INVESTIGATION OF THE ACTION
OF
CALCIUM CARBIDE
ON
CERTAIN ORGANIC
CO��OUNDS.
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A Thesis
Arizona
submitted to the
as
Faculty
partial fulfillment
of
of
the
for the degree of
Master
of
Science.
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By
Tucson, Arizona.
:May.4th,1916.
the
University of
requirements
E9??1
19J�
..2
OUTLINE.
I
INTRODUCTION.
of
the
1.
Object
2.
Acknowledgements.
3.
Carbides in General.
4.
Beneral
5.
Investigation.
Chemistry
of Calcium Carbide.
a-
Preparation.
b-
Physical Properties.
c-
Chemical
Properties.
Review of the Literature.
II EXPERIMENTAL PART.
1.
Calcium Carbide
and
Ethyl Alcohol.
2.
Calcium Carbide
and
Methyl
3.
Calcium Carbide
as
a-
a
Alcohol.'
Condensing Agent.
Its action upon Benzaldehyde.
b- The Substitution of Calcium Carbide for
Zinc Chloride in the Preparation of Fluorescein.
c-
4.
III
The Substitution
Zinc Chloride in
Green.
of Calcium Carbide
the"Preparation of
Indifference of Certain Compounds
Carbide.
CONCLUSIONS.
for
Ma�hite
toward Calcium
INVESTIGATION OF THE ACTION OF CALCIUM CARBIDE ON
CERTAIN ORGANIC COMPOUNDS.
INTRODUCTION.
I.
of
Object
1.
The
Investigation.
reactivity of calcium carbide with respect
to water
suggests possibilities of the activity of the carbide with.
organic compounds.
An examination of
of data
The
on
this
the
the
amount
is very meager.
subject
object of
that
journals showed
the
investigation
to
was
in which
possible, interesting syntheses
the
discover, if
carbide may
be used.
2.
Aclmowledgement.
The
investigation
W.
Professor F.
interest
as
well
Guild, to
as
P.
Brinton
of
the
3.
am
deeply indebted for his
also made
Desert
of
suggestions.
by Professor B. H.
Arizona, by Dr. H.
A.
and
by
Laboratory, Tucson,
Howard of Ohio
state
University.
Carbides in General.
Carbon combines with most
of
the metals
hig�emperatures
of
the electric furnace to
oxides at the
form
C.
were
University
Spoehr of the Carnegie
Professor C.
whom I
for many and valuable
Many helpful suggestions
M.
conducted under the direction of
was
carbides.
Those
'metals react with water
of
the
to form
-1-
alkaline
or
their
earth and alkali
acetylene
and the
hydroxide.
Aluminum carbide is
in its behavior in
exceptional
that it
yields methane when treated with water:
·AI40a+12 H20�4 Ai
The most
carbonUndum.
carbide,
Boron forms two
is
the
carbide
the
the
formation of the
carbon steels
at
steel,
is
are
third
or
One
Ara
takes
4.
or
carbide
theory
Ar1
to
important and in­
is
Chemistry
In the
re­
is doubtless due
Fe3C;
or
for,
none
when
of
this
the behavior of steels
this
formed the
is
compound
suddenly cooled.
If
place the sub-carbide decomposes .into
General
carbides of iron
stage
stage is that there
Fe24C;
in
cut diamond
hard to
A very
of iron,
as
as
diamond in hardness:
sufficiently
first
car­
the
B20!,
constitution ot steel.
ly hard sub-carbide of iron
changed if the· metal
and
BOG
suddenly cooled, little
found.
calcium
are
consideration of the
the
and their effect upon
calescence ot
the
to
than diamond dust.
slowly
teresting study
the
CH4•
commonly known
carbides,
carbide is
fact, �he powdered
more
later ·is
the
former compound ranks close
to
3
important carbides, commercially,
bide and silicon
but
(OB)3+
slow
FeaO
is
extreme­
found
un­
cooling
and iron.
of Calcium Carbide.
a-Preparation.
pure
Pure
Calcium carbide is
lime
by sugar charcoal
first used
small
a
prepared by the reduction of
in
the electric furnace.
current 350 amperes and 70 volts for
amounts of the
1
Moissan1
preparing
carbide, but in the preparation of
Moissan, Le
Four
Electrique,
p.
290.
larger quantities he
analysis�when
a
slight
with
used
calcium oxide must be
or
excess
carbon which the
the
equation for the
found that
furnace
reaction is
calcium carbonate
oxide but
the
would be
Ca
large bulk
C03+
4C
�
was
For
composition is desired,
of definite
p�Oduct
a
and 60 volts.
1000 amperes
combine
added to
The
always yields.
CaO+3C7
CO.
CaC2 +-
could be used in
Moissan
.
of
place
the
disadvantage; the equation
a
CO.
