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The reaction of trimethylamine with some inorganic acid chlorides

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The reaction of trimethylamine with some inorganic acid chlorides

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Content THE REACTION OP TRIMETHYLAMINE WITH SOME INORGANIC
ACID CHLORIDES
A Thesis
Presented to
the Faculty of the Department of Chemistry
University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
by
Herbert Oliver Carne
February 19^1
UMI Number: EP41528
All rights reserved
INFORMATION TO ALL USERS
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a note will indicate the deletion.
JUMI_
' Dissertation PabW ing
UMI EP41528
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
Microform Edition © ProQuest LLC.
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unauthorized copying under Title 17, United States Code
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o
c fi eas'f
This thesis, written by
.®BmT..O.„.OARNE............,
under the direction of k.ts- Faculty Committee,
and app ro ved by a ll its m embers, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fu lfill
ment of the requirem ents f o r the degree of
MASTER OF SCIENCE
D ean
Secretary
D a te F.ehruar.y.,.12.41.
Faculty Committee
Chatrmaj
TABLE OF CONTENTS
CHAPTER PAGE
I. PROBLEM AND REVIEW OF THE LITERATURE........ 1
The problem ...................... 4
II. EXPERIMENTAL TECHNIQUE AND RESULTS .......... 7
Preparation of reagents .......... 7
Experimental methods and results ...... 8
Reaction of antimony pentachloride in
carbon tetrachloride with trimethyl-
amine ....................... 8
Preliminary ..... ................ 8
Large scale .................... 9
Antimony trichloride in carbon disulfide
plus trimethylamine.................. 11
Chloroform plus trimethylamine ...... 12
Antimony trichloride in chloroform plus
trimethylamine 12
Decomposition studies of the antimony tri-
chloride-trimethylamine complex .... 15
Phosphorus oxychloride in carbon tetra
chloride plus trimethylamine.......... 19
Phosphorus oxychloride plus trimethyl
amine ............................... 19
Problems for future study ............. 20
Ill
CHAPTER PAGE
III. CONCLUSIONS......... 23
BIBLIOGRAPHY............... . 24
LIST OF FIGURES
FIGURE PAGE
1. Apparatus for Decomposition Studies............ 16
2. Loss of Trimethylamine from the Complex at
Elevated Temperatures....................... 18
CHAPTER X
PROBLEM AND REVIEW OP THE LITERATURE
The manner in which elements are held together to
form compounds has long been a subject of conjecture among
chemists. The most widely accepted theory, that of valence
forces, has served well in the answering of many problems
bearing on the subject, accounting especially well for the
formation and deportment in solution of such apparently
simple compounds as CuSCfy, NiCl2 and AgCl. However, the
old-fashioned valence theory fails to explain the capacity
of these saturated compounds to enter into combinations
with similar saturated substances to form either complex
compounds, as RIClg*6NH3, AgCl*2RH^ and CuSOij*5H2O, or
double salts such as (804)^*2^20 and MgCl2*ECl* 6H2O.
To explain the existence of these complex compounds, Alfred
Werner assumed that simple compounds are not completely
saturated but possess residual or auxiliary valences. On
the basis of this assumption he developed a theory of struc
ture known as the coordination theory. The testing of the
theory has been done with the aid of many subgroup elements
acting as central ions or atoms, the transitional elements
serving especially well to indicate the value of the as
sumption.
If the theory, however, is to explain in a satisfactory
manner all types of complex formation, it becomes necessary
to test It experimentally with the main group elements as
well as the subgroup elements, and especially in relation
to the non-metals near the metal-non-metal boundary.
Of the various elements falling into the latter
category boron has been found to exhibit a maximum coordina
tion number of four in such compounds as PH^'BFj1, PCl^’BBr^
and R^N’BClj^. Phosphorus, another main group metalloid,
has been investigated recently in the form of the penta-
