THE CHEMICAL NEWS.

VOL. CXXI., No. 3157.

EDITORIAL.

THE following papers have been received for publication, and will be inserted as soon as space permits :

"A Modification of Skraup's Quinoline Synthesis." By Edward de Barry Barnett, B.S.c., F.I.C. A convenient method of preparing quinoline in the laboratory is described in which ferric sulphate is employed as an oxidising agent. A catalytic modification of Skraup's process is also described.

"A New Form of Ozoniser for Laboratory Work." By Y. V. Ramaiah and M. V. N. Swamy, B.A., Indian Institute of Science, Bangalore, India.

ANALYSIS OF DROPPINGS OF CATERPILLAR (ANTHERAEA CYTHEREA). By Dr. CHARLES F. JURITZ, M.A., F.I.C.

A FEW months ago Mr. C. W. Mally, M.Sc., F.E.S., Government Entomologist for the Cape Province, handed me a parcel of caterpillar droppings from Uitvlugt, Cape Division, produced by larvæ of Antheraea cytherea. This caterpillar, Mr. Mally informs me, appears in great abundance on the wattle in early summer in certain years, when it completely strips the trees of leaves. In other years natural enemies cause it to disappear almost entirely. When abundant, the larvæ produce large quantities of droppings. The sample given me by Mr. Mally was analysed in this laboratory with the results stated below. After ascertaining that the weight of 100 particles was 44310 grms., the whole of the sample submitted was crushed in a mortar and passed through a sieve with meshes of 1 mm. diameter; a portion of this sifted material was ignited at a low heat and produced a greyish white ash.

as

The following analytical figures were obtained, calculated in percentage of the sample originally received :

:

Potash

2.87

Lime

...

1.86

0'87

The proportion of moisture in the original sample is low and compares better with the general type of kraal manure (which ranges from 9 to 20 per cent) than with the usual type of horse, cow, or sheep manure (in which it may be said to vary between 66 and 86 per cent).

In order to compare the fairly dry unburnt manure, averages on a 10 per cent basis have been compiled in the following table, the figures for

...

It will be noticed that, in the leaves, as in the droppings, potash is highest in amount of the three inorganic plant food constituents, and phosphoric oxide lowest; also that in the droppings these inorganic constituents, or, at all events, the potash and the lime, are present in a more concentrated form than in the acacia leaves.

The droppings were said to have been so abundant during the last season that it had been proposed to use them for fertilising purposes.

THE FIVE MAIN PRINCIPLES IN THE CONSTITUTION AND STRUCTURE OF THE CHEMICAL ELEMENTS.

By HAWKSWORTH COLLINS.

from

I. SINGLE chemical valences emanate elements or portions (of elements) whose masses are 1, 3, 7, 23, and 39.

2. The non-metallic nature of an element is always due to a pair or pairs of electro-positive forces, each pair emanating from a portion of the element, of which the mass is 4, taking the mass of an atom of hydrogen as unit.

3. Monadic Na (23) takes a prominent part in the formation of all elements of greater mass than itself.

4. In the simpler elements H (1) forms the connecting link between the other portions 3, 7, 23, and 39. In the formation of the heavier elements, masses of 23 sometimes unite by forces which are not chemically evident without any intervening unit mass.

5. Each of the heavier elements is formed by the union of simpler elements (which are indicated in each case by mineralogical and chemical facts combined).

The first four principles have already been fully demonstrated, so that the following matter chiefly concerns the fifth.

There are nine pairs of elements connected by a mass of 90 (Table I.).

Au (197)

Rh (102) Ag (107)

In six cases out of nine the heavier element happens to be in the same column of the Periodic Table as the lighter. There are nine columns, o, 1, 2, 3, 4, 5, 6, 7, 8.

The probability that the heavier of a pair would accidentally be in the same column as the lighter is 1:45, say 1: 4. E.g., if the lighter is in the column 4, the heavier might be in o, 2, 4, 6, or 8; or, if the lighter were in column 5, the heavier might be in 1, 3, 5, or 7.

