1 Symbols and signs in chemical education - Part 2: the historical evolution of conventions John Oversby, Institute of Education, The University of Reading, Reading, RG6 1HY, UK email: J.P.Oversby@reading.ac.uk Introduction A distinguishing feature of chemistry as a scientific discipline is its use of symbols and signs as a means of communication about chemical reactions. Although they seem to be much in common with algebraic use of symbols and signs, there are important differences when used in chemical contexts. An understanding of how the present use came about may shed light on some of the problems that learners in schools may have with chemical equations. This article aims to explore the relationship between symbolic explanation and the phenomena that require explanation. As a major source of evidence, it refers to textbooks use of chemical symbols and equations. The research questions were: 1. What signs and symbols appear in textbook of chemistry at school level?? 2. What changes in chemical symbolism has taken place over the last 150 years and what has contributed to these changes? 3. What can a study of chemical symbolism contribute to thinking about learning chemistry? Chemists use representations as part of their explanations. We use representations to communicate ideas even though the representations have limitations. When we draw a chemical formula, for example, we focus on some aspects of it. These might be just the elements in the formula, or the numbers of each component. We ignore some aspects or take them for granted. One of these might be the order in which the symbols are arranged. We might in one formula for water write H2O, and in another write HOH. In the first case, we may be emphasising the presence of two hydrogen atoms and in the second we might be emphasising that the oxygen is in the middle of the two hydrogen components. Often we do not make these distinctions clear. When the other person looks at the formula, they may not be aware of the meaning that is the focus for us. In the case of H2O, the other person may focus on the three atoms. In the second case, they may interpret it as having the three atoms in a line. The first interpretation is legitimate but not what was intended. The second one is not a legitimate interpretation since there is experimental evidence that the water molecule is not linear. What is likely is that the interpretation of the creator and the receiver are more likely to be the same if the creator explains clearly how the formula is to be viewed. We call this clarifying the representing process. In practice, creators often fail to make their representation clear and the receiver then has to make her or his own sense of the drawing or formula. This is how many misinterpretations happen. Representing faithfully therefore consists of the following steps: identification of significant features of the target or phenomenon to be explained; selection of one or more representations from a different source that is reasonably well understood; Chemical symbols, signs© John Oversby, October 2002 2 identification of features that correspond to some significant features of the target. In general, the more features that readily correspond, the better the representation; dismissal of non-corresponding features. This part of representing is more commonly omitted or poorly done. The consequence of this is that receivers of the representation may attempt to match inappropriate features of the representation and so be misled; consideration of corresponding features to elaborate explanation of the target; consideration of corresponding features in relation to similar representations and targets. A powerful representation will also explain similar targets or be consistent with other representations; in appropriate circumstances, corresponding features may prove fertile, that is spark off explanations of the target not initially recognised; development of the representation in the light of further data about the target. The representation may be refined or modified in the light of novel data. Powerful representations are those that can be refined or modified without losing their essential characteristics. comparison with other representations. The first comparison is in terms of universality ie how much of the target or phenomena is explained. The second comparison is in terms of satisfaction of explanation i.e. a subjective opinion of how far the representation succeeds in explanation. The third comparison is in terms of predictive power, that is, the ability to predict the outcomes of novel experiments. Quantitative predictions are preferred. The first + sign in a chemical equation means ‘reacts with’ and not ‘plus’, which would be an algebraic meaning. The second + sign means ‘and also’, implying that the chemicals are not combined. Again, use of ‘plus’ would be inappropriate. The arrow is another indication that these are chemical equations, not algebraic equations, where an = sign would be expected. The equations have an implied direction, from left to right. In algebra, 2+3 = 4+1 can be read either way. It implies complete equality in both directions. The = sign is an operator in algebra, meaning to sum the two values. This is clearly not the same as the chemical meaning. Dictionary definitions of symbols A symbol in Mathematics ‘is a character, letter or special mark taken as representing some quantity, etc.’ (James & Lee,1995). The same reference also defines ‘chemical symbol’ as ‘a letter or letters used to signify a chemical element’ This particular definition of chemical symbol is deficient, particularly in regard to whether it is an abbreviation of the name, or represents a sub-microscopic form such as the atom, or whether it represents a macroscopic quantity, such as a mole. Summary of symbols in equations The ideas indicated in this example have set the scene for an examination of the syntax of symbols and signs as parts of ways of representing macroscopic chemical phenomena. Chemical symbols, signs© John Oversby, October 2002 3 Ideas about symbols Chemists constructed a set of symbols for a purpose, that is, to express abstract ideas. These symbols are not identical to those used in algebra as Malvern (2000) has suggested. The table below provides a range of ideas about symbols against which data from textbooks can be evaluated. Ideas about symbols Progress in development A symbol represents the name of the element. This was an early development and remains important today A symbol represents a macroscopic quantity This came before submicroscopic representations, beginning late in the eighteenth century. At higher academic levels e.g. A level, the macroscopic representation is still significant and present as the mole but is not often made explicit This came soon after the use of symbols for macroscopic quantities but now is either the dominant, or often the only, known meaning of symbol. A symbol represents a submicroscopic quantity, at the atomic level. Chemical symbols, signs© John Oversby, October 2002 Challenges Invention of new pseudo symbols (see text) needs to be integrated The link between experimental phenomena and representation has been weakened at school level. There is a need for greater emphasis on macroscopic significance of symbols. The use of symbols at the submicroscopic levels to represent invisible entities should be greater explored during the learning process. Greater rigour in the use of pseudo symbols should be established by the community of chemists. 