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Meetings for the Week.

{CHEMICAL NEWS

Jan. 1, 1915

n3 - I, deduced on the assumption that the pro- | about within the molecule. This second type of change
changes in mass and intramolecular electrical force brought

n2+2

perty is additive. In the present experiments the molecular
solution-volumes are given, so that allowance can be
made for changes in their value when considering
the effect of substitution on the molecular refractivity :-
M n2 - I

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01507 gave 1132 cc. N2 at N.T.P; N 9'44;
C26H25O4N3 requires N = 9.48 per cent.
p-Toluenesulphonylcinchonicine crystallises from alcohol
in skew tetrahedra melting at 127°. These are sparingly
soluble in alcohol at 25° :-

01560 gave 8.06 cc. N2 at N.T.P.; N 65;
C26H28O3N2S requires N = 6.25 per cent.
Picrylcinchonicine was prepared from the base and
picryl chloride. It crystallises from acetone in lustrous
golden scales, melting at 180°, and is very sparingly
soluble in most organic solvents :-

0'1117 gave 12.70 cc. N2 at N.T.P.; N = 13'97;
C25H23O7N5 requires N=13.86 per cent.

The solutions of the above compounds were examined
at 25°. The rotatory powers were measured in 2-dcm.
tubes, the densities measured in pyknometers holding
about 10 cc., and the refractivities measured in a Zeiss
total reflection refractometer.

In the following table are collected the molecular
weights, rotatory powers, refractivities, and solution-
volumes at 25° of the above substances:-

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7.1° 342

117

p-Toluenesulphonyl- 0.9404 448

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135
136

cinchonicine
2.6240 448 9.4° 354
Picrylcinchonicine.. 07132 505 - 1968.00 361
12912 505-1881.0° 356 133

The results show some interesting effects. Like sec.-
butylamine (Pope and Gibson, Trans., 1912, ci., 1702),
cinchonicine has its rotatory power lowered considerably
by the introduction of the p-toluenesulphonyl group. The
introduction of the picryl group causes a complete change
in the sign of the rotation, and also increases the mag.
nitude very considerably. There do not seem to be any
details of other cases of the effect of the picryl group,
and it is hoped to examine further this behaviour.

Adopting the electronic theory of molecular structure
then, the effect of a substitution will be due partly to its
disturbance of the intramolecular electrical field of force
and partly to the mass of the substituent. If rotatory
power is due to vibrating electrons, then the relative effect
of these two quantities will depend on the value of e/m for
the vibrating electron, and on the magnitudes of the

may be deducible on lines similar to those used by
Flürscheim in his applications of Thiele's theory of partial
valencies, and has already been examined to some extent
by Hilditch.

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CHEMICAL NEWS,
Jan. 8, 1915

THE

Number Relations amongst the Elements.

CHEMICAL NEWS.

VOL. CXI., No. 2876.

NUMBER RELATIONS AMONGST THE

ELEMENTS.

By F. H. LORING.

13

able doubt on the probability of these two elements having a real existence.

Referring again to the same table, it is further to be observed that the number of stable elements in the vertical columns containing the branches and including the branch. members themselves is equal to the number of preceding non-branch members (reckoned in the same manner) by a regular difference of 2. Here, however, a very curious condition in respect to tellurium has to be postulated, which satisfies certain other requirements, most notably the one demanding 32 elements or members in the set (6th division) terminated by tellurium.

=

This regularity calls for 19 elements in Group VII. of the right-hand half of the table, as if tellurium were Ter....Tery (in which case Ter 7'5 and Te17 127'5). The following arrangement will make this clear:I. II. III. IV. V. VI. VII. 6+5+5 5+5

L.

....

In studying atomic weight relations, or the classification
of the elements by atomic weight, it is interesting to note
that two or three types of irregularity, common to one
element or a series of elements, so balance or cancel each
other as to leave a mean interpretation representing a
normal or regular condition, or, on the other hand, the
"irregularity" itself becomes regular by some symmetrical
peculiarity. This principle may be tentatively illustrated R....... I. II. III. IV. V. VI. VII.
by the following treatment:-

Referring to "Studies in Valency," p. 23, a periodic arrangement of all the elements is shown, which lends itself to certain uniform sub-divisions or arrangements of members which are fairly regular when interpreted in a certain manner, as will be seen from the following specification.

