1110
JOURNAL
OF
CHBMICALEDUCATION
OCTOBER, 1926
THE STRUCTURE OF MATTER: A BRIEF REVIEW OF PRESENTDAY CONCEPTIONS. I. THE ATOM MAURICEI,.
HUGGINS, S T ~ O RUNIVERSITY, D CALIFORNIA Introduction
Very few teachers of courses in general chemistry have had the opportunity to keep abreast of recent developments in the field of atomic, molecular, and crystal structures. That the teacher possesses a knowledge of these developments is of prime importance, both t o enable him t o give his students an up-to-date viewpoint on these matters and to prevent h i m from teaching them many things which are now known t o be incorrect. This series of articles is an attempt t o supply the need for a brief review of the present status of our knowledge of the structure of matter, especial care being taken to present only those conceptions which experiment has shown t o be practically certain facts, or where speculation and theory are dealt with t o label them dekitely as such. It will not be possible in such a condensed presentation as this, to give the historical development of the subject, nor can the evidence for most of the statements made be given. For these the reader must look elsewhere. The following books and articles are suggested for those who wish t o delve more deeply into the subject-matter of the present series: S i r William H. Bragg, "Concerning the Nature of Things." Bell, London, 1925. Andrade, "The Structure of the Atom," Bell, London, 1924. Berthaud, "The New Theories of Matter and the Atom," Mamillan, New York, 1924. N. Campbell, "The Structure of the Atom." University Press, Cambridge, England, 1923. Cranston, "The Structure of Matter," Van Nostrand, New York, 1924. Crowther, "Molecular Physics," Churchill, London, 1923. Mills, "Within the Atom," Van Nostrand, New York, 1923. Stock, "The Structure of Atoms," Methuen, London. 1923. H. S. Tavlor. . . "A Treatise on Phwical Chemistrv." .. Van Nostrand. New York. 1925, Vol. 1, Chaps. 1and 5. Wehster, Farwell, and Drew, "General Physics for Colleges," Century, New York, 1926, Chaps. XX, XXII-XXVI. G. N. Lewis. "Valence and the Structure of Atoms and Molecules," Chemical Catalog Co., New York, 1923. B o b "The Theory of Spectra and Atomic Constitution," University Press, Cambridge, England, 1922. Kramers and Holst, "The Atom and the Bohr Theory of Its Structure," Gyldendal, Landon, 1923. Sommerfeld, "Atomic Structure and Spectral Lines," Dntton, New York, 1923. Aston, "Isotopes," Longmans, London, 1924. Fajans, "Radioactivity," Methuen, London, 1923. Venable, "A Brief Account of Radioactivity." Heath, New York, 1917.
Bragg and Bragg, "X-Rays and Crystal Structue," Bell,London, 1924. Davey. "A Study of Crystal Structure and Its Applications," Genl. Elec. RN.,27, 742,795 (1924);28,129,258,342,586,721(1925);29,118,274,440(1926). Wyckoff, "A Survey of Existing Crystal Structm Data." J. Frank. Znst. 195,183, 349, 531 (1923). Wyckoff, "The Structure of Crystals." Chemical Catalog Co., New Yark, 1924.
