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Electrolysis: What textbooks don’t tell us

Cite this: DOI: 10.1039/c9rp00218a
Hasok Chang,a Katherine Duncan, a
Kihyang Kimb and Seoung-Hey Paik *b
We present a critical discussion of how chemistry textbooks treat the electrolysis of water and
aqueous salt solutions, based on a survey of general chemistry textbooks in English and Korean at
secondary and tertiary levels, also informed by the historical background of 19th-century debates.
Published on 23 March 2020. Downloaded on 6/3/2020 1:31:40 AM.
English-language textbooks present various and contradictory accounts of the electrolysis of water; a
key point of disagreement is whether hydrogen and oxygen gases originate from pre-existing H+ and
OH ions, or from the direct reduction and oxidation of H2O molecules. School textbooks in South
Korea all present the same account, with no indication of alternative views. A vast majority of all texts
ignore the possibility that H2 and O2 may result from secondary reactions, which was a standard view
in the late 19th century following the works of Daniell and Miller. Concerning the electrolysis of
aqueous salt solutions, all texts give oversimplified views of competing reactions based on standard
reduction/oxidation potentials. It is understandable that textbooks try to present sufficiently simple
Received 26th September 2019, pictures that students at each level can handle; however, this should not be done in a way that shuts
Accepted 22nd March 2020 down questions. We recommend that students should be made aware that textbook accounts are
DOI: 10.1039/c9rp00218a only models, and encouraged to extend their learning beyond the models. The plausibility of our
recommendations is shown in a pilot study we conducted with secondary school students in
rsc.li/cerp South Korea.
Introduction at the anode: 4OH (aq) - 2H2O(l) + O2(g) + 4e .
The electrolysis of water and aqueous salt solutions is a common In contrast, Pauling and Pauling (1975, p. 356) present the
and significant subject in chemistry instruction. The experiments reactions as the reduction and oxidation of whole H2O mole-
are easily performed, the expected results are simple, and the cules, as follows:
theoretical implications are important. However, those who have
thought much about the subject will easily admit that there are at the cathode: 4e + 4H2O - 2H2 + 4OH ,
many difficult underlying issues. Our inquiry began when we
realized that there were some points on which different textbooks
at the anode: 2H2O - O2 + 4H+ + 4e .
gave mutually conflicting accounts. The most salient point of
divergence is whether the hydrogen and oxygen gases produced
While H2 and O2 are released as gases, the OH and H+ ions
in the electrolysis of water are formed by the reduction and
produced at the opposite electrodes eventually meet and com-
oxidation of pre-existing H+ and OH ions formed by the
bine with each other to re-form water molecules. In addition to
spontaneous dissociation of water molecules, or by a direct
the equations quoted above, Pauling and Pauling also provide
decomposition of H2O molecules occasioned by the application
quite a literal picture of how these reactions are meant to take
of electricity. For example, Schmit and Pollard (2016, p. 132)
place at the molecular level (see Fig. 1).
give the story of the oxidation and reduction of OH and H+
Some other textbooks give a mixed picture, in which one
ions, as follows:
reaction is the oxidation or reduction of H2O but the other
reaction is the reduction or oxidation of the H+ or OH ion. For
at the cathode: 4H+(aq) + 4e - 2H2(g),
example, Oxtoby et al. (2016, p. 744) give the following account
(writing H3O+ instead of H+):
a
University of Cambridge, Department of History and Philosophy of Science,
Cambridge, Cambridgeshire, UK at the cathode: 2H3O+ + 2e - H2 + 2H2O,
b
Chemistry Education, Korea National University of Education, Taesungtapyuonro
250 Heungduk Gu, Chungju, Chungbuk 363-791, Republic of Korea.
E-mail: shpaik@knue.ac.kr at the anode: 3H2O - (12)O2 + 2H3O+ + 2e .
This journal is © The Royal Society of Chemistry 2020 Chem. Educ. Res. Pract.
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Paper Chemistry Education Research and Practice

