John Almon.

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fundamental.

A^ain, the Tin Group in Series I is in the same horizontal
division with the Carbon-Silicon Group in Series II. The mutual
relations of the two are thus recognized ; and, also, by the ar-
rangement in distinct series, the actual diversity as to their
grade in ternaries. For silicon stands on a virtually highet
level than tin and titanium, and throws the latter into the in-
ferior basic relation whenever they occur together. As Ti joins
with Fe to form with oxygen a sesquioxyd, closely isomorphous
with hematite (Fe^O*) and also physically like it^ so Ti may
join with Ca (as in Perofskite) or with any other metal of that
sub-group, in a sesquioxyd ; and so also it may be basic in any
combination with silica, as in sphene, etc., page 268. Accord-
ingly, also, SiO^ and ZrO' make together, not a mere combi-
nation of two coordinate isomorphs, but a true Unisilicate, as
recognized in the formula on page 255. The formulas of the
silicates which have been given and the classification we r^aid
as mutually illustrating and sustaining one another.



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G. F. Barker on Formic verttis Carbonous Acid. 963

Flaorine is placed amoog the Artiads, because of its frequent
replacement of oxygen, the analogies of its ternaries with those
of oxygen, and the nature of some other of its compounds,
although it acts in many cases as a Perissad. But with regard
to it no special relation m a horizontal view of the classification
is intend^ to be indicated.*



Abt. XXX. — Formic verstis Carbonous acid; by Geobge F.

Babker.

In studying the primary oxyds of the negative simple radicals,
(the acids) for the purpose of classification, it is evident that
the equivalence of the radical varies in each of the acids which
it forms. In sulphuric acid, sulphur is a hexad, while in sul-
phurons acid it is a tetrad and in hyposulphurous acid a dyad.
Conversely we may expect to find as many acids as the radical
by such changes m its equivalence, can produce. Phosphoric
acid contains phosphorus as a pentad ; but since this radical
may act as a tnad, phosphorous acid is thus predicted. In the
case of the tetrad carbon we have carbonic acid ; but since car-
bon may act as a dyad, carbonous acid is also possible. I pro-
pose to give here some of the arguments which may be adduced
to show that formic acid is the acid in question.

1. The formula of formic acid, usually written ^ H f ^»
may equally well be written ^ > O^, both being equal to
H2€JOa, corresponding to carbonic acid Hg^Og. * Potaesic formate
(€He) ) Q ^^^^ ^€ I ^^^ ^^^ ^j^^ ^^j^^^ {€„^af-^! } ^ °**y

2. Hofmann's formamid U > N may be viewed as
' ' *H f ^ carbimic acid, corresponding to carbamio acid

^€JO^H N ) (€/H0) J

2 f O. Especially since ethyl-formamid ^J^H- > N may

be ethylic carbimate ^^''1^^ \ e.

* N«fur the last of June, Prof. G. Hioncfa^ of Iowa UDiTersitj, published in
OennaD a iii«moir on Atw^ MechatUct, which, while the views are widely different,
has some Doints of agreement with mj paper in the July number of this JoumaL
A copy or the memoir reached this place July 2d, after my paper was printed, but
nearly three weeks before the July number was issued. I had intended to hare an
abstract of it in this number, but am unable to accomplish it» and therefore defer
it to our next



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HjSO



264 6. F. Barker on Fotmic vernts Carbonous Acid.

8. The radical formyl (€He), unlike acetyl (^aHjO), is not
required to formulate the derivatives of the acid. Moreover,
no chlorid or hydrid of this radical exists. The anhydrous add

(formylic oxyd), too, /£jh0\ [ O ifl unknown. If, however, the

acid be 2 f ^a» ^^^^ ^^ secondary oxyd would be €" }^0, car-
bonic oxyd.

