SOME RECENT DEVELOPMENTS IN THE CHEMISTRY OF BORON, FLUORINE AND THEIR COMPOUNDS

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• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600330143-6
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 7
• Document Creation Date: December 22, 2016
• Document Release Date: August 26, 2011
• Sequence Number: 143
• Publication Date: July 25, 1950
• Content Type: REPORT

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CLASSIFICATION SECRETVEq El
CENTRAL INTELLIGENCE AGENCY REPORT
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
COUNTRY USSR
SUBJECT Scientific - Chemistry,
HOW
PUBLISHED Periodicals
WHERE
PUBLISHED USSR
DATE
PUBLISHED 1949 - 1950
LANGUAGE Russian
TN If DOCUMENT CONTAINS INFORMATION ATFICTIMS THE NATIONAL DEFENSE
OT THE UNITED STATES WITHIN THE MEANING OF ESP GRASS ACT SO
S. I. C.. II ANO 5E. Af AMENDED. ITS TIAMSMI,SION OR THE YEVI ATIOM
OF ITS CONTENTS IN AMT MANNER TO AN UNAUTHOIIEED PINSON ID PROW
MIGITIO my LAW. REPRODUCTION OF THIS FORM IS PROHIIITEO.
5umbers in parentheses refer to appended list of sources_7
A new method for the quantitative analysis of toron by colorimetric
means with carmine indicator is suggested in a recently published paper
(1) by Soviet chemists in this field. They also show how to separate bo-
ron from fluorine by the use of synthetic resin? and have developed a .
method for the determination of the contents of boron and fluorine in a
number of minerals- tourmaline, wiluite, and axinite.
Addition compounds of boron fluoride have become important as cata-
lysts in the fuel industry, and. a series of articles on the theme "Com-
pounds of Boron Fluoride as New Catalysts in. Alkylation and Polymeriza-
tion" has appeared in recent issues of Soviet periodicals. The authors
are A. V. Topchiyev, newly designated Active Member of the Academy of
Sciences USSR. (2), and his collaborator, Ya. M. Paushkin.
Reports V and VI of this series (3, 4) are concerned, respectively,
with the alkylation of isopentane with propylene and.with the alkylation
of isopentane with ethylene or isobutylene. Both articles begin with his-
torical reviews of the application of boron fluoride addition compounds
as catalysts in this field and point out their increasing importance be-
fore going into experimental results. In the introductions to these ar-
ticles, five references (5-9) are given to previous Soviet research in
the field.
Results of two recent investigations (3, 4) by Topchiyev and Paushkin,
who employed spectroscopy. by the method of light-scattering for analysis of
the alkylation products, are as follows.
In connection with the alkylation of isopentane with propylene, they
discovered that in reactions of alkylation of isoparaffins with olefins,
only compounds of boron fluoride with nydroxyl-containing. substances (wa-
ter, an.acid, or an alcohol) are catalytically active. Compounds of these
substances with boron fluoride have the character of strong ids and their
STATE
ARMY
DATE OF
INFORMATION 1948- 1-949
DATE DIST.Frp Jul 1950
SUPPLEMENT TO
REPORT NO.
SOME RECENT DEVELOPMENTS IN THE CHENISTRT OF
P-1-10v FLUOR AND THEIR COMPOUNDS
NSRB
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catalytic activity amounts to ordinary acid catalysis. Addition compounds
of boron fluoride with simple and complex esters and amines, as well as pure
boron fluoride itself, are catalytically inactive in the alkylation of iso-
paraffins.
In the alkylation of isopentane with propylene, by using boron fluoride
compounds with water and phosphorus pentoxide, the product of alkylation was
obtained with a yield of 175-200 percent based on the original propylene or
70-85 percent of the theoretical. Under optimum conditions the product had
a specific gravity of D.?0..705-0.715, and 70-80 percent of the product boiled
away below 170 degrees centigrade.
Topchiyev and Paushkin state that the chemical composition of the pro-
ducts of alkylation depends very little on the catalyst used. Weakly branched
hydrocarbons, (2,3-; 2,1k- and 2,5-dimethylhexane) are the principal components
of the isooctane fraction. On the other hand, in the case of alkylation of
isobutane with butylene, the isooctane fraction contains trimethylpentane.
The alkylation of isopentane with propylene gives a product whose octane
number is 70.3; the isooctane fraction of the product has a boiling point of
98-120 degrees centigrade and an octane number of 80.6 (that is, a number
which is lower than that of the original isopentane which is rated at 89).
For this reason, the products of alkylation of isopentane with propylene are
not recommended as components of motor fuels in view of their low octane num-
bers, as compared with products of alkylation of isobutane with olefins.
