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Contributions to the chemistry of the chlorides, simple and complex, of beryllium

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Contributions to the chemistry of the chlorides, simple and complex, of beryllium

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Content CONTRIBUTIONS TO THE CHEMISTRY OF THE
CHLORIDES, SIMPLE .AND COMPLEX,
OF BERYLLIUM
A Thesis
Presented to
the Department of Chemistry
University of Southern California
In Partial Fulfillment
of the Requirements for the degree of
Doctor of Philosophy
by
Andrew Hansen
June 1939
This dissertation, written hy
todrew. - -Ha&s-eii-.................
under the guidance o f A . l S . . . F a c u lty C o m m ittee
on Studies, and a pp ro ve d by a ll its members, has
been presented to and accepted by the C o u n c il
on G raduate S tu d y and Research, in p a r tia l f u l
fillm e n t o f requirem ents f o r the degree of
D O C T O R O F P H I L O S O P H Y
D edr
Secretary
D a te Me.. . . 1 9 . 3 . 9 . .
C om m ittee on Studies
C hairm an
TABLE OF CONTENTS
CHAPTER PAGE
I. INTRODUCTION
The uses and extraction of beryllium 1
Scope of the investigation 6
II. NITROSYL CHLORIDE
Historical 8
Preparation 8
Chemistry 12
Thermal decomposition 15
Photo chemical decomposition 17
III* PREPARATION OF MATERIALS
Beryllium, oxide from beryl 19
Nitrosyl chloride from nitrosylsulfuric
acid and. hydrogen chloride 22
Nitrosyl chloride from potassium chloride and
nitrogen dioxide 26
Nitrogen dioxide 29
Nitrosyl chloride from aqua regia 32
Nitrosyl chloride from the addition compound
of aluminum chloride and nitrosyl chloride 34
Sugar charcoal 58
Discussion of the methods for preparing
nitrosyl chloride 40
CHAPTER
IV.
PAGE
EXPERIMENTAL WORE
The preparation of beryllium, chloride by means
of nitrosyl chloride and beryllium oxide 43
The preparation of beryllium chloride by the
action of nitrosyl chloride on beryl 49
The action of liquid nitrosyl chloride on
beryl 57
The preparation of beryllium chloride by means
of beryllium, metal and nitrosyl chloride 58
The preparation of beryllium chloride by eva
poration in an atmosphere of nitrosyl
chloride 59
The preparation of the nitrosyl chloride com
pound of beryllium 61
An attempt to prepare "metallic" beryllium by
the electrolysis of BeClgNOCl in nitrosyl 66
The action of beryllium chloride on beryl 69
The effect of beryllium, chloride on glass 70
SUMMARY AND CONCLUSIONS 74^
BIBLIOGRAPHY 76
INTRODUCTION
THE USES AND EXTRACTION OF BERYLLIUM
Of all. the beryllium that Is used In the United States,
the largest amount goes into the manufacture of alloys with
copper. The first alloys of copper and beryllium were pre
pared by Lebeau^, who studied their properties. Alloys con
taining from 2 to 2.25 per cent beryllium can now be obtain
ed in the form of sheet, rod, tube or wire. Besides copper,
beryllium alloys with aluminum, nickel, iron, and silver.
Those containing around 2.5- per cent beryllium are the most
successful. In all cases It gives to the alloy non-corrosive
properties. The eopper-beryllium alloys are resistant to
wear and fatigue as well as possessing properties of hardness,
strength, and conductivity of electricity and heat. Its non
magnetic and non-sparking properties are of great importance.
Many uses have been found for the alloy. Its hardness and
shock resistance make it especially good for non-sparking
tools and for firing pins in revolvers. Springs of all
kinds are used. These are non-corrosive and possess great
1 Lebeau, Ann. Chim, Phys., 16, 457-503, 1897.
2
resistance to fatigue as well as high resilience and low
hysteresis loss* Bearings, gears, and sliding contacts il
lustrate its resistance to wear.
Fink and Shen^ have prepared beryllium-copper alloys
containing about 3 per cent of beryllium by electrolysis,
using a molten copper cathode* The electrolyte is made up
of a mixture of beryllium oxyfluoride, sodium fluoride, and
barium fluoride* The process is continued until the alloy
contains about 3 per cent by weight.
A slightly modified method is to heat to about 950OC,
a mixture of two parts of beryllium fluoride with one part
of calcium or sodium fluoride. The beryllium alloys with
the copper cathode which is gradually pushed into the melt*
As the melting point of the alloy is lower than that of the
fusion, it melts and flows to the bottom.
Another method for forming alloys is to melt a mixture
of copper and beryllium metal. When heated, beryllium com
bines readily with oxygen as shown by the equation.
Be + ■ "gOg —* ^ BeO + ■ 136,000 cal*
This property makes the metal useful as a deoxidizing agent.
As a metal there are very few uses for beryllium* It
is used in x-ray work and in the study of atomic physics.
Of the compounds, beryllium oxide is one of the most
2 Fink and Shen, Trans, llec. Chem. Soc., 72, 317, 1937.
3
important., It is used to make glass, which has a melting
point around 1400°C. Its high resistance to heat makes it
useful as refractory material for crucibles. A small amount
of the oxide added to incadescent gas mantles gives them
greater strength.
The chlorides and fluorides are used as electrolytes
in the preparation of either the metal or the copper alloy.
Beryllium is found in the mineral beryl which contains
about 5 per cent of the metal. It is not a rare element,
being found in many places. Considerable quantities are
found in South Dakota, New York* and the New England states.
When the cost of beryllium is lowered, the copper-beryIlium
alloy, no doubt, will be one of the most important of those
with copper as a base. The future of beryllium not only
depends upon the extraction from the ore but also upon the
location of sufficient deposits of high beryllium content.
The countries which are most concerned with the deve
lopment of beryllium are Germany and the United States.
In Germany the method, is to sinter beryl with sodium
silico fluoride at a temperature around 650°C. Sodium bery
llium fluoride is then extracted with cold water. Calcium
fluoride and beryllium hydroxide are precipitated on the ad
dition of calcium hydroxide. When treated with hydrogen flu
oride, beryllium fluoride is formed, which on evaporation,
produces beryllium oxyfluoride. This product is mixed with
4
barium fluoride and heated to a temperature of 1350°C. The
heat is maintained by the electric current at a high poten
tial of 70-80 volts * Long rods of beryllium are formed with
a purity of 98 per cent*
In the American process,, the exact treatment of the ore
is not known. It is possible that the ore is fused with
alkalis or fluorides. A second method is to heat the
beryl to fusion and suddenly cool in water. A change in
the properties takes place which enables it to be extract
ed with sulfuric acid at high pressures and temperatures.
In a recent article C. G-. Fink3 states that a simple
method has been developed in their laboratories for the
extraction of beryllium from it ores. The beryl is chlor
inated in some manner and separated from impurities by
fractional distillation.
Whatever method is adopted,, the final product is beryl
lium chloride ??hich is used as the electrolyte in the elec-
trolytical production of beryllium. Sodium chloride is
added as a flux and the mixture heated to 8Q0°C. Six volts
are usually used. The metal is obtained in the form of
flakes which must be fused to form the solid metal. The
purity ranges from 99.25 to 99.50 per cent.
^ C. G. Fink,- Jour.. Chem. Educ. , . 16, 110, 1939.
The cost depends upon the power used, which is equal
to the product of volts and amperes. The divalence of
beryllium gives it a very low electrolytic equivalent.
This gives a yield of 4.5. The use of low voltages are ex
tremely advantageous in maintaining low costs. In the Ger
man process, the fluorine produced, is objectionable. How
ever, the production of the solid metal has its advantage
over the formation of flakes which must be treated to
create a solid metal.
THE SCOPE OF THE INVESTIGATION
6
With this recent interest in beryllium* any attempt
to add to the knowledge of it would be considered worthy
of further study. A review of the metallurgy of beryllium
shows that a large part of the cost is due to the method
of treating the ore to get it into the form suitable for
electrolysis* With beryllium chloride as the starting
material in preparing the metal or alloy, it would be ad
vantageous to develop a suitable method for the direct
chlorination of beryL. A number of gases, such as hydrogen
chloride, carbonyl chloride, carbon tetra chloride and chlor
ine, have been used, but with no great commercial importance.
In some of the industries especially in the manufacture
of potassium nitrate from potassium chloride and nitric
acid, large quantities of nitrosyl chloride are produced
which in some cases is quite pure. The recovery of the
lost nitrogen adds to the cost of operation. To date no
use has been found for this nitrosyl chloride.
A part of this investigation was to study the method of
preparing nitrosyl chloride and to determine whether it
could be used as a chlorinating agent to obtain beryllium
from beryl.
The chemistry of beryllium is made rather complex by
the ready action of water upon its salts, causing hydrolysis,
and by the fact that, beryllium chloride appears to have
some action, upon glass at high temperatures. It was with
this in mind that another of the objectives of the work,
a study of its chloride, was undertaken.
Beryllium is quite similar to aluminum in many of its
properties. It is known that beryllium forms coordinated
or addition compounds In many cases. This suggested the
investigation of possible formation of a nitrosyl chloride
addition compound with beryllium.
CHAPTER II
NITROSYL CHLORIDE
Historical* Aqua regia has been known for some time.
In the middle centuries a mixture of nitric and hydrochloric
acids, produced by using solutions of nitrates in hydro
chloric acid or chlorates In nitric acid, was used for dis
solving gold. J". L. Lussac found that at the boiling
point of water, a mixture of nitric and hydrochloric acids
gave off a gas which he condensed. This was found to con
tain what he called chloronitrous acid. It is now known
as nitrosyl chloride. Gay Lussac-*- was the first to prepare
nitrosyl chloride by the direct union of nitric oxide and
chlorine.
