 1.2 A at 1.3 V.

10.5. Davy’s isolation of potassium and sodium

Perhaps the best known of Davy’s chemical accomplishments is his isolation of
metallic potassium and sodium by electrolysis of their fused hydroxides. In his
second Bakerian Lecture,44 published in 1808, he explains that in one set-up a small
piece of KOH (which had been exposed to the atmosphere to make the surface
conductive) was placed on an insulated disc of platinum connected to the negative
44 See note 10.
 392 Allan A. Mills
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Figure 12. Reconstruction of a ten-cell Cu/Zn battery, with 4-inch-square plates.

Figure 13. Voltage versus load for a ten-cell, 4-inch-square, Cu/Zn trough battery with
sulphuric (1) and nitro-sulphuric (6) electrolytes.
 Early Voltaic Batteries: an Evaluation in Modern Units 393
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Figure 14. Voltage versus current for the ten-cell trough battery. Sulphuric (1) and nitro-
sulphuric (6) electrolytes.

side of a battery of 100 (or more) plates in a nitric acid and alum electrolyte. A
platinum wire connected to the positive pole was then brought into contact with the
upper surface of the alkali. All was in the open atmosphere. Under these circum-
stances a vivid action was soon observed. The KOH began to fuse at its points of
contact with the platinum electrodes owing to resistive heating, and there was violent
effervescence at the upper surface (anode). At the same time small globules with a
high metallic lustre appeared at the lower surface in contact with the cathode. Some
burnt immediately with explosion and a bright flame, but others persisted down to
room temperature as tarnished liquid metal globules soon covered by a white film.
Davy states that much the same result was obtained if the potash were fused with
an external flame. By subsequent experiments he proved to his own satisfaction that
these globules consisted of the desired potassium, but Knight (see note 40) has
pointed out that their liquid nature at ambient temperatures points to an alloy of
potassium with sodium derived from impure KOH. The fragments of this compound
electrolysed by Davy were stated to be about 4–70 grains (2.5–4.5 g) in weight, and
B inch thick. His battery consisted of 100 Cu/Zn plates, each 6 inches square, in a
nitric acid plus alum electrolyte.
Davy had more trouble with NaOH, being obliged to use smaller pieces only
15–20 grains (1.0–1.3 g) in weight, with the electrodes no more than A inch apart.
However, globules of sodium that survived to room temperature were solid, as
would now be expected for the pure element. Electrolysis of fused NaOH was the
basis of the Castner process for the industrial production of sodium metal,45 which
45 C. H. Lemke and V. H. Markant, ‘Sodium and Sodium Alloys’, in Kirk-Othmer Encyclopaedia of
Chemical Technology, 4th edn, ed. by J. I. Kroschwitz and M. Howe-Grant (New York: Wiley, 1997),
, pp. 327–54.
 394 Allan A. Mills
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Figure 15. Power versus load for the ten-cell trough battery, with sulphuric (1) and nitro-
sulphuric (6) electrolytes.

was used into the 1930s. There is therefore more information concerning mechanism,
with the overall reaction being represented as:
2NaOH
2Na+H +O
agbgc2 2
cathode anode

Individual stages are complex, with the yield of sodium never exceeding 50% of
theoretical on the basis of current consumed.
No information is, of course, available on the electrical parameters of Davy’s
experiments. Table 1 gives 0.62 V for a Cu/Zn couple immersed in nitric acid/alum
electrolyte (9), so his 100-cell battery should have given some 60 V standing potential.
This would have been important in initiating a sufficient current flow to begin fusion,
but would then have fallen drastically depending on the final resistance of the molten
alkali. To give some further semi-quantitative estimates, reconstructions of Davy’s
experiments were attempted. A battered platinum–gold crucible was available as
scrap, and its rim provided a length of wire of the same alloy. The latter was nipped
in the end of a short length of narrow copper tubing by hammering, and the
protruding wire coiled into a flat spiral. The crucible was supported by a silica
triangle, and the wire electrode clamped centrally within it with the horizontal spiral
a short distance above the bottom. Sufficient pellets of pure NaOH were then added
that, when melted with a small bunsen flame, the spiral electrode was covered. An
 Early Voltaic Batteries: an Evaluation in Modern Units 395

ohmmeter indicated a resistance of 0.3–0.5 V, depending on the temperature of the