chloride1 *, but no definite coordination number could be
established. With such variant findings concerning boron
and phosphorus, it seemed important to investigate the com
pound formations of a heavier member in the same group as
phosphorus, and if positive results were obtained, to re
examine the phosphorus problem using a compound other than
the pentachloride. A consideration of the properties of the
heavier elements in the group led to the choice of antimony
as the element to be so investigated.
1 E. Wiberg and U. Heubaum. Z. anorg. allgem. Chem.
225:270, (1935)
2 E. Wiberg and K. Schuster. Ibid. 213?94, (1933)
5 E. Wiberg and W. Sutterlin. Ibid. 202:22, (1931)
^ Stanley Edwin Tierney. Master’s thesis, University
of Southern California Library.
3
A survey of the literature indicated that a consid
erable amount of work pertaining to the complex formation
of antimony compounds has been done. M. H. Ross5 in 1836
reported the formation of SbCl- 5 • NH-3. Deherain^ confirmed
this compound in l86l. He wrote also of the preparation of
SbCl^*XNH^ and SbCl-^’XHHjjCl (where x = 1, 2, 3) and the
analogous compounds with antimony pentachloride, including
the SbCl^*4NH4Cl complex. Bosek? in 1895* replaced the
group by KC1 and prepared by fusion methods 2SbClij.* 3KC1;
the same studies being extended by Jordes® who reports
ratios of KC1 to SbCl^ of 2.3* 44.7 and 123* while Plats,
et al.9, using sulphuryl chloride as a solvent prepared
SbClcj* SClty. The problem was again undertaken in 1923 when
Kendall-*-® made a study by means of freezing point diagrams
of the previously reported and above noted compounds. He
was able to confirm the SbCl^’XNHjjCl (x = 1,2,3) complexes
but was unable to substantiate the complex formation with
potassium chloride.
5 M. H. Rose. 2nd series Ann. chim. phys. 322 (1836)
^ M. P. P. Deherain. Comp. Rend. j?2:734, (l86l)
7 Otto Bosek. Chem. Soc. Trans. jS7, (1895)
® Edward Jordes. Berichte 22:2539, (1903)
9 Plats, Ruff and Fischer. Berichte 22:4515* (^-904)
10 James Kendall, E. D. Crittenden and H. K. Miller. J. Am2
Chem. Soc. 4.5:963, (1923)
In spite of the conflicting findings, the fact that
antimony will form complex compounds seems well established.
In all of the previous work, however, no attempt was made
to ascertain the manner of bonding in the complex formations.
It may have been through hydrogen bonding or a rupture of
the antimony-chlorine linking. In many cases Indeed, the
reported "compounds" probably were mixtures. It was thought
that, if the demonstrable ability of antimony to coordinate
could be utilized for reaction with a compound of such
stability as to preclude molecular rearrangement, and yet of
such electronic configuration as to assure the nature of
bonding, a definite insight could be gained concerning the
true coordinating tendencies of antimony.
I. THE PROBLEM
The purpose of this study was to investigate the
reaction of the acid chlorides of antimony and phosphorus
with trimethylamine, either alone or in some suitable
solvent, to determine the conditions for obtaining the most
satisfactory reaction products, and to examine closely the
products so obtained with the purpose of assigning definite
coordination numbers and determining the nature of the bonds
existing therein.
For the investigation of antimony both the penta
chloride and the trichloride were used as the source of the
element. It was thought that the difference in electronic
configuration of the two compounds would he helpful in
drawing conclusions if positive results were obtained. In
the. case of phosphorus the oxychloride was used,, the elec
tronic configuration being sufficiently different from that
of the pentachloride, previously studied,^ to suggest the
possibility of a complex formation.
For a substance with the desirable stability and
electronic configuration with which the elements might
coordinate to form complex compounds, trimethylamine was
chosen. Like all tertiary amines, it is considered an
electron donor, with two electrons on the nitrogen atom
which are capable of being shared. As a molecule, trimethyl
amine is very stable, small possibility existing that a
rupture of the nitrogen-carbon link would result as a con