Fig. 1 The ‘‘whole H2O’’ account of the electrolysis of water, from Pauling and Pauling (1975, p. 357).
Historical background: the rise and fall of But entering into any level of detail revealed a number of
the Daniell–Miller theory of electrolysis difficulties.
Particularly instructive for our purposes is the work of John
Before entering into our survey of modern textbooks it would be Frederic Daniell (1790–1845), the first Professor of Chemistry
useful to give a brief historical introduction, in order to provide at King’s College London. His name remains recognizable
some background and to highlight some basic long-standing through the ‘‘Daniell cell’’ featured ubiquitously in modern
questions. Electrolysis was one of the earliest and most exciting lower-level textbooks. He invented that configuration of battery
phenomena uncovered through Alessandro Volta’s invention of in 1836, and the main thing he did with it was to investigate
the battery, but it was also a difficult one to explain theoretically. In electrolysis, reaching an important insight that the final products
retrospect, that is perfectly understandable. Electrolysis was dis- of electrolysis were not necessarily the actual components of the
covered almost a century before the discovery of the electron, or electrolyte. As T. M. Lowry (1929) explained: ‘‘When these primary
Svante Arrhenius’s conception of ionic dissociation. Many theore- products are liberated, they frequently undergo decomposition or
tical accounts of electrolysis came and went (Chang, 2012, ch. 2), chemical change, giving rise to secondary products by interacting
but a lasting general idea was that there must be electro- with one another, with the electrode, or with the electrolyte.’’
negative and electropositive components of molecules, which For example, ‘‘in the case of a solution of sodium chloride, the
moved to the positive and negative electrodes, respectively. sodium atoms immediately attack the water, giving caustic
Chem. Educ. Res. Pract. This journal is © The Royal Society of Chemistry 2020
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Chemistry Education Research and Practice Paper
soda [NaOH] and hydrogen, whilst the chlorine atoms unite in and the water is then resolved into oxygen and hydrogen by a
pairs to form gaseous chlorine.’’ (Lowry, 1929, p. 321) The same secondary action in the manner already explained.’’ Take, for
analysis of NaCl electrolysis is also given in J. W. Mellor’s classic example, the electrolysis of sodium sulphate, which Miller
textbook on inorganic chemistry (Mellor, 1951, p. 497). Any expressed as follows:
chemists would still accept the general view that there are
2Na2SO4 - 2Na2 + 2SO4 (primary action), followed by
primary and secondary products of electrolysis. However, when
it comes to the electrolysis of water most modern textbooks seem
2Na2 + 4H2O - 4NaOH + 2H2 (secondary action), and
to shy away from this well-established insight.
In a long series of experiments Daniell investigated the
2H2O + 2SO4 - O2 + 2H2SO4 (secondary action).
electrolysis of aqueous salt solutions. His first breakthrough came
with the electrolysis of a strong NaCl solution with a platinum One might imagine that the production of hydrogen and
cathode and tin anode (Daniell, 1839, p. 108). Much hydrogen gas oxygen gases would stop soon when it exhausts the added
was evolved from the cathode, but no oxygen at the anode; instead electrolyte; however, the 4NaOH and 2H2SO4 produced by the
the tin anode was dissolved, and the amount of tin dissolved was secondary reactions would combine with each other, to re-form
the chemical equivalent of the hydrogen produced at the other 4H2O and 2Na2SO4. So the net result is that two water mole-
side. Daniell now composed a novel interpretation: ‘‘chloride of cules are decomposed, and the sodium sulphate is recovered
sodium was decomposed . . . the chlorine of the latter being exactly (having worked as a catalyst). So this reaction can go on
absorbed by the tin [anode], and the sodium at the [cathode] indefinitely. All in all, Miller declared: ‘‘it is manifest that water
reacting upon the water, and giving rise to the secondary result of itself is not an electrolyte, but it is enabled to convey the current
an equivalent of hydrogen: upon this hypothesis, the current must if it contain only faint traces of saline matter.’’
have been transmitted by the chloride of sodium alone, and no We will call this the ‘‘Daniell–Miller view’’ of the electrolysis
water was electrolyzed.’’ In understanding such accounts we need of water and aqueous solutions. It introduced a clarity that was
to keep in mind that the Arrhenius theory of ionic dissociation was lacking before. For one thing, it assigns a precise role to the
still long in the future. added electrolyte in the electrolysis of water (unlike many of
Daniell recognized the possibility that the production of today’s textbooks, as we will show below). It also makes it clear
oxygen and hydrogen in the electrolysis of an aqueous solution that the electrolysis of water is the electrolysis of an aqueous
may not be an indication that water was being electrolyzed (if solution, just at the low-concentration limit.
‘‘electrolyzed’’ means being decomposed by the direct action of This view came to be widely accepted for a time, but hardly
electricity). In a follow-up paper, Daniell (1840, p. 219) concluded any trace of it can be found in today’s textbooks. The only
that the current flowing through a salt solution could ‘‘divide itself’’ textbook examined in our survey that features this view is the
between acting on the water and acting on the dissolved salt, rather old text by Andrews and Kokes (1962, p. 470), in its
decomposing some of each. This is not a possibility recognized in discussion of the electrolysis of sodium chloride solution.
most modern textbooks. In order to make this idea plausible, he (In modern specialist literature the production of Na in the
drew an analogy to the ‘‘well known fact that the voltaic current will electrolysis of an NaCl solution is admitted in exceptional
divide itself between two or more metallic conductors in inverse cases; for example, according to Pletcher (2009, pp. 202–203),
proportion to the resistance which each may offer to its course.’’ on a mercury cathode a sodium amalgam (Na–Hg) will form.)
This view was developed into a more decisive form by Why did the Daniell–Miller view disappear so completely, when
Daniell’s successor William Allen Miller (1817–1870) (Miller, 1867, it seems to make so much sense? Our best guess is that its
pp. 524–525): ‘‘the evolution of oxygen and hydrogen during the demise was a consequence of a distraction caused by Arrhenius’s
decomposition of such saline solutions is a secondary action.’’ If new theory of spontaneous ionic dissociation, first published in
the electrolyte is ‘‘a salt of a metal which, like copper or lead, 1887. If there are pre-existing H+ and OH ions in water itself,
does not decompose water at ordinary temperatures’’, then ‘‘no then it is not necessary to invoke secondary action to explain how
hydrogen should be evolved, but the metal itself should appear H2 and O2 could be produced.
upon the [cathode]’’. And if the anion of the salt is ‘‘unable to In Max Le Blanc’s well-known early textbook of electrochemistry,
take hydrogen from water at common temperatures, no oxygen the excitement of the ascendant Arrhenius theory is palpable
should be emitted.’’ For example, if a solution of copper (Le Blanc, 1896, p. 267): ‘‘This [Daniell–Miller] conception of the
chloride or lead chloride is electrolyzed, ‘‘the salt is resolved process cannot be called simple, and why the assumption of all
into metallic copper or metallic lead, and chlorine gas, but no these secondary reactions which no one has observed, and
oxygen or hydrogen is liberated.’’ which are in no sense necessary!’’ Le Blanc was quite confident
Miller invoked the well-known fact that ‘‘although water, about the new direction of thinking: ‘‘In electrolysis a primary
when pure, is scarcely decomposed by the current from 100 decomposition of the water takes place.’’ The actual electrical
[voltaic] cells or upwards, yet it appears instantly to become a conductivity is brought about by all the ions in the solution,
good electrolyte on the addition of a few drops of acid, or of but at the electrode that action takes place which proceeds most
solution of a salt of an earth or an alkali’’. In other words, Miller easily, and this is the separation of the hydrogen and hydroxyl
held that water by itself was not electrolyzable, but ‘‘upon the ions.’’ (Le Blanc, 1896, p. 260; emphasis original) To anyone
addition of the salt, it is this body which is decomposed, who might worry that there would not be enough pre-existing H+
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and OH ions in water, Le Blanc offered this reassurance: ‘‘Lack To give an additional and comparative perspective to this
of hydrogen and hydroxyl ions can never occur, since ions must be England-focused survey of English-language textbooks, we made
immediately generated by the undissociated water, the product of a survey of secondary-school chemistry textbooks used in South
the two ion concentrations always having a definite value.’’ Korea, all of them written in Korean. The choice of South Korea
In saying that the ‘‘ions must be immediately generated by is meaningful in giving attention to a high-performing nation in
the undissociated water’’, Le Blanc ignored the question of how the realm of science education in a very different linguistic,
quickly the dissociation of water molecules could happen in cultural and institutional setting from European-origin societies.
order to replenish the supply of the H+ and OH ions used up in the One important factor is that the Ministry of Education in South
formation of hydrogen and oxygen gases. If the reduction/oxidation Korea exerts a strong control over the national curriculum and
of these ions were a faster process than the spontaneous dissociation the approval of textbooks, and as a consequence there is much
of water, then there would be a bottleneck. A century later, Oxtoby more uniformity in the topics covered and their organization,
et al. (2016, p. 744) state that the rate of the electrolysis of water compared to the situation in England.
would be ‘‘exceedingly small’’ unless an electrolyte is added. Indeed, We analyzed the South Korean textbooks that were written to
all the classroom teachers and students doing experiments on the specification of the national secondary-school curriculum
electrolysis know that an added electrolyte is needed to get water of 2009. (The national curriculum is revised from time to time,
decomposing at a sensible rate at all. As we will show, modern and there was another revision in 2015, but not all of the
textbooks are split on the exact reaction pathways involved in the textbooks answering to the 2015 curriculum have been produced
electrolysis of water. But all sides seem to have forgotten the yet.) In the 2009 curriculum electrolysis is covered at three
possibility that H2 and O2 may be produced by secondary action. different stages, and we examined all of the approved textbooks
The rise and fall of the Daniell–Miller view of electrolysis makes at all of those levels. There are currently 9 approved chemistry
a worthwhile and complex topic for historical research, but in textbooks for the 8th grade (year 2 of middle school), and 4 each
the present paper we will focus on analyzing how modern for the 11th and 12th grades (years 2 and 3 of high school, just
textbooks deal with phenomena for which it is difficult to give before university). Even though the middle/high school division
simple and convincing explanations. in the South Korean secondary school system corresponds very
roughly to the GCSE/A-level gradation in England, what is
Scope of textbook surveys expected of 8th graders in Korea is not quite comparable to what
is expected of students taking the GCSE in England, which is
We examined the treatment of electrolysis in general chemistry roughly equivalent to the end of 10th grade. So our cross-national
textbooks at levels ranging from lower secondary school to comparison can only be made sensibly by taking the corpus of
introductory and intermediate-level university courses. For additional secondary-level texts as a whole.
insights, we made a cross-national comparative study. The compar- At the university level we did not make a cross-national
ison is basically between England and South Korea, but the situation comparison, since there is no real home-grown tradition of
is somewhat complex, as explained below. It would be interesting to university textbooks of chemistry in South Korea. Generally,
see how textbooks in other national and linguistic contexts university students in South Korea either use imported English-
compare. Note that we have not systematically surveyed specialist language textbooks, or Korean translations of them. In our survey
textbooks of electrochemistry, though we have consulted some of of English-language textbooks, we have taken care to include all
them for additional insights. the texts that are in use in Korean translation.
On the English side, the secondary school textbooks we One general remark before we enter into details: especially
examined were mostly intended for use in England, to support considering the clear and prominent place that electrolysis
study towards the GCSE and A-level examinations; we took care occupies in the popular imagination and the scientific common
to include textbooks recommended by each of the various sense concerning electrochemistry, the textbook discussions of
examination boards operating in England. At the university electrolysis are often surprisingly sketchy, sometimes even
level the textbooks are not so nationally bound; many UK altogether absent. Among the English-language textbooks we
universities freely use texts produced in the United States and surveyed, electrolysis is discussed in 84% of them at university
other Anglophone countries, and perhaps vice versa. The core of level, 59% at A-level, and 96% at GCSE level. Of those textbooks
the material we surveyed were textbooks found in the Cambridge that do discuss electrolysis, only 52% of the university text-
University Library system (chiefly the University Library, the books, 50% of A-level texts, and 74% of GCSE texts engage
Chemistry Departmental Library, and the Betty & Gordon Moore specifically with the electrolysis of water. The situation is more
Library). This was not only convenient for us, but also indicates uniform in Korean textbooks, all of which treat both topics.
our trust in the collective judgment of the chemical community
at a university with a long and venerable tradition in the natural
sciences. In total, we examined 24 textbooks at GCSE level, 17 at Results and discussion
A-level, and 63 at university level (see Appendix). Even though we
do not claim to have made an exhaustive survey, we are confident In the following exposition, we will first discuss how the text-
to have examined a clear majority of the important textbooks in books treat the electrolysis of water. After that we will discuss
use in England at all three levels. how the textbooks treat the electrolysis of aqueous salt
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solutions. In reality there is no sharp division between the two, abundance of H+ ions in the water; however, the textbooks that
since the electrolysis of water is almost always made with an give this picture do not mention low pH as a motivation. Type 4,
added electrolyte. which we have found only in one textbook, is the formation of
oxygen from pre-existing OH ions at the anode and the formation
The sources of hydrogen and oxygen of hydrogen by direct decomposition of H2O at the cathode. In an
Our survey of the English-language textbooks revealed a whole alkaline environment this picture would make perfect sense.
range of opinions on the source of hydrogen and oxygen Aside from the sheer diversity of opinion, it is interesting to
produced in the electrolysis of water. The treatments can be note that the majority of the GCSE-level textbooks present Type
classed into 4 types, as summarized in Table 1. 1 accounts, while the majority of the university-level textbooks
Type 1 is the formation of gases from pre-existing ions. The present Type 2 accounts. And the GCSE-level textbooks present
formation of H2 at the cathode is easy to conceptualize: 2H+ + either Type 1 or 2, while at university and A-level some are
2e - H2. The formation of O2 from OH at the anode is more found that present Type 3 or 4. (However, it is not the case that
complicated, and there are divergent accounts given in different only lower-level texts present Type 1 accounts. We even found
texts. Type 2 is the formation of gases by direct decomposition one specialist treatise of electrochemistry which favors it
of H2O. Many textbooks present this picture, in which a whole (MacInnes, 1961, p. 28): ‘‘In pure water, and in solutions of
H2O molecule breaks down as a consequence of receiving or neutral substances, the hydrogen and hydroxyl ions, H+ and
losing an electron, producing H2 or O2. Type 3 is the formation OH , are present in such slight amounts that their presence
of oxygen by direct decomposition of H2O at the anode, and the has, for moderate concentrations of the solute, almost no effect
formation of hydrogen from pre-existing H+ ions at the cathode. on the conductivity. These small concentrations of the ions of
As Tsaparlis (2012; 2019) points out, this picture makes sense water are, however, in this case [the electrolysis of NaCl solution
especially if the added electrolyte is an acid, providing an with inert electrodes] the ones that enter into the electrode
Table 1 Types of accounts of the electrolysis of water presented in English-language textbooks of chemistry
Level
Type University A-level GCSE
Formation of gases from pre-existing Negi and Anand (1985) Lewis and Berry (2000) Borley (2016)
ions on both sides (Type 1) Ramsden (2000) Daniels (2016)
Fullick and Fullick (2001)
Gallagher and Ingram (2000)
Hill (2002)
Honeysett et al. (2006)
Owen and King (2005)
Saunders (2016)
Schmit and Pollard (2016)
Walker (2007)
Direct decomposition of Blackman et al. (2016) Hirsch (2013) Clyde (2006)