molten alkali. This is so low that, once it was operating, the voltage across the
platinum electrodes in Davy’s apparatus is thought (from Section 7) unlikely to
have exceeded 10 V, with perhaps 80 W as the maximum power dissipated.
This voltage and power are readily available from a modern 12 V car battery,
so to give further data the crucible assembly above was connected in circuit with
such a source, a 20 A meter, a large 0.4 V variable resistance capable of handling
the currents involved, and a voltmeter between the central positive electrode and
the walls of the crucible. No current flowed until the alkali was remelted with a
small flame, but then electrolysis commenced. Adjustment of the rheostat to give a
current of 15 A, with 4 V across the crucible assembly (60 W ), maintained the alkali
molten in the absence of external heating, and produced vigorous evolution of gases
accompanied by yellow flashes and cracks. This appears to match Davy’s description,
although regrettably I was unable to find any globules of metallic sodium in the
blackened electrolyte when it had cooled. A similar result was obtained with potas-
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sium hydroxide. The platinum–gold crucible was blackened and corroded, and the
experiments had to be terminated when perforation of the base allowed molten
alkali to leak out.

10.6. The Royal Institution battery

The ‘Great Battery’ of the Royal Institution46 was funded by public subscription
for Humphry Davy. It was made up of 200 compartmented ceramic troughs, each
constituting a plunge battery of ten pairs of 4-inch-square copper and zinc electrodes
(i.e. 2000 elementary cells in total ). It was set up in a cellar of the premises in
Albemarle Street (Figure 16), and could be connected in various series/parallel
combinations.
The measurements made above on a single ten-cell battery of comparable con-
struction, and filled with nitro-sulphuric acid, indicate that an all-series connection
should achieve a standing potential of 8 V×200=1600 V. However, once connected
to a load, it could only deliver a current below 50 mA (corresponding to 80 W into
32 kV) before the voltage would start to fall. Nevertheless, the all-series connection
enabled experiments on the electrical discharge in vacuum to be initiated and
maintained.
Higher power outputs could be achieved with lower resistance loads. The ten-cell
battery tested above gave a maximum power of about 15 W delivered into a 0.5 V
load. So, 200 batteries connected in an appropriate series/parallel combination
should put up to 3 kW into a matching load, at the same time dissipating an equal
amount of energy as heat within the total electrolyte. Some combinations achieving
this might be those which resulted in the following:

Volts Amps Load (V)

100 30 3.3
50 60 0.8
17 176 0.1
12 250 0.05

46 See H. Davy (note 10, 1810).

 396 Allan A. Mills
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Figure 16. The 2000-cell ‘Great Battery’ built by Humphry Davy in a cellar of the Royal
Institution, London.

The last line of figures above shows that the maximum power output of the huge
Royal Institution battery was comparable with that put out by a modern lead–acid
secondary battery when starting a car on a cold morning.

10.7. Nitric acid and load-matching

Davy, Faraday, and Sturgeon achieved their epoch-making results by rarely
using the textbook electrolyte of dilute sulphuric acid alone, but commonly added
a vital proportion of nitric acid. This acted as an oxidant to reduce polarization,
and promoted an order of magnitude greater output of electrical power.
A second factor in their success was an unrealized application of the maximum
power theorem. Trough batteries have a low internal resistance (a few hundredths
of an ohm per cell ) and therefore give maximum output into low-resistance loads.
Most of the early electrical experiments embodied these high-current, low-voltage
characteristics, and were connected up with thick copper wire. If the experiment had
a higher inherent resistance, then groups of trough batteries were empirically con-
nected in mixed series/parallel arrangements to approach an optimal match.

11. Faraday and mercury poisoning

It has been explained in Section 2 that amalgamation of zinc electrodes with
metallic mercury was employed to extend the life of Cu/Zn batteries by preventing
the ‘local action’ experienced with metal of commercial quality. Davy examined the
 Early Voltaic Batteries: an Evaluation in Modern Units 397

electrochemical properties of zinc amalgam in 1826, but its general application to