Protons and Electrons It is now generally accepted as f a d by chemists and physicists that all matter is composed of .protons and electrons, the elementary unit charges of positive and negative electricity. The magnitude of the charge on either is 4.774 X 10-lo electrostatic units or 1.592 X 10-Ig coulombs.' g.; that of the proton is 1846 The mass of the electron is 8.999 X g.' times as much, or 1.662 X Calculations of the size of protons and electrons have been made on the assumptions, (1) that the mass of each is entirely electrical in origin, and (2) that the electric charge is uniformly distributed over the surface of a sphere (or throughout its volume). The radius of the proton, obtained in this way, comes out to be about 10-l6 an., and that of the electron 1846 times as large. We should, however, attribute little physical meaning to these figures, for we have no reason to believe that the assumptions involved are correct. Experiments on the scattering of one kind of atomic nucleus by anotherboth nuclei containing both protons and electrons-show that the repulsion between nuclei obeys the inverse square law (Coulomb's law) at all distances between their centers greater than 10-l2 cm. This seems to indicate that the nuclei, and so their component protons and electrons, must be smaller in diameter than this. Possibly, though, we shall never be able to give definite dimensions to protons and electrons, for they may not have sharp boundaries and, if not, how are we to d e h e what we mean by "size"? Nuclei A neutral atom of any element consists of a nucleus, charged positively with a charge equal to the atomic number (the charge on one proton being taken as unity), and surrounded by a number of electrons also equal to the atomic number. The diameters of atoms are of the order of magnitude of cm., but, if we are to accept the conclusions based on the scattering experiments already mentioned, the nuclei cannot be larger than about cm. The hydrogen nucleus consists of a single proton; others contain both protons and electrons. As the mass of the electrons is negligible, relative 1
vol. 1.
The values given for these constants are from International Critical Tables,
to that of the protons, the mass of the atom is practically equal to that of a single proton times the number of protons, except for a small diierence due to the "packing" of protons and electrons so close together. Within the error of measurement this packing effect is the same per proton, so if we take as our unit of mass oue-sixteenth the mass of the oxygen atom (which contains 16 protons) we obtain whole numbers for the masses of all atoms except hydrogen. The chemical properties of an element have to do wifh the outer electrons in the atom, but their numher and, to some extent, their distribution depend on the nuclear charge. Hence any two atoms having the same nuclear charge (atomic numher) are chemically practically identical. They may, however, have ditferent numbers of nuclear protons and electrons, and so diierent masses, for the nuclear charge is the difference between the numbers of protons and electrons in the nucleus (see Table I). Such atoms, of the same atomic numher but diierent atomic weights, are called isotopes. The atomic weights ordinarily used are average values, in those cases in which there is more than one isotope of an element. (Dierences, other than those artifidally produced, in the relative proportions of the isotopes of an element have been found only among the radio-active disintegration products.)
TABLE I THECowosmo~OP SOME OF TAE SIMPLER ATOMICNUCLEI* Element
-
Nuclear charge atomic nnmbec
-
Number of protons
relative mass'
Number of electrons in nvelevn
Some of the heaviest of the elements are radio-activethat is, decomposition of some of their nuclei is constantly taking place. As a result of
-
' F a a more complete list of isotopes, see International Critical Tables, vol. 1.
' Except in the case of H whose relative mass
1.008.
VOL. 3, NO. 10
Smuc+rmBon m
m~
1113
this decomposition, lighter nuclei are formed and or rays (helium nuclei) or B rays (electrons), or both, and r rays, which are of the same nature as visible light and X-rays hut of even shorter wave-length-higher frequency-than the latter, are emitted. The emission of the charged or and B particles changes the nuclear charge and so the kind of element which remains. No way has been found of artificially increasing or decreasing the rate of radio-active decomposition, hut by bombarding atoms of certain light elements (N, Al, and others) with or particles, Rutherford and Chadwick have obtained evidence of their decomposition. Hydrogen nucleiprotonsare the only products so far identified. Miethe in Germany and Nagaoka in Japan, working independently, have recently claimed to have changed mercury nuclei into those of gold by bombarding the former with electrons, but further careful experimentation is necessary before we can accept or reject their conclusions. Three distinct lmes of e v i d e n e t h e emission of helium nuclei by radioactive substances, the much greater abundance of elements having atomic weights divisible by four, and the fact that Rutherford and Chadwick were able artificially to decompose only atoms whose atomic weights are not so divisible--point to the probable existence within atomic nuclei of groups containing four protons, perhaps identical with helium nuclei. Further than this practically nothing is known concerning the distribution of protons and electrons within the nucleus. Extra-Nuclear Electrons4 Although, as will be shown in the second article of this review, the electrons in atoms may be in constant orbital motion, it simplifies our picture somewhat to treat each as though it occupied a definite position. I t must he understood, however, that i t may later become necessary to interpret these "positions" as mean positions or as centers of orbits. The electrons outside of the nucleus are distributed among one or more shells. The shell containing the valence electrons-those which take part in chemical combination-is distinguished by the name "valence shell." The rest of the atom is called the "kernel." Table I1 shows the number of electrons in each shell in each type of kernel known to exist, together with the kernel charge, which in a neutral atom is equal to the number of valence electrons. We shall now consider these extra-nuclear structures, taking the elements in the order of their atomic numbers. In hydrogen the kernel is the same as the nucleus and contains but one proton. The helium nucleus has a charge of f2. The two electrons 4 The present-day picture of the atom, as outlined in the remainder of this paper, is due largely to G. N. Lewis.