sequence of any compound formation, and further, the
physical constants of the substance make for easy handling.
Preliminary investigation with both the penta and
trichlorides of antimony with trimethylamine indicated
that compound formation did take place quite rapidly.at
room temperature. In the case of the phosphorus oxy
chloride, a compound was formed, but at a much slower rate
than in the case of the antimony compounds. Later work,
H Stanley Edwin Tierney, o£. cit., p. 22.
6
however, indicated that the compounds formed with antimony
pentachloride contained oxidation products of the amine,
a result which paralleled the recent work of Tierneyl2 with
phosphorus pentachloride. Antimony trichloride, on the
other hand, formed the rather stable compound SbClj*^(CH-^)^,
a material which could be prepared in pure form only after
some preliminary search for the best method of carrying out
the reaction. The compound formed with phosphorus
oxychloride proved to be quite unstable; hence only a cur
sory analysis of the material was effected.
12 rbid., P. 26.
CHAPTER II
EXPERIMENTAL TECHNIQUE AND RESULTS
To avoid duplication in the body of the thesis, a
thorough description of the preparation and purification
of the chemicals used in this work will first be given.
Any mention of them thereafter will refer to the materials
so described, unless otherwise stated.
I. PREPARATION OF REAGENTS
Since the presence of even a trace of water would
vitiate the results obtained, every effort was made to
exclude moisture from all reaction mixtures and chemicals.
Trimethylamine, obtained by distillation from a commercial
25 per cent solution, was finally purified by treatment
with sublimed phosphoric acid anhydride in a bomb tube.
The entire procedure was as described by Tierney.1 Antimony
pentachloride and phosphorus oxychloride were of the Merck’s
Reagent grade, and were not further purified. Their un
satisfactory behavior toward trimethylamine probably is not.
to be attributed to impurities. Antimony trichloride was
purified by reerystallizing from anhydrous carbon disulfide;
the recrystallized product was dried in a vacuum oven at
50 degrees and kept over phosphoric acid anhydride in a
Stanley Edwin Tierney. Master’s thesis, University
of Southern California Library, p. 8.
vacuum desiccator. All solvents used were shaken with
phosphoric acid anhydride and redistilled.
II. EXPERIMENTAL METHODS AND RESULTS
Preliminary reaction of SbClr in CC1 with
N(CH^)-^. For a solvent in which to carry out the reaction
of antimony pentachloride with trimethylamine, carbon,
tetrachloride was chosen; first, because of the solubility
of the salt in the substance and second, because of its non
reactivity with trimethylamine as demonstrated by Tierney.2
In order to determine the nature of the reaction a prelim
inary test was made using small amounts of reactants. To
a bomb tube which had been freed of moisture by heating
and passing in dried air, was added, by means of a long-
stera funnel, a small amount of carbon tetrachloride contain
ing 15 per cent by volume of antimony pentachloride. A
drying tube was then connected to the neck of the bomb
tube, which was then placed in an ether-dry-ice bath. When
the tube and contents had reached the temperature of the
bath, the drying tube was removed and Immediately replaced
by a long glass tube extending to the bottom of the bomb
tube, into which a small amount of pure anhydrous tri
methylamine thus could be distilled. The glass delivery
2 Ibid., p. 15
tube was withdrawn; the bomb tube then was removed from the
dry Ice bath, sealed, and allowed to warm to room tempera
ture. As soon as the solution (solid at the temperature
of dry ice) melted, a reaction took place, yielding a canary-
yellow precipitate. When the above procedure was repeated,
but without the use of the solvent carbon tetrachloride, a
reaction took place with explosive violence even before the
solid antimony pentrachloride had changed into the liquid
form. The conditions under which a reaction would take
place having been demonstrated and delimited, the prepara
tion of a quantity of the compound sufficient for analysis
was undertaken.
Large scale. For the preparation of a large