4. Its synthesis. We have — a, Berthelot's method,
HKe+€e=HK€ea ; just as HKe+SearrHESOa.

6, Kolbe's method by deoxj '* "



(Ha€e3)a+Na2=HNa€e,+HNa€e,+H2e.
Duprd's method, Ha€e,+€+H2e=(Ha€e2)a; similar to

flf, Chapman^ method, partial oxydation of carbon,

5. Its preparation, a, from oxalic acid H2€aO^=Ha€02+602,
as well as the reverse action; b, from cyanhydric acid

And in general its production from the oxydation of carbona-
ceous materials. In no case is the intermediate body formic
aldehyd, obtained ; this anomalous result is accounted for if the

acid be jCT f ^2-

6. Its decompositions. Like sulphurous and similar acids, it
readily reduces metallic salts ; it is oxydized readily by platinum
black; by action of H^SO^, HaeO, gives H^O and €0, the
anhydrid; the action of PCI5 produces no formylic chlorid,
Ha€e2+PCI,=PCl3e+€e+(HCl)a; chlorine gives E^ee^+
CJ2=€ea+(HCnj,.

7. Its acknowledged divergence from the acetic or fatty acid
series, in which it is usually classed. These acids resist Uie
oxydiziug action of dilute chromic acid, while formic acid on
the other hand is a powerful reducing agent.

From the above statements, it is clear that this question turns
on the fact whether this acid is mono or dibasic. J ust now, the
former has the preference. True we may view the formates as
acid carbonites, but the anomaly of an acid, all of whose salts

Pb" )
are acid salts, remains. A basic plumbic formate i{/£;h0) f ^»

corresponding to the acetate -q/q ^i On ^' ^^ known, might

have the formula Pb"€0a+H20, plumbic carbonite.

The fact of its formation by the partial oxydation of carbon,
and also, by the deoxydation of carbonic acid, are however,
most cogent arguments in favor of the acid of bivalent carbon.

New Haren, Sept. lit, 1867.



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Chemistry and Physics. 261^

' Abt. XXXI. — Observations on Skylight Polarization in Nebrasica
during the month of July ^ 1867; by Edward 0. Chase.

The following observations were made at various stations of
the U. S. Geological Survey, with an excellent Savart polari-
scope, of remarkable clearness. I mark the neutral points as
follows : Ar., Arago's ; Ba., Babinet's ; Br., Brewster's.
July 1. — Cloudy.

2.-6^ 80" P.M., Ar., Ba., both faint Clouds below the sun.

3, 4.— Cloudy.

6. — 12 M., Br., distinct 6*» 30"* p.m., Ba., faint

3. — Heavy rain in a.m. 6^ 30™ p.m., Ba., faint.

7.-7^ 16°» A.M. and 5^ 46" p.m., Ba., feint

8.-— 6^ 10" Aji., Ar., distinct, Ba., faint 6^ 30" p.m., Ar., Ba.,
equally distinct

0. — Cloudy in a.m. 7^ p.m^ Ar., faint; Ba., distinct

10. — ^Ba., distinct; Br., faint Stormy in p.m.

11. — ^Cloudy and stormy.

12. — 8^ 30" A.M., Ba., Br., both faint 7^ p.m., Ar., Ba., equally
distinct

13. — 7^ A.M., Ar., distinct; Ba., faint 7** 16"* pjf., Ar., very
distinct ; Ba., distinct

14. — Cloudy and rainy.

15. — 6^ 30" A.M., Ar., veir distinct; Ba., faint; Br., distinct
This was the only instance in which the three points were observed
simultaneously.* 7^ 26" p.m., Ar., very distinct ; Ba., feint.

16. — 8^ A.M., Ba., very distinct ; Br., faint 7^ p.m., Ar., very dis-*
tinct; Ba., faint

17, 18.— Cloudy.

19. — 6^ 30" pji., Ar., very distinct; Ba., distinct

20. — :0*^ pji., Ar., very distinct

21. — 6^ A.M., Ar., very distinct; Ba., distinct

22. — 6^ P.M., Ar., Br., equally distinct 7^ 16" p.m., Ar., very
distinct ; Ba., distinct

23. — 7^ 30" P.M., Ar., very distinct ; Ba., distinct*



SCIENTIFIC INTELLIGENCE.

I. CHEMISTBY AND PHYSICS.

1. On the synthesis of organic acids, — ^Carius has made the very in-
teresting and important discovery that chlorous acid like hypochlorous
add unites directly with hydrocarbons to form chlorinated organic acids.
"in his first memoir the author describes the product of the action of chlo-
rous acid upon benzol under the name of trichlorphenomalic acid, the
reaction by which the new acid is formed being represented by the equa-
tion C6He+(ciHe2)3=CeH,ci3e,+eH2.