There appears to be a constant ratio between the number of elements comprising certain branches and the preceding number of non-branch places into which elements fit, not counting those of the chemically inactive class and nitrogen. This reckoning is from branches of like type. The ratios may be expressed by placing the numbers representing the respective branch elements as denominators thus:-21/3-14/2 = 14/2=VII.* While this argument, as it stands, is opposed to the view that elements will ultimately be discovered which will take up places preceding ruthenium and osmium, that is to say, one before each, the observation in the main is true, since there is no reason to suppose that these relations are exact or precise to within, say, one unit or one element. There are, however, other relations which throw consider

From H to Ce (inclusive) 52 (a).

From Pr to Lu (inclusive) = 13 (b).

52/13 = IV.. which is the Group No. of b, just as VII. is the Group
No. of the other branches, these branch Group Nos. being one unit in
excess of the proper classification value, a stepping-back principle
being involved (see "Studies in Valency"). Similarly, from Ta to Pb
(inclusive)=9. The mean valency of the chemically active radio-
elements (2+3+4+5+6)/5=4. The ratio should have the same
characteristic as those above and differ from this figure by one unit,
but since the process of element formation in this case is probably one
of devolution rather than evolution (see CHEMICAL NEWS, cix., 241),
not only may the ratio be reversed, but the group number may coincide
with the mean valency value, so that x/9= IV. There appear to be 32
radio-elements proper, not counting the radio-gases. When including
the end products which must form part of the branch system and be
equal to four normal elements (Ac-end = Ac-end 1, Ra-end
Ra-end=1, Th-end-, Th-end ; sum = 4) the figure is increased to
36; therefore, 36/9= IV. Lead (a) is taken as an element of evolution
when considered separate from the isotopic end-products of radio-
active origin more or less mixed with it, or forming the entire com-
position (= 6); these may be designated thus-Pba; Pbb; Pba+b.
The table given on page 23 of "Studies in Valency" calls for 64
chemically active elements in the last (7th) division, including two
branches, which may be evaluated thus-1 Uri, 2 UrX1, 3 UrY,
4 UrX2, 6 Urz, 6 Io, 7 Acr?, 8 Acz (actinium), 9 RadAc, 10 Ra,
11 AcX, 12 RaA, 13 AcA, 14 RaB, 15 AcB, 16 RaC1. 17 ACC,
17 AcCa. 18 Ac-end, 19 AcD, 20 Ac-end, 20 RaC2, 21 Ra-end,
22 RaC, 23 RaD, 24 RaE, 25 RaF, 26 Ra-end, 27 Th, 28 MsThi,
29 MsTh2, 30 RadTh, 31 ThX, 32 ThA. 33 ThB, 34 ThC, 34 ThC2,
35 Th-end, 35 ThD, 36 Th-end, 37 Mendeleeff's prediction, 38 Bi (by
evolution ?), 39 Pb (by evolution, and those following), 40 Tl. 41 Hg,
42 Au, 43 Pt, 44 Ir, 45 Os, 46 W, 47 Ta, 48 Lu, 49 Ny (Yb), 50 Thu-
lium 1, 51 Thulium 2?, 52 Er, 53 Ho, 54 Dy, 55 Th, 56 Gd, 57 Eu,
58 Sa, 59 Nd, 60 Pr, 61 Ce, 62 La, 63 Ba, 64 Cs. The numbers are
attached to the radio elements in a manner merely convenient for
counting; moreover, the order might be reversed. It will be seen that
the emanations are, in a sense, interperiodic (see CHEMICAL NEWS,
1911, ciii., 71). and when the associates part company (see CHEMICAL
NEWS, cix., 241) in a homogeneous manner the separate products-or
those considered as such-are, consequently, pure half-elements relative
to the others, at least they may be so regarded for purposes of counting.

2

= 18

2 = 12

3 +3 +3 +3 +3 + 2

2 = 19

In this case the non-branch elements, nitrogen, potassium, and one supposed element immediately following bismuth (Mendeleeff), are reckoned as occupying their respective chemical places in the table. An alternative apportionment of the numbers is given below, in which the hypothetical element following bismuth is assigned to Group VII., somewhat after the manner of tellurium (see table), the constant to be added being in this case 3 instead of 2, whilst nitrogen and potassium remain in their nonchemical places as shown in the table, the disposition of the numbers being :

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From the above it might be supposed that some balanced proportion exists between the right- and left-hand branchbut excluding the three chemically inactive radio gases. members, when taking into account the radio-elements, Indeed, this appears to be the case since

VII. L VII. R IV. L IV. R

7 is to 17 as 13 is to 32

The proportion, though not exact, includes the " 17 little telluriums" (of course a fanciful conception, but not unlike the well-known idea of ten heliums forming argon), and implies that the radio-elements collectively form a one-branch system from lead, lead itself being a more or less composite element. There are exactly 32 distinctive radio-elements, omitting the chemically inactive radiogases, and four probably indistinguishable end products undiscovered member preceding actinium (see CHEMICAL which would be the equivalent of lead, and counting in one NEWS, cix., 241).