Preparation* Nitrosyl chloride has been prepared in
a great many different ways. Practically all the methods
depend upon the action of chlorine, or a chloride upon
some compound containing nitrogen, an oxide of nitrogen, or
nitric acid. The method of Tilden2 and of Girard and
Pabst®, or modifications of them, depend upon the action of
^-Gay Lussac, Ann. Chim., Phys., (3) 23, 203, 1848.
2Trans. Chem. Soc., 27, 630, 852, 1860.
3Bull, Soc-Chim., (2) 30, 531, 1778.
9
nitrosyl sulfuric acid upon dry sodium chloride. These
crystals, known as lead chamber crystals, may be prepared
by passing the vapors of aqua regia through concentrated
sulfuric acid. Chlorine is not absorbed. Mtrosyl chlor
ide prepared by this method is not pure, containing nitro
gen oxide as impurities.
Scott and Johnson^ have used a modification of this
method and obtained a very, pure product suitable for the
determination of the atomic weight of chlorine. Dry hydro
gen chloride is passed through nitrosyl sulfuric acid form
ed by passing sulfur dioxide through fuming nitric acid.
The product is purified by fractional distillation. It is
claimed that hydrogen chloride is more suitable than sodium
chloride. The reaction can take place in one reaction
flask. Oxides of nitrogen are eliminated and excess hydro
gen chloride is easily removed by distillation at low temp
eratures .
When nitric oxide combines with chlorine, nitrosyl
chloride is formed. This is sometimes known as Gay
Lussacrs method*5 The equation for this reaction is given
^Scott and Johnson: J. Phy. Chem. , 33, 1975, 1929.
^Ann. Chim*, Phys., (3) 23, 203, 1848.
10
as follows:
2ND ♦ Gig 2ND Cl
The procedure is to pass an excess of nitric oxide into
liquid chlorine at low temperatures. Nitric oxide is
quite soluble in nitrosyl chloride but can be removed by
distillation, whereas chlorine is more difficult to remove*
Chlorine may be used from a tank or made by the action
of concentrated hydrochloric acid on potassium permangan
ate. It is then passed through water to remove hydrogen
chloride and then through concentrated sulfuric acid and
phosphorus pentoxide for the removal of water.
2HN02 + 2KI » 2NO + Ig + 2E20
Nitric oxide and iodine are formed. Iodine is removed, by
passing the gas over moist red phosphorus. Hydrogen iodide
and nitrogen peroxide are removed by bubbling through
sodium hydroxide solution. It is dried in the same manner
as chlorine.
Nitric oxide is passed through liquid chlorine at -55
to -60°C and as the reaction proceeds, the chlorine changes
to a red color due to nitrosyl chloride. As nitric oxide
can be removed an excess is used. The gaseous nitrosyl
chloride is passed through a tube heated to 15Q°C in order
6Ber., 34, 1408, 1901.
7Moser: Z. Anal. Chem., 50, 401, 1911.
11
that any dichloride might be decomposed. Trautz® claims
that when nitric oxide and chlorine react, nitrosyl bi
chloride is formed as an intermediate product. It is de
composed at low temperatures.
Whittaker, Lundstrom and Mertz^ have prepared nitrosyl
chloride by the reaction between nitrogen doxide and potas
sium chloride.
2H0g + KOI KN03 + M)C1
Dry nitrogen dioxide is passed through a vertical tower
about 60 cm. high filled with potassium chloride contain
ing 2*4 per cent moisture. The reaction is regulated so
that the reacting zone does not reach the top. Without
purification 97 per cent nitrosyl chloride can be obtained.
Further purification is obtained by fractional distillation.
When concentrated nitric and hydrochloric acids are
mixed, nitrosyl chloride is formed*
3HC1 + HH03 ~¥ mo1 + Gig + 2HgO
This can be dried, by passing through calcium chloride. By
fractional distillation and freezing most of the impurities
are removed. Chlorine is the most difficult to remove.
This can be accomplished by allowing the dry vapors to pass
^Tautz ; A. Anorg. Chem.136, 1, 1925, 146, 1, 1925.
^Whittaker, Lundstrom and Hertz, Ind. Eng* Chem., 23,
1410. 1931.
12
over ferric chloride at 0°C* An addition compound having
the formula FeCl3N0Cl is formed* On heating10 in a vacuum
it decomposes forming ferric chloride and nitrosyl chlor
ide*
Several other methods for the preparation of nitrosyl
chloride are known, hut those described are the most impor
tant .
Other methods listed in the literature are given.
Dry hydrogen chloride11 passed into liquid nitrogen
trioxide gives impure nitrosyl chloride*
Nitrosyl chloride is prepared by distilling potassium
nitrite with phosphorus pentachloride*
i p
Nitric oxide-1 - * ' reacts with ferric chloride at high
temperatures to give nitrosyl chloride.
Hydrogen chloride reacts with nitrosaminesJ - to give
nitrosyl chloride*
Chemistry* Nitrosyl chloride at ordinary conditions
is a yellowish gas with a suffocating odor. It condenses
to a red liquid which boils at —5*8°C* It freezes at —61.*5°C
10Kali, Forschungs, Antalt Ger. 518, 165 Mar. 28, 1928.
11Briner and Pylokov, J. Chim. Phys., 1912, 10, 640.
12Thomas, compt* rend*, 1895, 120, 447.
^Lachmann, Ber*, 1900, ee, 1035.
13
into a red solid similar in appearance to chromium oxide.
Its critical temperature is -163°C and its critical pres
sure is 92.4 atmospheres. Its heat of neutralization is
32 calories and heat of formation is -7.2 calories. Ab-
14
sorption^ bands are found in the red and green portions
of the spectrum.
It combines readily with water to form nitrous and
hydrochloric acids.
NOCl + HgO HNOg + HC1
With bases, such as potassium hydroxide, it forms nitrites
and chlorides. When passed into sulfuric acid it forms
nitrosyl-sulfuric acid.
Nitrosyl chloride has powerful halogenating powers.
With metallic chlorides it combines to give yellow double
compounds such as AlCl^NOCl and ZnCl^NOCl. With some
metals it forms the addition compound and nitric oxide.
Sn * ■ 6N0C1 > SnC14.2N0C1 + 4N0
SnCl4 + 2NOCl SnCl4.2N0Cl.
It has no action upon platinum or gold.
It reacts very readily with many organic compounds.
Lynn and Shoemaker-^ have classified the reaction accord
*4Magnanimi, Z. Physikal. Chem., 1889, 4, 427.
^5Lynn and Shoemaker, Am. Phar. Assoc., 175, 1926.
14
ing to three types, addition, condensation with elimination
of water, and condensation with elimination of hydrochloric
acid,
(1 ) = c = 0 = + mai ~ * = cno - c c i = -
(2 ) RH2 + 0HG1 r n c i + k2o
f3) RH + Ca.NO RNO + HCX.
Primary amines react by condensation, forming water
and a diazo compound.
R M g + HD 01 HgO + RN = NCI RC1 + Ng
Urea forms phosgene while propyl amine forms propyl
chloride .
The splitting off of hydrochloric acid is more com
mon. With phenol acetanilide, dimethyl aniline, or ethyl
aniline, it reacts in the para position to form nitroso
compounds.
C6H5N (CH3)2 + NO Cl N0C6H4N(CH3)2 + HC1
It forms nitrosoamines with secondary amines.
R2NH + NO Cl RNNO + HC1
Acetone and acetophenone form nitroso compounds and
iso-nitroso compounds by rearrangement.
CH3C0CH3 + - CINQ CE3C0CH2N0 —* CHgCOCH = NOH.
It reacts with mercaptans forming sulfides.
RSH + NO Cl —» RSNQ (RS}g + NO
15
It condenses in sunlight with paraffin hydrocarbons16
to form nitroso compounds and on rearrangement produces ox-
imes.17 These on hydrolysis form ketones.18
(CH3CH2CH2)2CH2 CCHgCHgCHglgCHMO — > (CHgCHgGHgJg
CNOH (CHgCHgCHgHgC - 0
With methyl aniline it reacts to form an aldehyde.
C gH gC H g + C 1N 0 a 6H 5 C HN 0H ► C gH gC H O .
19
Thermal Decomposition* Taylor and Denslow have
studied the decomposition of nitrosyl chloride between
700° and 90Q°C using a dynamic method similar to that used
by Taylor20 in his study of the decomposition of hydrogen
iodide. The gases flowed through a capillary tube at con
stant pressure* In order that the reverse reaction be over
come, the gas was diluted with nitrogen. The gases, after
passing through a vertical silicon dioxide tube, heated by
a furnace, were passed into a solution of sodium arsenite
buffered with sodium bicarbonate* The decomposition amount
ing from 2-6 per cent was determined by titrating with
16Lynn and Hilton, Amer. Chem-Soc., 44, 645, 1922.
17Ibid., 41, 368, 1919.
18Lynn and Ackley,. J* Amer. Chem-Soc., 45, 1045, 1923.
19Taylor and Denslow, J. Phy. Chem, 31, 374, 1927.
20Taylor, J. Phy* Chem. 28, 984, 1924.
16
Iodine. By this method it was possible to. measure the free
chlorine from which they could determine the decomposition
of nitrosyl chloride. The results agreed graphically with
those obtained from the theoretical equation dx = Ici (a-x)2
3 dt Vn
- KgCXtj). The value for k was found to be 5.0 x 1010cc/mole/
min. (X)' is the amount of nitrosyl chloride decomposed in
CtJ minutes from the original concentration (a) of nitrosyl
chloride. On plotting the logarithm of the percentage of
decomposition against the reciprocal of the absolute temp
erature, a straight line was obtained. From the slope of
the line an approximation of the heat of activation and
temperature coefficient was made which was found to be
6000 and 1.025 calories respectively. An energy of acti
vation of 6000 calories would correspond to a wave length
of 4.769 . Nitrosyl chloride has no absorption band in
this region.