CaC2+:1
b-Physical Properties.
Calcium carbide
a
clean
is
crystalline surface.
ing opaque crystals
and have
the
microscope they
appear
red
tint.
c-Chemical
This
At red heat
the
phosphide
very
plates
reddish brown
some
carbide burns
with formation of
it
a
small
glisten­
are
under
colorf
a
deep
Properties.
The
action upon
The
presents
transparent and possess
substance exhibits
properties.
broken and
quite easily
in
oxygen at
vapor
without
the
cold
dull
red heat
at
or
high temperatures.
of phosphorus converts it into
incandescence
energetically
a
Hydrogen is without
calcium carbonate.
either in
interesting chemical
very
with
but
liberation
ar�enic
of
a
calcium
vapor reacts
great amount of heat
in the formation of calcium arsenide.
All
at
room
the
halogens react with calcium carbide:
temperature,
calcium fluoride
and
causes
it
to burn with
carbon
tetrafluoride.
-3-
fluorine,
formation
In
an
of
atmosphe�e
D
of chlorine at 245
we
the
,
find calcium chloride
3500
At
reaction.
substance becomes
and
carbon
the
as
incandescent and
of
products
it reacts with bromine,
and at
3050
the
is
decomposed ene�getically by the vapor of iodine.
In
the
of
case
is
sulphur vapor calcium sulphide
form-
II
ed; at about 500
not
and boron do
In
the
carbide beco�es
�eact with
incandescent.
at white
it
heat.
calcium carbide behav�s
general,
Silicon
indifferently
to-
o
ward metals.
In
nesium and tin
are
there
is
yield
a
hea t
the
In the
action.
dull
red heat but
sodium, mag-
,
case
antimony gives
is
most
and best
of
formation
the
iron
At
dull
red
crystlt,lline alloy enclosing calcium.
a
unique
of
high temperatures
carburized alloy of iron and calcium.
know
acetylene
reaction of
from water
calcium
car-
according to
equation
of heat
given off
is
than
that
this
action is
of
that
in
possible,
the
carbide
ate
30
that
hydrogen
perfectly
cuprous
the
be
and
and
the
reaction is
sodium upon water.
by ��niacal
ed
without
reaction at
no
The
bide
neighborhood of 1000
the
case
even
is
the
chloride
Acetylene obtain�d from
for
it
production
carbon
of gases,
acetylene�is greatly
It
might
absorbed
be
suppos­
this
is
not
if
the
case;
and calcium carbon-
consisting chiefly of
hindered.
acid reacts very
-4-
completely
the reaction would,
violent; however,
covered with
Fuming sulphuric
is
solution.
of water vapor
more
soon
pure
scarcely less violent
slowly
and
a
large
part
of the gas evolved is absorbed;
acts
�apidly
and
gives
nitric acid is lfithout
marked
a
the
acid
ordinary
odor.
aldehy4e
re­
Fuming
act.Lon in the cold and at
boiling
01
temperature there
i,s" barely
dilute acid
gives acetylene.
hydrocbloic
acids
with dry
a
mixture
acid,
of
hydriodic and
At
gasesJ rich in
in
acid
potassium nitrate
dull red heat by lead
metallic calcium enclosed by the
lead.
aqueous
are
a
peroxide
becomes
dull red
At
Ad
evolved.
interesting.
the
carbonic aCid;
down with formation of calcium carbonate.
oxidation at
is
yields only acetylene.
and
incan­
hydrogen �is
contact with this compound,
heat, potassium chlorate
the
red heat
bright
oxidizing agents
incandescent with evolution of
solution of this
The very
chloride gas the carbide becomes
The action of several
Fused chromic
Both dilute
give pure acetylene.
hydrogen
descent, and
perceptible reaction.
broken
result ot
we
find
ordinary tem­
At
peratures when ground with lead fluoride calcium carbide
becomes
5.
incandescent.
Review of the Literature.
1.
The Action of Water.of
Crystallization
on
Calcium
Carbide.
Irvine
Masson2
has made
hydrated salts when mixed
carbide.
one
minute
In
some
and in
2
cases
a
ac td on
others heat is
Jour.
of powdered calcium
with excess
the
Chern.
-5-
of many
thorough study
is
complete in less than
required
Soc.,
to
97 Pt.
cause
1,
rapid
851-867.
raPd�formation
The
action.
the action of
t�e
Acid salts and
of
acetylene is explained by
crystalline
acids do not react
with either the calcium carbide
produced with which they
2.
.
was
a
passed
carbon
over
the
as
calcium
acids
hydroxide
mixed.
are
acetylene
heated glass
a
rormed
are
or
mixture
or
or Calcium Carbide
New Reactions
When
hydrate emits.
water vapo� which the
3
and
Acetylene.
tetrachloride
and carbon
chloride
tube, hydrogen
and
according.to the equation:
2C,:)H2+ CCI'I�50 +4HCl.