quantity of the product, it was decided in the interest of
simplicity to carry out the reaction in a large bomb tube.
Accordingly, 50 ml. of 15 per cent antimony pentachloride
solution in carbon tetrachloride and an excess of trimethyl
amine were introduced into a 100 ml. bomb tube as described
for the preliminary experiment. The bomb tube was sealed
and allowed to warm to room temperature, with occasional
shaking. Simultaneously with the melting of the frozen
solution, there appeared a canary-yellow precipitate, which
showed no change in appearance during a twenty-four hour
period of standing at room temperature.
The tube was opened, and the excess trimethylamine
was distilled off at room temperature. The precipitate and
solvent were then rapidly transferred to a centrifuge tube
which was stoppered and centrifuged for a few minutes. The
precipitate was twice washed with fresh solvent, to remove
any unreacted antimony salt. The interchangeable glass
stopper of the centrifuge tube was exchanged for a stop
cock, and the remaining solvent removed by means of vacuum.
The dried product, canary yellow in color, amorphous, and
highly hygroscopic, was transferred to a weighing bottle
and placed in a vacuum desiccator over phosphoric acid
anhydride. After remaining in the desiccator twenty-four
hours, a sample was weighed out, transferred to a volumetric
flask and made to volume with four normal hydrochloric acid,
the acid being necessary to prevent oxychloride formation.
Aliquots were taken for antimony,? and nitrogen1 * determina
tions. The chemical analysis disclosed 11.15 per cent
nitrogen and 13.73 per cent antimony, results which repre
sent approximately seven atoms of nitrogen to one of
antimony. For the purpose of determining chloride content,
a second sample was weighed out and solution effected with
■3
^ Scott, Standard Methods of Chemical Analysis.
4th Ed., Vol. 1. p. 26.
4
Methods of Analysis of the Association of Official:
Agricultural Chemists, 4th edition, pp. 24 and 520.
11
the aid of tartaric acid. A gravimetric determination in
dicated 39.^ pei* cent chlorine.
The results of the analysis, reduced to the simplest
molecular formula, could be represented as: SbCl^Q*
Such a result is in accord with the findings of T i e r n e y , 5
who studied the reaction of phosphorus pentachloride with
trimethylamine, and reached the conclusion that phosphorus
pentachloride was reduced by trimethylamine yielding phos
phorus trichloride and possibly chlorine, both of which
react further with trimethylamine yielding compounds of
high chlorine content. In the light of such similar find
ings, the study of antimony pentachloride was abandoned.
2. SbCl-j in _CS2 Plus For the initial study
of antimony trichloride with trimethylamine, the salt was
dissolved in carbon disulfide and allowed to react with the
amine for a period of seventy-two hours. Analysis of the
material formed pointed to the possibility of a reaction
having taken place between the carbon disulfide and
trimethylamine, which was corroborated by a later experi
ment involving only the two substances. In searching for
a different and more stable solvent, chloroform was chosen.
However, it was decided to examine first its stability in
^ Tierney, op. cit., p. 26.
12
the presence of trimethylamine.
3. CHCl- z plus H(CH-^). In the same manner as here
tofore described, the two chemicals were placed in a bomb
tube. The tube was sealed and allowed to stand at room
temperature for forty-eight hours. At the end of that
time, although no change was apparent, the trimethylamine
was distilled off, the chloroform transferred to a distil
ling flask and its boiling point determined. The value, as
determined, indicated that the chloroform had undergone no
change.
SbCl- ^ in CHCl-j plus N(CH^ )-^. To a bomb tube con
taining 50 ml. of 10 per cent solution of antimony trichloride
in chloroform, was added by means of a distilling tube,
20 ml. of anhydrous trimethylamine; the tube was sealed and
allowed to stand at room temperature for twenty-four hours.
At the end of that period the excess trimethylamine was
distilled off, the insoluble material washed in a centrifuge