Waddington and Tolman claim that only the order of
magnitude of the rate of decomposition has been determined.
The rate of decomposition of nitrosyl chloride may be ob
tained from the reverse reaction and. the equilibrium con
stant. But as there is no precise information on the
kinetics of the reverse reaction,, the accuracy is limited.
21Waddington and Tolman, J. Amer. Chem. Soc., 57, 689*
1935.
17
The value of k is evidently too low. Although compensa
tion was made for the reverse reaction, it could not be
prevented outside of the furnace.
p p
Waddington and Tolman*'*' have studied the thermal de
composition of nitrosyl chloride between the limits of
150.1°C and 250.7°C. They found it to be a bimolecular
decomposition and a trimolecular reverse reaction.
Using a 200 ml. pyrex reaction flask which was heated
in an oil bath, they determined the course of the reaction
by measuring the increase of pressure at constant volume.
prz
Phot ochemiaa1 decomposit ion* Kiss has shown that
visible light decomposes nitrosyl chloride. The temp
erature coefficient of the photochemical reaction was
found to be 1.0 over the temperature range 0°C to 78°C.
Bowen and Sharp24 have carried out a determination of
the quantum, yield. They believe 0.5 molecule was decom
posed per light energy quantum absorbed. The light used
came from carbon arcs. The spectral regions 4380 - 5000A0
ana 4480 - 5200A° were isolated by means of filters. They
22Loc. eit.
23Kiss, Rec. Trav. Ghim. , . 42, 665, 1923.
24
Bowen and Sharp, U. Chem. Soc., 127, 1026, 1925.
18
They failed to notice any action of red Light. This was
accounted for by the very weak, absorption in this spectral
region.
25
Kistiakowsky has measured the photochemical decom
position of nitrosyl chloride manometrically. The pres
sure changes were recorded by means of a quartz spiral
manometer of the Bodenstein type. Changes of less than
0.1 mm of mercury could be measured. The source of light
was a 1000-watt tungsten lamp and a mercury quartz lamp.
Various spectral regions were isolated by light filters.
The absorption by nitrosyl chloride began above 6300A°
and increased toward the ultraviolet. Some maxima of ab
sorption were found. The quantum yield obtained was 2.1
with wave lengths from 6300 to 365QA0. Bowen and Sharp24
found 0.48 which evidently is incorrect.
Spectral evidence suggested the formation of excited
nitrosyl chloride molecules as the primary process in the
decomposition. The excited molecule on collision with a-
nother nitrosyl chloride molecule yields the decomposition
products, nitric oxide and chlorine. The reaction is given
NQC1 + hv —* HOCl^ (excited)
N0C11 ♦ N0C1 —♦ SNO ♦ Gig
25
Kistiakowsky, J. Amer. Chem. Soc., 52-102, 1930.
CHAPTER III
PREPARATION OF MATERIALS
I. BERYLLIUM OXIDE FROM BERYL
Although beryllium was discovered by Vaquelin in 1798,
the pure metal was first prepared In 1828* It has just
recently taken on commercial importance*
It is found as the first element in the second group
of the periodic table* It is not a good representative
of the alkali earths. It is considered as a ”bridgeM ele
ment, showing greater similarities toward aluminum than
magnesium* Aluminum and beryllium are so much alike that
it is difficult to separate them. Beryllium Is less basic
than magnesium, but more so than aluminum. The salts of
beryllium are readily hydrolyzed forming beryllium hydroxide,
which Is similar to aluminum hydroxide. Beryllium will
dissolve in an excess of sodium hydroxide, but differs from
aluminum in that It will reprecipitate on boiling.
Beryllium is found in many minerals but beryl is the
only one of importance for the extraction of the metal.
It is a double silicate of beryllium and aluminum, with
the formula 3Be0Al2036Si0g, containing about 5 per cent of
the metal.
Beryllium may be obtained from a number of minerals,
20
but is usually prepared from beryl. The basic beryllium
carbonate1 from which beryllium compounds were made in
this investigation was prepared from South Dakota beryl.
Beryl may be fused with an alkali or with a fluoride
compound. It was decided to use potassium hydroxide for
the extraction of beryllium. Beryl, which was finely
ground, was mixed with an equal weight of potassium hy
droxide. It was heated in an Iron crucible until the fu
sion was complete. The iron crucible was attacked by the
reaction but not enough to cause any trouble, as iron had
to be removed later. The melt was poured out and pulver
ized. Water was added to remove most of the excess potas
sium salts as well as some silica. It is claimed that
some beryllium is lost. The material was covered with
water and an excess of sulfuric acid added. A gel was
immediately formed. This was then heated until fumes of
sulfur trioxide were given off in order to make the silica
insoluble. The product was then treated with hot water to
which was added potassium sulfate in order that aluminum
might precipitate out as an alum. Beryllium forms no alum.
After boiling with nitric acid to oxidize iron, ammonium
hydroxide was added until the precipitate formed just re
dissolved. It was cooled and then saturated with sodium
1 Parsons, Jour. Amer. Chem. Soe., 1904, 26, 721.
21
bicarbonate and boiled for a minute. Aluminum and iron
hydroxides were filtered off and ammonium sulfide was
added to the filtrate. Any iron present was precipitated
as the sulfide and filtered off. In filtering, some dif
ficulty was experienced by having the iron sulfide pass
directly through the filter paper. This was overcome by
adding a small amount of ether, then heating and stirring.
Ether diminishes the surface tension of the liquid and
keeps the precipitate from going into the colloidal state.
The filtrate was diluted to about five times its volume
and steam was passed in until the beryllium basic carbon
ate settled out. Boiling is not resorted to because "bump
ing” takes place. The precipitate was white and very easily
filtered. This product was thought to be reasonably pure
but it was subjected to further treatment.
The carbonate was dissolved in concentrated hydrochloric
acid and added to two liters of saturated ammonium carbon
ate solution. Any precipitates of iron or aluminum carbon
ates were filtered off. Ammonium sulfide was then added
and the solution allowed to stand a day or longer. The
small precipitate which might consist of iron, zinc, and
nickel sulfides was filtered off. The filtrate was then
treated with steam as outlined above. The product was
carefully washed and dried. A very pure white product was
22
formed, from which beryllium oxide was made by heating
to red heat in a platinum crucible*
II. NITROSYL CHLORIDE FROM
NITROSYLSULFURIC ACID AND HYDROGEN CHLORIDE
p
Tllden has shown that nitrosyl chloride may be pre
pared by treating nitrosylsulfuric acid with dry sodium
chloride*. Scott and Johnson3 have adopted a modification
of this method which has certain advantages. By using
hydrogen chloride in place of sodium chloride, the reaction
may be aarried. out continuously in one reaction flask* It
avoids the introduction of oxides of nitrogen with boiling
points close to that of nitrosyl chloride. Hydrogen chlor
ide has a low boiling point and can be separated from
nitrosyl chloride by fractional distillation. Sulfur
dioxide is passed into fuming nitric acid forming nitrosyl
sulfuric acid crystals. These are treated with dry hydro
gen chloride, which yields nitrosyl chloride according to the
following reaction: S02 + HNO^ (Turning) (OH)(ONO)SOg
(0H)(0N0)S02 ♦ HC1 -* H2S04 + N0C1
2Tilden, J* Chem. Soc., 27, 630, 1874.
3
Scott and Johnson, J. Phy. Chem. Soc., 33-1975, 1929.
23
The apparatus for the preparation was entirely of glass.
This consisted of three sets of drying towers, a hydrogen
chloride reaction flask, and the bulbs for collecting the
nitrosyl chloride. The drying towers consisted of 12 inch
pyrex test tubes filled with broken glass which was moist
ened with concentrated sulfuric acid, recently boiled*
The three sets of drying towers were connected to the re
action flask consisting of a three-liter round bottom flask.
Glass valves were inserted as shown in the photograph. A
tube of magnesium perchlorate was connected to the outlet
tube of the reaction flask. Sulfur dioxide was obtained
from a tank and was passed through six drying tubes con
taining fuming sulfuric acid. The hydrogen chloride was
generated in a three-liter flask by allowing concentrated
sulfuric acid to drop on concentrated hydrochloric acid
and dried by passing through four towers of sulfuric acid.
Air was passed through one tube containing dilute silver
nitrate solution, one containing solid calcium chloride,
two of sodium hydroxide solution, and three of sulfuric
acid.
Two liters of fuming nitric acid were put into the re
action flask, which was cooled in cracked ice. Sulfur
dioxide was passed through for forty or fifty hours. This
need not be all at one time. Crystals of nitrosyl sulfuric
24
acid separated from the solution and collected on the in
let and outlet tubes* Whenever this happened, concentrat-
f ed sulfuric acid could be run in from the separatory fun-
x >
' nel. After the formation of crystals the brown gases were
no longer given off and the contents in the flask became
lighter in color, changing to a lemon yellow* Sulfur
dioxide was allowed to pass through three or four hours
longer. At the end of this time the material in the tube
was practically all solid*
About two hundred ml* of concentrated sulfuric acid
were carefully added while air was passing through the
flask which was heated, in a water bath at 100°C. The con
tents became liquid and nitrogen dioxide fumes were no
longer given off* Air was passed through for about seventy
hours in order to remove all the nitric acid and nitrogen
dioxide* The liquid was of a light yellow color. Dry
hydrogen chloride was now passed through the nitrosyl
sulfuric acid. Two bulbs were connected in series with
the reaction flask* The first bulb was cooled in a mix
ture of dry ice and alcohol to about -15°C* while the second
one was cooled to -25°G* As the hydrogen chloride was
passed in, nitrosyl chloride was given off and collected
in the two bulbs.