* For analogouB obMnrfttioni Me this Joamal, II, zH!, 112, 118.
Am. Joub. Sol— Sboond Sbbisb, Vol. XLIV, No. 18L— Sept., 1867.
34



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266 Scientific Intelligence.

Tricblorpbenomalic acid may be regarded as a cblorinated deriTatire of

( €/ H O

an acid bomologouB with malic acid, ^s l g^ ^ ^ ; the acid is color*

less, crystalline and soluble in water, alcobol, benzol and ether. Its den-
sity when ftised and solidified is 1*6, at 131^-182** 0. it fuses, and at a
few degrees higher gives off Tapors of water and a new acid. Redncing
agents convert the acid apparently into another acid having the formula
€gSio054 but with a larger excess of tin, and strong chlorhydric acid
succinic acid is formed, with small quantities of another acid not yet
studied. With an excess of solution of baryta trichlorphenomalie acid
yields a new acid, the reaction being

€eH^Cl,e5+(BaHe)e==:3BaCl+€^3Ba,e<^+6(eHa).

The author terms this acid phenaconic acid, and describes a number
of its salts. In addition to the crystallized trichlorphenomalie acid^ an
amorphous acid having the same constitution is found among the pro-
ducts of the action of chlorous acid upon benzol. This acid yields witb
reducing agents new acids free from chlorine which with their salts are
also amorphous. Chemists will await with much interest the results of
the researches of Carius upon the action of chlorous acid upon naphtalin
which promise to connect this body with the aromatic and through this
with the fatty series. — Ann. der Chemie und Pharm.^ cxlii, 129. w. o.

2. On the action of heocf upon benzol and analogous hydrocarbons, — *■
Bbrtbelot has studied the action of heat upon various hydrocarbons and
has arrived at many interesting and valuable results. When bensol i»
passed through a porcelain tube heated to bright redness, it is partially
decomposed with formation of several definite hydrocarbons which stand
in- very simple relations to bensrol itself. The chief product is phenyl^
a beaatiful crystalline substance which has the formula

(C,^H,)a = C,4H,o^(2C,,He = C,^H,^+2H).
The author considers it as formed from benzol by the replacement of
two atoms of hydrogen by an equal volume of benzol so that C^^H^
(CjpHe) results. The phenyl obtained in this way is identical with that
Fittig obtained by the action of sodium upon brominated benzol, bat the
method of preparation is more advantageous than that of Fittig. Above
960^ C, af waxlike yellowish substance very slightly soluble in alcohol
passes over, which is identical with chrysen. Berthelot gives this body
the formrula G^^Hij* C^i 2^6=^8 s^ia~M^) ^^ considers it a
polymer of the unknown hydrocarbon Q|,H^. After chrysen an orange
colored resinous solid body passes over which is almost insoluble in ah»-
hol which it however causes to fluoresce and which gives with picric acid
a slightly soluble peculiar conopound In the retort there remains a fluid
hydrocarbon which does not volatilize at a red heat and which on cook
ing gives a black and brittle bitunten. All these hydrocarbons residt
from the condensation of a variable number of molecnles of benzol with
evolution of hydrogen. Naphtalin and anthracen are not present even
in small quantities. Toluol like benzol is partially decomposed by
passing through a red hot tube. The products of the action by cardol
rectification were found to be benzol in large quantity, unaltered toluol
in still larger quantity, naphtalin, a small quantity of a ciystalliaed by-