batteries was first promoted by Kemp in 1837 (see note 8). The procedure involved
no more than pouring a few drops of mercury upon the faces of an abraded zinc
electrode, and rubbing with a cloth moistened with dilute sulphuric acid. Setting up
just one ten-cell battery with 6-inch plates would generate 5 square feet of glistening
mercury-rich surfaces, their cleanliness facilitating evaporation of the element into
the atmosphere. Evolution of mercury vapour would presumably be minimized when
the battery had been filled with electrolyte but, ironically, would re-commence as
soon as it was emptied and placed on a shelf for storage. The poorly ventilated
basement laboratory of the Royal Institution must have been heavily loaded with
mercury vapour whenever (after 1837) batteries were being constructed, ‘re-charged’,
or stored, and the contamination would have been exacerbated if (as so easily
happens) globules of mercury ran into inaccessible cracks, particularly near the
furnace.
It was not then appreciated that mercury vapour is toxic because of absorption
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via the lungs and concentration in the brain. The fact that the liquid metal was
administered as a recognized medical treatment was probably taken to indicate
relative harmlessness, but is misleading since little absorption occurs in the gut.
Concern about mercury in the environment has led to much more critical investi-
gation in recent decades, and it is now recognized that a variety of subjective
complaints such as headache, confusion, depression, feelings of weakness, and
impaired memory may be associated with chronic exposure to sub-acute levels of
mercury vapour.47 Once removed from the source of the latter, the body can slowly
eliminate combined mercury and substantial recovery follows.
It is well known that Michael Faraday experienced the above symptoms, particu-
larly from 1839 to 1844, and that a long holiday away from his beloved laboratory
worked wonders on all but his loss of memory.48 One might well speculate that a
naturally poor memory was exacerbated by long-term exposure to mercury vapour.49
Hare50 disagreed with this hypothesis, saying that it should have been manifest
during Faraday’s early years at the Royal Institution, but appears unaware that
large-scale amalgamation of zinc in multi-cell batteries only became general from
1838. He also confused the toxicology of mercury ingested as its compounds with
that of the element inhaled as vapour.

12. Conclusions
Quantitative studies of the performance of voltaic cells (mainly Cu/Zn) have
confirmed the superiority of aqueous solutions of strong inorganic acids as activating
electrolytes. The addition of oxidizing agents (e.g. nitric acid, dichromate ions) much
reduces polarization, and enables significant power to be delivered: Davy and

47 W. V. Farrar and A. R. Williams, ‘Mercury as a Poison’, and K. H. Falchuk, L. J. Goldwater and

B. L. Vallee, ‘The Biochemistry and Toxicology of Mercury’, both in The Chemistry of Mercury, ed. by
C. A. McAuliffe (New York: Macmillan, 1977), pp. 36–45 and p. 272 respectively.
48 L. Pearce Williams, Michael Faraday (London: Chapman & Hall, 1965); E. Hare, ‘Michael
Faraday’s Loss of Memory’, Proceedings of the Royal Institution, 49 (1976), 33–52; Geoffrey Cantor,
Michael Faraday, Sandemanian and Scientist (London: Macmillan, 1991), Chapter 10.
49 Alfred Stock, ‘Die Gefahrlichkeit des Quecksilbers’, Zeitschrift für angewandte Chemie, 15 (1926)
461–66.
50 See Hare (note 48).
 398 Early Voltaic Batteries: an Evaluation in Modern Units

Faraday were therefore able to make their pioneering discoveries in electrochemistry

and electromagnetism.
Series connection of single cells results in cumulative addition of their individual
potentials to the resulting battery. Parallel connections may enable higher currents
to be drawn, as does Wollaston’s ‘double-copper’ arrangement. The criterion for
maximum power is that the overall internal resistance of the resulting assembly
should equal the resistance of the load. Many of the classic electrical experiments
and devices were high-current/low-voltage applications. Amalgamation of the zinc
electrodes with mercury improved the life of batteries, and became general after
Kemp’s publication in 1837, but may well have been deleterious to the health of
long-term experimenters such as Michael Faraday.
The early discovery of the electrolysis of water by Nicholson and Carlisle, made
with a classic silver/zinc voltaic pile, was aided by the ready visibility of microgram
quantities of gaseous hydrogen and oxygen. Davy’s proof that very pure water was
made up from these elements alone was made possible by solution of atmospheric
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carbon dioxide raising its conductivity sufficiently to permit electrolysis.

A ten-cell Cu/Zn battery with 4-inch-square plates immersed in the much-used
nitro-sulphuric acid electrolyte was found by experiment to deliver a maximum
power of 8.3 A at 1.8 V (15 W ). The 100-cell 6-inch-square Cu/Zn battery used by
Davy for the isolation of sodium and potassium is estimated to have delivered some
60 W (15 A at 4 V ) under his experimental conditions. The giant 2000-cell battery
of the Royal Institution probably gave no more than 3 kW into a matching load,
with another 3 kW being dissipated as heat within the battery itself.
It is concluded that quantitative basic measurements combined with careful
reconstruction of significant experiments can usefully complement documentary
studies in the history of science.