August, 1958 SOLUBILITY TETRANITRATE

OF PENTAERYTHRITOL 1009

SOLUBILITY OF PENTAERYTHRITOL TETRANITRATE'

BY ROBERT
N. ROBERTS H. DINEGAR
AND ROBERT
University of California, Los Alamos Scientijk Laboratory, Los Alamos, New Mexico
R e c e i v e d May 14, 1068

The solubility of pentserythritol tetrsnitrate (PETN) in acetone, aqueous acetone, ethyl alcohol, ethyl acetate and ben-
zene has been measured as a function of temperature. The data have been analyzed in terms of the e uations of solutions
relating the tem erature coefficient of solubility with the heat of solution of the solute. The heat of !usion of PETN has
been estimated Lorn these experiments as 23-24 kcal. mole.-'

Introduction added to the flask and the entire sample heated to constant
weight a t about 9 0 O . 1 0 The weight of solid PETN was then
Pentaerythritol tetranitrate, PETN, is an ex- determined and the solubility easily calculated.
plosive organic nitrate ester that has been known
for more than fifty years. It is normally prepared Discussion of Experimental Results
by the simple nitration of pentaerythritol, during The solubility of PETN in g. PETN/kg. sol-
which process the four hydroxyl groups are replaced vent, for the solvents acetone, aqueous acetone,
by nitrate groups.2 ethyl acetate, benzene and ethyl alcohol, is given in
The preparation of pentaerythritol, however, by Tables I and 11.
the condensation of formaldehyde and acetalde TABLE
I
hyde, in the presence of Ca(OH)2,has been shown Solubility
Temp., g. PETN/&.
by Fredrick and Bruna to give rise to certain by- A. solvent
products, the most important being dipentaerythri- Acetone
tol. This latter consists of two pentaerythritol 288.2 208.10f0.10
nuclei, formed from two of the methylol groups pro- 293.2 248.40 f 0.50
duced by the reaction of three moles of formalde- 298.2 305.60f0.50
hyde with one mole of acetaldehyde and the sub- 303.2 345.30f0.20
sequent reduction of the aldehyde group of tri- 313.2 449.20 f 0.20
methylol acetaldehyde by a fourth mole of formal- 323.2 587.603t3.70
dehyde, joined by an ether linkage.
Dipentaerythritol, DIPE, gives a hexsnitrate Ethyl acetate
upon nitration, DIPEHN, which must be sepa- 293.2 106.19f2.07
rated from PETN by its solubility difference in 303.2 140.62 f 0.15
aqueous acetone. a 313.2 185.00f0.23
It is thus evident that for purification reasons 323.2 241.93f0.43
alone precise solubility data on PETN are desirable. Benzene
An investigation of the available literature brings 293.2 2 75f0.15
to light that this problem has been investigated at 303.2 4.96 f 0.08
least thrice bef0re.~.6 Since these data, however, 313.2 8 . 3 4 f 0.18
are not in agreement with each other, a general re- 323.2 14.48f0.31
investigation of the problem for certain common, 333.2 25.89f0.03
useful solvents was attempted. Ethyl alcohol
Experimental Procedure 293.2 1.25 0.01
Excess dried PETN, three times recrystallized from ace- 303.2 2.13 f 0.01
tone, (m.p. 140.1°),6was added to the solvent' in a solution 313.2 3 . 7 8 f 0.02
flask connected by an immersion filter to a weighing bottle. 6 . 5 7 i 0.18
The entire apparatus was then thermostated and the solution 323.2
stirred magnetically until equilibrium was attained.8 After 333.2 11.96It0.06
the given time a portion of the solution was transferred to
the weighing bottle by means of a hand as irator. After It easily can be demonstrated that a plot of the
removing the entire apparatus from the tfermostat, the natural logarithm of the mole fraction of solute
receiving flask was detached and the weight of PETN per dissolved (In Nz) versus the reciprocal of the abso-
wei h t of solvent was found in the following manner.
8eighing of the sample ffask enabled the weight of solute lute temperature is a straight line for all the sol-
plus solvent to be determined. Distilled water8 was then vents investigated. Their slopes, the temperature
coefficients of solubility, differ, however, and are
(1) Thia work was done under the auspices of the Atomic Energy shown in Table 111. In general, they are observed
Commission.
(2) L. Vignon and F. Gerin. Compt. Tend., 188, 690 (1901).
t o decrease with an increase in solubility.'l
(3) W. Fredrick and W. Brun. Be?., 63, 2681 (1930). (9) The addition of water is neoessary whether it be miscible with
(4) T. Urbanski and B. Kwiatkowski, Roczniki Chem., 18, 741 the aolvent (aoetone, ethyl alcohol, ethyl acetate) or not (benzene)
(1933). to prohibit the occlusion of solvent as the sample approaches dryness.
(6) J. Tranchant, Mcm. P o u d r e s , 84, 117 (1962); P. Aubertein, (10) Drying temperatures above 90° cannot be used due t o decom-
Mem. P O U d T e 8 , 84, 107 (1962). position of solid PETN.
(6) Original commercial product was obtained from Trojan Powder (11) The chance that a change in molecular weight of the dissolved
Company, Allentown, Pa. P E T N contributed to the various values of the slopes obtained waa
(7) Analytical reagent grade, used without further purification. obviated by measuring the apparent molecular weight by the method
(8)I t was found t h a t after several hours equilibrium was est,ab- of Lhe elevation of the aolvent boiling'point. The value obtained for
lished. All solutions mentioned in this report were held at constant P E T N in all four solvents was 318 zt 1-a figure less than 1% dif-
temperature for at least 8 hours before analysis of the Bolution took ferent from the monomeric PETN value of 316. It is evident that
plaoe. no appreciable assooiation, dkaociation, etc., oocura in these solvents.
1010 N, ROBERTS
ROBERT H, DINEGAR
AND ROBERT Vol. 62