A number of boron fluoride catalysts were used in the alkylation of iso-
pentane with ethylene and isobutylene, and it was confirmed that only the com-
pounds of boron fluoride with hydroxyl-containing substances, or acid [and
acid hydrates ] are catalytically active in this reaction, a fact also pointed
out by the authors in the previous article.
Acids such as hydrofluoric, sulfuric, and phosphoric do not induce
alkylation with ethylene unless they are in combination with boron fluoride.
Alkylation of .isopentanes with ethylene in the presence of the catalysts
phosphorus pentoxide, water, boron fluoride, and H2O ? HF3 proceeds under
conditions of atmospheric pressure, although at a slow rate. The yield of
the alkylate, in reference to the original ethylene, is 160-200 percent and
its specific gravity is 0.69. The alkylation of isopentane with isobutylene
proceeds at a greater rate with a yield of 180-220 percent based on the ori-
ginal isobutylene. The alkylate has a specific gravity of 0.71-0.72 and a
bromine number of 1-1.5.
The alkylates consist of a mixture of hexanes,,heptanes, octanes, and
even higher molecular hydrocarbons. The heptane fraction of the products
of the alkylation of isopentane with ethylene consist of dimethylpentanes;
trimethylbutane is not formed. In the alkylate of isopentane reacted with
isobutylene, the nonane fraction composes about 25 percent by weight of the
product.
The alkylation of isopentane With ethylene is not of commercial inter-
est because the isopentanes (dimethylpentanes) thus formed have lower octane
numbers than the original isopentane. Research on the alkylation of iso-
pentane with ethylene and with isobutylene is significant from the standpoint
of the study of activity of individual catalysts.
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Before closing the consideration of the recent work by Topchiyev and
Paushkin, it is interesting to note that they published a monograph, "Prop-
erties of Boron Fluoride as a Catalyst in Alkylation, Polymerization, and
Condensation" (10), in 1949, and that Topchiyev`published,anotherr^paper,,
Returning to the paper on the quantitative determination of boron and
fluorine (1), a summary of its contents is as follows:
Authors D. I. Ryabchikov and V. V. Danilova of the Institute of Geo-
chemistry and Analytical Chemistry imeni Vernadskiy, Academy of Sciences
USSR, state that the determination of boron and fluorine, when both are
present, is a very difficult' task, and that the determination
investi-
gation, of either is also a challenging proposition.
fluorine is determined with zircon alizarin by a previously de-
veloped colorimetric method (11); and boron is determined volumetrically
by titration of mannitoboric acid with an alkali (12). The latter method
is complicated and about 10 percent of the boron escapes detection. Fur-
thermore, commercial mannite almost always contains boron.
The authors (1) recommend their own colorimetric method, in which car-
mine is used in an indicator in a color action for boron, this having been
first suggested by Kazarinova-Oknina (13). In the presence of carmine, a
sulfuric acid solution containing boron changes from red to a dark blue.
By this method, 0.2 milligram of B203 in 25 milliliters can be detected.
This color and action is interfered with by the presence of oxidizing
agents (nitrates, chromates, hydrogen peroxide, etc.) which attack the
organic indicator. The presence of fluorine also inhibits the reaction
because it and the boron form a complex fluoride which leads to discolora-
tion of the indicator. On the other hand, chlorides do not interfere with
the color reaction.
Ryabchikov and Danilova (1) give the following description of their
method. A standard solution was prepared from twice recrystallized borax
by dissolving it in concentrated sulfuric acid. The original concentra-
tion of such a solution was one milligram of B203 in one milliliter, which
was then brought to a lower concentration by dilution (from 0.02 to 0.2
milligram of B203 in one milliliter). The solution was prepared in 25-
milliliter measuring flasks into which, after the introduction of a given
portion of the original solution, were added 15 milliliters of the indica-
tor (0.005 percent carmine dissolved in concentrated sulfuric acid). The
whole was then diluted up to the mark with concentrated sulfuric acid hav-
ing a specific gravity of 1.84. After careful mixing and letting the solu-
tion stand for an hour, a stable color was observed, and this color was
found to persist for not more than 10 days. The addition of water to the
solution was avoided, since it changes the color of the indicator.
For the distillation of the boron, Ryabchikov and Danilova used an
apparatus which ordinarily ser-es for the distillation of fluorine. To
check the method, a known quantity of boron in solution was put into the
apparatus along with 60 millimeters of distilled water and 25 millimeters
of concentrated sulfuric acid, in addition to a solution of sodium fluoride
in a quantity in excess of that necessary for the formation of boron fluo-
ride. The boron was then distilled from the solution at a temperature of
140 degrees and the combined distillates of three such distillations were
found to comprise 200 milliliters.
