SECTION 14

Boron
H. J. BECHER
Boron

I. According to Moissan, very impure amorphous boron, containing

about 80-90% B, is obtained by the reaction of B 3 O 3 with magnesium.
According to Kroll the optimum yields are obtained as follows: A
fireclay crucible, approximately 20 cm. high and 16 cm. in diameter, is painted with a paste of ignited MgO and sintered MgCl3 and
dried in a low-temperature oven. A mixture of 110 g. of B 2 O 3 ,
115 g. of Mg shavings (the use of Mg powder frequently leads to
explosive reactions) and 94 g. of powdered S is placed in the crucible. The reaction is started with an ignition pellet, after which it
proceeds vigorously. After the mixture has cooled, it is extracted
in water and then in dilute HC1 for a week. The residue is treated
several times by heating with HF and HC1, washed with water and
dried in vacuum at 100C. The yields are variable, with a maximum
of 46%.
II. According to Kiessling, pure boron can be made by reducing
BBr 3 with H 3 at 800C. The reaction takes place in the apparatus
shown in Fig. 238. The BBr 3 is prepared by the method of Meyer
and Zappner from B r s and commercial boron (usually 70-80% pure)
(cf. the method described on p. 782). Thus, 15 g. of B is pressed
into pellets, and the quartz tube b is filled with them. The tube is
heated to 700C and dry Br a is added in drops from dropping funnel
a. The resulting BBr 3 will then collect in trap c, which is cooled
with an ice-salt mixture. After about 30 minutes, 5-10 ml. of
BBr 3 will have accumulated. The addition of Br 3 is stopped and
excess B r 3 from b and c is flushed out with H 3 . The resulting
BBr 3 should be colorless. The H 3 flow is then adjusted to 2-4
bubbles per second, the temperature of the quartz tube heater is
raised to 750-800C, and the BBr 3 in a allowed to evaporate in the
H 3 stream at ambient temperature. As a result elemental B precipitates in d. Unreacted BBr 3 recondenses in e, which is cooled
with ice-salt mixture. When no further BBr 3 is left in o, traps e
and a are interchanged and the decomposition continued in d. When
the BBr 3 is all reacted, more material is prepared by allowing
fresh B r 3 to drop into quartz tube b. One charge of 15 g. of B will
770

14.

771

BORON

be sufficient for preparation of 75 ml. of BBr 3 . Boron that has

precipitated in d appears to catalyze further decomposition. Therefore, this tube should not be emptied too early. The resulting B is
washed and dried with hot HSO. According to Kiessling the composition is: 98.9% B, 0.04% Al, 0.1% Si and traces of O, H and Mg.

hood

1
Fig. 238. Preparation of high purity boron,
adropping funnel for Br s , protected against
atmospheric moisture; bquartz tube for B
pellets (10 mm. in diameter and 700 mm.
long); cfirst condensation trap for BBr 3 ,
capacity about 25 ml.;dquartz tube for r e duction of BBr 3 ; esecond condensation trap
for BBr 3 , capacity 25 ml.; otubular electrical heaters, about 600 mm. long; pjoints
cemented withpicein; gmercury seals; their
design is shown enlarged next to the principal
figure; it illustrates the seal for the top of the
condensation flask.
PROPERTIES:

Atomic weight 10.82. Gray-brown to yellow-brown powder.

M.p. 2300 C; d 2.3. Ignites in air at 700 C. Reacts violently with
concentrated HNO3.
REFERENCES:

I. H. Moissan. Compt. Rend. Hebd. Seances Acad. Sci. 114, 392

(1892); W. Kroll. Z. anorg. allg. Chem. 102, 1 (1918).
II. R. Kiessling. Acta Chem. Scand. 2, 707 (1948).
For other procedures, cf. A. W. Laubengayer, D. T. Hurd,
A. E. NewkirkandJ. L. Hoard. J. Amer. Chem. Soc. 65, 1924 (1943).

780

H. J . BECHER

interrupted and the excess BC13 still remaining in the flask is

allowed to recondense on the inlet cold finger for another hour.
The cooling is then stopped and the excess BC1 3 distilled off. The
liquid phase is siphoned out from the flask and centrifuged for
further clarification, if necessary. The chlorobenzene is distilled
until solid (ClBNH) 3 remains as a residue. The latter is purified
by vacuum sublimation at 50-60C. The yield is approximately
40%. If the recovered chlorobenzene is recycled back to the flask
which still contains the solid residue and if fresh NH4C1 is added,
the yield can be increased appreciably by further reaction.
PROPERTIES:

Colorless crystals, exceedingly sensitive to moisture. M.p.

84C; d (25C) 1.58. Soluble in benzene, CC14 and other organic
solvents.
REFERENCES:

Ch. A. Brown and A. W. Laubengayer. J. Amer. Chem. Soc. 77,

3699 (1955).
R. Schaeffer, M. Steindler, L. Hohnstedt, H. S. Smith, Jr., L. B.
Eddy and H. I. Schlesinger. J. Amer. Chem. Soc. 76, 3303
(1954).
For preparation and properties of some other borazole derivatives, see E. Wiberg, Naturwiss. 35, 182, 212 (1948); H. J. Becher
and S. Frick, Z. anorg. allg. Chem. 295, 83 (1958).
Boron Trichloride
BCI3

Fairly large quantities of BC1 3 can be produced by heating

dilute borax with charcoal in a stream of Cl 3 at temperatures of
400 to 700C. In the laboratory it is more convenient to produce it
from BF 3 and A1C13.
I.

BF3 + A1C13 = BCI3 + A1F3.

67.8

133.4

117.2

84.0

The reaction is carried out in the apparatus shown in Fig. 241.

