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B 3N 3 H
LlH o
~rom
this value t he J:eat of formation of liquid borazin e may be calculated as LlHr (25
C) = - i?48.5 13.4 kJ /mole (- 131.1 3.2 kca1 /mole), and for the gas, LlHr( 25 0c) = - 519.2
13.4 kJ /mole (- 124.1 3.2 kcaI/ mole).
1. Introduction
I-
3. Experimental Procedure
The .borazine samples, 0 ..5 to 1.0 g, were transferred ill the vapor phase at room temperature into
spherical soft-glass bulbs cooled to about - 5 DC
with an ice-sal t mL'{ture . The filled bulbs were
sealed u~der vacuum , weighe~ carefully, and stored
at - 15 9. In the first experunent, the sample was
enclosed.m a Pyrex-!Sla~s bulb and ignited by means
of a platmum fuse WIre mstead of the usual iron wire
to eliminate possible complications from the irol{
?xides durin.g analysis of the products; thereafter,
Iron fu se WIre was used. Pyrex-glass bulbs were
un satisfactory for this work because only a small area
of the glass was softened upon ignition and incomplete combustion resulted. Soft-gl~ss bulbs
usually shattered upon ignition and the ample
burn ed with free access to oxygen.
In a~sembling the bomb , the sample bulb was
placed lJ1 a quartz crucible, 3 cm in diameter and 1.5
em deep , which was supported a little below the
center o~ the bomb. The carefully weighed fuse-wire
of p.ure. lyon, 5 cm long and 5 mils in diameter, used
fo!' Igmtmg the sample was placed in direct contact
WIth the sample bulb. After 2 ml of distilled water
had been added to the bomb , it was closed and
flushed to displace air before filling with oxygen to
a pressure of 30 atm. The bomb was placed in a
calorimeter can containing 2968 g of water, the
standard amoun t for the systdm.
The energy equivalen t of the calorime tric system
was determined in calibration experiments in which
benzoic acid, NBS Standard Sample 39g, was
burned, The heat evolved in the combustion of
this sample is certified to be 26.4338 0.0026
kj/g at the standard bomb conditions.
Tempe~ature. observations during the experiments
were chvlded mto four groups, an initial rating
period (20 min), a combustion period (5 min) , an
equilibration period (11 min), and a final rating
101
period (20 min). The rapid temperature change i.e., d28 = 0 .871 g/cm3 [14] and Op(28 C) = 32.5
during the combustion period was recorded by cal/mole C or 16.7 jig-ohm [15]. The unit of
means of a chronograph (Gaertner Scientific Co.) en ergy was the joule, and for conversion to the
having a synchronous motor and two pens marking thermochemical calorie the following relation was
a waxed tape which advanced uniformly at 10 mm used: 1 thermochemical calorie = 4.1840 joules.
per sec. On e pen recorded time in seconds as obThe products of combustion of borazine contained
tained from standard signals transmitted by the grey-white material which was insoluble in water
National Bureau of Standards, the other recorded and which was not attacked during digestion in
the times when a telegraph ke y was tapped indicating aqua regia; the material was assumed to be boron
when the resistance of the thermometer in the nitride. This assumption was supported by an
calorimeter passed certain previously selected values. X-ray diftraction analysis 3 although positive identiT emperatures were recorded at I -min intervals fication was not possible because the X -ray powder
during the equilihration period, and at 2-min in ter- pattern was not clearly defined .
vals during the rating periods.
Elemental boron was not present in the products
The gaseous products of the experiments reported of combustion in detectable quantity. The insoluhere were not analysed since nitrogen oxides were ble residue of combustion was digested in aq1la regia
not detected in any of the preliminary experiments for several hours to oxidize the boron to boric acid.
in which the product gases were bubbled through The solution was then filtered, and the filtrate was
distilled water and the solution titrated with 0.1- neutralized with sodium hydroxide, nlade slightly
N sodium hydroxide.
acid, and titrated to the first end point. When
The solid products remaining in the bomb were D-mannitol was added, no significant decrease in
washed with hot distilled water; the washings were pH occurred indicating that boric acid (or boron)
filtered to remove fragments of the shattered cruci- was not present. Since elem~ntal boron was not
ble , glass bulb , and undissolved products of com- found , it was assumed that any boron in the sambustion . The filtrate , containing nitric and boric ple which was not titrated as boric acid in the water
acids, was titrated with O.I-N sodium hydroxide, soluble products remained in the insoluble residue
using a Beckmann pH meter to determine the end as boron nitride ; furthermore, it was assumed that
points. The amount of nitric acid present was any nitrogen in the borazine sample which was not
determined from the first titration curve; D-mannitol accounted for as nitric acid or boron nitride, was
was then added to the solution to form a complex present in the products as gaseous nitrogen. Nitrowith the boric acid and a decrease in the pH resulted; gen oxides were not found in the gaseous products
the amount of boric acid was determined from the of preliminary experiments.