When the last bulb was almost full, it was disconnected
f*
i^. I* The preparation-of nitrosyl chloride from nitrosyl.su If uric acid*and '
chloride.
26
from the other. The outlet tube had a drying tower con
nected to it in series with a safety bottle and a suction
pump. Full suction was applied and the nitrosyl chloride
was allowed to boil until the bulb was about half full.
It was then sealed off from the air. The nitrosyl chlor
ide may be further purified by fractional distillation in
an all glass apparatus similar to that described by Baxter
4
and Scott. Nitrosyl chloride prepared by this method
takes much longer but the product is especially pure.
III. NITROSYL CHLORIDE FROM
POTASSIUM CHLORIDE AND NITROGEN DIOXIDE
R
Mehrmg, Ross and Merz^ have shown that when nitrogen
peroxide reacts with a saturated solution of potassium
chloride, a solution containing potassium nitrate and
nitric acid is obtained. When the acid concentration
reaches a certain value, nitrosyl chloride is produced
along with hydrogen chloride. Whittaker, Lundstrom, and
Pi
Mertz° have shown that if nitrogen dioxide reacts directly
with solid potassium chloride containing 2.4 per cent
4
Baxter and Scott, Proc. Am. Acad. Arts and Sci.,
59, 21, 1925.
5
Mehring, Ross, and Merz, Ind. Eng. Chem., 21, 379, 1929.
6Whittaker, Lundstrom, and Mertz, 23, 1410, 1931.
87
moisture, all of the chlorine is converted into nitrosyl
chloride according to the following equation:
2m2 ♦ KC1 ~* KNO^ ♦ N0C1
Nitric acid is a liquid at ordinary temperatures, having
a boiling point of 86°G at normal pressure* Hydrochloric
acid boils at -83.5°G and is a gas at ordinary temperatures*
If nitric acid is added to a saturated solution of potas
sium chloride, the partial pressure of the hydrochloric
acid in solution would be greater than that of nitric
acid* Some replacement of the acid radical should occur.
This, they found to take place but in excess of certain
limiting concentrations. Nitric acid and hydrochloric
acid react to from chlorine and nitrosyl chloride.
HN03 + 3HC1 -•* NO Cl + Cl2 + 2E20
A mixture of three mols of hydrochloric acid and one
mol of nitric acid has an acid hydrogen content of about
one per cent. This mixture at ordinary temperatures re
acts to form nitrosyl chloride and chlorine. If the acid
hydrogen concentration is less than 0.58 per cent at room
temperature or 0.36 per cent at 100°G, no appreciable re
action takes place. Potassium chloride, containing 8*4
per cent moisture was put into a glass tower about sixty
centimeters high with an inlet and exit tube attached.
Nitrogen dioxide was allowed to enter at the bottom of the
Fig. II. The preparation of nitrosyl chloride from
potass iuia chloride and nitrogen dioxide
29
tower. The exit tube is connected to a bulb which is
placed in a mixture of dry ice and alcohol. A drying
tube is attached to the outlet of this bulb.
As the nitrogen dioxide passes up in the tower the re
action can be seen as it proceeds. The potassium chlor
ide beloy; the point of reaction is of a reddish color
due to nitrogen dioxide, while that above is of a straw
color, due to the nitrosyl chloride being formed. This
reaction is exothermic as indicated by the increase in
temperature in the tower. The moisture present acts as
a catalytic agent. If no moisture is present, practically
no reaction takes place. The reacting zone was kept just
below the top to prevent any nitrogen dioxide from pass
ing over with nitrosyl chloride. The gas coming over had
an amber color which condensed to a red liquid and finally
to a blood red solid. With no purification this method
produces a gas of about 97 per cent purity. The three per
cent impurities consist of oxygen for the most part.
IV. NITROGEN DIOXIDE7
Fifty grams of arsenious oxide were placed in a 500 ml.
flask and treated with 100 ml. of concentrated nitric acid.
7Hasenback, J. Pra. Chem., 1, 1871, (2) 4.
A T tube was connected to the flask and the other end to
a tower with a few centimeters of concentrated sulfuric
acid. This was then connected to a series of towers, an
empty one, one filled with glass wool, another empty tow
er, and last, to a tower containing glass beads. This
last one was immersed in a mixture of dry ice and alcohol.
Dry oxygen was slowly passed through a tube in the first
tower whose outlet was just below the surfact of the acid.
The empty towers and the one with glass wool were to allow
any moisture to settle out. Freshly heated calcium nitrate
may be used to remove moisture. This apparatus was entirely
of glass. Rubber or corks, even if treated, are quite
readily acted upon.
The arsenious acid was heated gently and dry oxygen Yms
allowed to pass through the apparatus. Nitrogen dioxide
condensed in the last tower to a yellow liquid. It is us
ually colored green, blue, or brown, due to dissolved ni
tric oxide and nitric acid. The oxides of nitrogen are
changed to the dioxide by the passing of oxygen through
it. Too much oxygen will cause volatilization of the
dioxide which will be lost. This was overcome almost
entirely by adding another condensing bulb with the
freezing mixture at a lower temperature. The incoming
oxygen must be dry, as moisture reacts with the oxides
Fig. III. The preparation of nitrogen dioxide
32
forming nitrio acid, which will cause the liquid to split
into two phases, nitric acid and nitrogen dioxide. It
has been found that they cannot be separated by fractional
distillation. As oxygen was passed through the colored
solution, the color changed to a light amber when the re
action was complete. The boiling point is 22°C; the melt
ing point is -10°C. If the liquid is to be purified, it
may now be done by fractional distillation. Nitrogen di
oxide on freezing becomes a snow white substance.
V. NITROSYL CHLORIDE FROM AQJJA REGIA
Aqua regia has been in use for a long time. As far
back as the thirteenth century nitric acid was prepared
by distilling salt petre, copper sulphate, and clay. Geb-
er added sal ammoniac to nitric acid, forming aqua regia.
Q
According to Gay Lussac two volumes of nitric oxide
combine with one of chlorine to form a gas which condenses
to form a mixture of nitrosyl chloride and possible ni
trosyl dichloride. Chlorine and nitric oxide are dissolv
ed and can be removed by distillation at low temperature,
chlorine at -80°C and nitric oxide at -150°C. Ordinarily,
aqua regia is prepared by mixing three parts of hydrochlor
ic acid with one of nitric acid. This reaction is repre-
®Gay Lussac, Am. Chim* Phys., 1848 (3) 23, 203.
33
sented by the following reaction:
3HC1 4 HNO„ -4 N0C1 4 Ho0 4 Cl
3 2 2
Water is formed in this reaction and it would be nat
ural to suppose that little or no nitrosyl chloride would
be formed* Nitrosyl chloride combines readily with water
forming hydrochloric and nitrous acids* Taylor and Den-
slow^ mention the possible use of aqua regia, but because
of the water, stated that little nitrosyl chloride could
be prepared by this method* The results from this inves
tigation shows that they are definitely wrong in this
statement* Kiss10, however, states that the formation of
nitrosyl chloride is accelerated by water* Vapors from
aqua regia were made use of quite extensively in this in
vestigation and part of the work was to determine what
percentage might be nitrosyl chloride.
Six hundred ml. of concentrated hydrochloric acid and
200 ml. of concentrated nitric acid were mixed in a two-
liter flask* Delivery tubes led through two towers filled
with calcium chloride. The gas then was cooled and con
densed. Considerable liquid of a dark red color condensed
and became a solid at lower temperatures. The boiling
°Taylor and Denslow, J. Phy* Chem., 31, 374, 1927.
10Kiss, Rec. Trav* Chim., 42, 112, 1923.
34
point was found to be -5.2°C. On evaporating at 0°C, no
residue was left.
Some of this liquid was distilled into tubes and seal
ed. These tubes, with their contents, were weighed. The
tubes were then broken under water. This is quite dif
ficult to do as the gas vaporizes very readily and some
will bubble through the water. The analysis was done in
this manner and titrated with standard sodium hydroxide
using phenolphthalein indicator. Results showed that it
consisted of 92 per cent nitrosyl chloride. The loss of
some gas occurred which would indicate that the percent
age of nitrosyl ohloride was even greater. The gas foim-
ed from the nitrosyl chloride had the characteristic yel
low color.
VI. NITROSYL CHLORIDE FROM THE ADDITION COMPOUND
OF ALUMINUM CHLORIDE AND NITROSYL CHLORIDE
Aqua regia is the most convenient source for the pre
paring nitrosyl chloride. Dissolved chlorine makes it
somewhat difficult to purify. When passed through con
centrated sulfuric acid, nitrosylsulfuric acid is formed.
If this is heated with dry sodium chloride, nitrosyl chlor
ide is given off which has to have oxides of nitrogen re
moved. Nitrosyl chloride forms addition compounds with
35
many metallic chlorides. When it is passed over ferric
chloride at a low temperature (0°C) a compound NeClg.NOCl
is formed. Chlorine passes on and is eliminated. If this
is heated in a vacuum, decomposition takes place and fer
ric chloride and nitrosyl chloride are formed.
11
Sudborough , on passing vapors of aqua regia over
aluminum, failed to get an addition compound of aluminum
chloride and nitrosyl chloride. He obtained only the
anhydrous aluminum chloride.
In the preparation of nitrosyl chloride from aqua re
gia, chlorine is the principal impurity. Most methods de
pend upon making a fairly pure product followed by frac
tional distillation. No method has been devised for the
removal of chlorine allowing pure nitrosyl chloride to
pass on. If only aluminum chloride is formed from alum
inum and aqua regia vapors, a method is suggested, where
by the chlorine might be removed. This was tried as a
possible means of preparing pure nitrosyl chloride.
