Escolar Documentos
Profissional Documentos
Cultura Documentos
HERBERT E. MORRIS
Department of Chemistry, University of Alberta, Edmonton, Canada
CONTENTS
..................................................... 465
11. The decomposition of ethyl alcohol
1. Pyrolysis.. . . . . . . . . . . .................................... 466
2. Catalytic decomposition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
3. Decomposition by electrical means.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
111. The catalytic oxidation of ethyl alcohol
1. Enzymatic oxidation. . . . . . . . .
2. Electrolytic oxidati
3. Ozonization.. . . . . . . . . . . . . . . . . . . . . . . . . .
4. Catalytic oxidation .................................. 477
5. Photochemical oxidation.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
2. Potassium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
........... 487
........................................ 489
V. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
I. IKTRODUCTION
Ethyl alcohol is capable of undergoing several of the general
types of reaction under a variety of conditions. Partial dehydra-
tion with the formation of ethyl ether is one of the simplest reac-
tions, while complete dehydration produces ethylene.
2 CzHaOH = (CzH6)zo HzO +
CzHsOH CZHd HzO +
Ethyl alcohol is also readily dehydrogenated to acetaldehyde
and possibly to a ketene under certain influences.
CzHsOH = CHsCHO Hz +
CzH60H = CHzCO 2 H2 +
465
466 HERBERT E. MORRIS
Greene (48) found that if alcohol was dropped on hot zinc chlo-
ride the products were numerous and varied. In addition to
hydrogen chloride, several other substances were identified, in-
cluding ethylene, ethane, hydrogen, water, acetaldehyde, and
ethyl ether. Oils which were attributed to the polymerization of
ethylene were also obtained. Hydrogen and ethylene were pres-
ent in nearly corresponding quantities. The ether was formed by
dehydration, but no suggestion was advanced for the source of
the ethane.
In 1880 Jahn (58) found that the products obtained on passing
alcohol over zinc dust a t dull red heat were almost exclusively
hydrogen, methane, and carbon monoxide. However, at a tem-
perature of 300-350C. the products included both hydrogen and
ethylene. Somewhat later Keiser and Breed (60) stated that
magnesium and iron glowed when heated in alcohol vapor. In
both cases a large volume of gas was produced which consisted
of 11 per cent of methane, 0.5 per cent of carbon monoxide, 14
per cent of unsaturated hydrocarbons, and 73 per cent of hydro-
gen when magnesium was used. With heated iron the products
included 8 per cent of carbon monoxide, 13 per cent of methane,
0.5 per cent of carbon dioxide, 4.0 per cent of unsaturated hy-
drocarbons, and 63.8 per cent of hydrogen.
Ipatiev (52), continuing his work on the thermal decompo-
sition of ethyl alcohol, observed that the presence of zinc in the
reaction tubes lowered the temperature necessary for decompo-
sition. The ratio of ethylene to aldehyde varied with the amount
of zinc employed. Rods of zinc a t 620-650C. produced very
little ethylene but about 80 per cent of aldehyde which was prac-
tically undecomposed. With zinc dust a t 550C. the dehydra-
tion and dehydrogenation reactions were about equal, with some
of the water produced by the former decomposing to increase
the hydrogen content of the exit gas. Brass containing 33 per
cent of zinc gave results very similar to the zinc rod.
The utilization of graphite as the catalyst made the reaction
proceed almost completely to the formation of unsaturated hydro-
carbons with ethylene produced only in small quantities (53).
Ipatiev (54) also reported that the passage of alcohol through a
REACTIOXS O F ETHYL ALCOHOL 469
wr cent
Dehydration catalysts
.............................. 98.5
crzo3. .............................. 91
. . . . . . . . . . . . . 84
63
Be0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
U80 8. . . . . . . . . . . . . . . . . . . .
45
24
Mixed dehydration and dehydro-
genation catalysts
M0205, ............................. 23
14
VZOS.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5 ,
RiInOz...............................
SnO ................................
CdO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
MnSOc.............................. > Dehydrogenation catalysts
MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
c u .................................
Ni. .................................
TABLE 3
Decomposition of ethyl alcohol b y the silent electric discharge
PRODUCTS AT 2 MM. AT 100 MM.
PREEBURE PRESBURE
These results have not been fully confirmed and in several cases
it has been reported that the photochemical oxidation of alcohol
is negligible, as will be shown later.