Data for the borazine combustion experiments
second titration curve. No method was found for
making a quantitative separation of the insoluble are given in table 1. The am01lnts of nitric acid
products and glass fragments .
and of boric acid found in titrations are given in
the second and third columns. The ratio of boric
acid titrated to the boric acid calculated from the
4. Data and Discussion
weight of sample may be used as an indication of
completeness of combustion. BN is the amount
The atomic weights used are given in the Inter- of boron nitride in the products (by assumption);
national Table of Atomic Weights [12]. All heat it is the difference between the number of moles of
capacity data were taken from [13] except that of boron in the sample and the number of mol es of
borazine. No values for the density and heat boron titrated as boric acid.
capacity of liquid borazine were available, so the
, Made by the Consti tu tion and Microstructure Sectiou of t he Mineral Prod
corresponding val1les for liq1lid benzene were used, ucts
Division.
TAB LE
liNO,
Expt. No. t itrated
li 3BO,
titrated
--1
2
3
4
5
6
7
8
]v[ole
0.000980
. 000935
. 001073
. 001567
. 000996
.000878
. 000838
.000749
Mole
0.02016
. 02662
. 02362
. 03452
. 02745
. 01809
. 01908
. 02308
U,BO, titr.
II, BO, calc.
0.9920
. 9818
. 9885
. 9866
. 9850
. 9904
. 9856
. 9656
BN
1.
<
t.e
t.Rc
E.
q,
q.
W.C .
qBN
- t.EO(28 C )
- - - - - - - - - - - - - - - - - - --- - - Mole
0.000163
. 000493
. 000274
.000468
. 000419
. 000175
. 000278
. 000821
i /ohm
16.2
34. 6
41. 7
43.4
34.1
38. 5
32.5
41. 6
j/ohm
141,731. 3
141,749. 7
141 , 756.8
3 141, 726.8
141, 749.2
141, 753.6
141,747.6
141, 756.7
Ohm
0. 109885
. 145888
. 130025
. 189172
. 150439
. 099485
. 104598
. 128189
10.0
36.3
38.2
37. 1
37.0
37.5
37.4
37. 4
56.6
54. 0
62.0
90. 6
57.6
50.7
48.4
43.3
26.1
8.8
'7. 8
11. 5
9.1
6. 1
6.4
7.8
67.6
204.6
113. 7
194. 2
173. 9
72. 6
115. 4
340. 7
Gram
0.54555
. 72782
. 64141
. 93923
. 74811
. 49030
. 51966
. 64159
102
kjJmole
2301. 52
2301. 79
2316.90
2305.51
2305. 05
2314. 75
2303. 26
2314.50
2307. 91
2.26
(2)
919.131 .
I
6 39278
ogPmm= .
-(T-67 .198)'
this m ay b e used wit h the Cla usius-Clnpeyron
equation to obtain
M1v(25 DC) = 7.01 keal/mole.
6. References
[1] E. Wiberg and K . H er twig, Z. anorg. u. allgem. Chern.
255, 141 (1947).
[2] H . I. Schlesinger, D . M . Ritter , a nd A. B . Burg, J . Am.
Chern. Soc . 60, 1296 (1938).
[3] 'vV. V. Hough, G. W. Schaeffer, M. DZurLl S, and A. C.
Stewart, J . Am. Che rn. Soc . 77, 864 (1955).
[4] A. B. Burg and E. S. Kuljian, J. Am. Chern. Soc. 72,
3103 (1950).
[5] G. W . Schaeffer and E . R. Anderson, J . Am. Chern .
Soc. 71, 2143 (1949).
[6] E. R. va n Artsdale n and A. S. Dworkin, J. Am. Chem.
Soc. 74, 3401 (1952).
[7] A. Stock, E. Wiberg, and H . Martini B er . 63, 2927
(1930).
'
[8] A. Stock a nd E. Pohland , Ber . 59, 2215 (1926).
[9] E. Wiberg a nd A. Bolz, Ber. 73, 209 (1940) .
[10] R. Schaeffer, M. Steindler, L. Hohnstedt, H. S. Smith,
Jr. , L. B. E ddy, and H. 1. S chlesinger, J . Am. Chem.
Soc. 76, 3303 (1954).
[11] W . H . Johnson, E. J. Prose n, a nd F. D . Rossini , J .
R esearch NBS 35, 141 (1945) RP1420.
104