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Chemhiry and Physics. ^m

drocarboii boiling at about 2W C, and a larger quantity of a fluid hy-
drocarbon which is perbapa benzyl (CjHr)^ or an isomer. The boiling
point then rises above 360® C, when a large quantity of an indistinctly
crystallized hydrocarbon passes over mixed with a liquid. ^ The first is
anthracen (Cj^H^k ; the otbers are analogues of chrysen and the last
derivatives of benzol. Benzyl is derived from toluol in the same manner
a sphenyl from benzol ; 2C ^^HaSsCg jH j 4+H2. Anthracen is derived
from toluol by a similar condensation and subtraction of hydrogen
2C,4Hg=C28H|^j-|-3H2. As, according to Berthelot's view, toluol
may oe derived from benzol by the substitution of marsh-gas for bydrogen,
benzol ssCjjH^fflj), toluol =^0^2^ ^{02^2)' Anthracen may be con-
sidered as formed by the union of the benzol residue Cj^H^ with the
marsh-gas residue C^H and bas therefore the rational formula [Gj^H^
(CaH)]^, that is, C^2^^[^^2^^{C^R2))' This explains why a maiah-
gas residue is necessary for the formation of anthracen and why this
hydrocarbon is not formed in the decomposition of pure benzol. The
formation of benzol from toluol is according to all analogy, being merely
the derivation of a lower from a higher homologue. The marsh-gas
residue serves to form naphtalin according to the equation

^^l4^8=3^12H«+^2oHs+^H2.

When a mixture of benzol and ethylen, C^H^, is passed through a red
hot tube the following products are obtained. {1) Styroien O^gHg in
large quantity well demied and without any more volatile product, except
benzol; (2) naphtalin, €3 qH^; (3) another crystallizable hydrocarbon
resembling phenyl and boiling at about 260® C, but forming a characo
teristic compound with picric acid which phenyl does not do; (4) anthra-
oen in considerable quantity mixed with a fluid hydrocarbon, etc The
formation of styrolene may be represented by the equation

^ 1 2H6+^4H4=^ I sHs+Ha.
Naphtalin is formed by the reaction C^aHg+SC^H^zzCj^Hj-l-SBL,
which, according to Berthelot, leads to the rational formula, Cj2^4
[C4H2(C4H2)]9 80 that naphtalin is formed from benzol by two succes-
sive substitutions, one of H^ by J3^ forming styrolene, Cj3H4(C4H4),
the second of H, in C4H4 by C^H,. Anthracen is formed according
to the reaction ^C^aHe+C^H^^CasHjo+SHa.

which leads to the rational formula C^2^^[Gl2^^,{^^,^9)]'

Pure styrolene is partially, decomposed at a red heat with formation of
benzol and acetylene C^^li^::zC^2^e'^^4,^9'
Again benzol and acetylene heated together produce a certain quantity
of styrolene, though this hydrocarbon is not the chief product When
Btyrolene and hydrogen, CjeHg-j-Ha, are heated together in a closed
tube, benzol and ethylene are formed. In this case, however, the greater
part of the styrolene is directly converted into benzol according to the
equation SC^^B^z^iC^^^^.

Styrolene and ethylene heated together, Cj^Hg-f-C^H^, yield benzol
and naphtalene both in considerable quantity. The benzol results from
the decomposition of the styrolene itself but the naphtalin is formed by
the direct action of ethylene upon styrolene :

C.,H,[C4H,(H,)]+C.Hj(H,)=C„H^[C,H,(C,H,)]+2H,,



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268 Scientific Intelligence,

Benzol and gtyrolene passed together through a red hot tube gave
anthracene in large quantity, together with naphtalin and a hydrocarbon
resembling phenyl. The anthracene results from the direct action of tbe
styrolene upon benzol according to the equation

C^,H,[C.H,(H,)]+C,aH.(Ha)=C,,H,[C„H.(C,Ha)]+2H,.
Berthelot thinks that in this case the naphtalin results from the action
of the free hydrogen upon the styrolene forming ethylene and benzol,
while the ethylene reacts upon another portion of styrolene to join
naphtalin. Benzol and naphtalin exert no action upon each other at a
red heat, but the benzol is alone decomposed. At a bright red heat
anthracene is found in large quantity.

CiaHjC^H2(C^H,)]-f3C,2H^(Ha)=2C,2HJC,2HJC^H2)]+8H,.
Phenyl heated to redness with hydrogen in a closed glass tube is par-
tially decomposed with formation of benzol and chrysen :

3C24Hio=3Ci2HQ+C3gH,2.
In this case phenyl, Cj2H4(Cj2He), separates into benzol and phenylene,
which last is then converted into its polymer chrysen, C36Hi2=:(0i2H^)8.
— Cwnptes Rendus, Ixiii, 788, 834. w. 6.