Trillat and Santon (106) also believed that acetaldehyde was
not a normal product of the fermentation of alcohol but that its
formation was due to the oxidation of alcohol by air. Verifica-
tion of this premise was obtained by Palmore (82), who found
that if ethyl alcohol, free of aldehyde, was saturated with carbon
dioxide, there was no appreciable formation of aldehyde even after
standing for two and one-half years.
A statement by Voisenet (111) that formaldehyde was a nor-
mal product of the oxidation of ethyl alcohol whether the reac-
tion was promoted by physical, chemical, or biological means,
seems to have been neither refuted nor corroborated in connection
with enzyme reahtions. This aldehyde has been fairly frequently
observed, however, in the products of oxidation by other methods.
2. Electrolytic oxidation
In 1875 Renard (88) investigated the electrolysis of ethyl
alcohol which had been slightly acidified with dilute sulfuric acid.
Hydrogen gas was liberated a t the cathode, but the oxygen which
might have been evolved a t the anode was consumed in the oxida-
tion reactions of alcohol. As the products of a 48 hour run under
these conditions the following were identified,-acetaldehyde,
ethyl formate, ethyl acetate, and a small amount of acetal. There
was also a very small quantity of another substance present which
was called ethylidine monoethylate, C2H60CH(OH)CH3. A
later paper (89) noted that after a considerable time formic acid,
acetic acid, and oxygen were evolved in appreciable quantities at
the anode. Separating the electrodes with a porous partition
effected no change in the end products.
Bartoli and Papasogli (9) studied this electrolytic activity in
an alkaline solution and found large quantities of aldehyde
produced; this aldehyde polymerized quite readily as far as a
resin. A small yield of acetic acid was also obtained. These
workers used carbon electrodes which were slightly disintegrated
with the formation of a deposit of carbon.
476 HERBERT E. MORRIS
reaction, using either form of platinum, are acetic acid and acetal-
dehyde. The use of platinum wire electrically heated to various
temperatures was investigated by Trillat (105). The oxidation
proceeded readily even when the temperature of the platinum
was as low as 225"C., and the products of such a reaction included
16.8 per cent of acetaldehyde and 2.3 per cent of acetal. It was
also observed that aldehyde was formed even in the absence of
air. The use of platinum for the production of formaldehyde
from ethyl alcohol and oxygen has been patented (83). The
platinum should be heated to redness and the flow of reactants
adjusted to prevent complete combustion. The vapors must be
cooled rapidly to obtain satisfactory yields of formaldehyde.
Recently Muller and Schwabe (76) studied the oxidation of
aqueous ethyl alcohol in the presence of sodium hydroxide and
acetic acid using platinum, palladium, and rhodium powder as
catalysts a t 20C. The essential point of study in this case was
the mechanism of such a reaction, and it is compared with that of
acetic acid and formic acid.
Duchemin and Dourlen (32), while observing the reactions of
ethyl alcohol at its boiling point, noticed that with long refluxing,
either alone or in the presence of a catalyst, a considerable quan-
tity of acetic acid was produced. The catalysts tested were copper,
lead, tin, and zinc; copper proved to be the most efficient of these.
A possible mechanism was formulated which gave a metallic
hydride and acetaldehyde as the primary products; in such a
case the hydride would decompose with the existing conditions
and the aldehyde would be further oxidized to acid. Copper has
been more fully studied by Orloff (79) by passing air and alcohol
over copper gauze. The products of this reaction were varied;
acetaldehyde was the chief derivative, but carbon monoxide, car-
bon dioxide, saturated and unsaturated hydrocarbons, as well as
small quantities of acids and ketones were also detected.
Alcohol and air were passed over finely divided copper at
260-270C. by Mailhe and de Godon (116). It was observed that
the catalyst aged, favoring aldehyde formation; 60 cc. of alcohol
produced 18 grams of acetic acid and 12 cc. of acetaldehyde.
Moreau and Mignonac (117) studied the action of silver on asbes-
REACTIOXS O F ETHYL ALCOHOL 479
acid, and carbon dioxide, with the latter being the main product
if the temperature rose to 360C. The most satisfactory operat-
ing conditions with vanadium pentoxide produced 9-13 per cent
of aldehyde and 2-5 per cent of carbon dioxide. The action of
zinc oxide was similarly investigated and an optimum yield of
10.7 per cent of aldehyde and 4.8 per cent of carbon dioxide was
obtained.