4 Textbook ideas about symbols Date Author Meaning of the term symbol 1785 Lavoisier Lavoisier used symbols to denote both constitution and quantity. 1810 Dalton 1833 Turner (cited in Nye, 1993) ‘Such symbols referred to the atom and were therefore conceptually very different from alchemical symbols or those of Hassenfratz and Adet which had only a hazy or qualitative meaning. Earlier symbols had been a shorthand; Dalton’s circles conveyed a theoretical meaning as well as being a convenient abbreviation.’ (p139 in Brock (1992), referring to Dalton’s (1810) New System The symbols ‘are only fitted to be a convenient abbreviation among educated chemists, but may be made a powerful instrument of instruction by teachers of chemistry.’ (p vii-viii) 1856 Wilson 1856 Miller 1864 Wurtz 1866 Frankland 1868 Naquet It should never be forgotten that chemical symbols are not like cyphers, mere substitutes for words. But are further supplements to them. Thus the symbols HO, NO5 and NH3, are not simple synonymes of water, nitric acid, and ammonia, but tell us the nature and relative amount of the elements in these bodies, which the words do not. [Note on p 57] The use of the comma in his book: P434 MgO,SO3,7H2O P497 (KO,NO5 + (KO,HO,2SO3) = HO,NO5 + 2(KO,SO3) Used barred formulae to indicate new atomic weights (these were twice the old ones) e.g. H2O = H2O CaO = CaO He also used the comma for combination. Uses typical subscripts although he is not particular about the order of the symbols. P9 NO3H + ONaH = NO3Na + OH2 SO4H2 + 2OKH = SO4K2 + 2OH2 Frankland (1866) also has something to say about notation (p14): formulae symbols "denote a certain definite proportion by weight of each element" Notation on p27: … a symbol is used which represents the atom (not the molecule) of each simple body Footnote. Some symbols are employed barred, to indicate they are taken with the value they have in atomic notation, and merely to avoid the Chemical symbols, signs© John Oversby, October 2002 Comments Quoted in Brock (1992) (p118) relating to a paper on the composition of water published by Lavoisier in 1785. Dalton used a set of iconic symbols for his representations. Nye reports that Turner introduced the symbols half way through the text after confronting the difficulty of using ordinary language to give an account of Liebig’s and Wöhler’s work on cyanogens. Wilson is probably writing for what we would now understand to be undergraduate chemists. Miller is probably writing for what we would now understand to be undergraduate chemists Wurtz is probably writing for what we would now understand to be undergraduate chemists Frankland is probably writing for what we would now understand to be undergraduate chemists Naquet is probably writing for what we would now understand to be undergraduate chemist 5 1870 Odling 1886 Fittig 1887 Gautier confusion which might arise, as several authors still use the notation of equivalents. As, however, the latter notation is becoming disused, I have not thought it necessary to continue the use of the bars. p28 superscripts, thus SO3. In writing symbols it has been agreed to place first, that one of the different components which is the most electro-positive; but this rule is only followed exactly when there are not more than two elements present. In the book he uses superscripts throughout but uses braces for some formulae, a practice that was common at the time.. P39 H2O + COCl2 = CO2 + H} + H} Cl} Cl} Wrote a chemistry textbook for a mainly medical readership, using subscripts in a special way: P23 HgO + Cl4 = Cl2O + Cl2Hg For elements he does not use coefficients but multiples of atoms in formula. A German chemist who used superscripts towards the end of the nineteenth century. Note the use of names under the symbols. P29 C6H8(OH)6 + 11HJ = C6H13J + 6H2O + 11J Or C3H5(OH)3 + 5HJ = C3H7J + 3H2O + 4J Glycerin isopropyljodür Used superscripts, for example: P29 H2O CO2 P418 2C2H5 + 2Na = 2NaBr + (C6H5)2 P53 2HCl + Fe = Acide chlorhydrique Fer 1894 Jago FeCl2 + H2 Chlorure ferreuse Hydrogène P169 6KOH + 6Cl = 5KCl + ClO3K + 3H2O [Bold type is original.] ‘For convenience of description each element has an abbreviation of its full name, called its symbol. This is, where practicable, the first letter of its Latin name. Simply as abbreviations of the full names symbols and formulae are of great service; this, however, is but a small part of their significance and value in chemistry. Their further use may best be explained by reference to certain information gained by experiment, to which careful attention is requested. [ … ] It is possible to assign to every element a number, which number or its multiple shall represent the proportionate quantity by weight of that element which enters into any chemical compound. These numbers are termed the ‘combining or atomic weights’ of the elements, and are deduced from results obtained on actual analysis. [ … ] The symbol represents the quantity of the element indicated by the combining weight; where multiples of that quantity exist in a compound the fact is expressed by placing a small figure after the symbol and slightly below the line. A large figure placed before a symbol signifies that number of the whole compound.’ (p33-34) Chemical symbols, signs© John Oversby, October 2002 Odling is writing for what we would now understand to be undergraduate medical students Fittig is probably writing for what we would now understand to be undergraduate chemists Gautier is probably writing for what we would now understand to be undergraduate chemists Jago’s book is an inorganic textbook, probably aimed at undergraduate chemists. 6 1899 Newth States (p52) that the symbol is atom and mass. 1904 Moissan French chemist was still using superscripts in 1904 e.g. p 9 Cs2O and on P39 K2SiF6 + 4KOH = 6KF + SiO2.2H2O 1930 Hooton 1954 Holderness & Lambert 1954 Brown 1964 Fowler & Fowler 1980 Ramsden 1984 Hunt & Sykes ‘For every element there has been adopted as short symbol to represent in these [formulae] equations. … the symbol stands not only for the name of the element, but also a definite quantity by weight of it; thus, Hg represents 200 parts by weight of mercury, and O 16 parts by weight of oxygen.’ (p48) ‘The symbol of an element consists of one or more letters which denote one atom of the element. It is important to keep clearly in mind that the symbol of an element does stand for a perfectly definite amount of it, and that amount is one atom.’ (p21) ‘… it is possible to represent an atom of a particular element by means of a symbol. … It is very important to realise that the symbol O, for instance, does not just refer to oxygen; it represents a definite amount – one single atom – of oxygen.’ (137) ‘…thing regarded by general consent as naturally typifying or representing or recalling something by possession of analogous qualities or by association in fact or thought. Mark or character taken as the conventional sign of some object or idea or process e.g the astronomical signs for the planets, the letters standing for chemical elements … From the Greek (sumbolon), mark or token’ ‘C stands for one atom of carbon. Cl stands for one atom of chlorine, Co for an atom of cobalt, Cr for an atom of chromium. A symbol stands for one atom of an element.’ [the term symbol is not explained in this text.] 1993 Jones, Jones and Acaster ‘Each element has its own symbol. Hydrogen, for example, has the symbol H. Helium has the symbol He.’ 1994 Ramsden For every atom there is a symbol. For example, the symbol for sulphur is S. the S stands for one atom of sulphur. ‘A single capital letter, or a combination of a capital letter and a small one, which is used to represent either an atom or a mole of a chemical element: eg the symbol for sodium is Na, for 1995 Larousse Chemical symbols, signs© John Oversby, October 2002 Newth is probably writing for what we would now understand to be undergraduate chemists Moissan is probably writing for what we would now understand to be undergraduate chemists Hooton’s book for older school pupils (16-18 years old) is typical of this period. Holderness and Lambert’s work was one of the dominant textbooks in the 1930s, 1940s and 1950s in the UK. Brown’s book was one of the do`minant textbooks in the 1950s and 1960s in the UK. This definition is given in a standard dictionary. It is written for the intelligent lay person rather than the specialist chemist. Ramsden writes here for the secondary student (11-14 years old) This textbook by Hunt and Sykes supported the very popular Nuffield chemistry course widely used in secondary schools at this time. These authors are writing for secondary students (14-16 years old) Ramsden is writing for secondary students (1416 years old) Larousse is used as a reference of good practice in recent times. 7 1999 Wilson sulphur is S.’ ‘Symbols: hydrogen is H and calcium is Ca while chlorine is Cl.’ 2000 McDuell [the term symbol is not explained in this text.] Wilson is writing for teachers of chemistry in secondary schools (1416 years old). McDuells’ book is aimed at teachers of chemistry in the secondary school (1116 years old). Pseudo symbols Chemists also use a range of chemical symbols that are similar to those used for elements. The table below indicates the symbols, their uses, and the approximate stages at which they are introduced. Pseudo symbol Meaning and comment Age at which introduced in the UK e An electron (free electron) with or without the minus Ligand entity Cyanide – used by Wilson (1856) Ethylene diamine tetra-acetic acid – used in complex metal chemistry Diamino ethane – used in complex metal chemistry Oxalic acid – used in complex metal chemistry General symbol for metal, used in general formulae and equations e.g. for alkali metals 2M + Cl2 2MCl General symbol for non-metal, used in general formulae and equations e.g. for halogens 2Na + X2 2NaX General symbol for anion, used most frequently in algebraic functions relating to weak acids e.g. HA. CH3 – the methyl group. Used to identify this group in condensed and display formulae C2H5 – the ethyl group. Used to identify this group in condensed and display formulae C3H7 – the propyl group. Used to identify this group in condensed and display formulae C4H9 – the butyl group. Used to identify this group in condensed and display formulae (CH3)3C – trimethyl methyl or tertiary butyl group. Used to identify the goup in condensed and display formulae Acetate (CH3COO) or acetyl (CH3CO). Used to identify this group in condensed and display formulae Phenyl, (C6H5). Used to identify this group in condensed and display formulae Any alkyl group. Used to identify this group in condensed and display formulae Any aryl group, containing a benzene ring Upper secondary (14-16) and post 16 Post 16 and university Post 16 and university Post 16 and university L Cy Edta En Ox M X A Me Et Pr Bu t-Bu Ac Ph R Ar Chemical symbols, signs© John Oversby, October 2002 Post 16 and university Post 16 and university Upper secondary school (1416) and post 16 Upper secondary school (1416) and post 16 Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university Post 16 and university 8 type structure. Used to identify this group in condensed and display formulae Pseudo symbols appear to be most frequently used in generalising about reactions, or in chunking parts of a formula to aid recognition. In many respects they are used in place of element symbols in condensed and display formulae. A textbook discussion about good practice in the use of symbols The original Nuffield Chemistry Handbook for teachers (Coulson, 1967) was very clear about the issues behind the use of symbols. ‘With the idea of the atom comes the idea of the symbol, the sign to represent the atom. In some ways it is unfortunate that the ideas of Berzelius prevailed over Dalton’s picture symbols. … Had chemists adopted picture symbols, beginners might have found it easier to remember that a symbol can represent a single atom. With the less able children it is sometimes helpful to write the symbol in a circle e.g. Mg, S, H, until the idea is well established.’ (p 64) [The Nuffield Scheme suggested that learners should ‘use symbols and formulae in an experimentally meaningful context’ (p111) i.e. from a macroscopic origin.] ‘symbols are used to represent atoms of elements, but when they are used to give information about material in a bottle, the symbol by itself is insufficient – the idea of giant structures and molecules is by now established and we can write: Cu(c) for a copper atom that is part of a crystal lattice Hg(l) for an atom of mercury in a liquid H2(g) for a molecule of hydrogen in the gaseous form’ (p 23-25) S8 (orthorhombic) and S8 (monoclinic) when there is a need to distinguish the allotropes Zn(c) meaning ‘an atom of zinc as it is in crystalline metal’ Zn(g) meaning ‘an atom of zinc as it is in the gas’ [this comes after a section on counting atoms in a bag and invoking the idea of proportionality of mass.] Zn represents one mole of atoms of zinc and S one mole of atoms of sulphur. … the symbol will later be used to represent one atom of an element (p 49) … we can represent these atoms by symbols: we could use circles or triangles to represent atoms taking part in chemical reactions, for example We still use symbols to represent the atoms of elements but these are now related to the names of elements. (p 66) They may revise the symbols for the elements and learn that these may be used to represent the quantity of element expressed in moles of atoms (gramatoms). This change in the use of symbols requires emphasis. (p 112) Commentary on the Nuffield Handbook (Coulson, 1967) discussion Chemical symbols, signs© John Oversby, October 2002 9 The Nuffield Handbook, almost uniquely, provides some advice about suitable pedagogy about symbols. It provides: some of the history of the origin of symbols with an evaluation of the effect of decisions taken then on potential teaching challenges today; clear identification of the meanings of symbols at all three levels a comparison of the use of algebraic symbols with the use of other representations such