YYhen aqua regia fumes were passed through a tube filled
with aluminum foil at low temperatures no reaction took
place. On increasing the temperature around 300°C, a
white deposit of aluminum chloride was produced. The re
action, however, being exothermic, became hot enough to
11Sudborough, J. J*, J. Chem. Soc., 59, 659, 1891.
36
react with nitrosyl chloride, which formed a liquid in
the tube where the metal was, while beyond this, in the
cool part of the reaction tube, a yellow compound
(AlCl^NOCl) collected. So much of this formed that the
reaction tube was soon full, preventing further action
from taking place. The liquid condensed in the tube, on
turning off the heat, into reddish yellow crystals mixed
with some blue. Blue is characteristic of the lower ox
ides of nitrogen, indicating that nitrosyl chloride had
been partly decomposed. While the reaction was going on,
very little nitrosyl chloride collected in the bulb im
mersed in dry ice and alcohol, which was connected with
the exit of the reaction tube. This showed that the
chlorine as well as most of the nitrosyl chloride reacted
with aluminum.
From the results obtained, aluminum cannot be used to
remove chlorine above from aqua regia fumes. It is un-
believable that Sudborough failed to obtain the yellow
compound of nitrosyl chloride and aluminum chloride.
As the nitrosyl compound of aluminum chloride was
easily made, this offered a method for the preparation of
pure nitrosyl chloride from vapors of aqua regia. Alum
inum foil was put into the combustion tube which could be
op. c 11.
37
heated in a multiple unit electric furnace* Vapors from
aqua regia, prepared from concentrated hydrochloric and
nitric acids in an all glass apparatus, were allowed to
pass through the reaction tube after being dried by two
towers of magnesium perchlorate. A two way valve was in
serted in the line just before the combustion tube so that
it could be shut off from the aqua regia generator. A con
densing bulb cooled in dry ice and alcohol, was connected
at the exit of the combustion tube. A tower fillsd with
magnesium perchlorate was connected to this.
The aqua regia was gently heated and the vapors came
in contact with the aluminum, forming the addition com
pound of aluminum chloride and nitrosyl chloride, which
condensed as a yellow sublimate in the unheated portion of
the tube. Just a trace of nitrosyl chloride condensed in
the bulb, showing that all the gases were practically ab
sorbed. It is thought that chlorine from the vapors com
bined with aluminum, which, in turn, reacted with nitrosyl
* chloride.
When most of the nitrosyl chloride had been expelled
from the aqua regia, indicated by the light color, and the
reaction in the combustion tube stopped, the valve next
to the entrance of the reaction tube was closed. Two bulbs
immersed in solid carbon dioxide and alcohol were connect-
■ r _v •
{
Fig. IY. Nitrosyl chloride from the addition compound of aluminum cfylori ' : © and
n it r o k v 1 ch. Tori Ae.
L
3 9
ed in series with the combustion tube. These were con
nected to a drying tower and a suction pump with the neces
sary traps in between, A part of the electric furnace was
slid over that portion of the tube containing the yellow
compound. The pressure was diminished and the heat grad
ually increased until the yellow compound began to decom
pose, Nitrosyl chloride collected in the condensing bulbs.
This gave a product which had a boiling point of -5.6°C,
indicating that it was quite pure.
This method has the advantage of having the formation
and decomposition of the addition compound to take place
in the same apparatus. The yield is good and the purity
is high.
VII. SUGAR CHARCOAL
13
According to the directions taken from Friend , pure
sugar charcoal may be prepared by heating pure cane sugar
until all volatile material has been burned,. After heat
ing, it becomes a shining black porous mass. It is then
heated in an electric furnace to 1000°C while dry chlorine
is passed over it. This will remove organic impurities.
After carefully washing with hot water, it is ignited in dry
hydrogen gas until all hydrogen chloride has been removed.
13J. N. Friend, Text Book of Inorg. Chem. , Vol. V.
40
This product will have a density of about 1.8 and an igni
tion temperature of 450°C.
VIII. DISCUSSION OF THE METHODS FOB PREPARING
NITROSYL CHLORIDE
Several methods have been described for the prepara
tion of nitrosyl chloride.
The first method was that of passing sulfur dioxide in
to fuming nitric acid forming nitrosulfuric acid* It was
next treated with dry hydrogen chloride forming nitrosyl
chloride and sulfuric acid. If a very pure product is de
sired, this method is satisfactory. It has been used for
the determination of the atomic weight of chlorine. As in
all of the methods, some impurities are present. These can
be removed by fractional distillation.
On resorting to five or six distillations, it is claim
ed that any hydrogen chloride, chlorine, nitric oxide, nitro
gen, or oxygen, can be completely removed. Hydrogen chlor
ide is the principal impurity, but is comparatively easy to
remove. The reaction takes place in one reaction flask.
The quantity of nitrosyl chloride is not very large consid
ering the time required for its preparation. A disadvant
age is, that it takes a large amount of apparatus to make
certain that all moisture has been removed.
The second method of preparing nitrosyl chloride is
that of passing nitrogen dioxide through a tube containing
moist potassium chloride crystals. The product from this
method is sufficiently pure to use for most experimental
work without further purification. A purity of 97 per
cent is claimed. The reaction is easily controlled and
is exothermic, requiring no heating. As long as the react-
ion zone does not reach the top, there is no danger of
getting any nitrogen oxides as impurities. The apparatus
which is all glass is quite easily made. The main diffi
culty is the preparation of pure nitrogen dioxide. Of the
many methods available for its preparation, that of using
nitric acid and arsenious acid is the most suitable for con
siderable amounts. This gas must be made in an all glass
apparatus. Corks or rubber stoppers are acted upon readily
even when treated. There is no ready drying agent that
does not react with nitrogen dioxide to some extent. When
changing the lower oxides to nitrogen dioxide by passing in
dry oxygen, there is some lost due to volatization. Frac
tional distillation must be used to get a pure product.
The handling of two volatile liquids with low boiling
points is an added disadvantage. If it were possible to
get nitrogen dioxide already prepared, the method would be
most suitable.
Nitrosyl chloride from aqua regia is easily made and
can be purified by fractional distillation* The method is
very simple, distilling it from a mixture of concentrated
hydrochloric and nitric acids* This method is rapid and
the yield larger than in the other methods* It contains
considerable chlorine*
The method worked out in this report, bases on the de
composition of A1C1_N0C1 at diminished pressure, gives a
o
pure product. Nitrosyl chloride for this method is obtain
ed from aqua regia.
CHAPTER IV
EXPERIMENTAL V/ORK
I. THE PREPARATION OF BERYLLIUM CHLORIDE BY MANS OF
NITROSYL CHLORIDE AND BERYLLIUM OXIDE
By passing chlorine gas over a mixture of beryllium
oxide and sugar charcoal, Awdejiw, in 1842, prepared
anhydrous beryllium chloride. The chloride sublimes at
500°C and melts at 405°C.
In the preparation of anhydrous beryllium chloride,
all materials used must be free from moisture. If the
oxide is used, hydrogen must be absent to prevent the form
ation of water by combination with oxygen.
To date, several methods have been in use. Beryllium
chloride has been prepared by passing chlorine gas,'*’ car
bon tetra chloride and sulfur monochloride over a mixture
of Beryllium oxitie and sugar charcoal. It may also be
prepared by passing dry hydrogen chloride gas over the
heated metal.^
^Meyer, Ber., 20, 681, 1887.
^Bourion Compt. rend., 1907, 145, 62.
^Nilson and Petersson,
44
The usual method is to pass chlorine over a mixture of
the oxide and charcoal or by chlorine or hydrogen chloride
4
over beryllium carbide.
Booth and Torrey5 found that by using charcoal as the
chlorinating agent, the product was contaminated with car
bon. It was necessary to sublime the chloride in order
to purify it. They found that phosgene (carbonyl chloride)
could be used alone with beryllium oxide and that it gave a
pure product. The reaction taking place may be represented
by the following equation:
C0C1 ♦ BeO —♦ Be01o Go
Carbon monoxide, from the decomposition of phosgene, serves
as a reducing agent, being oxidized to carbon dioxide.
As phosgene is extremely dangerous to use as a means
of preparing beryllium chloride, another method was tried.
It was thought that nitrosyl chloride might be used
equally well in the preparation of the beryllium chloride.
By using nitrosyl chloride prepared from aqua regia, advan
tage can be taken of the chlorine which also comes off.
Nitrosyl chloride is easily prepared from a mixture of three
parts of concentrated hydrochloric acid and one part of con-
^Lebeau, Compt. rend., 1895, 121, 496.
5Booth and Lorrey, J. Phy. Chem., 35, 2476, 1931.
4 5
centrated nitric acid. In some instances, mixtures of
gases, such as carbon tetra chloride and chlorine, have
been used to obtain beryllium chloride from the oxide.
Nitrosyl chloride quite often contains chlorine as an im
purity. It was thought that this combination of gases
might work out to some advantage. An excess of chlorine
would have a greater tendency to cause the reaction to go
in the direction in which more beryllium chloride is form
ed, thus making the reaction go in the desired direction.
/ *
Sudborough and Miller have studied the decomposition
of nitrosyl chloride between 500°C and 750°C,^ At the
lower temperature the gas is only 5.34 per cent dissoci
ated while at 750°C the dissociation is 41.85 per cent.
g
Lewis and Randall have used the data of Trautz and Wash-
Q
enheim and have calculated the free energy change for the
^Sudborough and Miller, J. Chem. Soc., 59, 271, 1891.
^Temperature Per cent Temperature Per cent
Absolute dissociated dissociated
784 5.34 928 25.17
796 18.22 968 39.19
815 20.64 985 41.85
8
Lewis and Randall, 'Thermodynamics, 1923.