H2O on both sides (Type 2) Brady and Holum (1993) Deloughry (1997)
Brady et al. (2012) Holman and Stone (2001)
Brady et al. (2000) Hoong et al. (2006)
Brown et al. (1994) Roebuck (2003)
Burrows et al. (2009)
Dillard and Goldberg (1978)
Kotz et al. (2008)
Malone and Dolter (2013)
Masterton et al. (2011)
McMurry and Fay (2000)
Pauling and Pauling (1975)
Petrucci et al. (2017)
Sisler et al. (1980)
Tro (2015)
Ucko (1982)
Zumdahl and Zumdahl (2010)
Pre-existing ions on the cathode, Andrews and Jelley (2013) Toh (2016)
direct decomposition on the anode (Type 3) Chang (2000)
Housecroft and Constable (2006)
Olmsted and Williams (2002)
Oxtoby et al. (2016)
Direct decomposition on the cathode, Verma et al. (2009)

pre-existing ions on the anode (Type 4)
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reactions to the exclusion of ions present in much higher or oxygen gas may be due to a secondary reaction, or that more
amounts.’’) than one reaction can be happening at the same time at each
In the Korean textbooks the situation is interestingly different. electrode.
In the 8th grade textbooks the electrolysis of water is covered in In summary, the treatment of the electrolysis of water is
two different contexts (Hyun et al., 2013a and b; Im et al., 2013a uniform in all of the Korean textbooks, giving Type 2 accounts.
and b; Lee et al., 2013a and b; Lee et al., 2013c and d; Lee et al., This consistency is useful in orienting the students. However, it
2013e and f; Lee et al., 2013g and h; Lee et al., 2013i and j; Park is also disturbing: accounts of Types 1, 3, 4 (or at least 1 and 3)
et al., 2013a and b; Sin et al., 2013a and b). When electrolysis are clearly considered as possibilities in some respectable
appears as an illustration of the atomic–molecular theory, by English-language textbooks, but not entertained at all by the
showing that water is a compound, it is simply noted that Korean textbooks. (One exception is the textbook by Chunjae
hydrogen and oxygen gases are produced, without the exact Education (Noh et al., 2012a, p. 260), which gives a Type 3
chemical equations. In 4 of the 9 cases, the teachers’ guides account for the photolysis of water, but this is presented in a
accompanying the textbooks do present chemical equations. It is wholly different section of the book.) It is not clear to us how
very interesting to note that all of them give Type 2 accounts. such uniformity emerged in South Korea, since the directives of
The 8th grade textbooks also discuss electrolysis as the the Ministry of Education do not reach down to such fine levels
conduction of electricity in order to introduce the concept of of detail. As for the English-language textbooks, each presents
ions, but in those sections they only focus on the movement of its account as the accepted truth. Then what are we to make of
ions, not the reactions at the electrodes. It is not mentioned the disagreements? What happens when a student encounters
that gases are generated at both electrodes. The texts published differing stories in going from one level of study to the next, or
by the Kumsung press (Lee et al., 2013i, p. 42) and Dusan perhaps in changing schools? Considering the Korean side again,
Donga press (Lee et al., 2013a, p. 45) are good examples, giving how should we guide the experience of high school students who
diagrams of ions moving towards electrodes but not showing learn the Type 2 account of the electrolysis of water, who may go
anything about what happens to those ions once they reach the on to university and encounter English-language textbooks that
electrodes. So the same phenomenon of electrolysis is presented give a different account?
here in a totally different way from how it is done in the unit on
atoms and molecules. The only exception in this regard is the Reaction mechanisms for the electrolysis of water
Sinsago textbook (Hyun et al., 2013a, p. 33) and teachers’ guide Only some of the textbooks discuss the specific reaction
(Hyun et al., 2013b, p. 70), which note in the unit on ions that mechanisms for the formation of oxygen and hydrogen. Once
different types of products are made, yielding either gases or again there are some disagreements among the accounts given
solid deposits on electrodes. (Note that in South Korea school by the English-language textbooks, as summarized in Table 2.
textbooks are commonly referred to by the name of the pub- The disagreements are occurring even among accounts
lisher, rather than the authors. In many of our citations below belonging to the same type. For example, all Type 1 accounts
we will be mentioning both.) are agreed that hydrogen ions receive electrons to form hydrogen
In the 11th grade textbooks electrolysis is treated in the unit molecules, but they describe the situation differently. For exam-
on molecules, in order to teach the role of electrons in chemical ple, Owen and King (2005, p. 39), Honeysett et al. (2007, p. 139)
bonds (Kim et al., 2011a and b; Noh et al., 2011a and b; Park and others write this as 2H+ + 2e - H2, while Negi and Anand
et al., 2011a and b; Ryu et al., 2011a and b). In these books there (1985, p. 491) present it as H+ + e - H twice, and then H +
seems to be a requirement to arrive at the conclusion that H - H2. The former authors seem to suggest that two hydrogen
electrons are involved not only in ionic but in covalent bonds, by ions and two electrons physically come together and form a
showing that covalent compounds such as water can be electro- hydrogen molecule at once. The latter authors seem to suggest
lyzed (e.g., Park et al., 2011a, p. 156; Ryu et al., 2011a, p. 135; that individual neutral hydrogen atoms exist for a time in the
Noh et al., 2011a, p. 132; Kim et al., 2011a, p. 132). As in the case solution being electrolyzed, and then they come together pairwise to
of 8th grade teachers’ guides, 2 of the 11th grade textbooks and form hydrogen molecules. Or are they all simply balancing equa-
all 4 of the 11th grade teachers’ guides present the Type 2 story tions and not suggesting actual reaction mechanisms? But in that
about the electrolysis of water. case, why don’t all Type 1 accounts do as Owen and King do, which
In the 12th grade textbooks (Kim et al., 2012a and b; Noh would be the simpler solution? Specialist electrochemical treatises
et al., 2012a and b; Park et al., 2012a and b; Ryu et al., 2012a and point out that the formation of H2 happens because a neutral
b), electrolysis is treated in the unit on chemical equilibria. All hydrogen atom can be stable in a state of adsorption on an electrode
4 textbooks and teachers’ guides state that whenever oxygen surface (Pletcher, 2009, Sections 1.1 and 1.7; Bockris and Reddy,
and hydrogen gases are produced in the electrolysis of water or 1970, vol. 2, p. 1246). It is interesting to note that Pauling and
an aqueous solution, this is due to the reduction or oxidation of Pauling (1975) show an adsorbed hydrogen atom in Fig. 1, and
whole H2O molecules. As we will discuss further below, all Atkins (2011, p. 51) is a rare popular science book that goes into
of the Korean 12th grade textbooks display a clear awareness adsorption, though interestingly his renowned university textbooks
that at each electrode there are different possible reactions do not discuss the electrolysis of water.
(reminiscent of Daniell’s discussion from 1840). However, there These questions arise more significantly in the formation of
is no mention of the possibility that the formation of hydrogen oxygen gas in Type 1 accounts. OH being not purely oxygen,
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Table 2 Reaction mechanisms for the electrolysis of water presented in English-language textbooks of chemistry
Type Mechanism University texts A-level texts GCSE texts