I1
TABLE with fa = activity coefficient of the solute in the
Aqueous
acetone Solubility,
saturated solution.
Temp., % wat,e; g. PETN/kg. If one considers the relationship between the
A. by wt. solvent temperature dependence of the Gibbs free energy
293.2 6.23 162.91f0.17 change and the thermodynamic equilibrium con-
12.30 93.12f0.05 stant, the van’t Hoff isochore results
18.22 52.22f0.10
In-K
-d = AH0
23.99 28.68f0.05 (4)
35.11 6.80 f 0.03
dT RT’
55.80 0.25 f 0.004 where AHo = difference in the molal heat content
298.2 6.23 19O.86fO0.09 between the standard state of reactants (pure sol-
12.30 1 1 4 . 6 2 f 0.10 ute H) and products (solution of infinite dilution,
18.22 66.12f0.08 HO). Substitution of K = fZNzin (4)gives
23.99 36.66f0.05
35.11 9.25 f 0.03
55.80 0.38f0.003 Since
303.2 6.23 225.92 f 0.26
12,30 137.37 f 0 . 2 1
18.22 81.83f0.10
23.99 46.53f0.04 Equation 5 becomes
35.11 12.57 f 0 . 0 3
55.80 0.57f0.009
313.2 6.23 314.21 f 0.03.
12.30 202.53f0.17
18.22 126.58f0.26 Nowla
23.99 76.60f0.19
35.11 23.30f0.17
55.80 1.26 f 0.01
Substitution in (6) gives
I11
TABLE
A In Nz
Solvent cal. mole-1
Ethyl acetate 4300
Acetone 4970 and, for any concentration of solute
Benzene 10945
Ethyl alcohol 11000
Consider the following equation which repre- In general
sents the solubility equilibrium
solid solute (SZ) = saturated solution (SSz)
AH8,,1 = AHi + AH,
(1) with
The thermodynamic equilibrium constant K in AHf = heat of fusion of solute (at the specific conditions)
terms of activities ( A ) ,is AHm = heat effect of mixing liquid solute with solvent
AssnlAsn (2) AHf = AHf*,the calorimetric (true) heat of fusion
Since the activity (Asz) of the pure solute is only when there is no interaction between solute
unity, by definition and solvent-and at this point AH, = 0, making,
K (3)
or IV
TABLE
A In N2 V
K fzNz wt. %
water
I 1
0 4.97 x 108
6.23 5.89
12.30 6.99
18.22 8.10
23.99 8.97
35.11 11.36
55.80 15.06

190.00 23.4 AHt*

simultaneously AHsOl = AHf”. Thus [d In Nz/
10 20 30’ 40 50 60 70 80 90 d(l/T)],,t is proportional to aMf*, a constant, only
Wt. 70HzO. (12) G. N. Lev& and M. Randall, “Thermodyasmica,” McGraw-
Fig, 1. Bill Book OQ., Now York, W. Y,, 1823, p. W0.
August, 1958 REACTION ATOMSWITH SOLIDOLEFINS
OF HYDROGEN I011

(1) when the solution is ideal, or (2) when the
solution is at infinite dilution.
Since none of the PETN solutions are ideal the or-
ganic solvent experimental results are in line with
equation 8 which predicts a lower temperature coef-
ficient of solubilitv in those solvents that have the
greater disso1ving"power as indicated by [b In fi/
bNz]~.
The PETN aqueous acetone solutions likewise are
non-ideal and it is seen in Table IV that R [A In Nz/
A(l/T)ISatincreases as the weight per cent. water in
the aqueous acetone mixture increases-the solu-
tion becoming correspondingly more dilute at sat-
uration with respect to PETN. In addition to an
interpretation similar to that mentioned for or-
ganic solvents. the aaueous solutions allow an es-
h a t i o n of A k f * , f o r an extrapolation of R [ A In
N2/A(l/T)]sat to pure water (infinitely dilute
PETN solution) meets criterion (2) of equation 8.
Table IV and Fig. 1 show these results.