9
Trautz and Washenheim, Z. Anorg. Chem. 136, 1,
1925; 146, 1, 1925.
46
reaction between 500°K and 750°K. For the equilibrium re
action:
NO + 1/2C1 ++ N001
AF r -9100 + 14.3T.
AF will be negative for low temperatures
changing to positive at 363°C. If nitrosyl chloride is
considered as breaking down into nitric oxide and chlor
ine, it is thermodynamically stable at low temperatures
and unstable at higher temperatures. The decomposition
of nitrosyl chloride has been found to be a bimolecular
decomposition and a reverse trimolecular reaction.
If beryllium chloride is formed to any extent, the
temperature must be above 500°C. If nitric oxide is to re
act as a reducing agent, the temperature must be between
about 150°C and 600°C. On cooling from 600°0, nitric ox
ide begins to combine with oxygen forming nitrogen dioxide.
The forward reaction
3N0 + 02 2N0g
is almost complete at 140°0. It would seem that the upper
temperature limit for the oxidation of nitric oxide with
oxygen is too low for the decomposition of nitrosyl chlor
ide to take place.
In the first experiment pure beryllium oxide was put
into an all glass apparatus and nitrosyl chloride was pas-
47
sed through at temperatures from 400°G to about 700°C.
The appartus was constructed of pyrex glass, and all joints
were ground connections. Beryllium oxide was put in the
glass tube, which was put into an electric furnace and
heated for two or three hours at about 450°C, to make sure
that all moisture was removed. Dry air was passed over
the oxide while it was drying. Nitrosyl chloride was then
passed over the oxide. The exit tube of the glass appar
atus was connected to a tower containing magnesium per-
chlorate. This is a more efficient drying agent than
phosphorus pentoxide. No beryllium chloride was found in
the cooler portion of the tube. The absence of any bery
llium chloride shows that nitrosyl chloride cannot act as
a reducing and a chlorinating agent at these temperatures
with beryllium oxide.
A second experiment was tried by passing nitrosyl
chloride over a mixture of beryllium oxide and carbon. As
before, the material was preheated, but in a dry current of
carbon dioxide to remove any moisture. Nitrosyl chloride
was then passed through while the tube was heated to red
heat. A deposit of beryllium chloride was formed in the
cooler portion of the tube. By moving the movable furnace
10G. F. Smith, Dehydration Studies; The G-. F. Smith
Chem. Co.
48
along the tube toward the mixture of oxide and carbon, a
considerable portion of the tube may be filled with bery
llium chloride. This can be sealed off and used when need
ed, This investigation led to the opinion that this meth
od is superior to that of using chlorine gas.
During this experiment a sublimate formed on the re
action tube which flaked off and had the appearance of
glass that had been blown thin enough to show interference
colors. These flakes were analyzed spectrographically
and were found to consist of a beryllium compound. The
constituents of glass were also shown. That portion of
the tube where the flakes had come off was boiled with
sulfuric acid. After drying the glass tube, it was found
that it had been attacked. This was very easily seen with
the unaided eye.
As there is some controversy ?/hether glass is attacked
by beryllium chloride at high temperatures, it was decid
ed to investigate this further. This will be referred to
in a separate section.
49
II. THE PREPARATION OF BERYLLIUM CHLORIDE BY THE
ACTION OF NITROSYL CHLORIDE ON BERYL
The formation of chlorides by heating a mixture of the
metal oxide and carbon, over which chlorine is passed, was
first done by Oersted. Later Wohler used the method for
the preparation of a number of chlorides from their oxides.
This reaction illustrates the displacement of an
equilibrium by removing product from the field of reaction.
The rate of a chemical reaction is favored by increasing
the concentration of the reactants, according to the law
of mass action. Carbon cannot reduce beryllium oxide, but
beryllium can reduce carbon monoxide or carbon dioxide.
In a mixture of beryllium oxide, beryllium, carbon, carbon
dioxide, and carbon monoxide, only a small amount of bery
llium can exist in equilibrium. If chlorine is allowed
to react with beryllium, the chloride is formed and if re
moved immediately the equilibrium is shifted in the direc
tion so that more beryllium is formed by the reduction of
its oxide.
L. Burgess11 has prepared beryllium chloride from
beryl by heating beryl and carbon in an electric arc furn
ace, forming the carbide. Dry hydrogen chloride was then
11L. Burgess, Trans. Amer. Elec. Chem. Soc., 47, 317, 1925.
50
passed over this. Beryllium chloride has a higher melt
ing point than those of iron, aluminum, or silicon, which
are usually found in beryl. Beryllium chloride was then
separated on condensation.
1 p
Matignon and Piettrex have prepared beryllium chlor
ide by passing carbon tetra chloride over beryllium oxide
at 800°C•
13
Winters and Yntema claim an eighty per cent yield
of pure beryllium chloride by the action of a mixture of
carbon tetra chloride and chlorine on beryl in a graphite
crucible. The best yield was found to be at 800°C. Iron,
aluminum, and silicon chlorides were separated by fraction
al distillation.
This part of the investigation had to do with the
action of nitrosyl chloride on beryl.
Beryl, which had been finely ground was put into a
poreclain tube and heated by means of an electric furnace.
Nitrosyl chloride prepared from aqua regia and dried by
passing through two towers of calcium chloride was passed
over the heated beryl. No test for beryllium could be
12
Matignon and Piettre, C. R., 184, 853, 1927.
13
Winters and Yntema, Trans. Amer. Blec. Ghem. Soc.,
55, 20.5, 1929.
le action of nitrosyl chloride orrberyl
52
obtained by using this method. Iron chloride was readily
formed. This experiment was carried out several times by
varying the temperature between about 600°C and 1000°C.
The results showed that beryllium chloride could not be
obtained by this procedure. #
In the next series of experiments, beryl was mixed
with carbon. It was then heated to about 400°O, while dry
carbon dioxide was allowed to pass through the reaction
tube. All moisture was removed in this way. With the
mixture of beryl and carbon heated from 800°C to 900°C,
nitrosyl chloride was passed through. Qualitative tests
showed that beryllium chloride can be produced by this meth
od. The amount, however, was not very great. The chlor
ides of iron, aluminum, and silicon were also formed. By
allowing *the mixture of chlorides to pass through a tube
heated to 400°G, it was found that beryllium chloride con
densed in quite a pure form.
With nitrosyl chloride passed over heated beryl no ap
preciable amount of beryllium chloride was produced. When
nitrosyl chloride is heated to a temperature above 700°C
decomposition takes place, forming nitric oxide and chlor
ine. Nitric oxide and oxygen are known to combine spontan
eously at room temperature. Considerable heat is given off
when the two gases are brought together.
NO + NO g — 8.93Cal.
53
The formation of nitrogen dioxide from nitric oxide shows
that there is a free energy decrease,
-AF r 8*93 Calories.
This reaction takes place at lower temperatures* It is
known that those compounds that are formed with a large
decrease of free energy are stable while those with a
large increase of free energy are unstable. From the
above equation it can be seen that nitrogen dioxide is an
unstable compound. At the temperature under which the ex
periment took place with beryl, nitrogen dioxide would be
decidedly unstable* In this case there is a reversible
exothermic process.
NO ♦ i02 m 2 ♦ 14.OCal.
An increase in free energy shows that this reaction does
not take place at the high temperatures at which the work
was carried out.
Under these conditions, nitric oxide, formed by decom
position of nitrosyl chloride, could not take the place of
a reducing agent and liberate beryllium from beryl. This
offered an explanation why little or no reaction between
beryl and nitrosyl chloride would be expected to take place
above 700°C. Belov? 700°C, nitrosyl chloride is stable and
if any reaction takes place, it would be due to the free
chlorine which comes over in the aqua regia fumes.
54
To determine whether chlorine alone had any effect,
two runs were made. In the first case nitrosyl chloride
produced from aqua regia was passed through three towers
containing concentrated sulfuric acid. This completely
removed nitrosyl chloride. The gases were then allowed to
pass over heated beryl, as described earlier. The results
showed that chlorine had no effect upon heated beryl.
In the second part, chlorine from a tank was allowed
to pass over the heated beryl. The results were as before.
The outcome showed definitely that some reducing agent
must be present before the reaction would take place. This
was found to be true as described in the previous experi
ments. In these experiments, the ore was intimately mixed
with carbon. Nitrosyl chloride was passed over the heated
beryl. Some beryllium chloride was formed but not in suf
ficient quantities to make it appear worth while.
When nitrosyl chloride was allowed to pass through con
centrated sulfuric acid, thus allowing only the chlorine to
pass over the heated beryl, a slight reaction took place,
but not to as great an extent as when the mixture of ni
trosyl chloride and chlorine was used.
Carbon is a good reducing agent at high temperatures.
Ordinarily, carbon will not reduce beryllium from its ores,
but in the presence of chlorine, this reaction does take
55
place to a very slight extent. Metallic beryllium com
bines readily with chlorine and passes on, and removes
beryllium. According to the law of mass action, the re
action would procede in this direction. Carbon combining
with oxygen will form carbon monoxide, which is mare ef
ficient than carbon alone as a reducing agent. Phosgene,
which contains both carbon monoxide and chlorine, should
be quite satisfactory in this respect.
Many experiments similar to the one just described
have been carried out, varying the temperature as well as
using mixtures of nitrosyl chloride and other gases such as
hydrogen chloride, chlorine, and carbon tetra chloride.
In all of the experiments some beryllium chloride was ob
tained but not in sufficient amount to consider it as a
possible means of its extraction. Carbon tetra chloride
mixed with chlorine gave the best results, but even this
was not too encouraging.