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The remaining water was then distilled off from the sulfuric acid into
an Erlenmeyer flask containing 2 milliliters of a one-percent solution of
caustic soda by heating the apparatus to the point of formation of vapors
of sulfuric acid. The product of this distillation was then added to the
first three distillates. The amount of boron remaining in the sulfuric
acid was quantitatively determined by colorimetric comparison with stand-
ard solutions.
The authors claim that by this method, separation of boron proceeds
considerably more rapidly than with methyl alcohol and that it eliminates
the loss which occurs in the methyl-alcohol method.
Most of the boron is then contained in the form of boron fluoride
in the distillates in which the excess of fluorine is held in the form of
sodium fluoride. Determination of boron in the presence of fluorine by
ordinary methods is not sufficiently accurate, and that is why the sepa-
ration of the boron from the fluorine is accomplished with the aid of syn-
thetic resins.
To accomplish this, Ryabchikov and Danilova employed a glass burette
with a porous filter. Five to 6 grams of a resin of the type wofatit P
pulverized to a grain size of .05 millimeter were placed in the burette.
The cationite was treated with dilute hydrochloric acid, 1 to 5, and then
was washed with distilled water to the point of a neutral reaction with
methyl red. According to the authors, the exchange reaction occurring
during the passing of a solution containing boron fluoride through an H-
cationite can be designated by the following equation:
3H (KAT) + BF3-4 B (KAT)3 + 3HF.
The 'boron in the form of the cation (B3+) was absorbed by the resin
and the fluorine anion interacted with the individual hydrogen ions form-
ing hydrogen fluoride and thus passed into the filtrate. The rate of the
filtration of the solution through a column with an H-cationite was 50 mil-
limeters per hour. it was necessary to pass the boron fluoride containing
solution through the column three or five times. After wash g the column
with distilled water, the boron was extracted into a separate container with
a 2 percent. solution of hydrochloric acid (about 200 milliliters) introduced
into the column at the original rate, only a small portion of the boron being
lost at this rate. Next the column was again washed with distilled water
heated.to 50 degrees centigrade. The washing water was then added to the
main hydrochloric acid filtrate containing boron, and, the contents of the
measuring flask were brought to the mark.
For the determination of boron, 10 to 20 milliliters of the prepared
solution were neutralized with soda in a platinum dish and evaporated to
dryness.
Ryabchikov: and Danilova (1) give the following table to show the ac-
curacy of the method they recommend, pointing out that the degree of error
is decreased when smaller quantities of boron are used:
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Boron Boron Ex-
Found tracted Total Fluorine
in H2SO4 From Boron Variance in in Fil-
Residue Cationite Found in Theoretical and trate After
Fluorine After Dis- With 2% Experi- Experimental Separation
Boron Used Used tillation HC1 ment Values of Boron of Boron
(in ) (in m) (ice) (in H) (ice) (11_M) (in %) (in mg)
0.433 1.2 0.3255 0.0930 0.4185 0.0145 3.35 1.18
0.433 1.8 0.3224 0.0992 0.4216 0.0114 2.63 1.18
0.346 1.0 0.1302 0.2092 0.3394 0.0066 2.0 0.97
0.216 0.65 0.0558 0.1550 0.2108 0.0052 2.40 0.63
0.130 0.40 0.0418 o.o86o 0.1278 0.0022 1.69 0.38
0.087 0.25 0.0471 0.0387 o.o858 0.0012 1.38 0.24
To check the possibility of a simultaneous determination of fluorine
by this method, Ryabchikov and Danilova investigated the remaining filtrate
after the separation of the boron. The solution containing hydrogen fluo-
ride was again passed through the column, this time filled with an anionite
of the type MGG1. The degree of pulverization of the resin and the rate at
which the solution was passed through the column were the same as in the case
of the cationite and the boron determination.
The authors found that the fluorine was completely absorbed by the
anionite which had previously been washed with a 4-percent solution of soda,
and therefore was in the form (An)2C03. In this case, the reaction can be
represented by the equation: (An)2C03 + 2HF -~P 2AnF f H2C03.
The fluorine was recovered from the anionite by washing the column
with a 4-percent solution of soda or caustic soda, which resulted in the
formation of sodium fluoride. The column could then be used in subsequent
experiments. The regeneration reaction was as follows:
2AnF + Na2C03 (An)2C03 + 2NaF.
After the column was washed with soda to extract the fluorine from the
anionite, the column was again washed with distilled water to attain a neu-
tral reaction. The alkali solution, together with the water used in the
washing, was introduced into the apparatus for distillation of the fluorine
prior to the determination of the fluorine colorimetrically by the ordinary
method with zircon alizarin. Data on the determination of the fluorine are
also given in the above table. According to the authors, from the results
depicted in the table, it is apparent that the presence of boron does not
interfere with the determination of the fluorine.