�
Chloroform,
calcium
bromide
or
carbide,
the
polysulphides
compounds
were
When
heated between 200
in
heat-
chloride,
hydrogen.
equivalent quantities
o
over
calcium
Awmonium Chloride
3.
sult;
passed
were
by-products
and
analagous
and bromoform gave
disulphide,
when any of the
resuitsl
ed
carbon
of
the
two
o�
in Presence
reagents
are
�
and 300
,
many different
reaction may be
general)the
compounds
re-
represented by the
equation:
3 Ca
At
C2"" 6NB4Cl
relatively
amine
strong
low
compounds
odor of
--72
NH4Me + 2 NH2NH
Me
+C2H2+3
C12•
and
temperatures, acetylene, hydrazine
are
formed.
pyridene
3
Sandman.,
is
Zeit.
At
higher temperatures
a
noticed; carbon is deposited
angew.
Chern.,
4
Studi
Ca
Sassaresi, I,
-6-
106-108,
12, ·543-545,
(190�.
and
�902�
methane
A
small
is
quantity_or phenylhydrazine
increase.
amines
decreases and the
formed; acetylene
formed, especially at
high temperatures.
4.
Absorption of Nitrogen by Calcium Carbide.
The
of
presence
ee1erates the
rate
of
such
aS�Odides,
absorption
oxygen free calcium compounds
some
of
absorption
is
nitrogen
also increased
or
the
lithium
absorption
in
than do chlorides.
this
and
the
not
influence
is
case
formation of lithium nitride
ph1des do
even
at
salts
ferrous
With the
excep­
the
thought
The behavior of
to be due
to
and calcium chloride.
the
high temperatures.
the
Sul-
Calcium fluoride
absorption.
alkali fluorides affect
slightly
of
The
chloride, bromides and iodides accelerate
more
lithium chloride
ac­
carbide.
by the addition
chlorides
alkali
brom�des,
�calcium
chloride which reacts with calcium carbide.
tion of
5
rate of
Metals,
absorption
oxides,
or
p
salts of oxy-acids
ion
Pollacci6
cause
found that
effect at 800.
no
a
mixture
4�
potassium carbonate containing
accelerates
the
absorption
of
In
this
connect-
of calcium carbide
of the
nitrogen.
and
latter compound
To
about
two
atmospheres the rate of absorption is favored by increased
pressure.
s.
A
Decomposition
of Calcium Carbide
sample containing
63%
of
by
Heat?
calcium carbide
:
after heat-
Poleniusz., Chern. Zeit., 31, 958-959 (1907)
Zeitsch. E1ekrochem., 14,-S65-566
7
Zeitsch. Elekrochem., 17, 177-179
�911
-
-7-
�908?
II
for five hours
ing
at 500�contained
36.6�
after
heating
•
hours
thirty
chloride
at
1000
accelerate
Although
remaining
still
The residue
hydrogen
that
on
this
zation
or
the
carbide
absorb
decomposes�the
sodium
is
sUbstances
nitrogen.
from calcium for it
is free
treatment with water.
of calcium is
absence
or
decomposition; calcium fluoride
the
very active.
can
Certain calcium salts
•
Br.ner
gives
Kuhne8
and
probably due
no
think
to volatili-
com�ination with the substances of which
the
tube
is made.
6.
Alcohols andr.Calcium
As
the
of
result
Carbide��
passing isobutyl, amyl, ethyl
and
tI
methyl alcoho14.over
calcium carbide heated to about 500
mixture of gases is
obtained which in all
chiefly
(60-70%)
of
3.6%, ethylene 9.1�,
carbons
0.31�,
ethane
carbon monoxide
9.610,
methyl alcohol, acetylene
oxide
to
4.5�,
1.3%.
1.4%,
With
alcohol
and
e
the
of
eth�ne
exception
the
of
4.4%;
from
carbon
mon­
13.8�,
and
methyl alcohol
aldehyde corresponding
10�
of the
620-622
�91t)
amounted to about
consists
t.hy Lene hydro­
4.2%,
ethylene
cases
yields acetylene
and carbon dioxide
liqUid products consisted
the
alcohol
8.3%, ethylene hydrocarbons 2.5�,
carbon dioxide
the
Ethyl
hydrogen.
four
a
�
al.ohol
used.
:
Corupt.
P.
rend
Lefervre,
-8-
�,
Compt. rend., �,
1221-1223
Alcoholates.
7.