Hay (49) noticed that colloidal clay was a fair catalyst for the
oxidation of alcohol to acetaldehyde, and a patent (38) developed
along similar lines indicated that alcohol could be oxidized by the
use of a catalyst consisting of finely divided clay dispersed in a
fluid medium, by the addition of a deflocculating agent such as
ammonia, sodium hydroxide, or sodium carbonate. The catalytic
activity of such a preparation may be much further enhanced by
the addition of metallic catalysts known to promote the oxida-
tion. Somewhat similar metals are included in a patent (26)
which states that ethyl alcohol may be oxidized by passage over
barium oxide a t a temperature of 400-500C. The products of
this reaction contain some of the higher alcohols, such as butyl
alcohol, in addition to acids, esters, acetals, and aldehydes. Simi-
larly magnesia, lime, manganese dioxide, or the alcoholates of
magnesium and sodium may also be used to promote this
oxidation.
Slaboszewicz (101) in 1902 made the general observation that in
the oxidation of ethyl alcohol by air a large number of higher
oxidation products were obtained in addition to acetaldehyde.
This early observation rather anticipated the above mentioned
patent. The general process of oxidation of ethyl alcohol is
mentioned in a patent (67) which states that the passage of air
and alcohol over a catalyst yields acetaldehyde, which may thea
be mixed with more air and passed over another catalyst to pro-
duce acetic acid.
Recently several workers have conducted more thorough inves-
tigations of the catalytic oxidation of ethyl alcohol, using a wide
variety of catalysts and studying the reaction in the vapor or
liquid phase. Simington and Adkins (99) passed alcohol mixed
with air over numerous catalysts and obtained aldehydes, ke-
REACTIONS O F ETHYL ALCOHOL 481
1, Hydrogen peroxide
Various oxidizing agents have been studied to determine their
action on ethyl alcohol; of these hydrogen peroxide was probably
the first to be investigated. In 1877 Fairley (37) stated that
peroxide solutions of 2-5 per cent have no appreciable action on
80 per cent alcohol, while in 1880 Renard (89) also observed that
this oxidizing agent had no action on dilute or concentrated alco-
hol solutions, in an acid, alkaline, or neutral medium, even after
several days standing.
Following these negative results it was discovered that the
oxidation of alcohol by hydrogen peroxide depended upon the
presence of an iron salt. Fenton and Jackson (39) found that
the addition of ferric or ferrous acetates catalyzed the reaction,
but that the production of acetaldehyde was negative, the entire
product being acetic acid. Considerably later Doroshevskii and
Bardt (31), while examining the effect of charcoal on the oxida-
tion of ethyl alcohol, found that it was dependent on the presence
of ferrous salts such as chloride, sulfate, or oxalate. If ferrous
sulfate and hydrogen peroxide were added to alcohol, it was noted
that the oxidation proceeded readily with the formation of acetic
acid and acetaldehyde, but when ferrous oxalate was employed
as the catalyst, the reaction proceeded almost completely to the
formation of acid. Oxidizing the ferrous salt to the ferric state
seemed to inhibit its activity to a certain extent. It was also
remarked that dilute solutions were more readily oxidized than
pure alcohol. Chauvin (22) observed that the action of peroxide
on ethyl alcohol was greatly influenced by 0.01 per cent of man-
ganese acetate, while the products of this oxidation using only 1
per cent of peroxide contained aldehyde, ester, and traces of higher
alcohols.
The most thorough study of this reaction is due to Walten and
REACTIONS O F ETHYL ALCOHOL 485
(109) TROKOV, LUKANIN,AND PAVLIKOV: J. Russ. Phys. Chem. SOC. 69, 1173
(1927).
(110) TRONOV, UDODOV,A N D CHIZHOVA: J. Russ. Phys. Chem. SOC.69, 1149
(1927).
(111) VOISENET:Compt. rend. 160, 40 (1910).
(112) WALTENA N D CHRISTIANSEN: J. Am. Chem. SOC.48, 2083 (1926).
(113) WILLIAMSON: J. Chem. SOC.4, 106, 229, 350 (1852).
(114) WOOG:Compt. rend. 146, 124 (1907).
(115) WRIGHT:Am. J. Sei. 131 6 , 1 8 4 (1874).