3. On the acids of the lactic series, — By the action of metallic zinc
upon a mixture of iodid of amyl and oxalate of ethyl, Franklakd and
DuppA have obtained the ethers of several new acids belonging to the
lactic series. The ether with the lowest boiling point, 203^ C, has the
formula O^HigO,. The authors assign to ifr the rational formula

* j €AmHHo
( eOEto
calling It amyl-hydroxalate of ethyl and regarding it as oxalate of ethyl
in which one atom of oxygen is replaced by one of amyl and one of
hydrogen. This body may be compared with lactate of ethyl from which
it may be theoretically derived by replacing an atom of methyl by an
atom of amyL

j €MeHHo j €AmH. Ho

]€eEto leOEto

Lactate of ethyl. kmj\ hydrate of ethyl.

The new ether is a rather oily, transparent, faintly straw-yellow liquid of
density 0-9449 at 13^ C, with an agreeable odor and burning taste.

A second ether formed at the same time has the formula \ f^figf^

The authors term it ethylated amyl-hydroxalate of ethyl. Its density is
0*9399 at 13" C. ; it boils at 224''~225*, is faint yellow, and oily with an
aromatic somewhat amylic odor and burning taste.
A third ether has the formula

j eAm^Ho
(€eEto
The authors term this liquid diamyloxalate of ethyl ; it closely resem-
bles these last mentioned in appearance and properties. From the ethers
the authors have also prepared the corresponding acids, for the descrip-
tion of which, however, we must refer to the original paper.

« Am=e»Hji. Et=:€,H,, Ho=(ne). EtG=C«H*0). ^



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Cliemistry and Physics. 269

The action of zido upon a mixture of iodid of ethjl and oxalate of
amjl gives rise to a new ether which the authors term diethoxalate of

amyl and which has the formula < ^^2^, •

It is colorless and oily with an agreeable somewhat amylic odor and boils
at 225** C. It will be readily seen that this ether is isomeric with ethyl-
ated amyl-hydroxalates of ethyl. By the action of zinc upon a mixture
of iodid of amy] and oxalate of amy] the authors obtained two ethers,

( -PAfn TIo

the first of which has the formula < ^^kt^Q *°<^ ^^7 ^ termed di-
amyloxalate of amyl, while the second had the formula and properties
of capronic ether -j rj^ a ^ • ^^ conclusion the authors give an elab-
orate and extremely interesting discussion of the classification and theory
of the acids of the lactic series, for which however we must refer to the
original. The following summary of their results is in their own language.

Tl.) All the acids of the lactic series are essentially monobasic.

(2.) Theee acids are of four kinds, namely, normal, secondary, nor-
mal define acids and secondary define acids ; and each of these has its
own aeries of etheric acids in which the hydrogen of the hydroxyl con-
tained in the positive or basylous constituent of the acid is replaced by a
positive or negative compound radical.

(3.) The normal acids are derived from oxalic acid by the replacement
of one atom of oxygen either by two atoms of hydrogen, or by one atom
of hydrogen and one atom of an alcohol radical.

(4.) The secondary acids are derived from oxalic acid by the replace-
ment of one atom of oxygen by two atoms of monovalent alcoholic rad-
icals.

(6.) The define acids are derived from oxalic acid by a similar sub-
stitution of two positive monovalent radicals in place of one atom of oxy-
gen with the simultaneous insertion of an define hydrocarbon or divalent
rsdical CnH^n between the two atoms of oxatyl.

(6.) The acids of the lactic series stand to the acids of the acetic series
in the very simple relation just pointed out by Kolbe ; namely, that if
in any acid of the lactic series, the hydroxy], ethoxyl, etc., in the positive
radical is replaced by hydrogen this acid is converted into a member of
the acetic series.

(7.) The acids of the lactic series stand in an almost equally simple
relation to the acids of the acrylic series as appears from a comparison

Lactic acid.

— Ann, der Ckemie und Pharmacie, cxlii, 1. w. a.

4. Tkallie acid. — K Carstanjbn states that when thallic oxyd, pre-
cipitated from the chlorid of ammonia, is suspended in a strong solution
of potash, gently heated, and a quick current of chlorine gas passed
through the liquid, it becomes of an intense violet red color, and con-
tains potassic thallate. It may be evaporated, and even filtered through
paper, but is decomposed by acids, evolving oxygen. The author is still
at wofk upon tiiis interesting compound. — J, pr, <7A., ci, 65, June, 1867.