Winters and Yntema used carbon tetra chloride and
chlorine on beryl and found an 80 per cent yield. In the
work carried out in this report ten gram samples of beryl
were used, mixed with carbon. Although the best results
in this work were with a mixture of these gases, only
small amounts were obtained. No quantitative tests were
made on the amount extracted from the ore, but from exper
56
ience it could be ascertained that no such yield took place.
For a ten gram sample, containing about 10 per cent beryl
lium oxide, and 80 per cent yield would give about 0.8 gram
of the oxide. As this would be in the form of the chlor
ide, the weight would be in the neighborhood of 2.5 grams.
Yields as large as this were not obtained in any of the runs
carried out in this investigation.
In the next experiment beryl was heated almost to fu
sion and dropped into cold water. Substances heated and
suddenly chilled in this manner have their physical proper
ties changed, and the higher thermodynamic potential is
often associated with greater solubility. After drying,
the beryl so treated, was put into a porcelain tube and
heated in an electric furnace as described above. Nitrosyl
chloride was allowed to pass over it at various tempera
tures. The treated beryl was then mixed with carbon and
the process repeated. The results in this experiment were
comparable to those in which the beryl had not been previ
ously treated.
57
THE ACTION OF LIQJJID NITROSYL CHLORIDE
ON BERYL
Nitrosyl chloride was next tried as a solvent for beryl.
The gas was condensed over dried beryl which was finely
ground. The liquid was kept at the boiling point for about
two hours. Iron chloride was formed in considerable amounts.
After removing iron and aluminum by means of the sodium
bi-carbonate method, a small amount of beryllium was found.
This experiment was tried again using liquid nitrosyl
chloride and finely ground beryl. The beryl was placed in
a flask which could be stoppered so as to create a pres
sure. This was maintained at 0°C under pressure for about
the same length of time. This, on analysis, gave consid
erable beryllium hydroxide. As a result of this, it was
decided to determine the precentage yield of this method.
One gram samples of beryl, ground in an agate mortar
and weighed by difference, were put into 250ml. flasks.
About 25 ml. of liquid nitrosyl chloride were condensed
over the beryl samples. All were stoppered and the temper
ature kept near the boiling point of nitrosyl chloride.
They were shaken every few minutes for a period of about one
and half hours. The stoppers were removed and the excess
nitrosyl chloride allowed to evaporate. Dilute sulfuric
58
acid was added and the solution was evaporated to fumes of
sulfur trioxide* Water was added and the silica filtered
off. From this point on, the method of Parson and Barnes
was followed.
Results showed that some beryllium had been extracted.
Analysis showed that 18.2 per cent of beryllium as beryl
lium oxide, had been extracted. It is possible that an in
crease in pressure might favor this considerably.
THE PREPARATION OF BERYLLIUM CHLORIDE BY MEANS OF
BERYLLIUM METAL AND NITROSYL CHLORIDE
14
Nilson and Petersson passed hydrogen chloride over
beryllium metal obtaining anhydrous beryllium chloride.
The purpose of this experiment was to observe what
would take place when beryllium metal was treated with
15
vapors of nitrosyl chloride. Sudborough passed nitrosyl
chloride over metallic aluminum and obtained aluminum
chloride. Metallic beryllium was put into a procelain boat
which was placed into a pyrex combustion tube. This was
heated while dry carbon dioxide was passed through the ap
paratus in order that all moisture be removed. Nitrosyl
^Nilson and Petersson, Ann. Chim. Phys., 9, 554, 1886.
15J. I. Sudborough, Jour. Chem. 3oc. London 59, 659,
1891.
59
chloride was then passed in. The ignition tube was heated
in an electric combustion furnace.
Immediately after nitrosyl chloride came in contact
with the metal, a white deposit formed on the walls of the
tube. Crystals of beryllium chloride formed just outside
of the position of the tube heated by the furnace. The
temperature was not measured by the coils were just begin
ning to take on a red color as the reaction took place.
The metal glowed while the chloride was being formed. It
appeared to be an exothermic reaction at that particular
temperature. This reaction was much faster than that of
passing nitrosyl chloride over beryllium oxide and carbon.
THE PREPARATION OF BERYLLIUM CHLORIDE BY EVAPORATION
IN AN ATMOSPHERE OF NITROSYL CHLORIDE
Anhydrous beryllium chloride has not been prepared by
treating the oxide with hydrochloric acid. On evaporation,
a gummy mass results, which on further heating decomposes
and forms the oxide. Mieleitner and Steinmetz16 claim that
a compound like BeCl *4H 0 cannot be completely dehydrated
A 2
even when heating in a current of dry hydrogen chloride or
chlorine.
16Mieleitner and Steinmetz, Z. Anorg. Chenu, 1913,
80, 71.
60
Beryllium oxide was dissolved in concentrated hydro
chloric acid and evaporated until the resulting solution
was quite thick. The evaporation was then carried out in
a flask which allowed dry nitrosyl chloride to pass over
the chloride when nitrosyl chloride reacts with water,
hydrogen chloride and nitrous acid are formed as in the
following equation:
noci * HgO hoi + m o2
No beryllium chloride was formed in experiments carried
out in this manner. Beryllium oxide was obtained instead.
It is possible that a nitrate was formed which on further
heating was converted into the oxide. By carrying out the
evaporation under dimminished presence and heating on a
water bath a yellowish crystalline like substance was
formed. On drying in a desiccator, containing sulfuric
acid, crystals appeared which were white in color and were
assumed to be those of hydrated beryllium chloride.
61
THE PREPARATION OF THE NITROSYL CHLORIDE
COMPOUND OF BERYLLIUM
17
Weber has shown that if the vapors of aqua regia are
passed over freshly sublimed aluminum chloride, a lemon
yellow substance is formed. The formula for this compound
was found to be AlGl^.NOCl. Sudborough***® passed nitrosyl
chloride over aluminum chloride. Rheinboldt and Wasser-
19
fuhr made a number of compounds consisting of metallic
chlorides and nitrosyl chloride. They dissolved the chlor
ide in some solvent such as carbon tetra chloride,
BiClg.NOci, FeClg.NOCl,. SbCl .N0C1* AlCl^OCl, and IlgCl^NOCl
were prepared in this manner* Quadrivalent tin, titanium,
and lead combined with two molecules of nitrosyl chloride.
The following addition compounds have been described
in the literature:
Cu Cl N0C1 Zn Cl N0C1
T1 Cl T1C13 2N0C1
T1 Cl 3N0C1
Bel N0C1 Sn Cl4 2N0C1 sbC15 N0C1
- * * 7Weber, Pogg. Am. Phys., 118, 471, 1863.
J. Sudborough, dour. Chem. 3oc. London, 59, 659, 1891.
-**^Rheinboldt and Wasserfuhr, Ber, 60B, 732, 1927.
62
Aicigiroci
BiClgNOCl
FeClgHOCl
AuClgJJOCl
3SnCl4 4N0C1
TiCl4 2N0C1
3TiCl4 4NOC1
PtGl 2N0C1
2SbCl 5NOCl
5
No reference in the literature could be found which showed
that a compound of beryllium chloride and nitrosyl chlor
ide has been made. Three methods were used in an attempt
to prepare a compound of the formula BeClgNOCl.
The first method consisted of passing vapors of aqua
regia over a mixture of beryllium oxide and charcoal. As
in the preparation of anhydrous beryllium chloride, the
material was heated in an atmosphere of carbon dioxide to
make certain that all moisture had been driven out. Nitro
syl chloride was then passed over beryllium oxide and car
bon which was heated in a combustion tube to red heat.
Beryllium chloride crystallized out in the portion of the
tube just outside of the furnace. In the portion of the
tube between the place where the beryllium chloride formed
and the end of the heated furnace, a yellow deposit of crys
tals was formed. These crystals were sealed off in the
glass tube and photographed. The melting point of these
crystals was over 400°C.
A second method for preparing an addition compound of
63
beryllium chloride and nitrosyl chloride as to condense
nitrosyl chloride over freshly prepared beryllium chlor
ide. The temperature was kept at about -15°C in a mix
ture of alcohol and dry ice. As the chloride dissolved, a
reaction, attended by effervescence, was observed. The ex
cess of nitrosyl chloride was distilled off. A yellow pre
cipitate was found which produced a hissing sound when add
ed to water. Heat was also given off. A brown gas was lib
erated which was assumed, to be nitric oxide combining with
oxygen to form nitrogen dioxide. Then starch potassium
iodide paper was held above the moist product, it turned
blue showing the presence of the NO group. These two tests
showed that it is a compound containing the NO group. The
substance on exposure to air gradually absorbed moisture.
The compound formed was analyzed for beryllium as
beryllium oxide, chlorine as silver chloride and nitrogen
as nitrate after oxidation with hydrogen peroxide^ Dilute
ammonium hydroxide was added to the solution, which preci
pitated. beryllium as the hydroxide. After boiling for a
few minutes, the hydroxide was filtered off, ignited, and
weighed, as beryllium oxide. The filtrate was acidified with
nitric acid and the chloride precipitated with silver chlor
ide. This was filtered in a Gooch filter and weighed as sil-
ja»*— \ ' "unk-
Si. ,.,-CryfiCals formed by thS 'flofica of nitrosyl ohloride and Bf*“
65
ver chloride. To determine the amount of nitrogen, a new
sample was taken and dissolved in five per cent sodium
hydroxide and hydrogen peroxide. It was then analyzed by
the iljeldahl-Jodlbauer method
The results of the analysis is given below:
Elements Be Cl NO
Theoretical ratio 1 3 1
Experimental ratio 1 2.85 0.93
On dissolving the material to be analyzed, consider
able nitrojln dioxide was given off as well as hydrogen
chloride. The last of these gases consequently gave low
results. To prevent this, the compound was prepared in a
weighing bottle which was put in an Erlenmeyer flask and
water added, so that it would not come in contact with it.