The lower flask has a capacity of one liter; the upper bulb, half
that. Anhydrous A1C13(67 g. = 0.5 mole) is placed in the lower flask.
The inlet tube is connected to a B F 3 generator and the BF 3 flow
adjusted in such a manner that 132 g. or two moles of B F 3 are
added to the vessel over a period of 30 minutes. At the same time,

781

1 4 . BORON

Fig. 241. Preparation of boron trichloride.

the lower flask is heated with an open flame. Later the bulb is also
heated. The BC1 3 distills off while the A1F 3 peels off from the
walls of the flask as a light powder. The BC1 3 is cooled in a U
tube cooled to 80C. Moisture is excluded by means of a drying
tube. The impure product is shaken with some Hg and recondensed.
The yield is 47 g.
KBF 4

II.

A1C13 = BC13

125.9

133.4

KF

A1F3

117.2

An i n t i m a t e m i x t u r e of 1 3 3 . 3 g. of A 1 C 1 3 a n d 62 g. of K B F 4 i s

placed in the apparatus described above, which is then slowly

heated in an oil bath to 150-170C. Using the method described
above, the BC1 3 that has been distilled off is trapped and purified.
The yield is poorer than that produced by method I.
PROPERTIES:

M.p. 107C, b.p. 12.5C;

fuming in moist air.

(0C) 1.434. Colorless liquid,

REFERENCES:

I and II: E. L. Gamble in: L. F. Audrieth, Inorg. Syntheses, Vol.

Ill, New York-London, 1950, p. 27. Synthesis of BC1 3 from
amorphous B and Cl 3 : L. Gattermann. Ber. dtsch. chem. Ges.
22, 195 (1889).
Boron Tribromide
BBrs
I.

AlBr3 + BF 3 = BBr3 + A1F3

266.7

67.8

250.6

84.0

One half mole (133.4 g.) of AlBr 3 is distilled into the flask
described for the preparation of BC13; BF 3 is added while heating

782

H. J . BECHER

the flask. After some time the flask contents solidify. The heating
and admission of B F 3 are continued. As a result, the BBr 3
product distills over into the 78C trap. The distillate still contains some B r 2 which can then be removed by shaking with Hg. The
BBr 3 must be distilled for further purification. Theyield is 87.7 g.
(70%).
An alternative is to heat a mixture of AlBr 3 and KBF 4 in the
flask itself, but this results in a much lower yield of BBr 3 .
II.

B + 17a Br2 = BBr3

10.8

239.8

250.6

This procedure has been previously described in connection with

the Kiessling method for preparing pure boron. If BBr 3 is desired,
the apparatus shown in Fig. 238 is closed off by means of a drying
tube inserted behind condensation trap o. Before the reaction the
boron is thoroughly dried by prolonged heating at 600C in a
quartz tube flushed with a stream of H 3 . Then dropwise B r 3 addition is started, and the temperature of the reaction tube is
raised to 700-750 C. The product BBr 3 is purified as in method I.
PROPERTIES:

M.p. -46C, b.p. 90.8C; d (0C) 2.65. Colorless, easily hydrolyzed liquid.
REFERENCES:

I.
II.

E. L. Gamble in: L. F. Audrieth, Inorg. Syntheses, Vol. Ill,

New York-London, 1950, p. 27.
Fr. Meyer and R. Zappner. Ber. dtsch. chem. Ges. 54, 551
(1921); H. Menzel. Unpublished.

Boron Triiodide
BI3
3LiBH4 + 8I2 = 3LiI + 3BI3 + 4H2 + 4 HI
65.37

2030.56

401.55

1174.65

8.06

511.67

The apparatus shown in Fig. 242 is used and 170 g. of I a is

added to flask a, while 5.1 g. of LiBH 4 is placed in addition bulb b
under an N s blanket. The entire assembly is thoroughly flushed
with N 3 by evacuating it several times through u and introducing

4. FLUORINE COMPOUNDS

223

Potassium Fluoroborate
KBF4
H3BO3 + 4HF + KOH = KBF4 + 4H 2 O
61.82

80.04

56.11

125.92

72.05

Boric acid (6.2 g.) is added to 25 g. of 40% hydrofluoric acid

solution contained in an ice-cooled platinum dish. The solution is
allowed to stand at room temperature for six hours. At the end
of this period it is again chilled with ice, and 5N KOH solution is
added with constant stirring until the color of methyl orange changes.
Crystalline KBF4 precipitates out at the same time. The mother
liquor and subsequent water washings are decanted and the crystals
dried under vacuum. The yield is 90%.
PROPERTIES:

White, crystalline salt, nonhygroscopic.

M.p. 530C, d% 2.505. Solubility in water (20C) 0.45; (100C)
6.3 g./lOO ml. Dimorphous: rhombic-bipyramidal and cubic
structures (trans, temp. 276-280C).
REFERENCES:

D. Vorlander, J. Hollatz and J.

Ges. 6jj, 535 (1932).

Fischer. Ber. dtsch. chem.

Potassium Hydroxyfluoroborate
KBFSOH
2 KHF2 + H3BO3 = KBF3OH + KF + 7 H2O
156.22

61.84

123.96

58.1

36

Technical grade KHF3 (100 g.) is dissolved in 250 ml. of water

contained in a polyethylene beaker. The KgSiFs and the undissolved
KHF3 are filtered off after several hours of standing; the clear
solution is placed in an ice-cold water bath and 40 g. of boric acid
is added with stirring. Rapid dissolution occurs. Small crystals
separate from the solution within an hour. They are suctionfiltered on a fritted glass filter, washed with a small amount of
ice-cold water and with 95% methanol solution and acetone. The
salt is then dried at 120C.
PROPERTIES:

Melts without decomposition. Less soluble in water than KBF 4 .

Yields no precipitate with nitron acetate; hydrolyzed by KOH