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270 Scientific InUUigenct.

6. The n$to Ohmkal Caleulut.—On the 3d of May, 1866, Sir Ben-
jamin Bbodis, Professor of Chemistry id the University of Oxford, read
a paper before the Royal Society, entitled ''The Calculus of Chemical
operations ; being a method for the invesU^tion by means of symbols,
of the laws of the distribution of weight m chemical change; Part L
On the construction of Chemical Symbols." This paper was published
in the Philosophical Transactions for 1866, part ii, 856, and, in abstract,
in the Philosophical Magazine, iv, xxxii, 227. On the 6th of June, 1867,
Prof. Brodie delivered a lecture before the Chemical Society, " On the
mode of representation afforded by the chemical calculus, as contrasted
with the atomic theory," which was quite fully reported in the ** Chem-
ical News'* of June 14, and the ''Laboratory" of the 16th, together with
the subsequent discussions by Professors Frankland, Williamson, Odling,
Foster, Wanklyn, Maxwell, etc. Of the critical articles called forth by
Sir Benjamin Brodie's communications, those of Williamson, Chem. News,
xvi, 8, July 6 ; of Wanklyn and Davey, Phil. Mag., IV, xxxiv, 26, July,
1867; of Eekul6, The Laboratory, i, 303, July 27; and of A. Crum
Brown, Phil. Mac;., IV, xxxiv, 129^ August, may be mentioned. The
views of Prof. Eekul6, contained in the first of a series of papers oa
Theoretical Chemistry, contributed ft) that valuable little journal, are
stated so clearly, and at the same time are so just, that we reproduce the
article entire. It should be remarked, however, that Professor Brodie*s
"Ideal Chemistry'* is to be comprised in three papers, the 1st being on
"The construclion of chemical symbols;" the 2nd on "The theory of
chemical equations;" and the 3d on "The principles of symbolic classi-
fication." Only the first of these has yet appeared. Q. f. b.

On the existence of Chemical atoms ; by Aug. EjbkuiJ.

The question whether atoms exist or not has but little significance in a
chemical point of view ; its discussion belongs rather to metaphysics. In
/chemistry we have only to decide whether the assumption of atoms is an
hypothesis adapted to the explanation of chemical phenomena. More
especially have we to consider the question, whether a further develop-
ment of the atomic hypothesis promises to advance our knowledge of the
mechanism of chemical phenomena.

I have no hesitation in saying that, from a philosophical point of view,
I do not believe in the actual existence of atoms, taking the word in its
literal signification of indivisible particles of matter. I rather expect
that we ^all some day find, for what we now call atoms, a mathematico-
mechanical explanation, which will render an account of atomic weight,
of atomicity, and of numerous other properties of the so-called atoms.
As a chemist, however, I regard the assumption of atoms, not only as
advisable, but as absolutely necessary in chemistry. I will even go fur-
ther, nnd declare my belief that chemical atoms exist^ provided the term
be understood to denote those particles of matter which undergo no fur-
ther division in chemical metamorphoses. Should the progress of science
lead to a theory of the constitution of chemical atoms — important as
euch a knowledge might be for the general philosophy of matter — it
would make but little alteration in chemistry itself. The chemical atom
ivill always remain the chemical unit; and for specially chemical con-



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ClumUtry and Physics* 27 1

8idention» we ma^ always start from the constitution of atoms, and avail
ourselves of the simplified expression thus obtained, that is to say, of the
atomic hypothesis^ We may, in fact, adopt the view of Dnmas and of
Faraday, ^ that whether matter be atomic or not, thus much is certain,
that granting it to be atomic, it would appear as it now does."

After these remarks, it is scarcely necessary to say that I set but small
value on most of the attacks recently made against the atomic hypothesis.
In many of them I see merely words and phrases, not ideas. It is, how-
ever, quite otherwise with the endeavors of those who seek to discover
chemical laws independently of the atomic hypothesis. All endeavors
of this kind possess great merit; and if they lead to actual results, the
laws thus discovered independently of the atomic hypothesis, will be re-



Online LibraryJohn AlmonThe American journal of science and arts → online text (page 82 of 102)