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north of St. George, a protected cove in which small boats can
find refuge and alluvial deposits on which a garden can be
made. Most of the streams of the western coast have ancient
deltas bordering one side or other of their entrances to the sea,
and these places have invariably proved atti'active to the settlers
as places in which to locate their houses ; so that the relation
of n\it to cove is exceedingly intimate, and one on rounding a
headland expects to find a "livier's" homef and rarely is he
disappointed, the size of the settlement being correlated with
the extent of the cultivatable ground, the protection afforded
by the cove, and the excellence of the fishing.

Note on Labbadob.

About two weeks were spent on the coast of Labrador, and
here on the western end of the Strait of Belle Isle were
observed elevated beaches in a magnificent state of preserva-
tion, at least eight being seen at one locality, the highest of
which was 350 feet above high tide. No careful measurements
of slope were made, but the general impression is that they
slope to the east, an impression supported by observation made
with a hand clinometer. Some of the elevated beaches are
covered with myriads of rounded bowlders exactly similar to
those of the present shore, only the water being needed to com-
plete the picture of a modern beach from which, however,
shells would be lacking, as none was seen in these old beaches.

•Daly, BnU. Mub. Comp. Zool., xxxviii, p. 259, 1902.

f The name ^^livier '' is used on the west coast for an inhabitant of a viUage.

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W. H. Txoenhofel — Physiography of Newfoundland. 23

Above the terraces the Cambrian sandstones and limestones
rise to about one level, presenting a flat-topped upper surface
which truncates the structure.

A trip was made westward along the coast to Brador Bay,
the site of the ancient French settlement of New Brest, to
examine the contact between the Cambrian and the gneiss. It
was not found, having been completely eroded out by a river

Fig. 8.

FiQ. 8. Elevated beaches cut in the Lower Cambrian sandstones and lime-
stones, Blanc Sablon, Labrador. Photograph by Charles Schuchert.

which follows it back into the country, forming a lowland
between the Cambrian strata and the crystallines. Inquiry
along the coast elicited the information that this depression
exists almost everywhere between the Cambrian and the
gneiss. If this be correct, then the Cambrian strata form a
cuesta and the line of contact with the Laurentians an inner


(1) The physiography of Newfoundland owes most of its
detail to the structure and texture of the rock which have local-
ized erosion along the zones of the softer sediments and frac-

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24 W. H. Twenhofd — Physiography of Newfoundland.

ture. Still other detail is due to variations in the position of
the strand-line and the work of ice.

(2) The extensive distribution of wide flat-topped uplands
with local elevations of a few hundred feet, and the horizon-
tality of the summit levels truncating an exceedingly complex
structure, show the former presence of a plain at this level,
assumed to be a plain of subaerial erosion completed in Cre-
taceous time and correlated with a similar plain in the Appa-

(3) The presence of faulting of great magnitude, the upx-
turning of the beds at the foot of the western face of the Long
flange, the extreme straightness of this face, and the elevation
on the foreland of large blocks of sediments no different ffom
those contiguous, render untenable the hypothesis that the cliff
face and the foreland are due to marine erosion, and practi-
cally prove that the Long Eange owes its origin to the faulting
upward of this block from the foreland's level.

(4) Wide elevated flat-floored valleys along the western
face of the Long Bange are thought to have been formed in
an uncompleted cycle of erosion interrupted by renewed uplift
of the Long Kange in pre-Glacial time.

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J, C. Brcmner — Hydrocarbon Found in Brazil.

Art. II. — A JBydrocarion Found in the Diamond and Car-
honado Dist^^ct of Bahia^ Brazil; by J. C. Bbannek.

Among the minerals obtained by me in the diamond wash-
ings of Bahia was one known among the miners as "gelo" —
ice. The only specimen I have seen was originally about the
size of a man's hst, but upon drying it crumbled into angular
lumps about as large as peas. It is jet black and opaque ; it
has a conchoidal fracture, a hardness of 2*2, a specific gravity
of 1'51, and is very friable.

The following note was sent me by my Brazilian friend Dr.
Alencar Lima of Bahia in regard to this hydrocarbon : "This
specimen is from the Caetano Martins diamond washings at
Chique-Chique, State of Bahia. The diamond miners call it
'gelo' (ice). It is found in the beds below the diamond-bear-
ing gravels, and it occurs in big pieces, sometimes nearly as
large as a man's head. It is solid only so long as it retains its
natural moisture, for as soon as it dries it becomes friable in
proportion as it dries out. While it is moist it yields a black
mky substance, but once dry it does not absorb moisture again."

I have had an analysis made of this material with the fol-
lowing results :

Analysis of a Hydrocarbon from the Diamond-bearing Gravels
at Chique- Chique^ State of Bahia, Brazil,

L. R. Lenox, analyst.

Water 19-43^

Volatile combustible matter 35*47

Fixed carbon 40*06

A^h 5-07


The ash is mainly alumina with a little silica, calcium, and

Tested for solubility it was found to be :

Insoluble in Soluble in

Cold water Concentrated sulphuric acid

Hot water (to a dark brown liquid)

Alcohol Nitric acid

Ether (to a dark brown liquid)

Petroleum ether Strong potassium hydroxide

Chloroform (to a dark brown solution)


Carbon disulphide

Hydrochloric acid

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26 J. C, Branner — Hydrocarbon Found in Brazil,

Professor F. J. Rogers of the Physics Department of Stan-
ford University kindly tested the conductivity of this material,
but, owing to the small size of the fragments and to its fria-
bility, no absolute measure of its conductivity could be made.
The general conclusion was reached, however, that it has a low
conductivity, about like that of bituminous coal. As an insu-
lator it is not as good as elaterite, Cuban asphaltum, or alber-

When I first heard of this hydrocarbon I thought it possible
that it might be genetically related to the diamonds and car-
bonados of the region in which it was found. But the size
and occurrence of these lumps in recent gravels do not bear
out such a theory.

Attempts to obtain specimens of this material from other
localities disclosed the fact that the term "gelo" is also applied
to material other than hydrocarbon. For example, Mr. Arthur
K. Turney of Cachorros has sent me several specimens of what
is called "gelo" at the diamond washings at Mosquitos, a few
miles south of the city of Lenjoes. The materials from near
Lensoes, however, are simply hard beds of various thicknesses
in the recent gravels. They are made up of sands and water-
worn pebbles firmly cemented. They contain no lime and
very little iron, and it is therefore inferred that the cementing
matter is silica.

Stanford University, California.

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W, A. Drushel — Hydrolysis of Esters in Fatty Adds. 27

Abt. III. — On the Hydrolysis of Esters of Substituted Fatty
Acids ; by W. A. Drushel.

[Contribation from the Kent Chemical lAboratory of Tale Univ. — ccxxviii.]
2. Ethyl Cyanacetate,

When hydrogen is replaced by halogens in fatty acids the
strength of the acids is increased and greater stability of the
esters of snch substituted acids than of the estera of unsubstituted
acetic acid toward the hydrolytic action of water in the presence
of a strong catalyzing acid, may be expected. It was snown in
a previous paper* from this laboratory that the methyl, ethyl,
propyl and isobutyl esters of chlor and brom substituted acetic
acias have smaller velocities of hydrolysis in the presence of
hydrochloric and hydrobromic acids than the corresponding
esters of unsubstituted acetic acid. These results are in accord
with the theory that a substance most readily undergoes hydrol-
ysis if it is formed by the combination of a weak acid and a
weak base.f

In view of the results obtained from the esters of halogen
substituted acetic acids it seemed desirable to make a further
study of the rates of hydrolysis of esters of substituted acids.
Cy^nacetic acid being more strongly dissociated than the mono-
halogen substituted acetic acids, it is to be expected that ethyl
cvanacetate would be even more stable than the ethyl esters of
tiiese acids. However the great difference in the rates of
hydrolysis of ethyl cyanacetate «nd ethyl chloracetate under the
same conditions of temperature and concentration of ester and
catalyzing acid, recorded in Table I, can scarcely be explained
on this theory alone. The dissociation constants of acetic
acid, chloracetic acid and cyanacetic acid are in the ratio
1 : 86 : 206, and the velocity constants of the ethyl esters of
these acids taken in the same order have a mean ratio, calcu-
lated from Table I, of 6*5 : 4*2 : 1. The rate of hydrolysis of
ethyl cyanacetate is lower than would be expected from a com-
parison of the dissociation constants of the acids and the rates
of hydrolysis of ethyl acetate and ethyl chloracetate.

Preparation of Esters, — The ethyl cyanacetate used in the
hydrolysis experiments recorded in this paper was prepared
from recrystallized monochloracetic acid by the method of
Phelps and Tillotson.J Five hundred cubic centimeters of
the crude ester were fractioned under diminished pressure and
200*°*" of the pure ester boiling at 95i°C. at a pressure of 12"°'
were obtained. The ethyl monochloracetate was prepared by
boiling for six hours with a reflux condenser a mixture of 100

♦ This Jonrnal, xxx, 72. \ Nernst, Theoretical Chemistry, p. 521.

Jlbid., Mvi, 267.

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28 W. A. Druahel — Hydrolyais of Eaters in FaWy Acids.

ffrm. of recry stall ized monochloracetic acid and 800*^™' of abso-
ute ethyl alcohol containing 1*25 per cent of dry hydrochloric
acid gas. The crude ester was separated from the excess of
alcohol by fractional distillation and purified by the method of
Phelps and Eddy.*

Hydrolysis in Decinormal Hydrochloric Acid. — Purified
commercial ethyl acetate, and ethyl cyanacetate and ethyl
monochloracetate prepared as described, were hydrolyzed at
26°, 35**, and 50° C. by making decinormal solutions of the
esters in decinormal hydrochloric acid in 250^'"* and 500^"' flasks
fitted with ground glass stoppers and keeping the flasks well
submerged in a thermostat during the course of the reactions.
The reaction velocity was determined by titrating at intervals
25*™* of the reaction mixture, diluted with lOO*^*"* of cold water,
with decinormal barium hydroxide, using phenol phthalein as
an indicator. For the purpose of comparing the velocity con-
stants the three esters were hydrolyzed under the same condi-
tions of temperature and concentration of catalyzing acid. The
velocity constants recorded in Table I were calculated as for
monomolecular reactions from the titration formula,

K =4-[log(T„-T.)-log(T„-T.)],

since cyanacetic and monochloracetic acids are relatively very
weak acids in comparison to hydrochloric acid, used as a cata-
lyzing acid, although they are many times stronger than acetic
acid. The results of the hydrolysis experiments are given in
detail in Table I and in summary form in Table III. It will
be observed that the velocity constants for ethyl cyanacetate
are very much lower than for ethyl acetate and also consider-
ably lower than for ethyl monochloracetate, in fact, lower than
would be anticipated irom the dissociation constants of the
three acids, acetic 0*0018, monochloracetic 0*155 and cyan-
acetic 0*370. This is the result which may be expected if the
molecules of ethyl cyanacetate exist, at least in part, in poly-
merized form in dilute acid solution.

Hydrolysis in Water Solution. — Decinormal solutions of
ethyl acetate, ethyl monochloracetate and ethyl cyanacetate in
water alone were hydrolyzed at 35° and 50° C. and 25^™' por-
tions of the reaction mixture were titrated at intervals in the man-
ner previously described. In this case the hydrolytic action of
water is accelerated only by the acids liberated from the respec-
tive esters, a simple instance of autocatalysis. The results were
calculated in per cent of ester hydrolyzed at given intervals
and are recorded in detail in Table II and in summary form
in Table III. It would be expected that the ester which
liberates the most strongly dissociated acid would hydrolyze
♦ This Journal, xxvi, 258.

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W. A. Drushel — Hydrolysis of Esters in Fatty Acids. 29

most rapidly. Table II shows that both ethyl cyanacetate and
ethyl monochloracetate are hydrolyzed much more rapidly
than ethyl acetate, and that ethyl monochloracetate is hydro-
lyzed more rapidly than ethyl cyanacetate although cyanacetic
acid is a stronger acid than monochloracetic acid. This again
is the result which may be expected if the etliyl cyanacetate
molecules exist partly in polymeric form in aqueoUs solution.
Suspecting the rapid increase in acidity of the ethyl mono-
chloracetate solution to be partly due to a decomposition of
the ester molecule with the liberation of hydrochloric acid, a
portion of the reaction mixture was occasionally titrated with
decinormal silver nitrate. No measurable decomposition in

A. At 25* C.

Table I.
Ethyl eyanacetaU in N/10 HCL

Ethyl acetate Ethyl chloracetate

Tinmin. 10* K T in min. 10* K

180 64-6 75 46-0

300 69-3 1120 46-1

390 69-1 2700 45-7

1260 66-4 4000 46-3

1780 67-3 4610 45'1

2746 68-6 5770 46-8

3195 68-6


B. At Zb'' C.





0. At 50" C.


498 6








Ethyl cyanacetate

T in min.


10* K



T in min.







10* K










23 2




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30 W. A. Druahd — Hydrolysis of Eaters in Fatty Acids.

this direction was observed even at 60** C. The hydrolysis
reactions apparently proceeded smoothly according to the fol-
lowing equations :

Cl-CH -COOC.H, +H0H^I±CI-CH,-C00H4-C,H,0H, and

A. At85'C.
Ethyl acetate

T in hr. % hydxol.


111-6 0-3

163-6 0-6

281 1-4

386 2-2

476 3-1

673 3-9

B. At50'C.

24 0-2

63 0-4

76 0-6

96 0-7

120 0-9

145 1-2

Tablb II.
Eithyl cyanaeetate in loater alone.

Ethyl chloraoetate
T in hr. % hydrol.

















Ethyl oyanacetate

T in hr. % hydrol.

30 2-6

50-6 4-4

149 13-3

173-5 16-8

201 22*3

240 27-3

294 33*9

337 38-1

Tablb III.

Hydrolysis in N/10 HCl

Ethyl acetate

At 26° C.
At 35° C.
At 60° C.



159 3

















Hydrolysis in water alone
in hr. % hydrol.

At 35° C. 337 1-8

At 50° C. 145 1-2

in hr.


% hydrol.



% hydrol.

Hydrolysis in Alkaline Solution. — Decinormal solutions of
ethyl cyanaeetate in decinormal and fifth normal solutions of
barium hydroxide were placed in a thermostat at 25° and 35° C.
The decomposition of the ester apparently took place in two

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W, A. Drushel — Hydrolysis of Esters in Fatty Acids. 31

stages. The first reaction proceeded too rapidly to make accu-
rate velocity measurements, having reached an equilibrium in
from five to ten minutes with a loss in the alkalinity of the
solution nearly equivalent to the concentration of ester used.
No apparent formation of ammonia occurred in this first reac-
tion and it no doubt resulted only in the liberation of alcohol
and the formation of basic or neutral barium cyanacetate accord-
ing to the equations :

CN-CH -COOC,H. -h Ba(OH). >

CN-CH,-C00-.Ba-0H4-C,H-0H, or
2CN-CH -COOC.H. 4- Ba(OH), — >

(CN-CH,-COO-),Ba+ 2C,H-0H

Several hours after the alkalinity of the reaction mixture
had reached an equilibrium the presence of ammonia became
apparent and clusters of needle-shaped crystals began to
deposit on the walls of the flasks containing the reaction mix-
tures. This reaction continued for several days at 35*^ C. and
for more than two weeks at 25° C. with an increase in the
amount of crystalline product and ammonia without any
increase in the alkalinity of the reaction mixture. This reac-
tion evidently consists of the hydrolysis of the cyanogen group
with the formation of free ammonia and barium malonate
according to the following equation :

CN-CH,-COO-Ba-OH + HOH — >Ba(COO),CH, + NH, .

The crystalline salt formed in this reaction on analysis
proved to be barium malonate.

Summary, — When ethyl cyanacetate is hydrolyzed in deci-
normal aqueous hydrochloric acid the rate of hydrolysis is
much lower than that of ethyl monochloracetate under the
same conditions, the efEect of the replacement of hydrogen by
cyanogen in the acetyl group being a much greater depression
of the velocity of hydrolysis than would be expected from the
strength of the cyanetic acid generated in the reaction. In
water alone the hydrolysis of ethyl cyanacetate also proceeds
more slowly than the hydrolysis of ethyl monochloracetate
although cyanacetate acid is more strongly dissociated than
monocnloracetic acid. This marked retardation in the hydrol-
ysis reaction in the presence of the cyanogen group may be
due to an efEect analogous to what in the esterification reaction
is called steric hindrance, or the possibility of the existence of
polymerized molecules of cyanacetic ester in aqueous solution
may be suggested as an explanation of the retarded action.

In alkaline solution the nydrolysis of ethyl cyanacetate pro-
ceeds in two stages. The first is a very rapid decomposition
of the ester into alcohol and the alkali cyanacetate, and the
second is the hydrolysis of the alkali cyanacetate to the alkali
malonate and ammonia.

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32 C, R, Keyes — Lcbss Ma/iiUe and Kansan Drift-SheeU

Art. IV. — Relations of Missouri River Iabss Mantle and
Kansan Drift-Sheet ; by Charles R. Keyes.

For the enormous deposits of loess which border the Missouri
River a glacial origin has never proved a very satisfactory
explanation. Their genetic relations have long continued to
be one of the most puzzling geologic problems of the region.
Regarding them as wind-formed accumulations has only par-
tially removed the difficulties presented. There have always
remained many seeming incongruities.