Therefore, the probability that a pair would happen accidentally to be in the same column in six cases out of 9 is 1: 49-3×3 = 1 : 45=1: 1024. Therefore, the probability that this state of affairs is not due to accident is 1024 : 1. But the probability against its being an accident is greatly increased (1) by the fact that Zr (90) is especially found intimately associated with most of these elements, and (2) by the fact that the difference of 90 in the atomic weights of four of the pairs of elements is due to something which produces no alteration in the atomic volume, and which, therefore, is in all probability the same thing in all the four cases. This will be demonstrated later.

The 46 integers in the last paper were obtained from only one set of data, viz., the two columns of experimental atomic weights, with the help of the Odd and Even Rule. No other consideration influenced them in the slightest.

From the integers so obtained it has been proved :

I. That a mass of 23 with one valence takes a prominent part in the formation of the elements. 2. That a mass of 90 takes part in the formation of some elements which happen to be especially associated with Zr in mineralogy. Taking these two proofs into consideration, and also the three following statements (a), (b), and (c), the constitution and structure of 26 of the 46 heavier elements can be obtained.

(a) Mineralogical facts with regard to Na and Zr have only been mentioned as coincidences, and have taken no part in arriving at the above results (1 and 2), so that these facts are free for independent reasoning.

(b) Although the maximum valency of each element has been mentioned, it has not influenced the obtaining of the integer in any way. Only the differences of the valences of pairs of elements have been employed, and the observation as to whether the maximum valences were odd or even; so that the actual number representing the maximum valency of each element is free for independent reasoning with regard to each integer.

(c) The distinction between metallic and nonmetallic valences has not been employed at all in arriving at the 46 integers, so that these are also free for independent reasoning.

Gallium (69) = Na,.

(a) The matrix of Ga is said to be: Si-Alminerals from which most of the Na has been dissolved. This undoubtedly suggests that Ga has been formed from the extracted Na.

(b) The number 69 exactly explains the valency of Ga, one from each portion of 23.

(c) It also explains why Ga cannot act as a non-metal, for there is no free H-H,.

(d) If it had not happened that when oxygen is taken as 16 some of the simple elements are whole numbers, the atomic weight of Ga would now be given as 696 (H= I).

(e) The integer obtained is especially suitable for explaining the mineralogical and chemical facts with regard to Ga; for there are no associated elements, the sum of whose atomic weights is equal to either of the two adjacent integers, and by means of which the valency of Ga can be explained.

(f) The probability that this particular number (obtained independently and not arbitrarily by means of the five proofs mentioned in the last! paper) would be exactly equal to the sum of the atomic weights of intimately associated elements, and at the same time exactly explain the valency, and that neither of the two adjacent integers would be at all suitable for this purpose, is 1:3

(a) Arsenic is found especially associated with Cu. Domeykite, algodonite, and whitneyite are compounds of As and Cu. Tennantite, a common mineral, is a sulphide of Cu and As.

(b) By the Interrelationship of the Elements there are eleven pairs of elements, the sum of whose atomic weights is 75, and the sum of whose valences is always an odd number, 5, 7, or 9; so that a pentad could always be formed; but CuC is by far the most likely method of formation from the facts of mineralogy, and its structure would then be

(a) Ag2S is almost invariably found intimately associated with As,S,, and their molecular weights are equal, so that if each atom of As combined with one of S, the latter molecule would become Ag2S by atomisation.

(b) The difference of the valences of As and S is one, so that the monad Ag could be formed by five pairs of valences becoming quiescent.

(c) Since there is only one valence there can be no free H-H,, and therefore, by the theory Ag cannot be a non-metal.

Zirconium (90) = NaCaAl.

(a) Zr is found in astrophyllite with Na, Ca, Al; also in scapolite, a silicate of Na, Ca, Al; and in elaeolite, a silicate of Na, Ca, Al, K. The zircon-syenite or augite-syenite of Norway contains much elaeolite.