In his researches
carbide Moissan
calcium
on
vestiagted the action of the
carbide with
10
in-
anhydr-ous e.thyl
1:1
alcohol in
that
the action takes
2
However"
Forcrand11
such
to the
ana�ous
of barium oxide
on
ethyl
sealed tubes
Several
bide \vith
to
excess
of
he states
;
Ca.
alcoholate
the
secure
eXists)�but
really
of calcium oxide
porducts
them is
�2H50)2
unable
was
sUbstance
a
180
place according to the equation:
C2H50H+CaC2"""'7C2H2'"
(if
itself
tion
sealed tube heated to about
a
found addi­
ethyl alcohol.
and
of
One
substance obtained by the action
aloohol whioh gives 4
1.5 grams
containing
(C2Hso).3Bao.
of calcium car-
anhydrous ethyl alcohol
heated to
were
()
for
180
several hours.
and at
acetylene
least
of which is methane
number
large
evolved is
The gas
one
or
and the
two
other
of carbon atoms.
other
an
hydrocarbons,
over
4
(C2H50�.
Prolonged drying
mains
the
compound
tubes
are
opened the walls
on
which
drying.
to
11
is
lost
a
sul­
over
the formula
and there
Before
that
the
to
these
a
white
rend.
-9-
sealed
amorphou�powder
crystals
are
Moissan, Le Fou� Electrique, 298
Compt.,
re-
covered with colorless
are
gradually change
He concludes
10
one
After further drying for many weeks
sulphuric aCidJethyl alcohol
crystals
of
olefine containing
phuric acid gave the compound corresponding
3 CaO.
mixture
a
�,
1266-1268
due
to
the
union of calcium oxide with excess of
reaction between calcium carbide
ethyl alcohol.
and the
The
ethyl alcohol
is
con-
sidered to be:
There
no
seems
doubt
therefore
that
alcoholate
the
is not
produced by this reaction but only addition products of the
I
'W'�Oa
type
and the
° +N
other Oa 0.
Ohablay12
sought for
on
a
in his efforts
02H50Na
also in
the
.:#
liquid
(NOa) 2'
2
the
resulting
al-
ammonia fulfilled these
and barium nitrate
liquid ammonia; the equation
NaN0a+
(C2H50)
Ba
He
2.
is:
succeeded
preparing calcium ethoxide by the action of alcohol
presence of
liquid
H3)4 �
(C2H59:a
ammonia
according
equation:
2
02H50H
In his
cribes
of
presence
and calcium ammonium in
to
only would be without action
Sodium ethoxide
perfectly.
-r Ba
402H508
prepare barium ethoxide
to
but would dissolve
found that
He
used in the
were
of which is 3 Oa 0.
solvent which not
salt.
conditions
one
,
C2H50H.
any�� reagents
ka1ine
2
C2H50H
+ Ca
(N
researches
further the
on
Ca
+ 4
metallic alcoholates
alcoholates
of
calcium.
NHa+ H2.
Ohablay13
These
are
des-
easily
prepared he states either by the double decomposition between calcium nitrate ..
and
an
alkaline
(Whi�h
alcoholate
or
is very
by the action
12
13
Compt. rend.,
�J
819-821.
Compt. rend.,
�,
953-955.
-10-
soluable
of
in
liquid
ammonia)
calcium ammonium
upon the
corresponding alcohols.
reactions may be
These
represented by the equations:
(!l 03) 2-7 2
Na + Ca
2
CH30
2
C2H50H+Ca(N
All ·alcoholates
substances
Na
Ha)4-?�2H50)2
are
white
and
N03+ Ca
Ca+4
(c H30)2
and
If Ha-l-H2.
exceptionally sensitive
are
to both heat and moisture.
14
Action of Calcium Carbide
8.
Acetone
from its
prepared
Some
on
sodium
Ketones.
�)
hydrogen sulphite
compound reacts vigorously and almost immediately
on
calcium carbide with evolution of
distilla­
yellow liquid which
tion of the
(II
acetone
nishes" unchanged
products going
of
acetone
alone
or
rormed
dilut�With
of
cial
acetone which
cium
carbide
in
carbide
one
case
is
half to
of
The
reacts
the
were
of
quantity
The
the
hour
once
proportions
conditions
acetone
found that
when
of
the
the
-11-
4,
:1,
commer-
upon cal-
the
carbide
is
experiment.
attack upon the
but with commercial
Chim.
is
substances, which
vaporou�state
lapses before the
Soc.,
the
(1700 -350?
action
14
Bull.
complex
mesityl �xide
portion
authors
in its
"bisulphite"
produced at
one
the
pieces remains unchanged
powdered, whatever
the
Whatever
of many different
seperated.