So long and so closely have the southern limits of the drift-
sheet, a remarkable belt of Bluff deposits, or loess, and the
course of the Missouri River been associated with one another
that something of a genetic relationship between them has
been often inferred. The older glacial boundaries practically
follow the course of the river from its headwaters to its mouth.
In southeast South Dakota a younger drift-sheet also touches
the great stream.

Noteworthy among the peculiarities of the loess of the region
are : (1) Its great thickness and conspicuous capping of the
blufEs on both sides of the river, a circumstance which early
gave it the name of " BlufE Deposit " * ; (2) its effectual man-
tling of the Kansan drift-sheet f ; (3) its position in many locali-
ties both above and below the drift X \ i^) its greater thick-
ness and higher elevation on the east bluff of the river than on
the west side, as first suggested by me in Missouri, and after-
wards determined by Bain in Iowa ; (5) its extension far for-
ward from the drift-border § ; (6) its expansion indefinitely
backward over the Kansan drift-sheet || ; (7) its notable non-
restriction to the immediate vicinity of the drift-border, but, as
recently shown, its extension for great distances westward from
the river^^ ; (8) its deposition on the surface of the country inde-
pendent of hypsometricconditions** ; (9) the multiple terranal
character which it displays in many placesft ; (10) its develop-
ment beneath the Kansan drift-sheet. :|:t

Since presenting §§ reasons, a decade and a half ago, arguing
for an eolian origin of the Missouri River loess, the conclusions

*Swanow : Geol. Surv. Missonri, let and 2d Ann. Repts., p. 69, 1856.
tTodd: Mieaonri Geol. Snrv., vol. x, p. 129, 1896.

X CaU and McGee : This Journal (8), vol. zxiv, p. 202, 1882 ; aUo, Todd
and Bain : Proo. Iowa Acad. Sci., vol. ii, p. 20, 1895.
8 Todd : Missouri Geol. Surv., vol. x, p. 182, 1896.
I Bain : Iowa Geol. Surv., vol. ix, p. 91, 1890.
^ Bull. Geol. Soc. America, vol. xxii, 1911.
*♦ Calvin : Iowa Geol. Surv., vol. xi, p. 444, 1901.
t+ Wilcox : Iowa Geol. Surv., vol. xiii, p. 716. 1904.
MUdden : Iowa Geol. Surv., vol. xi, p. 249, 1901.
§g Keyes: This Journal (4), vol. vi, p. 299, 1898.

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C. R. Keyes — Lceas McrnUe and JKansan Drift-Sheet. 38:

then arrived at have been without reserve accepted by Lever-
ett,* Bain,t Shimek,:]: Calvin,§ Udden,|j and others who have
worked in the region. When I first set forth this evidence I
was inclined to derive all of the loess-materials directly from
the extensive mud-flats and sand-bars which line the great
stream. These sources no doubt are more than ample to sup:
ply the necessary matter for the loess deposits as tiiey appear
to-day ; yet it now seems probable, in the light of wider investi-
gations, that a greater part of the silty materials comes from
more distant localities. Although, at the present moment,
quantitative determinations are not available, the volume of
wind-borne dusts derived from the dry, upland plains to the
west and settling upon and beyond the Missouri River belt
must be very great. The latest considerations on this point
suggest that not only the contiguous country and the semi-
arid belt but the desert regions of southwestern United States
are large contributors to the loess of the Mississippi Valley.

Notwithstanding the fact that it had been long known that
the Missouri River loess extended forward from the limits
of the drift, there has been little attempt to ascertain the prob-
able distances. In all physical respects, except perhaps color,
the loess is indistinguishable from the so-called " Plains marls,"
which so deeply mantle the surface of Kansas and Nebraska ;
and it cannot be told from the adobe soils of the arid regions
that are unquestionably accumulations of wind-blown dusts.
The recognition of the identity of the three deposits not only
greatly simplifies the consideration of their origm, but it indi-
cates clearly the complete independence of formation of the
loess and the drift. The similarity in physical characters i8^
more than co-incidental ; and once the comparison is made of
the three soils in the field there remains no hesitancy in pro-
nouncing them identical in origin.

What is really presented by the drift and loess sections at
the Missouri River is a marked overlap of eolian dusts coming
from the southwest and of glacial deposits derived from the
northeast. In spite of the fact that the eolic formations attain
vast development in the region under consideration, their true
relations and character are greatly obscured by the vigorous
action of the rains, this belt being within the influence oi moist
climate ; they are confused by the presence of extensive glacial
formations ; they are easily misinterpreted because the typical

Online LibraryJohn Elihu HallThe American journal of science → online text (page 4 of 61)