(116) MAILHEAND DE GODON:Compt. rend. 170, 517 (1920).
(117) MOREAU ATD MIGKONAC: Compt. rend. 170, 258 (1920).
(118) FAITHAND KEYES:Ind. Eng. Chem. 23, 1250 (1931).
(119) DAY:J. Phys. Chem. 36, 3272 (1931).
(120) BOWEN,PEACOCKE, AND WELLBURN: J. Chem. SOC. 1931, 1866.
(121) MARDLES: Trans. Faraday SOC.27, 700 (1931).
AUTHOR INDEX
VOLUMESI TO X
ADAM,NEIL K. The properties of sur- BROOKS, BENJAMINT. The manufac-
face films on liquids, 3, 163 ture of alcohols from hydrocarbons,
ANDREWS,DONALD H. Valence forces with particular reference to petro-
as calculated from specific heats leum as a raw material, 2, 369
and absorption spectra, 6, 533 BRUNI,GIUSEPPE. Solid solutions, 1,
AUDRIETH, L. F., AND NELSON,H . W. 345
Electrodeposition of metals from BURGESS,WAYLAND M., AND SMOKER,
non-aqueous solvents, 8, 335 EDWARDH. A study of the re-
AND W A L D ~ NP. , Free inorganic ducing action of sodium upon salts
radicals, 6, 339 in liquid ammonia solution, 8, 265
DANIELS,
FARRINQTON. The radiation The activity coefficient of non-elec-
hypothesis of chemical reaction, 6, trolytes in aqueous salt solutions
39 from solubility measurements.
DARKIS,F. R . , AND KHARASCH, M. S. The salting-out order of the ions,
The theory of partial polarity of 4, 285
the ethylene bond and the existence The activity coefficient of the undis-
of electro-isomerism, 6, 571 sociated part of weak electrolytes,
DARROW, KARL K. Dissociation of 4, 291
molecules as disclosed by band FALKENHAGEN, HANS,AND WILLIAMS,
spectra, 6, 451 JOHNWARREN. The interionic at-
DAVEY,WHEELER P. Contributions of traction theory of electrical con-
x-ray studies of crystal structure to ductance, 6, 317
organic chemistry, 6, 143 FISHER,HARRYL. The chemistry of
The radii of atoms and ions, 2, 349 rubber, 7 , 51
DAVIDSON, ARTHURW. An introduc- FRANCIS, ALFREDW. Directive influ-
tion to the chemistry of acetic acid ence in the benzene ring, 3, 257
solutions, 8, 175 FRY, H A R R YSHIPLEY.A pragmatic
DUFRAISSE,CHARLES,AND MOUREU, system of notation of electronic
CHARLES.Catalysis and auto- valence conceptions in chemical
oxidation. Anti-oxygenic and pro- formulas, 6, 557
oxygenic activity, 3, 113 FUSON,REYNOLD C. Some recent ad-
DUSHMAN, SAUL. Line spectra and the vances in theoretical organic chem-
periodic arrangement of the ele- istry, 7, 347
ments, 6, 109
DYSON,G. MALCOLM.Phosgene, 4,109 GERKE,ROSCOE H. A summary of elec-
trode potentials, 1, 377
EGLOFF,GUSTAY,AND SCHAAD,RAY- GIBBS, H . D. Phenol tests. I. A
MOND E . The oxidation of the classification of the tests and a
gaseous paraffin hydrocarbons, 6, review of the literature, 3, 291
91 GOMBERG, M . Organic radicals, 1, 91
SCHAAD,RAYMOND E., AND LOWRY, Elements with anomalous valences,
C. D., JR. The halogenation of the 2, 301
paraffin hydrocarbons, 8, 1 GORDON, F. G. The theory of mem-
EMERSON, B. K. The helix chemica, 6, brane equilibria, 1, 73
215 GRAY,HARRY LE B., AND STAUD,CYRIL
EVANS,WILLIAMLLOYD. The mech- J. Recent advances in cellulose
anism of carbohydrate oxidation, and starch chemistry, 4, 355
6, 281
EVANS, W. V. Introduction to the HALL,NORXIS F. Acid-base equilibria
symposium on non-aqueous solu- in non-aqueous solvents, 8, 191
tions, 8, 167 HARKINS, WILLIAMD. The synthesis
EYRING, HENRY. Quantum mechanics of atoms, the whole number rule,
and chemical reactions, 10, 103 and the periodic system of the
atomic species, 6, 371
FAILEY,CRAWFORD FAIRBANKS AND HARTUNG,WALTERH . Epinephrine
RANDALL,MERLE. The activity and related compounds: influence
coefficient of gases in aqueous salt of structure on physiological ac-
solutions, 4, 271 tivity, 9, 389
AUTHOR INDEX-VOLUMES I TO X 497
HEIDELBEAGER, MICHAEL. Immuno- KEENAN, GEORGE L. Substances which
logically specific polysaccharides, affect photographic plates i n the
3, 403 dark, 3, 95
HENDRICKS, STERLING B. The crystal KEYES,FREDERICK G. Present status
structures of organic compounds, of the molecular field problem, 6,
7, 431 175
HENRI,VICTOR. The structure of the KHARASCH, M. S., AND DARKIS,F. R.