Pre-existing ions (Type 1) ( ) H + e - H, H + H - H2
+
Negi and Anand (1985)
(+) OH - OH + e ,
OH + OH - H2O + 0.5O2
( ) 4H+ + 4e - 2H2 Lewis and Berry Gallagher and Ingram (2000)

(+) 4(OH ) - 4(OH) + 4e (2000) Saunders (2016)
4(OH) - 2H2O + O2 Schmit and Pollard (2016)
( ) H3O+ + e - H + H2O Ramsden (2000)

2H - H2
(+) OH - OH + e
4OH - O2 + 2H2O
( ) 2H+ + 2e - H2 Borley (2016)

(+) 4OH –4e - 2H2O + O2 Honeysett et al. (2006)

Owen and King (2005)
Direct decomposition at ( ) 4H2O + 4e - 2H2 + 4OH Blackman et al. (2016)

both electrodes (Type 2) (+) 2H2O - O2 + 4H+ + 4e Brady and Holum (1993)
Brady et al. (2000)
McMurry and Fay (2000)
Petrucci et al. (2017)
Zumdahl and Zumdahl (2010)
( ) 4H2O + 4e - 2H2 + 4OH Pauling and Pauling (1975)

(+) 2H2O–4e - O2 + 4H+
( ) 2H2O + 2e - H2 + 2OH Brady et al. (2012)

(+) 2H2O - O2 + 4H+ + 4e Brown et al. (1994)
Burrows et al. (2009)
Dillard and Goldberg (1978)
Kotz et al. (2008)
Malone and Dolter (2013)
Tro (2015)
Ucko (1982)
( ) 2H2O + 2e - H2 + 2OH Sisler et al. (1980)

(+) 6H2O -O2 + 4H3O+ + 4e
Direct decomposition ( ) 4H+ + 4e - 2H2 Andrews and Jelley (2013) Toh (2016)
at anode only (Type 3) (+) 2H2O - O2 + 4H+ + 4e Chang (2000)
Housecroft and Constable (2006)
( ) 4H3O+ + 4e - 2H2 + 4H2O Olmsted and Williams (2002)

(+) 6H2O - O2 + 4H3O+ + 4e Oxtoby et al. (2016)
Direct decomposition ( ) 2H2O + 2e - H2 + 2OH Verma et al. (2009)