Dr. H. G. J. Moseley (Phil. Mag., xxvii., 703), in recent work on the X-ray spectra of the elements, shows clearly the lacunæ for undiscovered elements, one preceding ruthenium and one preceding osmium, and confirms the inference that may be drawn from this study, that practically all the elements are known with these possible exceptions, and one in the rare-earth group between neodymium and samarium; there are also thulium I. and thulium II. which may be taken as established, or at least the X-ray spectra require also an additional element to thulium to render the progressive steps of the series of lines regular. Dr. Moseley has not as yet published an extension of his series of lines beyond gold, but there is every reason to believe that, between aluminium and gold,

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NOTE.-The term "atom numbers" should not be confused with the serial numbers assigned to the elements by A. van den Broek.

all the elements are known except, at the most, four elements as above indicated. Rutherford and Andrade's (Phil. Mag., xxvii., 854) experimental analysis of matter by excited radiation gives lines which assign lead to its proper and expected place in the extension of the series as indicated by X-ray analysis, and therefore no new elements are to be expected between gold and lead.*

Upon careful consideration of these supposed elements, falling as indicated next to ruthenium, osmium, and samarium, it will be seen, however, upon referring to "Studies in Valency," p. 17, that the lacunæ for these three elements in question are of the same character in the valency plot shown, indicating possibly that these may be natural breaks in an otherwise continuous chain, since, by closing the table up at these points, the irregularity becomes in itself regular. The number relations herein given support this contention.

The table under further consideration, with respect to the right-hand half of non-radio-active elements, lends itself to a complete arrangement of associate atoms (see CHEMICAL NEWs, cx., 25) in suchwise as to bring into

The composite nature of the atom may be revealed by some characteristic radiation-such, for example, as the X-ray spectra of the elements as experimentally developed by Moseley. As a first approximation in theory, the two characteristic lines observed might arise from the presence of two types of atoms differing in atomic weight; but theoretical considerations do not necessarily point directly to such a view. These, however, are matters which the experimenters themselves can doubtless discuss to better purpose. For a general account of the interference and reflection of X-rays by crystals and the analysis of matter thereby, see "X-Rays," by Kaye (Longmans, Green, and Co., 1914), particularly Chapter XII., but the original papers should be studied. For a list of references leading up to the developments by Moseley, see "Text-book of Inorganic Chemistry," by Messrs. Friend, Little, Turner, and Briscoe (C. Griffin and Co., Ltd., 1914), vol. i. p. 50. See also Tutton, CHEMICAL NEWS, 1913, cvii., 277, 289, 301; but see particularly Moseley, Phil. Mag., December, 1913, p. 1024, and April, 1914, p. 703.

harmony the values by the elliptical method, those of the quaternian series when available (there being a limited number of these), and those by the summation method, also limited in number. Moreover, the values are not at variance with those obtained by experiment when the more accurately determined values are compared with the theoretical ones, as the accompanying table will show. In this table, however, the atomic weights enclosed by the circumscribed line are for one reason or another uncertain, notwithstanding the coincidences. The other atomic weights for the most part are probably correct; those obtained by taking mean values (m.v.) of the associate atoms as shown being the preferred ones, and these are supported by experiment. It must be remembered that the various methods employed represent tools which are capable of some adjustment, and finality is not possible in

every case.

The setting aside of the inactive gases in these numberstudies should not be taken as an indication that they are not true elements, but rather that they are chemically inactive, and consequently count as nought when balancing or otherwise arranging the chemically active members. They appear to fit into the X-ray spectrum series, and take up a normal zero place in practically all periodic tables, and from various considerations the universal opinion is that they are true elements (see Soddy, Science Progress, 1914, viii., 654).

Since these relations are largely based upon the idea of branch systems of elements, the peculiarity of these branches should be kept in mind, otherwise some of the statements would seem contrary to accepted opinion; whereas the method of treatment is, I believe, quite as comprehensive in its systematic expression of fact as any other method, but this is a matter for others of wider experience to judge.

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