methane molecule, 4, 189 The theory of partial polarity of
HESS, FREDG., MALISOFF,WILLIAM the ethylene bond and the existence
MARIAS,AND MARKS,ERNESTM. of electro-isomerism, 6, 571
A study of mercaptan chemistry, KILPATRICK, MARTIN,JR., AND KIL-
7, 493 PATRICK, MARY L. Acid and basic
HEVESY,G. The discovery and prop- catalysis, 10, 213
erties of hafnium, 2, 1 KISTIAKOWSKY, G. B. The rates of
The use of x-rays for the discovery of atomic reactions, 10, 91
new elements, 3, 321 KLARMANN, EMIL. Recent advances
HILDEBRAND, JOEL H . Factors deter- in the determination of the struc-
mining chemical stability, 2, 395 ture of proteins, 4, 51
HINSHELWOOD, C. N. Homogeneous KOBE,KENNETH, AND REYERSON, L. H.
reactions, 3, 227 Carbon suboxide, 7, 479
HOLLEUAN, A. F. Some factors influ- KRAUS,CHARLES A. Non-aqueous re-
encing substitution in the benzene duction reactions, 8, 251
ring, 1, 187 KRUYT,H. R., AND MODDERMAN, Jo-
HUGGINS, MAURICEL. Some signifi- HANNA G. Heats of adsorption
cant results in crystal structure and their bearing on the problem
analysis, 10, 427 of adsorption, 7, 259
IRVINE, J A M E S COLQUHOUN. The con-
LA MER, VICTOR K. Introduction to
stitution of polysaccharides, 1, 41
symposium on molecular constitu-
Progress in the structural study of
tion, 6, 445
carbohydrates, 4, 203
Reaction velocity in ionic systems,
JAEGER, F. M. The constitution and 10, 179
structure of ultramarines, 6,481 LANGE,E., AKD ROBINSON, A. L. The
JAUNCEY, G. E. M. Atomic structure heats of dilution of strong electro-
as revealed by crystal reflection of lytes, 9, 89
x-rays, 6, 437 LANQMUIR, IRVING.Forces near the
JOHNSON, WARRENC., AND MEYER, surfaces of molecules, 6 , 451
ALBERT W. The properties of LEDUC,A. The specific heats of gases
solutions of metals in liquid am- and vapors. A critical review of
monia, 8, 273 methods and results, 6, 1
JORISSEN, W. P. Reaction limits, re- LEE, 0. IVAN. The mineralogy of
action regions and reaction spaces, hafnium, 6, 17
6 , 17 LEVENE,P. A. Active glucose, 6, 1
The configurational relationships of
KABSEL,LOUISS. The dynamics of the sugars, hydroxy acids, amino
unimolecular reactions, 10, 11 acids and halogen acids, 2, 179
AND NOYES,W. ALBERT,JR. A re- LEWIS,BERNARD.Explosions in gases,
view of photochemistry, 3, 199 and their kinetics, 10, 49
498 AUTHOR INDEX-VOLUMES I TO X
SVEDBERQ,
T m . Some recent ad- WALDBAUER,L. J., AND PATTON,I.
vances in the field of colloids, 1,249 JOCELYN. The radioactivity of
the alkali metals, 3, 81
TANNER, FREDW. The bios ques- WALDEN,P., AND AUDRIETH,L. F.