at cathode only (Type 4) (+) 2OH - H2O + 0.5O2 + 2e
it is quite impossible to avoid the question of reaction mechanisms. The same questions raised so far also pertain to the relevant
The majority of authors focus on the overall result, to write: 4OH side of Type 3 and Type 4 accounts.
4e - 2H2O + O2, or 4OH - 2H2O + O2 + 4e . This seems to Very similar kinds of questions can be raised about Type 2
suggest that four hydroxide ions will collide together and lose four accounts (and the pertinent sides of Type 3 and Type 4 accounts).
electrons, to generate two water molecules and one oxygen molecule Interestingly, none of the accounts we have seen postulate any
in a single step. Anything physically possible will happen, but what process involving one water molecule losing or gaining one electron.
is the probability or frequency of the event? Perhaps these authors Presumably, this is because such a process would not result in
are just invoking the minimum number of ions and electrons to stable products; for example, H2O + e - H + OH would involve a
be able to balance the equation. But some authors do break the self-standing hydrogen atom. We saw that some Type 1 accounts
process down; Ramsden (2000, p. 238) writes OH e - OH, have no problem with that, but it seems that Type 2 authors are not
and then, 4OH - O2 + 2H2O. But is the second step here any keen to feature unstable products in their equations. But they do not
more plausible as a mechanism than the one-step account? all agree on how many water molecules ought to be involved in the
Ramsden may think that neutral OH can exist freely long electrolytic dance. The simplest processes involve just two water
enough for four of them to have a chance to come together. molecules: 2H2O - O2 + 4H+ + 4e , and 2H2O + 2e - H2 + 2OH
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(e.g., Kotz et al., 2008, p. 936; Brady and Holum, 1993, p. 771). Brady high potential (e.g., from the handy 9 V battery that students may try
and Holum (1993, p. 772) then go on to double the latter formula, to to use) fail to electrolyze distilled water at a good rate?
present the cathode reaction as 4H2O + 4e - 2H2 + 4OH . This Due to all of these questions and other complicating issues,
way they can balance this equation with the anode-side equation, it is actually more difficult to give a neat story at the higher level
with four electrons given and taken on the two sides. It seems of discussion. This could be why fewer higher-level texts (A-level
clear that the needs of equation-balancing are trumping the con- and university) discuss the electrolysis of water. It is also
siderations of reaction mechanisms. When Oxtoby et al. (2016, interesting to note that none of the GCSE texts that give Type
p. 745) write the anode-side equation as 6H2O - O2 + 2 accounts enter into the reaction mechanisms, which would
4H3O+ + 4e , they show concern for physical reality in writing complicate the presentation. In fact the electrolysis of water does
H3O+ instead of a naked proton (H+), but not about the physical not tend to occur as a separate topic in specialist texts on electro-
frequency of the six-molecule coincidence. chemistry (e.g., Bockris and Reddy, 1970; MacInnes, 1961) or more
Some textbooks do try to go beyond equation-balancing and sophisticated treatments of electrochemistry in general textbooks
present a microphysical picture of the processes, as with Pauling (e.g. Atkins and de Paula, 2014; Keeler and Wothers, 2013), even
and Pauling’s attempt shown in Fig. 1. Some of those textbooks though it is of course noted that water molecules can be broken
also try to present reasoning and evidence in favor of their down in the electrolysis of aqueous solutions (e.g. in the brief
accounts. One phenomenon commonly invoked in favor of Type passage quoted above from MacInnes, 1961).
2 accounts is the resulting acidity and alkalinity of the solution
on the anode and cathode side respectively. If the cathode-side What is decomposed – the electrolyte or the water?
reaction is 2H2O + 2e - H2 + 2OH , then the solution will We now broaden our focus to examine how the textbooks treat
obviously go alkaline due to all the OH ions being added to it; the electrolysis of aqueous salt solutions. We will begin with an
similarly, if the anode-side reaction is 2H2O - O2 + 4H+ + 4e analysis of the Korean textbooks, because the picture presented
(or something to that effect) the solution around there will go there is clear, unified and in many ways insightful. All of the
acidic. Such changes can be shown conveniently by adding some 12th grade textbooks treat electrolysis within the section on
pH indicators to the water. For example, Brady and Holum chemical equilibria, and they all present similar stories. The
(1993, p. 772) argue that the direct decomposition of H2O is 11th grade textbooks, also published by the same companies
the correct account by showing the solution of KNO3 turning and the same authors as the 12th grade texts, treat electrolysis
acidic around the anode and alkaline around the cathode. under the unit on chemical bonds and molecules, and the
These facts are indeed pleasingly consistent with the direct- discussion of electrolysis there is not uniformly thorough, but
decomposition account (Type 2). However, it is not clear that they agree largely with the stories given in the 12th-grade books.
they favor the Type 2 account in comparison to other accounts. The Korean textbooks discuss three main categories of
If we take the Type 1 account postulating the reduction and substances that are susceptible to electrolysis: molten salts,
oxidation of pre-existing ions, here, too, the depletion of H+ aqueous salt solutions, and water. Molten salts can be dealt
ions around the cathode will turn the solution in that vicinity with very straightforwardly. Water and aqueous salt solutions
less acidic, and the depletion of OH ions around the anode will are dealt with in separate sections, and the electrolysis of water
turn it less alkaline there. The observed pH changes do not help uniformly receives Type 2 accounts, as discussed in the previous
us discriminate between the direct-decomposition account and section. Concerning aqueous salt solutions, these textbooks share
the old Daniell–Miller account, either, because the final pro- the following basic premise: at the cathode there is competition
ducts predicted are the same for both theories. For example, for between the reduction of water and the reduction of the cation of
a dilute KOH solution at the cathode: the salt, and at the anode there is competition between the
oxidation of water and the oxidation of the anion of the salt.
Direct-decomposition of water (Brady and Holum): 2H2O + 2e See, for example, the Sangsang Academy 12th grade textbook
- H2 + 2OH (with K+ present but not participating in the reaction). (Kim et al., 2012a, p. 192). Which of these competing reactions
‘‘wins’’ is determined by the standard reduction potentials of the
Secondary reaction (Daniell–Miller, modernized): 2K+ + 2e reactions in question, and the outcome may be mixed, with water
reacting on one side and the salt ion reacting on the other. Some of
- 2K, and then 2K + 2H2O - 2KOH + H2, and then 2KOH GCSE-level English textbooks try to give rules about what will be
- 2K+ + 2OH (with K+ acting as a catalyst). produced in which situation (e.g., Gallagher and Ingram, 2000,
p. 108, and Honeysett et al., 2007, p. 139).
One further question can be raised about the Type 2 account Many pertinent things are ignored in this story: secondary
of the electrolysis of water. According to the reasoning based on reactions; the possibility that both of the competing reactions
standard electrode potentials, it would seem that the application of may happen at a given electrode, albeit at different rates; the
a small external potential should be sufficient to force water to take presence of H+ and OH ions originating from water; the fact
up or lose electrons. Using the standard reduction potentials and the that the electrodes will be electrostatically charged, attracting and
Nernst equation, Oxtoby et al. (2016, p. 745) calculate the ‘‘decom- repelling ions; and the effect of different levels of applied voltage.
position potential’’ of pure water to be 1.229 V. Given that, even if we The authoritative definitiveness of the textbook presentations
consider overpotentials, why should the application of a reasonably effectively steers students away from thinking about such things.
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On the side of the English textbooks the situation is not applies to the electrolysis of water: why can’t H2O molecules in
fundamentally different, though there is again less uniformity. pure water receive electrons even if the external voltage applied
They do not all share the same thematic structure, either, so the is very high? Second, the accounts based on standard reduction/
contexts in which electrolysis comes up tend to be more varied oxidation potentials do not take into explicit consideration the
as well. One of the most interesting accounts we have found is electrostatic attraction between a charged electrode and ions of
by Andrews and Kokes (1962, pp. 469–471). Using the case of the opposite charge (for a thorough discussion of the electrode–
sodium chloride solution, they give a thoughtful discussion of electrolyte interface see Bockris and Reddy, 1970, vol. 2, ch. 7).
the possible reactions at each electrode. At the cathode, H+ or For example, if the competing reactions at the cathode are the
Na+ could be reduced, and the final outcome of either reaction reduction of H2O and the reduction of a metal cation, the
would be the production of H2; when they consider what would electrostatic attraction between the cathode and the cation
happen if the reduction of Na+ produces Na, Andrews and should make the reduction of the cation more likely. This
Kokes give an account that is essentially the Daniell–Miller consideration adds to the plausibility of the Daniell–Miller
view, which sets their text apart from most other modern ones. account of electrolysis, and detracts from the confidence shown
Their view is cautious (Andrews and Kokes, 1962, p. 470): ‘‘The in many textbooks in Type 2 accounts of the electrolysis of water.
kinetic mechanism of the electrode process is far more complicated But aren’t the effects of all the relevant factors already included in
than we have indicated here; but regardless of the mechanism, the the empirically determined values of standard potentials? Here it is
over-all reaction is represented by this equation’’: 2H2O + 2e - useful to remember the operational meaning of standard potentials:
H2 + 2OH . At the cathode, Andrews and Kokes state that both Cl the measurement setup for these potentials is a Daniell-type voltaic
and OH are oxidized, producing chlorine gas and oxygen gas; in cell with the reference electrode on one side, and the redox reaction
dilute solutions the production of oxygen would predominate, with in question on the other side. This is not the same as an externally
the result that the overall outcome of the electrolysis is the decom- driven electrolytic cell. It is not reasonable to expect that the data
position of water. This is the most sensible discussion that we have gathered in one situation will help us straightforwardly in reasoning
found among the textbooks we have surveyed, except that Andrews about what happens in the other situation.
and Kokes curiously do not consider the direct reduction or The confusing state of the textbooks on the electrolysis of
oxidation of H2O molecules. aqueous salt solutions can be illustrated quite nicely through
Among all of the general chemistry textbooks we have the case of NaCl. Brady and Holum (1993, p. 773) acknowledge
examined in either language, the most systematic and detailed that there are complicated circumstances that determine which
account of competing reactions in electrolysis is provided by reaction will be dominant. As mentioned above, Oxtoby et al.
Oxtoby et al. (2016, pp. 744–746), in a ‘‘deeper look’’ section on (2016) state very confidently that oxygen, and no chlorine, will
the ‘‘Electrolysis of Water and Aqueous Solutions’’. Oxtoby et al. be disengaged at the anode. But Honeysett et al. (2007, p. 140)
give the basic story based on reduction potentials, and also give argue that the outcome depends on the concentration of NaCl,
calculations on the effect of the concentrations of the various producing oxygen if the concentration is low and chlorine if the
ions based on the Nernst equation. However, even this ‘‘deeper concentration is high. Andrews and Kokes (1962, p. 470) reach a
look’’ conceals some tricky issues, presenting an overly simple more nuanced conclusion, stating that both chlorine and
reliance on the order of reduction potentials to decide which oxygen gas will be produced, but primarily chlorine if the
reactions happen. It categorically states that only the most favored concentration of NaCl is high, and primarily oxygen if concen-
reactions will happen, and that a less favored reaction will not tration is low. The Korean textbooks also engage with this issue.
happen at all. For example, concerning the electrolysis of a 0.10 M They note that according to the standard potentials, it should
solution of NaCl they state: ‘‘O2(g) is generated at the anode, not be easier to oxidize H2O than to oxidize Cl ; however, if we do
Cl2(g). Increasing the potential above 1.229 V only increases the experiment, chlorine gas comes out instead of the oxygen
the rate of the electrolysis reaction. It is not possible to generate gas that would result from the oxidation of H2O. About why this
sodium and chlorine electrolytically in aqueous solutions of NaCl.’’ is so, the Sangsang Academy textbook (Kim et al., 2012a, p. 192)
(Oxtoby et al., 2016, p. 745; emphases added) The Kyohaksa 12th- says that it is due to ‘‘the ion concentrations and overpotentials’’.
grade textbook (Park et al., 2012a, p. 213) echoes this view, though It adds no further comment on concentrations, and concerning
less rigidly: ‘‘At the cathode. . . the standard reduction potential of overpotentials it states: ‘‘the voltage needed for electrolysis is
the sodium ion ( 2.71 V) is lower than that of water ( 0.83 V), so it always higher than what is computed from the standard elec-
is difficult for the sodium ions to receive electrons.’’ trode potentials. We use the term ‘overpotential’ to refer to this
Among the many questions that are not addressed by these phenomenon. If the difference in the standard electrode poten-
accounts, we want to highlight just two. First, if the applied tials involved is not large, it is not easy to predict which
voltage is considerably higher than the reduction/oxidation reaction would actually happen.’’ The Chunjae 12th grade
potentials required for enabling all of the competing reactions, teachers’ guide (Noh et al., 2012b, p. 191) gives a story of
shouldn’t all of them happen to some degree, as Andrews and how oxygen bubbles sticking to the anode would increase the
Kokes suggest? What we would want to calculate is the relative overpotential, which does not happen with the production of
frequencies of the different reactions. Oxtoby et al. (2016) do not chlorine. The Visang 12th grade teachers’ guide (Ryu et al.,
explain why they say that the less favored reaction cannot 2012b, p. 236) claims in the main text that the chloride ion will
happen at all even if the voltage is quite high. A similar question be oxidized in preference to water because that is the order of
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oxidation potentials, and then corrects itself in a sidebar note necessary. They say its role is ‘‘to maintain electrical neutrality
and gives the story about overpotentials. in the vicinity of the electrodes.’’ Without the added electrolyte,
if ‘‘the electrolysis were to occur anyway, the solution around
The role of the added electrolyte in the electrolysis of water the anode would become filled with H+ ions, with no negative
Having examined the treatment of the electrolysis of aqueous ions to balance their charge. Similarly, the solution surrounding
salt solutions, we can now return more insightfully to the the cathode would become filled with hydroxide ions with no
electrolysis of water, which is after all only the electrolysis of nearby positive ions. Nature simply does not allow this to
very dilute aqueous salt solutions (at least in the typical text- happen.’’ So, for example, the Na+ ions of NaCl do not themselves
book setup). Now we can ask again: what exactly does the added receive electrons from the cathode, but instead move toward the
electrolyte do in the electrolysis of water? Almost no textbooks cathode to balance out the OH ions being produced in that vicinity.
deny the fact that it is necessary to add a small amount of Thereby the Na+ ions assist with the continuing influx of electrons
electrolyte to water in order to enable the electrolysis to happen from the electrode to the H2O molecules. This would explain how
at a noticeable rate. But we have not found any textbooks that NaCl can improve conductivity without itself being electrolyzed in
give an entirely convincing account of why this is so, and the the sense of its constituent parts appearing as reaction products.
electrolyte does not appear anywhere in the formulae given for While the above account is coherent, what would stop the H+
the electrolysis of water. and OH ions from simply moving away from the regions near
All of the English GCSE and A-level textbooks that do discuss the electrodes, as depicted by Pauling and Pauling (1975) in
this issue simply state that adding the electrolyte increases the Fig. 1? It seems to us that the old Daniell–Miller account offers
conductivity of the water, thereby allowing electrolysis to take a more plausible physical story about the role of the added
place. That is, if they discuss the role of the electrolyte at electrolyte: a cation would be electrostatically attracted to the
all—only 5 of the GCSE textbooks and 1 of the A-level textbooks cathode, and take up an electron from there; an anion would be
do (Gallagher and Ingram, 2000; Holman and Stone, 2001; attracted to the anode, and lose an electron there. Having been
Roebuck, 2003; Owen and King, 2005; Hoong et al., 2006; neutralized, the particle would easily drift away from the
Hirsch, 2013). This is also what we find in most university- electrode and then react with one of the very abundant water
level textbooks. Negi and Anand (1985, p. 491), for example, molecules. Clearly the quantum mechanics involved in these
claim that the electrolyte (sodium hydroxide in this case) reactions would not be trivial to work out, but if these are the
‘‘simply provides the conducting medium’’. They do not make main mechanisms by which water is electrolyzed, then the
clear why the H+ and OH ions in water cannot themselves do necessity of the added electrolyte is obvious, since the electrolysis
the job of conduction, if the concentration of these ions will be cannot get going without the decomposition of the electrolyte (or,
replenished to the 10 7 level just as the existing ions are turned more likely, the movement and neutralization of pre-existing ions
into H2 and O2, as Ramsden (2000, p. 238) confidently states of the electrolyte).
(just as Le Blanc had). For those who give Type 2 accounts, it is not Having forgotten all about the Daniell–Miller view, the
clear why the H+ and OH ions produced through the oxidation and modern textbook-writers seem to have great difficulty coming
reduction of H2O cannot do the job of conduction. up with a story as to what exactly the electrolyte does in the
The Korean textbooks tend to offer accounts along the same electrolysis of water. The Sangsang Academy 12th grade tea-
line, too. They are in fact more definitive in their statements, chers’ guide (Kim et al., 2012b, p. 216) goes so far as to declare
yet quite vague. For example, the Sangsang Academy 11th grade that the suitable electrolytes to use for the electrolysis of water
textbook (Kim et al., 2011a, p. 132) writes, ‘‘when we cause are those that ‘‘do not participate in the reaction’’, listing
electricity sufficient for the decomposing-reaction to pass, the KNO3, Na2CO3, H2SO4, NaOH, and NaNO3 as examples. The
covalent bond is broken and water returns to hydrogen and Visang 12th grade teachers’ guide is similar, and clumsier
oxygen.’’ The Chunjae 11th grade textbook (Noh et al., 2011a, p. (Ryu et al., 2012b, p. 237): in the electrolysis of NaCl solution,
132) says: ‘‘If/when/as we let the current flow [ ], it first calls Na+ a ‘‘spectator ion’’ and then states that NaOH is
electrolysis occurs.’’ Similarly, the Sangsang Academy 12th- formed in the reaction! It is striking to observe to what lengths
grade teachers’ guide (Kim et al., 2012b, p. 215) says: ‘‘When the textbooks go, in order to avoid entertaining the production
we make a current flow through an aqueous solution of an of H2 and O2 through secondary reactions. For example, the
electrolyte or a molten salt, the ions of the electrolyte move teachers’ guide for the 11th grade Visang textbook (Ryu et al.,
toward the electrode of opposite charge to themselves, and 2011b, p. 135) makes no mention of Na+ at all in its discussion
engage in oxidation–reduction reactions.’’ In such presentations of what happens in the electrolysis of sodium chloride solution,
the flow of current is presented as if it were a separate event simply giving the decomposition of water as the cathode-side
from the movement of ions. reaction. So we are no better than those 19th century scientists
From those presenting Type 2 accounts, including all the whom Le Blanc criticized as follows (1896, p. 44): ‘‘It was desired
Korean textbooks, there is no clear story presented about why to know which really conducts the electricity, the water or the
the movement of the ions of the added electrolyte should dissolved substance. For a long time this was an open question.
enable the break-up of water molecules. Brady and Holum One spoke then of ‘water which by the addition of sulphuric
(1993, pp. 772–773) is the only textbook in our survey in which acid, for example, becomes a good conductor,’ without having
we have noticed a plausible story about why the electrolyte is apparently conceived any explanation of the fact.’’
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Summary of textbook surveys or 0.10 M), and using different electrodes (made of graphite or
We conclude the presentation of our textbook survey with a few stainless steel). They were divided into 6 groups, each group
overall observations with significant pedagogical implications. performing the experiment with a given concentration and a given
First, among the English-language textbooks there are significant electrode material, repeating the trial at least three times. In all
disagreements in the treatment of electrolysis, at each level of study. cases the external voltage applied was 9.0 V, and each run was for 7
This is not a matter of the common progression of accounts in minutes. Students recorded the volumes of gases produced at the
which the teachers might say to the students, ‘‘what we taught you cathode and the anode, and afterwards stirred the solution and
last year was wrong.’’ On the Korean side such disagreement is observed its acidity/alkalinity using a universal indicator.
absent, but it is not clear that the common account given by all the Before carrying out the experiments, students were asked to
textbooks is the best possible one. Comparing the two, we must ask: make predictions of results. In this special school students
is it better to be consistent in giving an inadequate answer, or to study all of the regular high school chemistry syllabus by their
disseminate mutually inconsistent stories, each presented as the 10th grade, so the students participating in this study had
right answer? Neither is a desirable option. already been given the lessons on electrolysis as discussed in
Second, many textbooks seem preoccupied with the task of our textbook survey above. Students in our study gave three
balancing equations, without considering the physical mechanisms types of predictions. (1) At the cathode water will be reduced,
involved. In many cases it is not made clear whether the reactions producing hydrogen gas; at the anode the chloride ion will be
implied by the equations are proposed as real, and the plausibility oxidized, producing chlorine gas; the gas volume-ratio will be
or probability of those reactions is not discussed. Even at the 1 : 1, and the solution will be alkaline at the end of the reaction.
university level the role of the added electrolyte in the electrolysis of 14 students (61% of the whole group) gave this type of prediction.
water is not considered carefully, and the precise operational (2) At the cathode water will be reduced, producing hydrogen gas;
meaning of standard reduction potentials is usually not explained. at the anode water will be oxidized, producing oxygen gas; the gas
Third, most of the general chemistry textbooks ignore volume-ratio will be 2 : 1, and the solution will be neutral. 8
secondary reactions in the description of the electrolysis of students (35%) gave this prediction. (3) At the cathode water will
water, and the Daniell–Miller view of electrolysis is almost never be reduced, producing hydrogen gas; at the anode, both water
mentioned. Its neglect seems to be partly a legacy of the initial and the chloride ion will be oxidized but mostly water, giving a
over-enthusiasm from a century ago about the then-new Arrhenius volume-ratio close to 2 : 1, and the solution will be alkaline. Only
theory. After Arrhenius theorized that small amounts of H+ and one student gave this prediction.
OH are automatically ionized in water, there seemed to be no The results on gas-volumes were as shown in Table 3. With
need to explain the role of electrolytes in the electrolysis of water. graphite electrodes, the gas-volume ratios were clearly much
What may have been a hasty judgment at that time has now greater than 2 : 1 (with the 0.10 M solution, the anode-side
turned into unthinking and unjustified neglect. volumes were too small to be measured reliably). With stainless
steel electrodes no appreciable amounts of gas were produced
at the anode, from which the students quickly learned that the
electrode material can participate in reactions; this was confirmed
A pilot study in the classroom
easily by the formation of visible precipitates. These results were
In order to begin the process of applying the insights from our clearly contrary to the students’ predictions (which had correctly
textbook survey to teaching practices, we carried out a pilot followed their textbook learning).
study with students at the end of their 10th grade year at the The results on acidity/alkalinity were also complex and intriguing.
Sejong Academy of Science and Arts, a secondary school for With graphite electrodes, the 1.0 M and 0.50 M solutions became
gifted students in South Korea. 23 students volunteered to alkaline, in line with prediction (1) above. This indicated that water
take part in this study, in which they conducted experiments was reduced at the cathode producing OH ions as well as hydrogen
and answered a questionnaire. The study was designed to allow gas, but it was not oxidized at the anode (which would have
students to encounter a situation in which experimental results produced H+ ions as well as oxygen gas); at least it must have been
were not in line with the simplified accounts given in their mostly Cl that became oxidized. At 0.10 M the solutions appeared
textbooks. The students were asked to perform electrolysis on neutral after the reaction, suggesting that the anode-side reaction
aqueous NaCl solutions of varying concentrations (1.0 M, 0.50 M was predominantly the oxidation of water in this case. Students also
Table 3 Gas volumes (cm3) resulting from the electrolysis of aqueous NaCl solutions, after the application of 9.0 V of potential for 7 minutes
Concentration
1.0 M 0.50 M 0.10 M
Electrode First Second Third First Second Third First Second Third
Graphite Cathode 5.5 5.7 5.4 3.2 2.9 3.2 0.68 0.68 0.57
Anode 0.57 0.57 0.45 0.57 0.34 0.45 — — —
Stainless steel Cathode 4.2 4.0 4.1 2.6 2.7 2.5 0.57 0.45 0.57
Anode — — — — — — — — —
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observed that the colors of the indicator became more faint as time (1) It is perfectly understandable that textbooks offer simplified
went by, suggesting the bleaching action of chlorine or chlorine accounts of electrolysis, which is a highly complex phenomenon.
compounds. However, we recommend that students should be advised clearly
After the experimental work we conducted a brief survey that the textbook accounts are models offering theoretical insights,
asking the students to give us their view on the relation between rather than exact predictions for actual experiments. Our
these experimental outcomes and what they have learned from recommendation is in line with Justi and Gilbert’s general
their textbooks. Choosing among 3 options we gave them, a recommendation that ‘‘students should: learn about the nature
clear majority (18 students, 78%) responded that the textbooks of models and their use as thinking tools; learn about the scope
articulated simple principles or regularities discernible within and limitations of specific chemical models; be encouraged to
complex natural phenomena, expressing an appreciation of the use multiple models for a given phenomenon.’’ (Justi and
value of the textbook account despite the discrepancy with Gilbert, 2003, p. 51) Concerning electrolysis in particular,
observations. A small number (3 students, 13%) responded that it is important that the students be taught the limitations of
the textbook account was correct and their experimental results reasoning just in terms of standard electrode potentials, and be
were in error. Another small group (2 students, 9%) responded made aware that a full account of the electrolysis mechanism
that the experimental results should be trusted and the textbook requires the considerations of kinetics as well as equilibrium
account may be in error. thermodynamics.