as circles or triangles. QCA Key Stage 3 Scheme of Work Unit 8E Atoms and elements In this unit: most pupils will explain that compounds are made when atoms of different elements join together; begin to use symbols for elements and to represent reactions in word equations some pupils will name some elements and represent these by symbols; distinguish between symbols for elements and formulae for compounds some will begin to represent compounds by formulae Comments: recognise the symbols for some elements; identify that elements are made from atoms of one kind; explain the existence of compounds in terms of atoms joining together; describe compounds e.g. water is made of hydrogen and oxygen joined together; describe some simple molecules, eg carbon dioxide is made of one carbon atom joined to two oxygen atoms; {some pupils make their own representations of some simple molecules and relate these to their chemical formulae} {it is important to avoid talking about a molecule of sodium chloride, for example}; establish the idea that when these materials are made the atoms combine or join. Introduce the terms ‘molecule’ and ‘compound’, show representations or photographs of representations, of simple and more complicated molecules, to illustrate the point. If possible also provide samples of the compounds and their formulae. Show pupil some reactions between elements eg - hydrogen and oxygen - sodium and chlorine - carbon and oxygen - copper and sulphur and ask then to record their observations in terms of appearance of the reactants and the products and to represent the reactions by word equations, simulation software, representations or diagrams, making clear that when the compound is formed the atoms join. Help pupils to represent the compounds formed by formulae and representations. Ask pupils to explain individual reactions in these terms and to question others about their representations. Explain compound formation in terms of atoms joining e.g. using equations, diagrams, representations. Pupils will need time to practise using the chemical names of compounds e.g. making the change from oxygen to oxide. It is helpful for pupils to become familiar with formulae for common compounds and to relate these to representations showing the numbers of atoms. Chemical symbols, signs© John Oversby, October 2002 10 Teachers will be able to judge how far to take explanations of differences in formulae with different pupils. For some pupils, list the formulae of the products of the reactions seen and introduce the idea of ‘combining power’, using a simple representation e.g. card cut-outs of elements; ball-and-spoke representations. Ask pupils to use the representations to predict the formulae of other metallic oxides, chlorides and sulfides. It is helpful to be explicit that the representations are not representations of real atoms. Help pupils to summarise the reactions of copper carbonate in a word equation, making clear which reactants and products are elements and which are compounds. Language for learning: understand, use and spell correctly: Scientific words eg element, compound, atom, molecule, symbol, formula Names of elements and compounds eg oxygen, carbon dioxide, sodium, chlorine, sodium chloride Words and phrases with different meanings in scientific and everyday contexts, eg element, equation, state Unit 8F compounds and mixtures In this unit pupils: Distinguish between elements and compounds and how they are represented by symbols and formulae Recognise chemical change as a process in which atoms join together in new ways That elements contain only one kind of atom. That compounds contain more than one kind of atom joined together. That formulae indicate the (relative) numbers of atoms in a compound. If ionic compounds are included, it is sufficient to treat the formula as a ratio, eg one atom of magnesium to one atom of oxygen in magnesium oxide. It is important not to imply that ionic compounds consist of molecules. Discussion of the QCA KS3 Scheme of Work The QCA Scheme of Work is unclear about the meaning of chemical symbols, referring only to the vague term ‘elements’. Similarly, the Scheme of Work is also unclear about the specific ways in which the symbols represent chemical substances. The only comment about formulae states that sodium chloride should not be considered as being made up of molecules, with only a little indication of why, or of how general this advice should be. The Scheme of Work is unhelpful in explaining reasons for its advice. Chemical symbols, signs© John Oversby, October 2002 11 The meanings of chemical signs in textbooks, including chemical arrows Date 1856 Author Wilson Equations p120 Before decomposition, KO,NO5 and HO,SO3; After decomposition, HO,NO5 and KO,SO3. Or more fully thus:- Signs See previous cell. No arrows are used in the text. Comments Letterpress p16 The sign +, …is placed between the formulae of the molecules of the different substances which are brought into contact before the reaction, and of those which result from the change. This sign must never be used to connect together the constituents of one and the same chemical compound. Na2O + H2O = 2NaHO Sodium oxide Sodium hydrate Letterpress KO NO5 = HO,NO 5 HO SO 3 = KO,SO 3 Here the dotted horizontal lines indicate the bodies in combination at the beginning of the process, the oblique unbroken lines the exchange of acid and base that occurs during the decomposition, and the double horizontal lines = (the algebraic sign of equal to) the bodies in combination at the end of the process. PO5 + 5C = P and 5CO This equation (p162) shows the symbol + on the left hand side and uses 'and' on the right hand side. 2HCl + MnO2 = 2HO:Cl and MnCl The coefficients can be seen from the word equation. 1866 Frankland 1894 Jago Na2O + H2O = 2NaHO Sodium oxide Sodium hydrate Chemical symbols, signs© John Oversby, October 2002 Letterpress No use of arrows in this book 12 p117 Chemical changes are most conveniently expressed by what are termed 'chemical equations'; these consist of the symbols and formulae of the bodies participating placed just before the sign =, while those of the resultant bodies follow. For example, the action of iodide of potassium and chloride of mercury on each other is thus expressed:- P117 HgCl2 + 2KI = HgI2 + 2KCl Mercury chloride Potassium iodide Mercury iodide Potassium chloride [The words are under the formulae in the original text] As no chemical change affects the weight of matter, the weight of the quantity of a compound represented by its formula must be the sum of those constituent elements; so, too, the weight of the bodies resulting from a chemical change must be the same as that of the bodies before the change, whatever it may be, had occurred. Also the same number of atoms of each element must appear on each side of the equation. Although from a chemical equation and table of combining weights it is possible to state what relative weight of each element is concerned in each reaction, it must never be forgotten that the combining weights were first determined by experiment, and then the table combined therefrom. 1897 Roscoe NH4NO2 = N2 + 2H2O P47 Chemical symbols, signs© John Oversby, October 2002 Letterpress Arrows are not used except as part of the reversible reaction 13 sign p69 1899 Newth P54 Atomic equation, Hg + 2Cl = HgCl2 Molecular equation, Hg + Cl2 = HgCl2 1906 Armitage No chemical equations provided 1913 Schmidt 1930 Hooton Used the arrow sign for formulae and = for line equations mainly using = signs. P65 C6H5AsCl4 + 3H2O = C6H5AsO(OH)2 + 4HCl But (on the same page) (C6H5)3As + Cl2 (C6H5)3AsCl2 Elements and Symbols Mercuric oxide = mercury + oxygen The sign of equality indicates that the total weight remains unchanged; mercuric oxide breaks up into the two elements, mercury and oxygen, and their weights are together equal to the oxide which yields them. HgO = Hg + O P47-48 P24 Zn + H2SO4 ZnSO4 + H2 This equation is interpreted in terms of 1954 Holderness & Lambert Chemical symbols, signs© John Oversby, October 2002 P22 The sign + has a different significance as used on the left side of the equation to that which it bears upon the right. On the left side it implies that chemical action takes place between the substances, while on the opposite side it has the simple algebraic meaning … "and also" P52 symbol is atom and mass P54 Atomic equation, Hg + 2Cl = HgCl2 Molecular equation, Hg + Cl2 = HgCl2 p109 referring to Berzelius SO3 and Cr2O3 sulphur trioxide Used the arrow sign for formulae and = for line equations mainly using = signs. P65 C6H5AsCl4 + 3H2O = C6H5AsO(OH)2 + 4HCl But (on the same page) (C6H5)3As + Cl2 (C6H5)3AsCl2 for reversible reactions P83 Up arrows and down arrows are mentioned on this page and occasionally Letterpress Letterpress This textbook is concerned with the history of chemistry Arrows are not used Offset litho Letterpress ↑↓ are not used. Offset litho 14 1956 Clynes & Williams molecules, not macroscopic. Later on the same page: Mg + H2SO4 MgSO4 + H2 Fe + H2SO4 FeSO4 + H2 The equations correspond to, and represent, the observed fact that when these two metals are brought into contact with dilute sulphuric acid, hydrogen is liberated and the metals are converted into their sulphates. P 135, 136 By use of equations the materials taking part in a reaction and the products of reaction can be shown, and it is possible, moreover, to calculate the weights of the different substances concerned. Magnesium and Oxygen give Magnesium oxide Or, Magnesium + Oxygen Magnesium oxide used elsewhere. Arrows are used throughout. The + sign on the left of the equation means “reacts with”, but on the right it means simply “and”, while the arrow means “producing”. Both arrows and = signs are used p176 Zn + 2HCl = ZnCl 2 + H2↑ Offset litho 2Mg + O2 = 2MgO 1959 Emeleus and Anderson 1973 Spiers & Stebbens 1978 Hall The book then treats the matter of balancing equations in terms of conservation of mass. Explicit explanation of coefficients is not provided. Used both old and new notation: P 322 6WO42- + 7H+ [HW6O21] 5- + 3H2O P392 3NaBH4 + 4BF3 = 3NaBF4 + 2B2H6 Chapter 12 Investigating Chemical Equations pp 114 ff This is entirely based on calculations. p 27 blue copper sulphate + heat {equil arrow} Chemical symbols, signs© John Oversby, October 2002 Used both old and new notation: P 322 6WO42- + 7H+ [HW6O21] 5- + 3H2O P392 3NaBH4 + 4BF3 = 3NaBF4 + 2B2H6 Other chapters use full symbol equations with arrows. Arrows used where equations are given. Offset litho 15 white copper sulphate + water 1980 Palmer & Shaw 1981 Shayer & Adey p31 ‘Chemical equations are shorthand ways of describing chemical reactions.’ Chapter 5: elements, compounds, and atoms explains how to write equations. i. The formulas of the reactants are written on the left. ii. The formulas of the products are written on the right. iii. An arrow, , is used instead of the ‘equals’ sign, =. iv. Like equations in maths, there must be the same number of each type of particle on the left as on the right. P94 2B late concrete Chemical combinations remembered without general rules being appreciated. Composition of compounds as a kind of mnemonic, e.g. water is made of hydrogen and oxygen, and will produce hydrogen and oxygen. Word equations could be used to indicate a reversible reaction, such as heat on hydrated copper sulphate. But ‘copper’ in that name is used only as a label, so word equation is only a statement of fact. 3A early formal. Can handle the conservation of elements in an exchange reaction, so for the first time has a representation of a chemical reaction. Use of balanced chemical equations is possible, providing that plenty of drill is given in learning the rules of the game. The relation of chemical equations to reactions will be perceived, but do not expect pupils to know how to use them to estimate Chemical symbols, signs© John Oversby, October 2002 Chapter 4: chemical change: elements and compounds explains word equations. The arrow means react to give. No discussion of signs Offset litho 16 1986 1989 Allen, CrockerMichell, Hannon, PageJones, Thornley Partington 1989 Gallagher & Ingram 1989 Hill, Holman, Lazonby, quantities except by practice in specified situations. May use atomic theory and simple representation of atomic structure to account for chemical change. 3B late formal. The functional use of chemical symbols. The Nuffield approach to equations – from the experimental situation, through the nearest idealisation of the facts that fits the measurement, to a balanced equation The term ‘equations’ is not in the index. Equation syntax is not explained in this text. P197 ‘Symbols were little used in textbooks early in the century {19th}. Turner’s Elements of chemistry (4th edition, 1833) explains symbols and uses them, together with chemical equations, but with an apology in the preface. Liebig (Traité de chimie organique, 3 vols, Paris, 1840-44) uses equations but not liberally. Symbols and equations are freely used in Gmelin’s Handbook (English translation, 1847-1872)’ Chapter 5 pp66-67 You could show the reaction by a diagram, like this: {particle representations of carbon and oxygen giving carbon dioxide and words stating molecules underneath} symbols C + O2 CO2 Equations are not mentioned in the index. P9: calcium + water calcium hydroxide + Chemical symbols, signs© John Oversby, October 2002 No explanations of signs is given in tis text. Arrows are used. Offset litho Partington does not give any detail about the signs. Offset litho A history of chemistry textbook p 67 Question 1: What do + and mean, in an equation? Offset litho no discussion of signs is apparent Offset litho 17 Raffan & Waddington 1993 Jones, Jones & Acaster 1993 Hill 1995 Larousse 1995 Lister & Renshaw 1996 Earl & hydrogen P12 questions: magnesium + copper(II) oxide copper + magnesium oxide p25: methane + oxygen carbon dioxide + water CH4(g) + O2(g) CO2(g) + 2H2O(l). Pp 58-61 (Equations) balancing equations – implicit reference to Law of Conservation of mass only referenced to atoms not being able to be added or removed.. Equations show what happens during a chemical reaction. Signs are not discussed. Offset litho heat bread carbon + carbon dioxide + water + toast food + oxygen carbon dioxide + water fuel + oxygen carbon dioxide + water iron + oxygen + water hydrated iron oxide Signs are not discussed Offset litho A quantitative symbolic representation of the changes occurring in a chemical reaction, based on the requirement that matter is neither added nor removed during the reaction. Chapter 6 Equations Word equations (p27) Equations are used as a simple way to represent what is happening in a chemical reaction, and the simplest is the word equation. … equations should always be based on experimental evidence. Equations do not say how fast a reaction happens. Conditions (heat, pressure, etc.) may be shown on arrows, for example –heat {heat over arrow} Signs are not discussed Offset litho Signs are not discussed Offset litho This is aimed at the 16-18 age range Word equation: No discussion of signs is given Offset litho Chemical symbols, signs© John Oversby, October 2002 18 Wilford copper carbon heat + carbon(s copper(s) + oxide(s) dioxide(g) (the reactants) (the products) 1996 McLean 2000 McDuell If we replace the chemical names of the reactants by their symbol or formulae we can produce a full chemical equation. The word equation for the thermal decomposition of copper carbonate can be replaced by: heat CuCO3(s) CuO(s) + CO2(g) Only reference to equations in the index is to balancing equations. This is treated as writing the word equation, then the formulae and then checking the atom numbers. Finally, adding state symbols. On this page the explanation is algorithmic. p41-45 (Chapter written by Pritchard) ‘Word equations should be seen by pupils as a way of summarising a chemical reaction, with the reacting substances (reactants) on the lefthand side and the substances produced (products0 on the right-hand side. An arrow is used rather than an equals sign because the two sides are not strictly equal and an arrow shows the direction of reaction. Pupils should be encouraged to write word equations whenever they come across a chemical reaction. For example: Chemical symbols, signs© John Oversby, October 2002 Signs are not discussed Offset litho p 41-45 An arrow is used rather than an equals sign because the two sides are not strictly equal and an arrow shows the direction of reaction. Offset litho This is aimed at teachers of chemistry at the 11-16 age range 19 magnesium oxide + sulphuric acid magnesium sulphate + hydrogen For many pupils, writing word equations will be the limit of their equation writing but for pupils who go on to write symbol equations, the word equation is still an important precursor. {The book then goes on to write about balanced symbol equations. Explanation in terms of the law of Conservation of Mass is not provided but is simply algorithmic. A full page of balanced symbol equations with arrows and states is given on p 43. State symbols are described on p 44. Ionic equations are explained on p44 but it says: ‘if an ionic substance dissolves in water it becomes split up into its component ions, i.e. it becomes ionised’. It also says that ‘solids, liquids and gases remain un-ionised in equations’ but ‘acids, alkalis and all soluble salts can be written as component ions’. No description of the meanings of other signs is given. Chemical symbols, signs© John Oversby, October 2002 20 The + sign This section is deliberately not headed ‘the plus sign’. The + sign in chemical equations has a meaning that is distinct and significantly different from the algebraic meaning. In historical terms, Berzelius, in 1813, had a great influence on chemical notation. Compounds were denoted at first (the early part of the eighteenth century) by a + sign between the constituents element symbols e.g. copper oxide was Cu+O. The exact meaning of the + sign is not made explicit, for example in Wilson (1856), but it would seem reasonable to suggest that it meant ‘combined together’. The + sign was dispensed with later but it may have been kept as a symbol for 'reacts with' or joins with’. The + sign on the right of the equation has a different meaning. It simply means ‘and also’. Wilson (1856) often writes symbolic equations with the term ‘and’ on the right hand side where we would put + today. The + sign then refers, at the macroscopic level, to the existence of a chemical reaction in which one or more new substances are formed. The use of the + sign here is peculiar to chemistry and contrary to the meaning in algebra.. The equation arrow This section deals with the meaning of the main equation arrow although other equation arrows will be treated later. It seems to mean the process of a chemical change, or ‘yields’, ‘to give’. When chemistry teachers from a variety of countries were questioned, they all responded with this meaning e.g. ça donne, by a French colleague. The arrow corresponds to chemical change and is thus fundamental to the nature of chemistry. The position about the development of equation signs is not entirely clear. There is a tendency for chemistry textbooks in the mid- and late nineteenth century to use the more descriptive form and restrict the use of equations. This is understandable in terms of printing technology for such equations would have to be specially set up by the printer. The equation arrow, , has not always been used to denote the process of chemical change. From the beginning of writing chemical equations (1830s) until about the 1960s, textbooks used the = sign for the process of chemical change. This is in contradistinction to other opportunities chemists chose to use symbols and signs in a different way to that used in algebra. Brock (1992) suggests that this may be the influence of the printers who did not have the in their printers’ box of type. I have identified that books that used the letterpress method of printing, where the type leaves an indentation in the page, always used the = sign for the equation arrow. This method of printing was in common use until the early part of this century. A survey of PGCE student science teachers demonstrated their unanimous preference for over =, many justifying this in terms of the chemical equation being distinct from algebraic equations. The symbol = is used in equations from the mid part of the nineteenth century. It was available as a standard printer symbol and was so easy to use. The arrow symbol was occasionally used from the middle of the nineteenth century, especially in organic chemical reactions using displayed formulae. In the early books, it was clearly a special symbol devised by the printers and so may have been something of a nuisance. Chemical symbols, signs© John Oversby, October 2002 21 Its use seems to be largely restricted to the line drawings used for displayed formula equations used in organic chemistry. Even until the 1950s, the = sign was commonly used. This may be the influence of the printing technology. Other equation arrows The two reversed arrows, as in the diagram below, became more popular in the early part of the twentieth century and are in common use today. It may be that these arrows were, by then commonly available to printers in their standard set of characters. The sign (note that, in this font, the arrows are the wrong way round with the upper arrow pointing to the left) appeared in the early twentieth century and gained ground, as printing technology became more versatile. Books printed by letterpress, as evidenced by the impression left on the printed page, use the = sign. Books printed by the litho process are more likely to use the modern form. This form is now prevalent with the advent of modern word-processing, even though it is the wrong way round. It has proved impossible to find explicit explanations of the meanings of these symbols in textbooks used for teaching chemistry. The few books that explain the form of chemical equations fail to explain the meanings of the signs +, and. They focus on the chemicals as reactants and products. The history of the development of chemical symbols Dalton (described in Brock, 1992) created a system of symbols for different elements based on circles with distinctive marks inside. These symbols referred to the atom and were therefore theoretical and not just some abbreviation for the names of the elements. Brock suggests that Dalton's symbols may not have survived because they were an additional expense for the printer; they required special type to be produced. Their main contribution to chemistry was to focus on the sub-microscopic atomic level of representation. In 1837, at the meeting of the British Association for the Advancement of Science, British chemists agreed to use the symbols of Berzelius. These were based on the alphabet and we can suspect the influence of the printing industry in this decision. Berzelius (1779 - 1848) had obtained a copy of Richter's writings on stoichiometry and these contained explanations of the law of reciprocal proportions and chemical equivalents. Richter first published in 1792 Anfangsgründe der Stöchyometrie (Outlines of Stoichiometry, or the Art of Measuring Chemical Elements) (cited in Partington, 1951). This work was based on the amounts of different acids that could neutralise given quantities of different bases. Richter coined the term stoichiometry from the Greek meaning to measure something that can not be divided. Richter had expressed the law of constant proportions that characterises a fundamental property of compounds. He also established the concept of chemical equivalents that was later embodied in elemental symbols. These ideas influenced Berzelius' textbook, Larbok i kemien, which was first published in 1808. Berzelius read about Dalton's work on Chemical symbols, signs© John Oversby, October 2002 22 multiple proportions at second hand, because of the European wars at the time, but obtained his own copy of Dalton's New System in 1812. Berzelius, in 1813, introduced a system of symbols based on the Latin names of the elements. Compounds were denoted at first by a + sign between the constituents element symbols eg copper oxide was Cu + O. The plus sign was dispensed with later but it may have been kept as a symbol for 'reacts with' as will be seen later in the Wilson (1856) text. Berzelius used superscripts for the number of atoms in elements and these were placed to the right of the symbol, eg S2O3 for a molecule of hyposulphuric acid. Brock states that these 'were criticised initially for being potentially confusing with algebraic symbolism'. We can only surmise that the argument about potential confusion was lost because of the influence of the printers in terms of ease of use. While most chemists used subscripts soon after it was introduced by Berzelius and adopted by the British Association for the Advancement of Science in 1837, many French chemists used the superscript form until the twentieth century. It may be possible that the use of the subscript form did make some distinction between algebraic notation and chemical notation. In 1827 Berzelius in the organic section of his textbook, used the barred form to indicate two atoms of the elements. Thus, Ħ represents two hydrogen atoms in the Berzelius symbolic form. H, the underlined symbol, was often used by printers for ease in place of the barred symbol, but the barred symbolism was virtually unused by Berzelius, except in part of his book, and it was never widely used. 1. What signs and symbols appear in textbook of chemistry at school level? Recent textbooks show a range of signs in chemical equations. Signs for the chemical process range from , to and . The reaction sign is + although this is rarely sated explicitly in modern textbooks. 2. What changes in chemical symbolism has taken place over the last 150 years and what has contributed to these changes? The use of the = sign was predominant throughout the nineteenth and early twentieth centuries, and was then replaced by a variety of arrows. Chemical symbols began originally as pictorial (e.g. Dalton) and developed through variations on alphabetic characters, the present format being adopted at a meeting of the British Association in 1837. This decision may have been influenced by the expense of producing special characters rather than the standard alphabetical symbols. The choice of superscripts or subscripts to denote the number of elementary components seems to have been dictated by the influence of significant journal editors. Eventually, consistency was achieved by the international nature of publishing research. The use of pseudo symbols was present in the mid nineteenth century and has developed to provide the power of generalisation as well as simplifying some complex formulae. The prevalent use of e for electron is in line with the widespread use of half equations as an explanatory tool. 3. What can a study of chemical symbolism contribute to thinking about learning chemistry? In the first place, choice of symbolism often arises through external factors such as the influence of technology. This makes learning symbols a rote learning venture with consequent demand on memory space. The origin of chemical symbols in Latin nomenclature is also a challenge to the learning process. Multipliers in chemistry are placed in the opposite position to that in mathematics, Chemical symbols, signs© John Oversby, October 2002 23 after the symbol. This can lead to a conflict that can diminish understanding. In addition, the use of sub-scripts is yet another irrational rule to learn. The meanings of signs such as + and needs to made explicit in texts, as it was in many texts from the nineteenth century. . The work reported here indicates that chemical notation is a neglected part of learning about chemistry in secondary schools now compared with the past. Reference to empirical origins is rare. Chemical word equations mean different things to different authors and the lack of consistency is obvious. Balancing chemical equations has little chemical purpose and is rule oriented rather than based on understanding of fundamental chemical laws. Lost beginnings Larousse makes it clear that there has been very little change in the meanings of symbols since they were first established at the beginning of the nineteenth century. However, recent textbooks are at odds with these very principled meanings. How may this have come about? With regard to the symbols, the loss is the quantitative macroscopic meaning. Chemistry has moved on from equivalents to moles and the discussion here recognises this change. Similarly, chemistry now recognises a range of entities and representations, such as the bull's eye diagrams for electronic structures. The language used in the textbooks appears to be one of finality. The authors leave no room for a development of the explanation they give. The message they leave us with is not one that accredits a progressive understanding of the meaning of symbols as the reader's knowledge improves. Rather, it is a cut and dried view, this is the meaning of symbol that will stand the test of your improving knowledge. There is no later reflection on these meanings at the end of these books to suggest there is any need for a rethink. Perhaps authors believe that their nitial explanation of the meaning of symbol is the end of the story. If chemistry is to come alive as a developing subject then this should be reflected in the structure of the textbook. A section at the end relating an improved meaning of the term and relating to the history of how this term was established would be a helpful contribution to understanding the structure of chemistry. Chemical formulae are poorly discussed in every single one of the recent textbooks. There is no indication of a quantitative macroscopic meaning and this original meaning has been lost. At the start of the nineteenth century the sub-microscopic view was a modern contribution. The use of symbols was an accreditation of the need to include this sub-microscopic approach. Now the macroscopic position has been left out and the result is a detachment from empirical evidence. This may go some way to explain why some students fail to maintain chemical formulae when balancing equations. They are simply not aware of the strength of the law of constant composition so well established by Richter and others at the turn of the nineteenth century. It is little wonder that they have such little regard for the constancy of the formulae. In a similar light, the focus on rules for balancing equations has led to a detachment of stoichiometry from the law of conservation of matter. This ought to be trumpeted in the texts as the basis for balancing equations. The place of the different notations of coefficients and numbers of atoms, crafted from the numerous discussions two hundred years ago, needs to be emphasised. The lack of explicit Chemical symbols, signs© John Oversby, October 2002 24 teaching of this part of the chemistry curriculum suggests that it may not be appreciated by the authors. Word equations are a more modern phenomenon, while retaining their roots in the Bergman-Berzelius forms. These are more used as a teaching tool. The teaching community, rather than the community of academic chemists, may better clarify their meanings. Chemical equations in The Journal of Chemical Education The Journal of Chemical Education is a journal that appears to be most closely related to teaching and learning of chemistry than most. It was, therefore, chosen to investigate the appearance of chemical equations in the articles it provides for US high school and college level chemistry. Nine issues from 2002 (January – September) were examined for the presentation of chemical equations. Many articles and three complete issues did not present chemical equations at all. Nevertheless, 35 papers provided examples of 116 chemical equations. While this does not constitute a rigorous or comprehensive survey, it provides a flavour of recent practice. Within this sample there were (the numbers do not all tally to 116 since there was multiple use in some equations): 4 word equations 50 formulae equations, many concerning molecular reactions that could not be represented as ionic equations 9 half equations in ionic form 57 ionic equations only 4 equations that were general ionic or formulae while the rest were specific 12 equations were provided with state symbols 8 equations that were only partial i.e. unbalanced a variety of arrows in use (, 86; , 1; , 1; , 20; =, 8). The use of the = sign was restricted to one paper which also used the ↓ arrow. The following pseudo symbols were used: Ac, Et, Ph, R, R’, py (pyridine), p-O2N-C6H5, Hb (haemoglobin), DNA, L (ligand), NAPDH, NADH, m-CPBA, t-Bu, M (for metal), e without the minus, e- with the minus. It would seem that there is a lack of consistency and very little editorial control over the representation of chemical equations. 7. A timeline of symbols and signs in chemistry 15th C and early16th C elements and compounds represented by icons eg gold as King 1718 Geoffroy's symbols for elements in his table of affinities 1808 Dalton's circle symbols with patterns and letters enclosed 1813 Berzelius letter chemical symbols - abbreviations of names and equivalents 1813 Berzelius proposes barred symbols for multiple letters. This finally disappears in the second half of the nineteenth century 1820s Symbols adopted as representing atoms Chemical symbols, signs© John Oversby, October 2002 25 1837 British Association for the Advancement of Science adopts Berzelius system 1830s German and British chemists adopt the subscript convention for multiple atoms 1856 Wilson uses + on reactant side and 'and' on product side of equation Wilson uses the = sign for 'reacts with' Wilson explanation of the order of symbols in a compound 1856 Miller uses the comma as a combination sign. 1864 Wurtz uses the barred symbols to distinguish equivalents. He also uses the comma for combination 1865 Frankland uses subscripts but symbols in order reverse to the convention of metals first. Formulae are related to reacting weights. The + sign is explained as it is today. 1868 Naquet: a symbol represents an atom not a molecule. Barred symbols represent reacting weights he uses superscripts with words under symbols. Use of electropositive element first in binary compounds.. 1870 Karlsruhe chemical conference to establish the meanings of chemical symbols. 1870 Odling uses multiple symbols for elements rather than coefficients. 1884 Arrhenius' paper on ions - a new particle to be represented. Arrhenius adopted the same symbols as the elements 1886 Fittig (German) uses superscripts and words under symbols. 1887 Gautier uses superscripts and = signs. He puts words under symbols. 1894 Jago uses + on both sides of the equation. Jago clarifies symbols as abbreviations for names, and representing both atoms and macroscopic quantities. 1899 Newth uses + sign but "and also" for different sides of the equation He characterises atomic and molecular equations. 1900s French chemists begin to convert to the subscript convention from superscripts 1904 Moissan still using superscripts 1900s The use of the = sign begins to be replaced by the in textbooks. This is not generally complete until the 1960s 1913 Schmidt uses and = signs 1920s Use of for reversible and equilibrium reactions. 1930s Use of the up and down arrows, and . These generally disappear in the 1960s and are generally replaced by state symbols. 1940s Use of sign for equilibrium reactions. The sign is less commonly used in the 1970s but never disappears entirely. 1959 Emeleus and Anderson using a mixture of sign and = sign, to differentiate equilibria and complete reactions. Chemical symbols, signs© John Oversby, October 2002 26 References Allen J, Crocker-Michell J, Hannon M, Page-Jones R, Thornley T (1986) Macmillan Integrated Science. An Examination Course. 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