With the flask stoppered, the v/eighing bottle was inverted
any gases formed were absorbed in water.
A compound prepared by the second method has been kept
in a glass stoppered bottle for several weeks. It retained
its lemon yellow color. A very slight odor was given off.
When exposed to the air it rapidly absorbed moisture.
A third method used to prepare the compound was un
successful. Nitrosyl chloride was condensed over metallic
beryllium. It was kept at the boiling point for about an
hour. On evaporation no yellow color appeared. The only
66
noticeable change was that the metal was slightly tarnished.
AN ATTEMPT TO PREPARE METALLIC BERYLLIUM BY THE
ELECTROLYSIS OF BeCl^NOCl IN NITROSYL CHLORIDE
Several experiments have been performed in an attempt
to get metallic beryllium20 by the electrolysis of beryl
lium compounds dissolved in liquid ammonia. Only traces
21
of the metal were obtained in a few of the experiments.
In this experiment nitrosyl chloride was condensed
over anhydrous beryllium chloride. At a temperature of
about -15°C and using voltages from 45 - 90, the negative
electrode was slightly darker than the anode. The elec
trodes were kept in contact with gaseous nitrosyl chlor
ide and the one with the darkened color became coated with
a yellowish substance, while the positive electrode re
mained unchanged. This might be explained by assuming
that either metallic beryllium or platinum chloride were
formed. In either case, in the presence of nitrosyl chlor
ide, the addition compound of nitrosyl chloride and the
chloride would be obtained.
20Booth and Torrey, J. Amer. Chem. Soc., 52, 2581, 1930.
2^Booth and Torrey, J. Phys. Chem., 35, (2465)(2492),
1931.
Apparatu
>N0C1 in nitrosyl chloride
69
A second attempt 7/as carried out by adding Be Cl NO Cl
to melted sodium nitrate and electrolyzing it, using plat
inum electrodes. Following the above procedure, no posi
tive results could be observed.
THE ACTION OF BERYLLIUM CHLORIDE UPON BERYL
The action of beryllium chloride upon glass has been
described earlier in this investigation. Since it had
such a definite effect upon glass, it was thought that it
might be used as a means of extracting beryllium compounds
from beryl. This experiment was carried out in an all py-
rex glass reaction tube that could be heated in a multiple-
unit electric furnace.
Two procelain boats, each containing approximately one
gram of beryl, were put into the reaction chamber. The
beryl in the first boat was mixed with carbon. A third
boat contained some beryllium metal. After drying the ma
terials in the reaction tube by heating and passing carbon
dioxide through, dry chlorine .was allowed to enter very
slowly. The temperature was increased until beryllium
chloride began to form readily. This reaction continued
for about four hours. Beryllium chloride condensed in the
cooler portion of the reaction tube. A sublimate formed
on the walls of the tube which was heated between 700°G
and 800°G. This deposit began to peel off indicating that
70
some reaction had taken place with the glass. After cool
ing, the porcelain boats were removed and weighed. The
boat containing only beryl lost 0.0151 gram while the one
with carbon lost 0.0315 gram.
The products in the ignition tube were dissolved and
heated with ammonium hydroxide. This precipitate which con
tained beryllium was dissolved in hydrochloric acid and sat
urated with ammonium carbonate. A precipitate was left due
to aluminum. This would indicate that the beryl had been
attacked by beryllium chloride. If aluminum was found, it
was assumed that beryllium was liberated as well.
THE EFFECT OF BERYLLIUM CHLORIDE ON GLASS
Nilson and Petersson22 and Humpidge2^ using the vapor
density method, proved that beryllium was divalent and had
an atomic weight of about 9.1. In their work they claim
ed that beryllium chloride attacked glass at high temper-
24
atures. Parsons, however, disagreed and thought the so-
called reaction was a thin film of beryllium oxide. If any
moisture is present, the chloride hydrolyzes and a deposit
of the oxide is formed on the glass. This substance is
22Nilson and Petersson, Compt. rend., 1884, 98, 988.
23Humpidge, Proc. Roy. Soc., 1885, 39, 1.
24Parsons, The Jour. Amer. Chem. Soc., 26, 729, 1904.
71
hard to remove. These deposits have been observed in this
investigation but no action upon pyrex could be noticed ex
cept in the case previously noted. This could not be due
to the high temperature alone, as no other portion of the
tube was so attached. As stated before, flakes of a glass
like substance peeled off and were found to consist of a
beryllium compound, while the glass underneath had been re
acted on.
As this has never been definitely determined, it was
decided to perform some experiments with dry beryllium
chloride on glass tubing to find if any reaction with the
glass would take place.
Two pieces of glass tubing, one of soft glass and the
othe of pyrex, were weighed. A small amount 'of beryllium
metal was placed on the inside of each tube and these were
then put in a larger tube which served as the reaction
chamber. Dry carbon dioxide was passed through the appara
tus while the electric furnace was heated to about 500°C.
This was to drive out any moisture that might be present.
Nitrosyl chloride which had been prepared from aqua regia
was passed through two towers filled with calcium chloride.
Beryllium chloride condensed just outside of the furnace,
while on that part of the reaction tube in the furnace, a
white deposit formed. The two smaller tubes were also
72
covered with a similar material. When the reaction had
continued for a short time, the tubes were removed and boil
ed in aqua regia and then in sulfuric acid. Both pieces of
tubing had been acted upon. This could easily be seen. The
soft glass showed a loss of 0.0081 gram for a five gram
piece of tubing. The pyrex tube showed a loss of 0.0043
gram* This does not necessarily mean that pyrex is not act
ed upon to as large an extent as is the soft glass. Itt so
happened that more beryllium chloride vapor passed over the
soft tube than the other.
To make certain that it was due to the action of beryl
lium chloride and not to that of the nitrosyl chloride, a
blank was run. This was done exactly as the other with the
exception of adding no metallic beryllium. It was found that
the glass was not attacked, as well as the fact that there
was no gain or loss in weight.
Another experiment was tried using chlorine gas, which
was passed through six towers filled with glass beads moist
ened. with concentrated sulfuric acid. Beryllium chloride
was formed as before, but the reaction was slower and the
temperature higher than when nitrosyl chloride was used.
As before, beryllium chloride was deposited in the cooler
portion of the tube. A white substance covered the reaction
tube in the furnace and the two pieces of glass tubing.
73
This reaction was allowed to continue at a high temperature
and for a longer time than the previous ones.
After carefully washing and drying, it was apparent
that the glass had been acted upon. On weighing, a six
gram sample lost 0.0117 gram, while the pyrex of approx
imately the same weight, lost 0.0143 gram.
From these three experiments it is evident that beryl
lium chloride does have an etching effect upon glass, and
Parson’s theory that the apparent attacking of glass by
beryllium chloride is nothing more than a deposit of beryl
lium oxide, is disproved.
CHAPTER V
SUMMARY AND CONCLUSIONS
On the basis of the experiments carried out in this
investigation the following conclusions have been drawn.
1. Anhydrous beryllium chloride cannot be prepared
by evaporating a hydrochloric acid solution of
beryllium chloride in an atmosphere of nitrosyl
chloride.
2. Beryllium chloride has been prepared by passing
nitrosyl chloride vapor over beryllium metal.
5. Beryllium chloride can be prepared by passing
nitrosyl chloride over a heated mixture of beryl
lium oxide and carbon. (No action was observed
with nitrosyl chloride on beryllium oxide alone)
4. When nitrosyl chloride is passed over heated
beryl mixed with carbon, beryllium chloride is
formed, but in small amounts.
5. Beryl is acted upon by liquid nitrosyl chloride
at a slight pressure.
6. Metallic beryllium cannot be obtained, by the
electrolysis of beryllium chloride in liquid
nitrosyl chloride.
7. A compound having the formula BeClgNOCl was
75
prepared by treating beryllium chloride with
liquid nitrosyl chloride.
8 . Beryllium chloride at high temperatures has a
definite effect upon both pryex and soft glass.
9. Beryl is very slightly attacked by beryllium
chloride at high temperatures.
10. A convenient method for the preparation of
nitrosyl chloride from aqua regia has been
developed.
11. A compound consisting of aluminum chloride
and nitrosyl chloride (A1G1 N0C1) has been
O
prepared by passing the vapors of aqua re
gia over metallic aluminum. A method for
preparing pure nitrosyl chloride from aqua
regia has been based upon this.
BIBLIOGRAPHY
BOOKS
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Charles Griffin and Company, Ltd., 1926.
Hopkins, B. S., Chapters in the Chemistry of the Less
Familiar Elements. Champaign, Illinois: F. Stipes
Publishing Company., 1938.
Lewis and Bandall, Thermodynamics.
Me 11or, Joseph William, A Comprehensive Treatise on Inor
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Parsons, Charles L., The Chemistry and Literature of
Beryllium. Easton, Pennsylvania: The Chemical”"Pub-
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Pimbach, Richard, and A. J. Michel, translators, Beryllium
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Smith, G, Frederick, Dehydration Studies using Anhydrous
Magnesium perchlorate. Columbus, Ohio: The G. F.
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77
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79
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Creator Hansen, Andrew (author)

Core Title Contributions to the chemistry of the chlorides, simple and complex, of beryllium

School Department of Chemistry

Degree Doctor of Philosophy

Degree Program Chemistry

Degree Conferral Date 1939-06

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

Tag chemistry, inorganic,OAI-PMH Harvest

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Contributor Digitized by ProQuest (provenance)

Advisor Brinton, Paul H.M.P. (committee chair), Roberts, L.D. (committee member), Weatherby, Leroy S. (committee member)

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