We also asked the students’ attitudes towards their experience (2) As Justi and Gilbert suggest in the passage just quoted,
of this work. Most of them (21 students, 91%) responded that they the plurality of models is not a problem. We recommend that
found these experiments with complex and unexpected results students and teachers should be helped in reaching a pluralistic
more interesting than those in which the textbook 2 : 1 gas-volume understanding of models. Ideally each textbook should be able
ratio was obtained (such as the electrolysis of NaOH solutions, to offer a variety of models, acknowledging that they all have
which reliably produces the 2 : 1 ratio even at high concentra- merit and they all have difficulties. Or at least one model can be
tions). 15 students (65%) affirmed that they experienced cognitive given along with a note that there are other plausible ones, too.
dissonance from the more complex experiments, yet all of these (3) In the same vein we can recognize the value of historical
students also said that the complex experiments were more knowledge. The explanations that were proposed in the past
interesting to them. All students agreed that they have learned may disappear from the explanations of modern chemistry, but
from these experiments that it was necessary to consider many this does not necessarily mean that the past explanations are
variables if they are to predict correctly the results of electrolysis. wrong. As we have seen through the case of the Daniell–Miller
In free-form answers describing their experience, many students view of electrolysis, a forgotten past model can offer useful
gave indications of sophisticated thinking, for example about the questions and answers for modern students. If we invite students
dominance of thermodynamics vs. kinetics, the methods for into the history of science and give them the opportunity to
handling of discrepancies between theory and experiment, the consider freshly the research questions from the past, it may help
process of adding refinements to theories, and the limits of them enjoy the true pleasure of doing chemistry.
predictions based on what we already know. Some also expressed (4) Recognizing textbook accounts as simplified models can
the desire for further specific learning, for example about what help encourage the more adept and motivated students to
would happen with other electrode materials, and about the engage in creative and critical thinking instead of accepting
secondary reactions of chlorine. one explanation as being true. Our pilot study points to clear
At least with these highly motivated and able students, we potential in this direction. We recommend that textbooks and
have confirmed the potential benefits of offering them oppor- teachers try to move beyond the kind of neat stories that have
tunities for research into the complexity of phenomena, even if the effect of shutting down questions that demand complex or
such work should go beyond the prescribed syllabus. This sophisticated discussions. Of course, it would be unrealistic to
would generate much greater potential for learning, compared treat all the complications in textbooks for schools and lower-
to the usual experiments in which students learn to produce the level university courses. However, textbooks and teachers at any
results dictated by simplified textbook accounts. level should be prepared to admit that there are important
questions that they cannot deal with fully, which constitute
Recommendations subjects for further inquiry either by students with extra
initiative or in later years of study. Recognizing the educational
On the basis of our textbook analysis and our pilot study with value of these questions can foster curiosity about unexplained
students, we would like to make four recommendations for the phenomena and provide an environment for scientific inquiry.
teaching of electrolysis. Our recommendations are broadly We should remember Charles Sanders Peirce’s motto: ‘‘do not
consonant with insights provided in Georgios Tsaparlis’s study block the way of inquiry.’’ (Hartshorne and Weiss, 1931, §135)
of the teaching and learning of electrochemistry (Tsaparlis, 2012),
in particular his advocacy of ‘‘active learning’’ about electrolysis
(Tsaparlis, 2019). We also find inspiration in the work of Rosária Conflicts of interest
Justi and John Gilbert (2003) on the use of models in chemical
education. There are no conflicts to declare.
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Appendix: English-language textbooks consulted for analysis
Text Publisher Author Year Level

Chemistry Oxford University Press Borley, M 2016 GCSE
AQA GCSE Science Applied Double Award Hodder Education Chenery, S. and Unsworth, S. 2006 GCSE
Science Uncovered: AQA Additional Science for GCSE Heinemann Clyde, B. 2006 GCSE
Student Book
AQA Chemistry for GCSE Heinemann Clyde, B. 2007 GCSE
OCR Gateway GCSE (9-1) Chemistry for Combined Science HarperCollins Daniels, A. 2016 GCSE
New Modular Science for GCSE (No. 1) Heinemann Deloughry, W. 1997 GCSE
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Appendix (continued)
Text Publisher Author Year Level

Chemistry: The Molecular Nature of Matter. (6th ed.) Wiley Brady, J.E., Jesperson, N.D. and 2012 University
Hyslop, A.
Chemistry: Matter and its changes (3rd ed.) Wiley Brady, J., Russell, J. and Holum, J. 2000 University
Chemistry: Matter and Its Changes – Student Study Guide Wiley Brady, J. E. and Senese, F. A. 2008 University
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Chemistry for Engineering Students Cengage Learning Brown, L. and Holme, T. 2006 University
Chemistry: The Central Science (6th ed.) Pearson Education Brown, T. L., LeMay, E. and Bursten, 1994 University
B. E.
Fundamentals of Chemistry (4th ed.) Pearson Education Burns, R. 2003 University
International
Chemistry3: Introducing Inorganic, Organic and Oxford University Press Burrows, A., Holman, J., Parsons, A., 2009 University
Physical Chemistry Pilling, G. and Price, G.
General Chemistry: The Essential Concepts (3rd ed.) McGraw Hill Chang, R. 2000 University
Chemistry: Reactions structure and properies (2nd ed.) Macmillan Dillard, C. and Goldberg, D. 1978 University
Concepts of Physical Chemistry Discovery Publishing House Goel, A. 2006 University
Pvt.
Fundamentals of Chemistry (5th ed.) McGraw Hill Goldberg, D. E. 2007 University

Essentials of General, Organic, and Biochemistry Macmillan Learning Guinn, D. 2014 University
(2nd ed.)
Chemistry for Changing Times (13th ed.) Pearson Hill, J., McCreary, T. and Kolb, D. 2013 University
Chemistry (3rd ed.) Pearson Education Housecroft, C. and Constable, E. 2006 University
Advanced Theoretical Chemistry Chatto & Windus Hughes, D. and Maloney, M. 1964 University
Chemical Structure and Reactivity: An Integrated Oxford University Press Keeler, J. and Wothers, P. 2013 University
Approach (2nd ed.)
Principles of Electrochemistry (2nd ed.) Wiley Koryta, J., Dvorak, J. and Kavan, L. 1993 University
Chemistry and Chemical Reactivity (7th ed.) Cengage Learning Kotz, J., Treichel, P. and Townsend, J. 2008 University
College Chemistry Addison-Wesley Mahan, B. 1966 University
University Chemistry Addison-Wesley Mahan, B. 1970 University
Basic Chemistry (9th ed.) Wiley Malone, L. and Dolter, T. 2013 University
Chemistry: Principles and Reactions (7th ed.) Cengage Learning Masterton, W. L., Hurley, C. N. and 2011 University
Neth, E. J.
Fundamentals of General, Organic, and Biological Pearson Education McMurry, J. and Castellion, M. 2006 University
Chemistry (4th ed.)
Chemistry (3rd ed.) Pearson Education McMurry, J. and Fay, R. 2000 University
International
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Physical Chemistry (2nd ed.) Harcourt Academic Press Mortimer, R. 2000 University
Textbook of Physical Chemistry (2nd ed.) PHI Learning Moudgil, H. 2014 University
Principles of Chemistry W. W. Norton, Inc. Munowitz, M. and Prigodich, R. 1999 University
A Textbook of Physical Chemistry Wiley Eastern Negi, A. S. and Anand, S. C. 1985 University
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in Environmental Chemistry and Related Fields
Chemistry: The Molecular Science (3rd ed.) Mosby Olmsted, J. and Williams, G. 2002 University
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Chemistry
Principles of Modern Chemistry Cengage Oxtoby, D., Gillis, H. and Butler, L. 2016 University
College Chemistry W. H. Freeman and Co. Pauling, L. 1964 University
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Introductory Chemistry Pearson Benjamin Cummings Russo, S. and Silver, M. 2001 University
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Roberts, J. L.
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General, Organic, and Biological Chemistry (6th ed.) Cengage Learning Stoker, H. 2013 University
Introduction to Chemical Principles (11th ed.) Pearson Education Stoker, H. 2013 University
General, Organic, and Biological Chemistry: Pearson Higher Education Timberlake, K. C. 2016 University
Structures of Life (5th ed.)
Chemistry: Structure and Properties Pearson Higher Education Tro, N. J. 2015 University
Basics for Chemistry Elsevier Science Ucko, D. 1982 University
Inorganic Chemistry: Theory Practice and Application Royal Society of Chemistry Zanello, P., Nervi, C. and de Biani, F. 2012 University
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Electrolysis: What textbooks don’t tell us

Introduction at the anode: 4OH (aq) - 2H2O(l) + O2(g) + 4e .

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