(3)
be, whether the acetone be used
8-12%.
rrom
mixture
a
have not been
In
ether,
reaction fur-
0
from 170-350.
over
var�
results from the
mesityl oxide and
II
and carbide may
never
composed
(2)
The
acetylene.
powdered
829-833,
acetone
from
begins energeti�
Q.90S)
It would
ally.
a
volatile
seem
inactive
found that
was
the
the reaction
Pure butanone
product
obtained 1s
of
The
the
molecule
one
mesityl oxide
a
ketone
or
CH2-CO��H=C
C:C(CBa\,CII2-CHa'
-CO-eH3.
nCH3-CH2-
and
a
mixture
�H3)
of the
of butanone.
following for-
two:
does not
bide under reduced pressure;
In
dinary pressure.
this
mass
"hich could not be
ied,
therefore,
only
liquid
elimination
effect
powdered ealcium
its vapor is without effect upon the
and
pieces.
(cH�
Boiling acetophenone
it
reacts, howeve�,
last
case
car-
under
resulted
a
or-
gummy
Among the ke t one s stud-
purified.
those which
there
lump
contain the
group
-CO-CH3
condencing influence
of
calcium carbide.
Action of Calcium Carbide
on
Some
suffered the
9.
from the
two
CHa-
carbide
of
in
The main
the
may be
and may hinder
increased to about
two molecules
to either
of
ingeniously devised
an
was
resulting
of water between
product corresponds
mu1as
of
use
reaction is very slow.
case
fractionationJ
quantities
reacts with calcium carbide
In this
contains
powdered calcium carbide.
of very small
By the
of
yield
by
retarding influence
a
entirely.
the
toward
presence
certain ether salts has
apparatus
to eliminate
substanceJimposs�ble
which renders it
It
commercial acetone
then�that
Ketones.
�I)15
s
Mesityl
oxide
reacts with
calcium carbide but
the
15
Bull.
Soc., Chim. IV
-12-
5, 950-952, 1909
ex�
pected ketone:
is not
formed.
A mixture
of
gives two semicarbazones,
other
colorless
obtained which
is
of which is
one
gummy and the
product could be isolat-
No definite
crystalline.
ed from the
products
which results from the
liquid
re­
duction of the mixture.
10. Action of Amyl
At dull
red heat
liquid products
Chloride
these
tuo
on
Calcium
substances
(.3 methyl
which include
-
Carbide.16
react
/jfJ_
to
give
butylene,
.(..
fl methyl
-
L1
butylene,
-
chlorides.
The gaseous
acetylene, ethylene
lene
The
series.
Ca
C2+2C5 H11C1
11.
Action of
Vanino17
with
a
much
s Lower-
and
secondary and tertiary amyl
products evolved
other hydrocarbons
and
Fomaldehyde Solution
the
rate
solution of formalin in
whan water,
stops the reaction
.
16
+-
C2H2+-2 C5H10
found that
while
almost
of
hydrogen,
the
ethy-
considered to be
primary action is
--)
are
Ca
C12•
on
Calcium Carbide.
of evolution of
acetylene
eight volumns of water
a
40%
completely
solution of
the
•
Compt. rend., 1900, �,
1036-1039.
17
Chern.
Pharm.
Centr., 1900,
i i� 1150· from
Centr.-H., 1000, !!, 666.
was
aldehyde
EXPERI!ffiNTAL PART.
II
1.
Calcium Carbide
and
Alcohol.
Ethyl
The first problem undertaken
ethyl alcohol
citun carbide would react with
of
vapors
alcohol
20
place
have
without
action
statement
that
on
calcium carbide.
As
on
the water bath
nothing
but
Next it
tion.
ethyl alcohol
was
proposed
substance4lfunctioning
ment described above
but
the
results
were
negative.
consideration in
ed at
this
point
calcium carbide
that
was
95�
to
is
heated with
at
the
negLtive�
were
obtained upon distilla-
was
to
try
effect
the
with
of
The
same
certain
experi-
platinum sponge
a
Aluminum chloride
conditions.
ethyl alcohol
one
one
intro-
of
matter
a
is
proved
In view
following section it may
the
in from
only
ethyl alcohol
The results
repeated
equally ineffective under the
the
In
catalytic agents.
as
was
by passing the
for three hours
boiling point of the alcohol.
for
or
calcium carbide
duction and verification,
condi tions
under
carbide19•
heated
the
over
found the
I
ethyl alcohol
reaction18,
ffclosed tube"
than the
other
if cal-
to determine
was
be
of
stat­
dehydrated by
two hours.
18
Moif;san Le
19
20
tour Elect.,
298
Compt., rend., �, 1221-1223
Allan Com. Org. Anal. 4th Ed.
Vol.
III P.ll
2.
Calcium Carbide and
In
alcohol
acetone21•
the
addition product with
an
Four hundred and
was
600
added to
and immediate
c.c.
and the
standing for twelve
acetone
the
the
solid
of
the
hours
This
mass.
mass
which forms
from activated
quick
the
ceiver
was
white
a
alcohol
The C.