TABLEI1 KERNEL STRUCTURES OP TEE ELEMENTS Charge on kernel
C o m p ~ t i o nof
0
+1
+2
+3
+4
+5
+6
f?
+8
kernel
N H. 1 N, 2 He.2 Li.3 Be,4 B.5 C,6 N,7 N, 2 , s Ne, 10 Na, 11 M g , 12 Al, 13 Si, 14 P, 15 N. 2. 8, 8 A, 18 K, 19 Ca, 20 Sc, 21 Ti, 22 V, 23 N, 2,8, 8, 1 Ti, 22 V, 23 N, 2, 8, 8, 2 Ti, 22 V, 23 N, 2, 8, 8, 3 V, 23 Cr, 24 Mn, 25 Cr, 24 Mn, 25 Fe, 26 N, 2, 8, 8, 4 Mn, 25 Fe, 26 Co, 27 N, 2, 8, 8, 5 Fe, 26 Co, 27 Ni, 28 N, 2, 8, 8, 6 Co, 27 Ni, 28 N, 2, 8, 8, 7 Ni, 28 N, 2. 8, 8, 8 Cu, 29 N, 2, 8, 8, 9 N, 2, 8, 8, 10 Cu, 29 Zn, 30 Ga, 31 Ge, 32 As, 33 N,2,8,8,10,8 Kr, 36 Rb, 37 Sr, 38 Y, 39 Zr, 40 Cb. 41 N, 2. 8. 8. 10, Cb, 41 Mo, 42 8, 1 N, 2, 8, 8, 10, 8, 2 Cb, 41 Ma, 42 N, 2, 8, 8, 10, 8, 3 Cb, 41 Mo.42 N, 2. 8. 8, 10. Mo, 42 Ru, 44 8,4 N, 2, 8, 8, 10, Ma, 43 Ru, 44 Rh, 45 8, 5 N,2, 8, 8, 10, RU, 44 ~ b45, ~ d45 , 8, 6 N. 2, 8, 8, 10. Pd, 46 8, 7 N, 2, 8, 8, 10, 8. 8 Pd, 46 N, 2, 8, 8, 10, 8, 10 Ag, 47 Cd, 48 In, 49 Sn, 50 Sb, 51 N, 2. 8. 8, 10. 8, 10, 8 Xe. 54 Cs, 55 Ba. 56 La, 57 Ce, 58 N, 2, 8, 8, ' 10,8,10, 8.1 to N, 2, 8, 8, Yb, 70 10,s. 10,
0,s F,9 S, 16 C1, 17 Cr, 24 Mn,25 Mn, 25 Fe, 26
Se, 34 Br, 35 Mo,42 Ma.43 Ru, 44 Ru, 44 Ru, 44 Rh, 45
Te, 52 I, 53
TABLE I1 (Conduded) Charge on
kernel
0
+I
+Z
+3
+4
+5
+6
+7
+8
Cornpositlo" on
kernel
N. 2. 8, 8. 10. 8, 10. 8, 14, 2 N. 2, 8, 8, 10, 8. 10. 8. 14.
W,74
Os, 76
Ir. 77 ~
~
~
~
8, 10, 8, 14, 4
W, 74
5
Re, 75 0s. 76 Ir, 77
Os, 76
Pt, 78
N,2, 8, 8, 10, 8. 10, 8, fi N, 2, 8, 8, 8, 10. 8, 7 N. 2, 8. 8, 8, 10, 8, 8 N, 2. 8. 8.