(b) Zr is a tetrad, and a tetrad could be formed from these three elements as follows:

Ca-Na-Na-H-H,

where the two valences from the Na portions are quiescent as they have been shown to be in several other cases.

(c) This formula also explains the non-metallic nature of Zr.

Gold (197) ZrAg.

(a) Silver always accompanies gold, and crystals of zircon are common in most auriferous sands.

(b) The monad Ag could combine with the tetrad Zr so as to form the triad Au, two of the valences becoming quiescent.

(c) The non-metallic nature of Au is explained by combining Ag with Zr in the following

manner :

Ag-Ca-Na-Na-H-H,

Ꮄ

exactly explains the valency of Sb, showing why it is tribasic and diacidic.

Ruthenium (101) = Na,Mn.

(a) Ru is found in iridosmine with platinum. This mineral occurs in situ in the Broken Hill district of New South Wales in a feldspathic rock. Feldspar contains Na with Si and Al, which together form Mn.

(b and c) The chemical compounds of Ru are exactly analogous to those of Mn, so that it is difficult to understand why the former is not put in a vacant place under Mn in the Periodic Table. The two valences from Na, are as usual quiescent. Osmium (191)=ZrRu.

(a) Ru and Os are found together in auriferous sands, and crystals of zircon are very common in such sands.

(b and c) The valency of Os being similar to that of Ru is explained by the two non-metallic valences of Zr uniting with two of the metallic valences of Ru.

Iron (56) Si,.

(a) Native iron occurs in most meteorites as a spongy cellular matrix in which are embedded grains of chrysolite or other silicates.

(b and c) The position of Fe in the Periodic Table indicates that it may be an octad, in which case its constitution and structure would conform with those of the first 25 elements (CHEMICAL NEWS, Dec. 26, 1919) and would be

H ¡

§ §
·H,—H—-Na—Na-H-H,-H
S S

But, since its valency is observed to be hexadic, if the valences of the two Na-portions were quiescent as usual, its valency (dibasic and tetracidic) would be exactly explained.

As this element is distinguished by its magnetic character, it would be expected that either its constitution or its structure or both would be distinguishable in some way from other elements. These requirements are satisfied, as (1) it is the only non-metallic element whose structure can be written down (in accordance with this theory) symetrically; (2) it is the first element (in the order of ascending atomic weight) whose experimental atomic weight is more than o'r below the nearest integer; and this is probably due in some way to its magnetic property. The symmetry of the atom would obviously enable it to lie in a magnetic field in a way that is possible for no other atom.

Rhodium (102) = Na,Fe.

(b and c) Rh seems to be analogous to Fe in valency according to the Periodic Table.

Iridium (192) = ZrRh.

(a) Ir and Rh are found together in auriferous sands, and crystals of zircon are very common in such sands.

(b and c) Ir is recognised as being a similar element to Rh.

Iodine (127)= Na,Cl.

(a) The evidence of mineralogy is that the ultimate matrix of iodine is seaweed, and that it has been and is being produced by the power of vegetable life in seaweed: four molecules of NaCl being converted into (NaCl)C, IC,, a wellknown compound.

(b and c) The heptadic valency is explained by the four valences from Na, being quiescent. Mercury (199) = Na,Ag.

(a) Ag is always found with Hg.

(b) The valency is explained by two of the valences from Na, being quiescent, the other two being unable to act at the same time as the single one from Ag, so that the element is either dyadic or monadic.

(c) Hg cannot act as a non-metal as there is no free H-H ̧.

Rubidium (85) = Na,K.

(a) Rb is found with Na and K in rhodizite. (b) It acts both as a monad and a triad, so that the two valences from Na, are sometimes quiescent and sometimes not.

(c) It cannot act as a non-metal, as there is no free H-H、

Selenium (78) = Na2S.

(a) Se is always found with S.

(b and c) Its similarity to S is explained by the two valences from Na, being quiescent.