P.
from
portion
of
crystalline
and
the mixture
dis-
was
and distilled
lime
forty-eight
a
to
again
sixty hours.
sulphate
large U tube containing
calcium carbide used
pieces about the size
This drives
anhydrous copper sulphate after
of
connected with
evaporating
obtained
so
two distillations with copper
last
an
(after
impurities but does not decompose
tilled twice
In
The mixture
boils.
stirring to 100.
The
each
vigorous
o
distillation.
over
action is
the
peas.
was
freshly
the
re-
soda
lime.
broken into
Immediately after the
last
distillation at 4:45 P.M.
the alcohol
eium carbide.
begins mildly but with immediate
evolution of
The
small
action
was
added to
the
cal-
gas bubbles.
21
Bull.,
quick
calcium chlmride
transferred to
subjected to'
standing
as
giving CaCI2.
taken up with water
then
from two fresh portions
of
grams
soon
)was
product
was
prepared
was
alcohol
methyl
alcohol;
alcohol
and other.
addition
important
calcium chloride
that
fact
twenty
dish and heated with constant
off
is
distilled twice from activated
was
taken of the
is
it
carbide
only anhydrous but also free from
be not
alcohol
Advantage
forms
the
Anhydrous acetone-free alcohol
follows:-
lime.
alcohol' with
using methyl
the
that
Alcohol.
Methyl
Boc
,
,
Chim.
-15-
IV 8,
829-833
(1908)
The reaction flask
to
soda lime
ing
vention of
preclude, of course,
for the
white residue.
a
At 7:55 A.
rapid.
stant
of
The
agitation.
alcohol
reaction
still
was
7:5� A. M.
in
activity.
the reaction had
small
The
8 A.
M.
of
and at 4 P.
total
the next
M.
The
displaced by
iod there
covered with
proportion
unti�at
to
the
the
to
end of
action the
evolved
was
disappeared completely.
odor of
acetylene
was
a
comple­
gradually
was
this per­
amount of alcohol
The
very small amount of the solution remaining.
carbide had
At
action.
This makes
During this time the alcohol
(in
still
day the action ,had moderated somewhat
the white residue
was�
was
not decreased
retard the
action could be detected.
cold.
very
following day
about 72 hours for this reaction to go
of
tion in the
a
no
to
was
cover-
continuing rapidly
of carbide were
seem
were
state of con-
a
apparantly had
pieoes
the residue but this did not
in
of inter­
reaction had
the reaction
was
when observed this date at 9:15 P. M.
at
the
of carbide
pieces
nex� day
of
contain­
th�possibility
evolution of gas
the
surface
The
in progress.
M.
The
U tube
a
At 8 P.M.
atmospheric moisture.
progressed considerably
ed with
connected with
was
used)
calcium
Throughout the whole
very marked.
re-
The gas
completely absorbed by ammoniacal cuprous chloride
solution with the formation of the
characteristic red copper
acetylide.
Examination of
ing
gave negative
the
small
tests for
-16-
amount of the
formaldehyde
solution remain­
with
(I)
Graf�s
�iPhenYlamine
reagent
resorcin in concentrated
acid
unsuccessful because
were
If
we
molecules why should
2
OH2H
0
we
no
would be
2
It
bromide
before
CHa
OH -I-
attempting
as
and take
0 H
two
ethylene:
-t-
C2�
Ca(OH)2.
upon brominating the gaseous proAnother
is formed.
��H3)2
Ca02
possibility
ro1lows:
added to 2.0
0+02H2+0aO.
study the behavior of methyl ether
to work with
ducts with the above
pared
CH2H
acetylene.
the formation or methyl ether:
considered best to
was
+
H+Oa02---7 02H4
ethylene
as
obtain
not
But this does not hold for,
ducts
the presence of
of
methyl alcohol
consider
Tests for formic
acid.
sulphuric
aCi�and (2)
s1nphuric
in concentrated
the gaseous
theory in mind.
1.3
of
parts
The
methyl
product
ether
pure
alcohol
parts of concentrated sulphuric
or
were
pro-
was
pre­
slowly
acid and the
1#
mixture heated to
140
The
•
flux condenser to prevent
into
concentrated
will
absorb 600 volumes
then obtained by
ume
ed
of
or
of
of
acid.
sulphuric
methyl
treating the
the gas
water�whereupon
directly
loss
flask
acid
is
passed into water.
connected with
was
alcohol�and
One
volume
ether.
the
of
gas
passed
an
ether
was
equal vol­
liberated and may be
Water absorbs
re-
this acid
The pure
solution with
a
collect­
37 volumes
<J
of
methyl ether at 18
The gas
alcohol
was
from
the
bubbled
•
reaction of calcium carbide with
gently
into water for
-17-
about
methyl
72 hours.