Therefore, the authors were able to show that, with the aid of ionic
exchange resins, it is possible to determine boron and fluorine, when both
are present, by the initial separation of the boron. This method has also
been tested on the following minerals (14, 15):
Tourmaline--(Na,Ca)R9B3Si16027(OH,F)
Wiluite--(Ca,Mn,Mg,Fe)o.Al,B,Fe,(OH,F)
Axalite--6(Ca,Fe,Nn)?2Al203'?85102.H20
These minerals were obtained from the Mineralogical Museum of the
Academy of Sciences USSR. In each case about 0.02-0.1 gram of the pulver-
ized mineral was mixed with soda, and the mixture was then lixiviated with
water and introduced into the apparatus for distillation. The solution was
carefully neutralized and then 25 milliliters of concentrated sulfuric acid
with a specific gravity of 1.84 were added, and the distillation of the bo-
ron fluoride carried out.
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N..=" F'
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Contents of B203 and F in mineral specimen were as follows:
First specimen of wiluite--4.66% of B203, 0.24% of F
Second specimen of wiluite--4.64% of B203, 0.26% of F
First specimen of tourmaline--7.53% of B203, 0.37% of F
Second specimen of tourmaline--7.59,E B203,
First specimen of axalite--4.66% of B203, no F
To check results, the authors used a known quantity of boron and
fluorine in one cff the parallel tests on the mineral specimens. The
known quantities were then compared with the experimentally obtained
quantities for each element.
Ryabchikov and Danilova submitted their article 5 November 1949.
The articles by Topchiyev and Paushkin were submitted 24 June 1948.
Other researchers at the Ural Scientific-Research Chemical Institute at
Sverdlovsk and the Laboratory of General Chemistry at Dnepropetrovsk kblems
Metallurgical Institute are known to be working on comp Antary rnnn.n+t-d with compounds of boron and fluorine (16, 17)
1. D. I. Ryabchikov and V. V. Danilova, "Quantitative Determination
of Boron and Fluorine When Both Are Present", Zhurnal Analiticheskoy
Khimii, Vol V, No 1, 28-31, 1950.
2. S. B. Shevelev, "General Conference of the Department of Chemical
Sciences of the Academy of Sciences USSR," Izvestas Akademii Nauk
SSSR, Otdeleniye Khimicheskikh Nauk, No 6, 53, 1949.
3. A. V. Topchiyev and Ya. M. Paushkin, "Compounds i f Boron Fluoride as
New Catalysts in Alkylation and Polymerization V? Alkylation of Iso-
pentane with Isopropylene," Zhurnal Obshchey Khimii, Vol XIY, No 12,
2175-2181, 1949.
4. Ya. M. Paushkin and A. V. Topchiyev, "Compounds of Boron Fluoride as
New Catalysts in Alkylation and Polymerization. VI. Alkylation of Iso-
Khimii Vol XIX
h
6. P. P. Shorygin and M. V. Vol'kenshteyn, Izvestiya Akademii Nauk SSSR,
Seriya Fizicheskaya, Vol V, 2-3, 1941.
7. Yu. G. Mamedaliyev, The Alkylation Reaction in the Production of Motor
Fuels, Aznefteizdat, 1945.
8. A. D. Petrov, Synthesis and Isomeric Conversion of Aliphatic Hydrocarbons,
Academy of Sciences USSR, 19 7.
9. A. V. Topchiyev and Ya. M. Paushkin, Uspekhi Khimii, Vol XVI, No 6, 664,
1947. `
ey
pentane with Ethylene and Isobutylene, Zhuxnal.Obshc
No 12, 2182-2190, 1949.
A. V. Topchiyev and Ya. M. Paushkin, Transactions of the Moscow Petroleum
Institute imeni I. M. Gubkin, No 5, Moscow, 19 7?
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10. "New Books," Uspekhi Khimii, Vol XVIII, No 6, 765, 1949.
11. V. V. Danilova, Transactions of the Biogeochemical Laboratory, Vol VII
1944.
12. S. G. Tseytlin, Transactions of the Biogeochemical Laboratory, Vol V.
325, 1939.
13. V. A. Kazarinova-Okaina, Zavodskaya Laboratoriya, No 3, 1948.
14. Doelter, Handbuch der Mineralchemie, No 2, 939, 1917-
15. P. P. Solov'yev, Handbook on Mineralogy, 1948.
16. I. G. Ryss and Ye. 14. Polyakova, "Preparation of Boron Fluoride by
the Acid Methods," Zhurnal Obshchey Khimii, Vol XIX, No 9, 1596-1603,
1949.
17. I. G. Ryan and M. M. Slutskaya, "The Rate of Formation of Tetrafluoro-
boric Acid-in Mixtures of Hydrofluoric and Boric Acids. I and II,"
Zhurnal Obshchey Khimii, Vol XIX, No 10, 1827-1842, 1949.
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