tube, the solvent removed under vacuum and the product placed
in a desiccator over phosphoric acid anhydride. The com
pletely dried product was a light yellow fine amorphous
powder, having a strong odor of trimethylamine and extremely
hygroscopic. Analysis indicated that the compound contained
4.90 per cent nitrogen, 47.61 per cent antimony, and 51*69
per cent chlorine, which gives an antimony to nitrogen
15
ratio of 1:0.87. In an attempt to determine whether the
length of time the antimony trichloride and trimethylamine
were in contact had an effect on the nature of the product,
two other similar experiments were carried out in which the
reacting chemicals were allowed to remain together at room
temperature seventy-two hours, and two weeks respectively.
That the interval of standing had little effect is shown
by the analytical data summarized in the table which follows.
TABLE I
EFFECT OF REACTION TIME ON THE NATURE OF THE
COMPLEX FORMED WITH ANTIMONY TRICHLORIDE
AND TRIMETHYLAMINE
Sample
Time
in
hours
Per cent
antimony
Per cent
nitrogen
Atomic ratio of
antimony to
nitrogen
1 24 47.61 4.90 1:0.87
2 72 38.63
5.80 1:1.30
5
356
39.39
6.38 1:1.41
The reaction time having been ruled out as an impor
tant factor in determining the amount of trimethylamine
which would coordinate with the antimony trichloride, it was
decided to investigate the result of changing the tempera
ture at which the two reacted. A convenient point to.begin
such studies was that of zero degrees. Since the vapor
pressure of trimethylamine at such a temperature is less
than one atmosphere, it was now convenient to employ a
125 ml. Erlenmeyer flask having a standard ground glass
joint, instead of the more cumbersome bomb tube. The flask,
containing the antimony trichloride in chloroform was placed
in a Dewar flask containing dry ice and ether, and tri—
methylamine distilled into it in the usual manner. The
delivery tube was removed and the flask immediately closed
by a ground glass stopper, and transferred to a second
Dewar flask in which it was packed with ice. With the re
plenishment of ice as needed, the flask was kept at 0°
for four days. No reaction was evident until twelve hours
after the flask had been placed in ice; then a small amount
of deposit began to appear on the sides of the flask. The
amount of the deposit increased slowly until at the end of
the fourth day the deposition apparently had stopped. The
flask was then removed from the ice bath, the glass stopper
replaced by a stopcock and the excess trimethylamine re
moved. Two portions of chloroform were used to wash the
precipitate, which then was dried under vacuum. The dried
material was a white amorphous powder, very slightly
hygroscopic and practically devoid of any odor. When
analyzed, it was found to contain 29.61 per cent antimony,
10.21 per cent nitrogen, and 26.10 per cent chlorine. Such
values give an antimony to nitrogen ratio of 1:2.99, in
dicating a formula of SbClj.^WfCHj)^. It thus appears that
15
the requirements for a maximum coordination of the antimony
compound by trimethylamine is the proper control of the re
action temperature.
5. Decomposition of SbCl-^.5N(CH-^). In order to
determine the stability of the prepared complex, and to
determine whether or not the formation of the compound had
entailed any ruptures of the trimethylamine molecule, the
behavior of the preparation was studied at elevated tempera
tures and reduced pressure. Using the apparatus as shown
in Figure 1, a weighed amount of material was placed in the
tared flask, the absorption tube filled with glass beads,
and concentrated sulfuric acid added. The system was main
tained at a reduced pressure by means of a water aspirator
connected by rubber tubing to the end of the absorption
tube, while the flask containing the sample was maintained
at elevated temperatures by means of a sulfuric acid bath
heated with a micro burner. With the pressure reduced, the
bath was heated to 55° where it was maintained for thirty
minutes. At the end of that period, the stopcock of the
flask was closed, suction stopped,and the flask removed
from the bath and allowed to cool. When the flask had
cooled, the outside was washed with distilled water, and
dried. Air, passed through a drying tube, was admitted to