The
no
acetylene
soon
escaped and the aqueous solu�ion yielded
In view
gas whatsoever.
ether in water
that
(see above)
of
it
the
solubility of methyl
only gaseous product obtained
the
therefore,
probable,
seems
is
acetylene.
a-Examination of the Residue.
The residue
thick
as
heavy grayish
lene and alcohol.
is
then
an
and
white
smelling strongly
mass
It drys
quickly
at
�
Ca
H3)2'
C
in water
insolubility
are
of
a
acety-
seem
possible
but its indifference
in accord with
not
and
temperature
room
It would
a�orphous white powder.
that this might be
heat
removed from the reaction flask is
to
Chablay's
22
statement
that
the
exceptionally sensitive
chars
readily/while
able musk-like
into
an
and cold
elude
One
the alkaline
Further
in amount
light.
heating
The
a
are
residue
very disagree­
the
converts
product
The gas driven off is
ana burns with
The
earths
and moisture.
the gases evolved have
odor.
in white
a
flame which is in-
compound is insoluble in hot
water, benzene, ether, pyrdine, hot ethyl alcohol,
and acetone.
In view
to heat
amorphous white powder.
considerable
visible
of
alkoxides
of
that
theory
Its aqueous 4Olution is
the behavior
or the
this must
be
some
metallic
was
that
this might be
advanced
residue
alkaline.
strongly
it
seems
-18-
to
con-
organic derivative.
an
addition pro-
22
Compt. rend., 153,
fair
819-821.
such
duct
4
3 Ca 0.
as
CH3�
to the
substances 3 Ca o.
tained
by Forcrand.
23
The
ed.
4
B
Ca o.
or
02H50H
and Ca o.
both
Perhaps
CHaOH, analagous
ob-
C2H50H
compounds
form-
are
equation
suggests the possibility of the formation of the rnethoxide.
Its extreme
into
ing methods
residue
of
(2)
with
as
treatment
no
�)
case
could break this up
follmfs:
of
(4)
ing
water bath
The
The
contents
canted and filtered.
the
was
flask
were
experiment
the
finely powdered
heated in
was
an
methyl alcohol
\fas
connected with
cooled and the
between 19
shown
treated with concentrated
10%
of
excess
a
liquid
reflux
de-
filtrate gives
0
and 97
•
The
presence
acid and
Compt. rend., 119,
(1) when
salicylic
23
-19-
boil­
sodium
by the follow'ing tests:
sulphuric
was
,actively
Distillation of this
over
sulphuric
The
0
product coming
4�
boiling
of
for 50 minutes with
hydroxide solution.
of
appreciable
the residue with sodium
28 grams
thoroughly dry residue
a
an
was
The follow'-
dry distillation of
successful.
was
and
condenser.
we
conversion
in mind it
theory
obtain alcohol.
boiling water
solution
carried out
that
its
cause
dry distillation with calcium hydroxide
However,
hydroxide
so
obtained:
alcohol
alone
and
ease
tried but in
were
(3) treatment
acid.
t�suppose
reasonable
wi th considerable
amount
With this
other compound.
some
would be
sensitiveness would then
1266-1268.
acid
obtained the
we
(2)
.�licylate
a
hot
last
solution
preciPitate(Which forms
sequently changes
red)With
in the
distillate has
D
contains about
imately
22�
to
By referring
•
18�
of
treated with
aqueous layer and sub­
resorcin and concentrated sul­
to
0.971 at 17
methyl
characteristic red ring and
the
gives
The
was
of
marked odor of formaldehyde results.
a
white
phuric acid.
winter-green odor
the distillate
of
portion
a
spiralJ
copper
This
characteristic
a
a
specific gravity
table24
find
we
methyl alcohol by weight
of
that
this
and approx­
by volume.
Treatment
acid results
of
the
the
in
product with dilute hydrochloric
immediate
and
copious evolution of
car-
bon dioxide.
to
Up
the
idue has failed and
be
purify
quantitative analysis
a
a
this
res­
therefore
cannot
Condensing Agent.
Benzaldehyde.
�ith benzaldehyde
in
cold
is
as
a-Its Action upon
'fe
obtain in from
phous substance.
it
to
attempt
any
reported.
a.Calcium Carbide
the
time
present
insoluble
soluble
in hot
This
one
to
two hours
and ether.
alcohol.
\fhi te
a
is not benzoic
product
in benzene
ethJI
contact with calcium carbide
It
is
amor-
acid, for
difficultly
Upon ignition only
a
stai�
24
Van Nostrands
Chem.
-20-
Annual
1913,
in
p.
436.
is left upon
salt.