Tin (8)=ZrSi.

(a) Cassiterite (SnO,) is found in parallel position with zircon (ZrSiO1).

Since, by the Interrelationship of the Elements, ZrSi=CuAlSi=CuMn; Sn might also have been formed by the union of Cu and Mn. The alloy CuMn is very like tin.

(b and c) If the two non-metallic valences of Zr are quiescent with the two metallic valences of Si, the valency of Sn, dibasic and diacidic is explained.

Radium (226) = ZrBa.

(a) The raw material from which Ra is prepared consists principally of Ba, Sr, and Ca. Ra is also found in pitchblende, which contains zirconium.

(b and c) If the two valences of Ba are quiescent with the two metallic valences of Zr, there would be left only the two electro-positive valences emanating from the portion H-H, of Zr. Ra cannot act as a non-metal because there is no electro-negative valence left to unite with a base.

Niton (222) = Na,Xe=Ra minus H-H,. (a) Nt is found with Ra.

(b and c) The fact that Nt has no valency is explained by radium's loss of two electro-positive valences when helium is given off; and also by the relation Na,Xe.

Cobalt (59)=AIS.

(a) Cobalt is especially associated with Alminerals, and is also found with sulphur.

(b and c) In luteo-cobalt hexchloride = Co2(NH3)2C1, cobalt has nine valencies, of which Al supplies three and S supplies six. The position of Co in the Periodical Table next to Mn and FevIII. indicates that nine valences may be expected from it. 59 is almost the only number which could represent an element of nonadic valency according to the theory.

Nickel (59) = SiP.

(a) Ni is found in schreibersite (Ni,Fe,P) in meteorites. Polydymite (Ni,S,) is found with

quartz. (SiO2). (b) Ni forms similar compounds to Co, indicating that it also has nine valences, four from Si and five from P.

Molybdenum (96) = Na,Al.

(a) Molybdenite (MoS2) occurs with cryolite (Na,AIF) in Greenland.

plained by the constitution Na ̧Al. (b and c) The valency of Mo is exactly ex

Tellurium (128) = MOS.

(a) Te is especially associated with Au, Pb, Ag, Bi, Hg; i.e., in the Ag-minerals. Mo is said to be always found with Ag. S is always associated with Te.

(b and c) Te, Mo and S are all hexads so that the valency is easily explained.

Germanium (72) = As minus H,.

(a) GeS2 is found with Ag2S (=As2S,) in argyrodite, which occurs in association with minerals containing much arsenic.

(b) If the pentad As could give off H, with one valence, there would be left an element of atomic weight 72 with four valences.

(c) There would be no free H-H, left, and therefore Ge would not be capable of acting as a non-metal.

Bromine (79) = AsHe.

(a) Br is chiefly found in combination with Ag, and therefore in ores containing much arsenic. (b) If the pentad As combined with the dyad He, a heptad would be the result.

(c) The addition of a free portion H-H, would make Br non-metallic to a greater degree than As.

The probability that the state of affairs here given with regard to any one of the foregoing 26 elements is the result of accident is 13 at least; for in nearly every case the combination of elements given is especially suitable in particular ways which cannot be brought into a probability calculation; and the particular integer is frequently the only one in the neighbourhood, considering six or more adjacent ones, which is at all suitable for explaining the scientific facts concerning the element. E.g., the fact that Ga cannot act as a non-metal has not been brought into the probability calculation, as given below, neither has the fact that none of the ten integers adjacent to 69 could represent a triadic element in accordance with the theory.

There is only one case out of the 26 given, in which an integer in the neighbourhood would be more suitable than the integer found; but this case only helps to emphasise the extraordinary

nature of all the other integers obtained. If Br had been represented by 81 (NaCl) instead of 79, it would have been a true arithmetical mean between C1 (35) and I (Na,Cl).

Of the 46 elements from Fe upwards (not including the twelve rare ones) Kr and Xe cannot be considered in any way mineralogically; so that only 44 can come into the following calculation.