the flask, which finally was weighed. The sulfuric acid in
mss
C o n e . r'fsSs^'tt
T f l . A5pr ^ > - ' " »
the absorption tube was washed, into a volumetric flask, made
to volume, and an aliquot taken for nitrogen determination.
Exactly the same procedure was repeated with bath tempera
tures of 75°> 100°, and 150°. The results of the experi
ment are indicated graphically in Figure 2 in which mol.
per cent of trimethylamine lost is plotted against the tem
perature to which the compound was heated. The loss in
weight of the sample so treated, aggregated 313 milligrams,
while analysis of the sulfuric acid used in the absorption
tube, during the heating at different temperatures, indi
cated that 291 milligrams of trimethylamine had been
absorbed. With such agreement, it is reasonable to con
clude that trimethylamine, as such, had been added to the
antimony trichloride to form the complex, the same trimethyl
amine being lost when the complex was heated. The decomposi
tion curve, shows that the complex was quite stable up to 60°.
From 60° to 150° the loss of trimethylamine becomes increas
ingly greater. Due to the rapid loss of trimethylamine at
150° , the decomposition was not attempted at higher temper
atures. Since the trimethylamine was only partially removed
during this process no data are at hand to indicate the
points at which the first and second molecules of trimethyl
amine were completely lost, though it is thought that these
points might later be determined by vapor pressure studies
at various temperatures.
18
slo:
JMD-JJEMlfflB 3T0EHLEX
N O . 6 1 0 3 . J E S S E R A Y M I L L E R . L O S A N G E L E S
6* POCl^ in CC1) [ plus N(CH^ )j . For a preliminary
investigation of the reaction of phosphorus oxychloride with
trimethylamine, the phosphorus compound was dissolved in an
equal volume of carbon tetrachloride in a bomb tube; this
was placed in a Dewar flask containing a dry-ice-ether mix
ture, and trimethylamine distilled into it. The tube was
removed from the Dewar flask and sealed. A slight cloudi
ness appeared when the tube and its contents reached room
temperature. At the end of a week a small amount of a
light brown precipitate had formed. On the basis of such
results there seemed to be no need of the solvent; hence
the experiment was repeated without the addition of carbon
tetrachloride to the phosphorus oxychloride.
POCl^ plus N(CH^)^. In the same manner used
throughout this investigation, trimethylamine was added to
phosphorus oxychloride contained in a bomb tube; the tube
sealed and allowed to stand. At the end of five days the
tube was opened, the excess trimethylamine distilled off
and the small amount of brown precipitate transferred, with
much fuming, to an Erlenmeyer flask fitted with a glass
stopcock. Kept’ at room temperature-under reduced pressure
for an hour, the compound dried to a light brown solid.
"When exposed to air, however, the material fumed and
absorbed moisture so quickly that in the process of
transferring the solid from the Erlenmeyer flask to a weigh
ing bottle the solid became quite moist. Placed in a desic
cator over phosphoric acid anhydride, the material changed
slowly to a semi-solid yellow mass. For the purpose of
analysis the entire contents of the weighing bottle were
dissolved in water and made to a definite volume. From the
weight of the empty weighing bottle, the amount of sample
so dissolved was determined. The solution was analyzed for
nitrogen and chlorine, which were respectively, 12.58 per
cent and 33*10 per cent, which give a value of 2.58 mols of
trimethylamine coordinated with phosphorus oxychloride,
assuming of course, the phosphorus oxychloride molecule
remained intact. Lack of time precluded further work on
the problem, but it is thought that with more refined tech
nique, a coordination of three molecules of trimethylamine
with the compound phosphorus oxychloride could be demon
strated.
III. PROBLEMS FOR FUTURE STUD3T
Although the results of this study are to be viewed
only as having qualitative significance, the successful
preparation of the tri-trimethylammino antimony trichloride
complex, which is in agreement with the preparation of* simi