It
platinumJ this proves
seems
it does
and zinc
of
absence
a
calcium
probable that the benzaldehyde has suffered
formation of triphenyl.Allethane derivitives,
condensation with the
as
the
in the
of concentrated
presence
reaction may be represented to be
The
chloride.
.,
CaH4CHO
0
OH
C6 H5
sulphuric acid
H
The aldehyde groups
At
the
end of fourteen days
bottom or
the
after
days more,
two
from the
the
by
test-tube
of
use
It
hammer.
was
thought
test
After
all
tube
of which
so
set away in
thirteen days
in
pieces
noticed that
several
of
places
this
indicates
a
tube had
the
test
the
experiment
a
place free
considerable expansion.
-21-
and
was
been
repeated
from any
reaction
form of
dirficulty
perhaps
tube had cracked like
definite
the
glass had rallen
broken with considerable
that
cracke4 accidentally,
the
was
acid.
The mixture had assumed the
was
a
it
wasicracked
several
test-tube.
container and
converted into
doubtless
are
and
jarring.
the
first;
accompanied by
b-The
for Zinc
Substitution or Calcium Carbide
Chloride in the Preparation or Fluorescein.
The preparation of fluorescein
method in the
following
manner:
anhydride
ground up
and
was
this
attempted by
was
of
15 grams
phthalic
intimately mixed with 22 grams
•
of resorcinol
of
and the mixture heated to
finely powdered calcium carbide
molten
amount
small
the
with constant
mass
time
3 grams
slowly
added to the
a
very
and
rapid thickening
causes
added the misture
are
Three grams
Addition of
stirring.
carbide
the
of
was
180.
by
is
practically dry.
of
acetylene during
o
The whole
the
is heated to 210.
process
is very marked.
only constant
and very
from
coursing
over
melt
is
case
when zinc
readily
of
the
removed from the
chloride
can
and after
as
a
repeatedly
prevent the
this
crucible;
must
we
The
chisel.
and
badly
container.
is used for here
finely pulverized
longer reacts acia.
foams
The mixture
sides
the
such
acid is washed
odor
rapid stirring
sharp instrlment,
no
The
cold
The
is
mass
not
use
some
fluorescein is
treatment with
hydrochloric
with water until
the filtrate
Yield,
about
the
20 grams.
In view
�
of the
foaming,
and rather
the
this
use
of
low
the
disagreeable�of
yield,
there
calcium carbide
seems
in
acetylene, bulkiness,
to
place
be
of
advantage in
no
chloride
zinc
in
reaction.
c-The
Substitution of Calcium Carbide
for Zinc
Chloride in the Preparation or Malachite Green.
As
a
further illustration of the
-22-
use
of
calcium
car-
bide in
place
prepared
small
a
small
scale
amount
of calcium carbide
then added and the
After
to
Indifference
dimethylaniline,
was
added,
pinch
was
of Certain
and
of lead
fifteen minutes
istic green color of the dye
4.
A
and
heating continued
for ten
standing
was
green
follows:
as
ture heated for five minutes.
was
malachite
chloride,
portions of benzaldehyde
small
To
a
on
of zinc
plainly
the
mix-
peroxide
for two minutes.
the
character-
visible.
Compounds toward Calcium
Carbide.
Benzol
were
The
results
boiled with
with and without
eac� both
sults
was
calcium carbide for three hours
a
platinum sponge but the
re­
negative.
following
obtained:
amyl alcohol,
and
ly without action
were
heated with calcium carbide but
to�uol, benzyl�alcohol,
aniline, phenol,
ethyl ether.
on
no
The
following
calcium carbide
in the
are
apparent­
cold:
benzyl
chloride, quinoline, glycerine, nitrobenzol O-nitro-toluol,
dimethylaniline, tetrachlorethane,
ethyl acetate.
I
-23-
benzal
chloride,
and
CONCLUSIONS.
III
Calcium carbide
1.
t�mperatures
which
and
with' formation of
probably
acetylene
addition
of
consists
ducts
of calcium methoxide
Further
is
investigation
of the
or
composition
2.
Benzaldehyde undergoes
white
substance
of calcium oxide
probably
a
a
of
deriv�tive
dehydrating agent
in
this
case
seems
clear up the
to
substance.
Calcium carbide may be
3.
the methoxide itself.
even
condensation
calcium carbide with formation of
but
a
products
necessary in order
real
as
and
ordinary
methyl alcohol together perhaps with disintergration pro­
and
is
react at
alcohol
methyl
•
white
presence
of
sUbstance which
triphenylmethane.
substituted for zinc chloride
in the
to
a
in the
preparation of fluorescein
offer
no
advantages
Bine
over
chloride.
4.
to
The
principal property
organic compounds
dehydrating agent.
now
in
is
to
In this
of calcium carbide
as
function
as
a
respect
it
is inferior
use.
-24-
referred
condensing
or
to
those