The probability that in each of 26 elements the particular number (obtained independently and not arbitrarily by means of the five proofs mentioned in the last paper) would be exactly equal to the sum of the atomic weights of intimately associated elements and at the same time exactly explain the valency, and that neither of the two adjacent integers would be at all suitable for this purpose, is : 344-18×1: 317 at least; or, considering Ge and Br as exceptions, the probability is 1: 344-20x=1: 3" at least 14 million.

14

The remaining 18 elements will be considered in the next two papers, and although they have had to be considered as exceptions to the above reasoning, the facts concerning them will strengthen rather than weaken the conclusions arrived at in this paper.

As an example of the way in which the above reasoning might have been upset, suppose that the two elements which are especially associated with Ag had been As and P instead of As and S, then it would have been impossible to explain how the union of two pentads could produce a monad, knowing that the valences are quiescent in pairs. If it were merely a matter of chance, this sort of thing would be as likely to happen as not; but it never seems to happen except in one or two cases which are only apparent and not real. E.g., the hexad titanium is found with Cb, which is apparently a pentad. But since it is impossible to completely separate these two elements, they must be exactly similar chemically, and therefore, Cb is probably a hexad, the explanation being similar to that given for hexadic Mn (CHEMICAL NEWS, June 4, 1920).

conductivity of most insulating materials even below the melting point of lead. Through the kindness of Professor Harvey N. Davis and Dr. F. Wheeler Loomis, asbestos-insulated copper and nickel wire were available for the construction of the elements. This combination has thermoelectric advantages. The thermoelectric effect (about 23 microvolts per degree at 327°) is much higher than that of noble-metal elements, although not so high as copper-constantan; moreover, both sorts of wire are generally very free from the inhomogeneity often met with in alloys, and both metals are sufficiently resistant to oxidation under ordinary conditions.

The use of copper here as well as for connections to the rest of the measuring apparatus diminishes the danger of parasitic effects to a minimum.

The asbestos insulation, which had an inflammable binder, was removed from a few millimetres at the ends of the wires, and the ends were twisted together. They were then soldered with a minimum amount of silver solder, using borax as a flux.

The junctions were insulated from each other by a thin glaze of lead borate prepared from litharge and boric anhydride in a nickel crucible in the proportion represented by Pb,B,O.. For convenience in introducing into the glass tube the several separately insulated elements were twisted together and the whole glazed so as to form a single bead. The single element used to measure the bath temperature was simply enclosed in a glass tube. All the "cold ends" were contained in a single glass tube under paraffin. The free ends were, after several windings, soldered firmly to thin copper strips which made contacts through strong clamps (W. P. White, loc. cit., p. 1861).

The furnace consisted of two tall glass beakers, of which the smaller was wound with a commercial resistance wire wrapped in asbestos and placed in the larger beaker. The beakers thus nested were set in the centre of a fibre pail, of which the bottom had been covered with magnesia and asbestos, the whole being packed in this mixture. Around the top of the beakers a smooth covering was made of plaster of Paris. The heavy tempering oil placed in the inner beaker and used for the bath needed renewal from time to time; it carbonised and evaporated but never burned, and its odour, while unpleasant, was not unbearable. The viscous oil was rapidly stirred with a brass stirrer, and the bath was covered with a block of asbestos nearly 3 cm. thick. After the stirrer, the melting point apparatus, the thermo-couples, and a mercury thermometer had all been inserted through the cover, all the holes were luted with a paste made of magnesia, asbestos threads, and oil. The whole furnace was thickly surrounded and covered with wool felt. The rapidity of stirring was such that no difficulty whatever was found in keeping the temperature of the two samples of lead the same within o1° while the furnace was rising in temperature at the rate of 10° per minute, or in keeping the furnace temperature constant within oo5° for hours at a time with proper regulation of heating current. The alternating 110volt lighting circuit was used as a source of heat, but on account of fluctuating voltage needed frequent regulation if constant temperature was