tion, 1, 397 Free inorganic radicals, 6, 339
TAYLOR, HUQHS. Chemical reactions WATERS, W. A. The substitution of
a t surfaces, 9, 1 linked aromatic ring systems, 7,
TROPSCH, HANS. Problems in the 407
chemistry of coal, 6, 63 WATSON,HERBERT BEN. Reactions of
halogens with compounds contain-
ing the carbonyl group, 7, 173
URBAIN,G. Twenty-five years of re- WEBB,T. J. A review of the theory of
search on the yttrium earths, 1, metallic conduction, 7, 139
143 WELLS, P. V. The present status of
UREY, H. C. Discussion of paper by turbidity measurements, 3, 331
R. S. Mulliken, 6, 546 WHITMAN,WALTER G. Corrosion of
iron, 2, 419
VANVLECK,J. H. The new quantum WHITTIER, E. 0. Lactose. A review,
mechanics, 6, 467 2, 85
VAUQHAN, VICTORC. A chemical con- WILKINSON,JOHN A. Liquid hydrogen
cept of the origin and development sulfide as a reaction medium, 8,237
of life. A preliminary presenta- WILLIAMS, JOHNWARREN. The be-
tion, 4, 167 havior of electrolytes in dilute
VAUQHAN, WILLIAME., AND WOYES, W. methyl alcohol solution, 8, 303
ALBERT, JR. The thermal, elec- The structure of molecules as re-
tronic, and photochemical decom- vealed by dielectric constant data,
positions of solid bodies, 7, 239 6, 589
VICKERY, HUBERTBRADFORD, AND A N D FALKENHAQEN, HANS. The in-
SCHMIDT, CARLL. A. The history terionic attraction theory of elec-
of the discovery of the amino acids, trical conductance, 6, 317
9, 169 WILSON, P. W., AND PETERSON, W. H.
VON WEIMARN,P. P. The precipita- The energetics of heterotrophic
tion laws, 2, 217 bacteria, 8, 427
SUBJECT INDEX
VOLUMESI TO X
Absorption spectra and valence forces, Atoms, radii of, 2, 349
6, 533 structure of, as a periodic property,
Acetic acid solutions, chemistry of, 8, 6, 85
175 structure of, in relation to valence
Acid and basic catalysis, 10, 213 and ion-formation, 6, 85
-base equilibria in non-aqueous sol- synthesis of, 6, 371
vents, 8, 191 Auto-oxidation, 10, 295
catalysis, 6, 231 and catalysis, 3, 113
Activation by light and by collisions, Azoxy compounda, 9, 117
7, 231
chemical, by light and by ionizing Bacteria, heterotrophib, energetics of,
agents, 7, 203 8, 427
Activity coefficient of gases, 4, 271 Band spectra, 6, 503
coefficient of non-electrolytes, 4, 285 spectra and the dissociation of mole-
coefficient of undissociated part of cules, 6, 451
weak electrolytes, 4, 291 Rase exchange and micelles, 7, 369
Adsorbed phase, nature of, 9, 47 Basic and acid catalysis, 10, 213
Adsorption, heats of, 7, 259 catalysis, 6, 231
Albumin, 8, 81 Benzene ring, directive influence in, 3,
Alcohol, ethyl, reactions of, 10, 465 257
Alcohols from hydrocarbons, 2, 369 ring, factors influencing substitution
Aliphatic compounds, structure of, 6, in, 1, 187
549 Bimolecular reactions, kinetics of, 10,
241
Alkali metals, radioactivity of, 3, 81
Bios question, 1, 397
Amino acids, configurational relation-
ships, 2, 179 Carbohydrate oxidation, mechanism of,
acids, history of the discovery of, 9, 6, 281
169 Carbohydrates, structural study of, 4,
Ammonia, liquid, reducing action of 203
sodium in, 8, 265 Carbon suboxide, 7, 479
liquid, solutions of metals in, 8, 273 Carbonyl group, compounds contain-
Anthraquinone, chemistry of, 6, 157 ing, 7, 173
Association, molecular, 6, 381 Carotenoids, 10, 265
Atomic reactions, rates of, 10, 91 Catalysis, acid and basic, 6,231; 10, 213
structure and valence, 6, 361 and auto-oxidation, 3, 113
structure as revealed by crystal re- Catalytic actions, 6, 67
flection of x-rays, 6, 437 Cellulose, recent advances in chemistry
weights, 1, 1 of, 4, 355
501
502 SUBJECT INDEX-VOLUMES I TO X