10, 8
14.
Os, 76 Ir, 77 Pt, 78 10, 14, Ir, 77 Pt. 78 10, 14, Ir, 77 Pt, 78 An, 79 10,
Rn, 86
-, 87 Ra, 88 Ac, 89 Th, 90 UX,,91 U, 92
The nucleus N has a positive charge equal to the atomic number (the number following the symbol of each element). Some of the kernel assignments for elements of variable kernel may be in error. Also, certain elements may in some compounds possess kernels other than those assigned to them in this table. The kernel structures given above may be considered as quite definitely known, except perhaps as regards the (complete or incomplete) 10- and 14-electron groups. These should probably he divided into "4,6" and "6,8" shells, respectively.
outside of the nucleus in the neutral atom do not take part in ordinary chemical combination: hence we consider them as belonging to the kernel. A similar two-electron shell exists in the kernels of all heavier atoms. Lithium has one valence electron outside of such a shell, beryllium two, boron three, etc., until in neon there is a second shell containing eight electrons. As neon atoms are inactive chemically we call this shell Compounds of helium with mercury, iodine, sulfur, and phosphorus haverecently been reported. These, however, were not obtained by ordinary chemical means and can hardly he classed with the well-known compounds of other elements.
also a part of the kernel. A third shell starts with sodium and is complete when it too contains eight electrons, in argon. For some reason, not yet understood, the electrons in these 8-electron shells are in pairs, four pairs being oriented around the nucleus as are the four comers of a tetrahedron around its center. Potassium, calcium, and scandium have kernels like that of argon, except for the nucleus, with one-, two-, and three-valence electrons, respectively. The elements from titanium to copper, however, seem to have different numbers of electrons available for chemical combination under different environmental conditions. Manganese, for instance, seems to have at different times 2-, 3-, 4-, 6-, or 7-valence electrons. This may be explained by assuming that the kernel varies accordingly, containing, outside of the argon-like structure, 5, 4, 3, 1, or 0 electrons, distributed in space in a manner as yet unknown. The elements from copper (monovalent) to bromine all have the same distribution of electrons within the kernel-(N, 2, 8, 8, 10)-the last 10 electrons being perhaps in two shells, one containing four, the other six, electrons. Krypton completes another &electron shell (containing four pairs tetrahedrally disposed). Beginning with Cb, or possibly Zr, the kernel is again variable, ten electrons being added to it before a really stable arrangement is obtained, in silver. Then another shell of eight electrons-four pairs-is formed, being complete in xenon. Starting with cerium, electrons are once more added to the kernel as we proceed from element to element, this time much more regularly than before, one electron "dropping in" each time the atomic number is increased by one, until fourteen have done so. These probably form two groups, one of six and one of eight electrons, but this is not certain. Beginning with tantalum, ten more electrons drop into the kernel, somewhat irregularly, much as in the middle of the first two long periods of the table. A stable kernel is formed again in monovalent gold, around which another shell of four pairs is built--complete in radon. The remaining elements apparently have radon-like kernels, although it is possible that under certain circumstances electrons drop into the kernel in the cases of the last two or three elements as in the corresponding positions in the previous long series. The foregoing is not speculation, but definitely proven fact. Some of the details of the system are yet to be worked out, and much is yet to be learned concerning why electrons distribute themselves as they do, but the general scheme as described above and given in Table I1 is certainly correct.