lar compounds with ammonia and ammonium chloride, as pre
viously noted, would seem to point rather strongly to a
21
maximum coordination number of six for antimony.
Concerning the matter of the bonding forces of the
prepared compound, it should be pointed out that although
the reactants chosen were of such electronic configuration
as to limit the bonding possibilities, and the complete
insolubility of the complex in water points to an unioniz-
. able molecule, the unqualified conclusion that a truly hexa
coordinated complex was formed is unwarranted until it can
be demonstrated beyond a doubt that a complex ion of
antimony trimethylamine chloride was not formed as a result
of a detachment of a chlorine atom from the antimony, with
subsequent replacement by a trimethylamine radical. The
demonstration of the existence or non-existence of such an
ion might possibly be demonstrated by conductometric studies
of the compound provided a solvent could be found which
would effect ionization of the complex without causing
hydrolysis. The successful use, by other investigators, of
liquid sulfur dioxide as a solvent in reactions involving
trimethylamine would point to its feasibility as the solvent
possessing the necessary properties. Assuming that it would
prove satisfactory, the conductometric studies would form
an excellent problem for further contributions to the
chemistry of complex formations. >
The formation of the tri-triraethylammino antimony
trichloride complex only at the low temperature gives rise
to the question of the effect of pressure on the reaction.
Perhaps with proper control of pressure the complexes of
SbCl^.x N(CHj )j (x= 1,2,5) could he produced at will.
Though as a result of this work only a small contri
bution is made concerning the coordinating tendencies of
phosphorus, both phosphorus trichloride and phosphorus
oxychloride with trimethylamine should be investigated
under conditions of controlled temperature and pressure.
In the light of the complex formation of antimony and boron
it seems that phosphorus might well demonstrate a similar
tendency under favorable conditions.
CHAPTER III
CONCLUSIONS
The results of this investigation have shown the
following:
1. A solution of antimony pentaehloride in carbon
tetrachloride reacts with trimethylamine to form a pseudo
addition compound.
2. Carbon disulfide and trimethylamine react with
each other forming degradation products, the nature of which
were not determined.
3. No reaction takes place between chloroform and
trimethylamine.
4. At a temperature of zero degrees, trimethylamine
and antimony trichloride react, yielding a true addition
compound of three molecules of trimethylamine with one
molecule of antimony trichloride. The compound is relative
ly stable.
5. Phosphorus oxychloride reacts with trimethyl
amine yielding an extremely unstable compound.
BIBLIOGRAPHY
BIBLIOGRAPHY
Bosek, Otto, Chem. Soc. Trans. 67 (1897)
Deherain, M. P. P., Comp. Rend. ^52:73^ (l86l)
Jordes, Edward, Berichte. 37:2539 (1903)
Kendall, James, E. D. Crittenden, and H. K. Miller, Jour.
Araer. Chem. Soc. 4^>:963 (1923)
Methods of Analysis of the Association of Official Agricul
tural Chemists. 7th edition, 1935, published by
Association of Official Agricultural Chemists,
pp. 24 and 520.
Plats, Ruff and Fischer, Berichte. Hi 4515 (1904)
Rose, M. H., 2nd series Ann. chim. phys. 322 (1836)
Scott, Standard Methods of Chemical Analysis, 4th edition,
Vol. 1. p. 215 T
Tierney, Stanley Edwin, Master's thesis, University of
Southern California Library
Wiberg, E., and U. Heubaum, Z. anorg. allgem. Chem.
225:270 (1935)
Wiberg, E., and K. Schuster, Z. anorg. allgem. Chem.
213:94 (1933)
Wiberg, E., and W. Sutterlin, Z. anorg, allgem. Chem.
202;22 (1931)

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Asset Metadata

Creator Carne, H. O (author)

Core Title The reaction of trimethylamine with some inorganic acid chlorides

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-788934

Unique identifier UC11348036

Identifier EP41528.pdf (filename),usctheses-c17-788934 (legacy record id)

Legacy Identifier EP41528.pdf

Dmrecord 788934

Document Type Thesis

Rights Carne, H. O.

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA