Abbas Labbauf? The A. 8M, Collegeof Texos The Carbon-12 Scale of Atomic Masses | Callege Stotion A, student is not far into his first chem- for abandoning the old reference scales and the factors | istry course before he enconnters the concept of atomic “that. have led to the adoption of the new C scale, | weight. If it has not already been made clear to called the unified mass scale, are closely related 10 him, some discussion and careful definition of the the progress of science and the refinement in its tech terms “mass” and “weight” should be presented. niques over the past 30 years | Also the distinction between relative or assigned a } values and the absolute or inherent values of these The Concept of Atomic We { properties should be made. All weights are relative, Only comparatively recently, in the early part of | though precisely defined in terms of the force exerted the 18th century, was the idea of the atom widely | | on matter in a gravitational field in comparison to aceepted. By “about 1800, however, the laws of that for a standard. The amount of matter is its definite proportions and multiple proportions were | mass, Due to long established usage, the term “atomic well established. At that time the chief concer Secight” scoms still to be preferred by most chemists was the assigning of weights to atoms, a process whieh Ze present, Thus we speak of the atomic weight hs continued for over 130 years to the present dav defined as the relative weight of the element—being A short but interesting history of these developments the measured property of its atomic mass with respect from the time of Dalton to the present is given in to that of an intentionally agreed upon standard the Information Bulletin, No. 4A, July, 1901, of Homie mass the International Union of Pare and Applied Ches For nuclides, a term suggested by Kohman (1) stry. This survey also outlines the activities of the and defined as “a species of atom characterized by various national organizations whose. efforts finaly {its nucleus, in particular by the number of protons eqlminated in the formation of the TUPAC | fand neutrons in its nucleus,” the corresponding term —“"‘The chemical method of determining the atomic | ‘nuclidie mass is used. Correspondingly, the nuelidie weight of any element is, in many cases, dependent on } mass has a weight relative to that for the mass of previous knowledge of the molecular weight of con | an internationally agreed upon nuclide. Our use pounds in which the element isa constituent part, ‘Thr | of the term “weight” when referring to mass follows determination of molecular weights is based. fancl i the precedent of the IUPAC in its presentation of mentally on Avogadro's hypothesis. The application the Atomic Weight Table [sce Tas Jounsat, 38, of this hypothesis can yield only relative molecular 625 (1961)]. weights and not absolute values; therefore, a defined The Commission on Atomic Weights of the Inter- standard is required on which one ean base the atomic | national Union of Pure and Applied Chemistry weights of other elements, Since hydrogen is the — | (IUPAC) had, prior to the mecting of the Union in lightest element, it appeared best to choose this element | 1959, proposed the adoption of a reference mass scale as standard and assign the value of unity to its atom 1] dased ‘on HC (earborel2 isotope = 12 exactly) to weight. Prout’s hypothesis that the elements wer | which the atomic weights of all elements would refer composed of a varying number of hydrogen atons and which would serve as a common seale for use by favored this choice. This would have been an ad: 1 } both chemists and physicists. In August, 1958, the quate selection if the atomic o molecular weights || TUPAC approved the recommendation for a unified alone were to be considered. But since these values atomic weight scale providing that similar action must be used in connection with combining weights. — | would be taken by the physicists. ‘The corresponding oxygen serves as a better standard for comparison | Vieeq representative organization for physics, the Inter because of its abundance and reactivity. Sine | national Union of Pare and Applied Physics (TUPAP), oxygen is @ better working standard for chemically | {tte at its meeting in 1960, approved the adoption of the determined ratios, a scale based on oxygen gradually - carbon-12 atomic weight scale, permitting the chemists cafe to be preferred, Jt was natural to use an ine ig to take final action at the recent meeting of the IUPAC tegral value for the atomic weight of this cleme 1961, The choice of © = 16 had the fortunate coin idhis nearly identical with their in 1961. This meeting was held August 2-5, Be itinconircd Grama ihe ratrence wale beoet ot at making sneha - C © 12 exactly, was formally adopted. The reasons mass numbers. Re ——________________—_ te ‘This investigation was performed under the American Petroleum K mlo wean caloyeet Se ‘and Coexistence of Two Seales atitate Research Projeet 4 and the Manfaetaing Chemiste Siienoaete factory atomic weight scale. It remained a happy “Prosent address: Lord Mg. Co, Erie, Pa choice until it was discovered that some elements 282 / Journal of Chemical EducationTable 1. Comparison of the Chemical Scale, the Physical Scale, end the Unified Mass Scale Based on 'C = 12 (exactly) ~ a 1957 (or 1950) ~108r International International "able (25) table (27) L 2 oy Oster n16 unit an err i ( H otra 1,008 0 1.007 07 © (natural 12011 © uaa) 16 oxactl no 18.0160 . ious ct 16.043. 0° Cal 282.550" Chemical Physical stale stale 0 3) exactly 1.ow On 05 0. 35 1 exactly 1000 8, (0 Oss 0.540 ne Vexacily tor 865, Tons U2 (20) 007 832 (08 O1L 10s 288 L008 67 OL ISL 2'on4 735 (21) 2014 O04 0 516,12 00s St ‘exactly Ou gine 12.014 931 2.011 100 93 WL UB exactly 15.004.912 exact 18,004 100 13.00 312 18.016 18.020, 18.015 347 AOU GIs HLuas 16.08 Gol 18.018 282 58 B00 280-645 510 All the vals in scale umina (4) and (6), except those that are based on definition, were calculated from the values based on the physical “Calenlated by using the 1957 ternational Table for the Momie Weighta ng the 1961 International Table f the walle 12 DLL3 © 0.0004 (based on & ica eatin technique and mass we 120tlt saul HC faotopes by vind War (2 Caleta The discovery of isotopes would not have altered the situation at all were it not for the fact, that ordinary oxygen, the standacd itself, was found? to eonsist of a mixture of isotopes: "0, "0, and 0, the latter two being discovered by Giauque and Johnston (2) in 192%. The physicists, working with mass spectrometers in their study of isotopes, naturally: chose for their standard system the oxygen nuclide of mass 16, while the chemists continua to use 16 for the atomic weight of the isotopic mixture, Iu reports on atomie weights for the years 1953 and 1956, respectively, Wichers (3) diseussod the problem of the two seales.” Wiehers 4, 8) has also tovwched upon certain aspects of the problem elsewhere, ‘The importance of a unified seale has been discussed in tuts Jovesat. by: Kielfer (©) and more recently by Cauzgenheim (7). Pertinent articles by Kohman, Mattauch, and Wapstea (8) and also Mattauch (9) have discussed the problem in the light of the proposed "Cas a unified reference basi The unit of the physical «cal is called the “absolute mass unit” (ama) oF “isotopic mass unit” and the ‘unit of the chemical seal is ealled the “atomie weight unit (awn), -Atomie masses are given on the physical seale while atomic weights are given on the chemical seale, For isotopic elements it would be more rigorous to use the term “mean atomie mass or weight,” but there is no evidence of confusion resulting, from the shorter designation used by chemists, ‘The unit of the physical seale is Yis of the mass of MO atom, The unit of the chemical scale is Vi of the weight of consisted of isotopic mixtures, the mean mass of an atom of natural oxygen and is therefore slightly greater than the physical unit (see able 1), he quantitative relationship between the two seales is established in the following manner: A detailed diacumsion of the iaotopes of oxygen in reference (11). contained e eheanira ‘rmcopic ivtermination if thelr telative abundance, aa reported by Seott fron hati sas and isotope abuniances given in reference (12) the Atomic Wrights Teale), The mean value based on mass determination of *C appendix G. Let MAX) = atomic weight, on the chemical ecale, of any nat~ ‘ural element X atomic weight, on tho chemical sale, of natural oxygen X) = atomie mast, on the physical seal, of element X Ar,L0*) = atomic mass, on the physieal scale, of natural oxygen, By definition of the chemical scale, M(O*) = 16 exactly. The following relation exists among the above four quantities: o M,(0) is the average atomic mass of natural oxygen roferred to “0, and may be expressed in terms of mass, M,,, of each isotope and its abundance (atom tion), Ai, MAO*) = = BAe x My ey By definition, the conversion factor rere | i403 ~ Seiareaaens —o Hence from (1) ares) = MO anus = Ego w ‘The conversion factor, r, may also be defined in terms of the ratio of the units of atomic weight, (chem- ical seale) to the units of atomic mass (physical scale). it ofthe atom weight _ aww uit of the atomic maa aa ey ‘The numerator and the denominator are magnitudes of the units when referred to the same reference base scale, We could say that the ratio is defined as a pure number, ‘Thus, one may write for rand r* the following identity har 6. lune 1962 / 282Avhe value of r ean be calculated from a knowledge of he masses and the abundance ratios of oxygen muclides “40,70, and "0, mean atomie mans of ‘O) + ACMDMOO) isotopie abundances from reference emasses from reference (1), 001588) + = 100s ‘The disparity between the chemical and the physieal seales was further heightened when it was observed that the isotopic abundance of oxygen in nature varies from souree to souree (10, 11). This led to the value of varying between 1.000268 and. 1.000278, In 1940 the IUPAC Commission on Atomic Weights adopted ‘value of 1.000275 for r corresponding to a “typical” natural oxygen. We thus note that the physical scale differs from the chemical seale by 275 parts per million, "The factor r has at. times been referred to as the Mecke-Childs factor. For historical interest it may be pointed out that Mecke (12) and Mecke and Childs (15) gave a value of ¢ = 1.00022, basing their ealeula- tion on their spectroscopic meastirement of the abun- dances of 0, "0, and 0, The Avogadro number, which was defined as the number of oxygen atoms in 16 grams of oxygen (now defined as the number of atoms in 12 grams of earbon- 12), also depends on what scale is chosen, So also do other properties which are functions of the mole,* for example the Faraday constant, or the gas constant, R._ The value based on one scale differs from the value based on the other scale by the factor r The following quotation from the report of the International Commission on Atomic Weights for 1931 (27) indicates the manner in which this problem was Viewed at that time: “The discovery ofthe oxygen isotope has ereted the undesirable situation that chemistry and. physice are onng to ilferet esl forthe dsterminaion of stom weghte.Beesune of this the question of am abmolute standard hs already een ore ot tes widely dixcosed and various proposals mae, for insane, HX ="1.00000; He = 4.00000, 0 = 16.0000, as well ae the eso chemical standard = 16,0000 TW. Aston, who dieeuced the question comprehensively tefore he Britah Atocation fa 103, eames that ii advis- able fr chemist to retain the presen chemical standard, eine ie amply stises all requirements of Totemational” Atomic ‘Weights vo far as accurary i conoemed. For the more exact requirements of physicn the oxygen iotope MO seems Tettr standard ‘The Commitice agres unanimously with Ason's opinion and sce no reason for proposing change in the peeent stands of ‘tome weights, O © 16.000. Proposals for Unification of the Two Scales It is immediately clear that the key to the solution of the problem of two scales would be to agree on a single reference substance and assign a value to its * For the def article by Guggenheim (7). U8). ition of mole the reader is referred to 8 recent ‘ee aleo Feferenees (74), (15), and 284 / Journal of Chemical Education fare at Teast two regirements that this reference substance should meet. ‘These are: (1) that its mass should be an invariant, and (2) that its mass should be intereomparable with the masses of other nuclidie species. Requirement (1) is elear in the Tight of what has already been discussed. | Require- ment (2) is closely connected with ‘the spectroscopic method used hy: the physicists in mass determinations and will be diseussed later, Of course, even if the ess of the chemical seule could’ have been removed by another better definition, we still would have been left. with two lists of atomic weights and also two sets of values for those constants that are dependent on the mole. Proposals for the giving up of one seale in favor of the other met with objections, despite the fact that the adopted seale might have improvements over the discarded one Many of these objections were well founded, To appreciate the seriousness of the problem, Iet us assume that the chemical seale was to be abandoned in favor ‘of the physical seale. On the basis of this seale, "0 = 16 exactly, the atomie weight of natural oxy would be 16.00440. This would mean a change of 275 parts per million in the atomic weights and related values, an amount which cannot, be regarded as neg~ ligible. ‘The need would then arise for the immediate revision of all mass and related quantities reported in handbooks, scientific tables, and the great collection of reference Works where relative masses on the discarded seale have been reported. It is well to note that the ahandoning of the chemical seale would have involved the greater burden and difficulties involved in the revision process, It was on such grounds that the alternatives to abandoning either of the scales were being sought, both by the chemists and the physicists AL this time the necessity for giving up both the physical and the chemical scales and the need for adopt- ing a “universal” scale were receiving more urgent attention. Several proposils were made. Among these a scale based on 'H = 1 exactly was suggested. ‘The great disadvantage of such a scale was that-on this basis the masses (on the chemical scale) of all atoms ‘would have had to be reduced by 7870 parts per million This, indeed, is too great a change to be ignored Hence it was argued by some that a large change of this magnitude might provide the spur for the total revision of all mass and related quantities Another proposal was put forward, urging the soy tion of a seale based on #F, with an assigned mass of 19 exactly. Fluorine consists of a single naturally ‘occurring nuclide. Nier (10) gives the valve 18.012 for its atomic weight on the chemical seale, On the physical scale the value is 19.0044. We thus note that if this clement, used as a reference mass, were to have a value of 19 exactly as its assigned atomic mass, all the values based on the chemical seale would have to Iw revised upward by 42 parts per million. Qn the oilier hhand, the values based on the physical scale would have to be decreased by 231 parts per million, It might be added that fluorine-19 as the reference species appealed to some chemists not only beeause it is in variant (so far as we now know), but because it is a naturally occurring clement, and therefore, po=sibl direct working standard for chemical determination of atomie masses. The atomic mass of 4) on the mass, However, the