THE REACTION OF HYDROGEN ATOMS WITH SOLID OLEFINS AT -19501

BY RALPHK L E I NAND
~ ~ MILTOND. S C H E E R ~ ~
National Bureau of Standards, Washington, D.C.
Received May 16, 1068

Hydrogen atoms, produced on the surface of a hot tungsten ribbon, react readily with certain olefins condensed a t - 195'.
Of the olefins investigated, propene, butene-1, 3-methylbutene-1, 2-methylbutene-1 and isobutene show rapid hydrogen
uptake. Butadiene-1-3 pentene-1 and 3,3-dimethylbutene-l react very slowly. trans-Butene-2 and hexene-1 show no
measurable reaction. +hese rate differences are ascribed to small differences in activation energies which readily are ob-
served at these low tem eratures. The mechanism of the reaction appears to involve two consecutive H atom additions
in which an alkyl radicaf resulting from the hydrogenation of the olefin, can be further hydrogenated to the alkane. The
possibility of alkyl radical stabilization in sizeable concentrations is indicated.

I. Introduction action at -195". Darwent and Roberts give the

Hydrogen atoms react with some solid olefins at value 5 kcal./mole for D atom addition to propene.
- 195°.3 The occurrence of this reaction provides Analysis of the dimerization products for this re-
action shows that addition occurs almost completely
a possible method for the preparation of alkyl
radicals stabilized in a matrix. A study of the on the terminal carbon of a primary ~ l e f i n . Our
~
kinetics of the low temperature hydrogen atom observations are in accord with this work.
addition process gives detailed information concern- II. Experimental
ing the relative reactivities of various olefins. It is The addition of H atoms to solid olefins a t -195' was
found that hydrogen atoms diffuse readily through observed by exposing the olefin, uniformly condensed on
solid hydrocarbons and, in the case of olefins, the inner surface of a one-liter bulb, to atoms produced on a
reaction can occur through the bulk of the solid. heated tungsten ribbon.8 The ribbon, 2 cm. by '/z cm.,
The existence of measurable rates of reaction under was welded to heavy nickel leads. These in turn were
mounted in the vessel through kovar-glass seals. The metal
these conditions makes possible the detection of components were electropolished prior to final assembly.
small differences in activation energy. Propene, The ribbon was heated electrically and the current was con-
for example, can be hydrogenated almost com- trolled by an auto-transformer operating from a constant
pletely, while hexene-1 does not react. voltage source. The temperature of the filament was ob-
served with a micro-optical pyrometer.
Extensive work has been reported on the gas A layer of high purity olefin, lO-6-lO-* cm. thick, was
phase H atom addition to ~ l e h s , ~ -but
- ' ~consider- deposited on the inner surface of the reaction vessel. Hy-
able variation exists in reported values for the acti- drogen was introduced by diffusion through a heated palla-
vation energy, Melville and Robb give the value dium thimble to pressures of from 20 to 100 p . Pressures
were measured by a thermocouple gauge, overdriven for in-
of 2.5 kcal. per mole with little difference among creased sensitivity, and calibrated for hydrogen with a
the olefins studied. Rabinowitch, Davis and Wink- McLeod gauge. Changes of as little as 0.1 p could be
ler give 10.8 kcal./mole for propene, but this is not measured. Rates of reaction were followed by recording
consistent with the occurrence of the addition re- the preRsure drop, pressure measurements being made with
the tungsten ribbon a t operating temperature.
(1) This researoh wag performed under the National Bureau of Observations have been made on the hydrogen pickup by
Standards Free Radicals Research Program, supported by the De- the following olefins, listed in order of decreasing rate: pro-
partment of the Army.
(2) (a) Guest Scientist, Oh-Mathieson Chemioal Corporation;
gene, butene-1, isobutene, 3-methylbutene-1, Z-methyl-
utene-1, pentene-1, 3,3-dimethylbutene-1, butadiene-1,3.
(b) Guest Scientist, General Electrio Co., Cincinnati, Ohio. The last three of these have very slow rates. Hexene-1 and
(3) R. Klein and M. D. Scheer, J . Am. Chem. Soc., 80, 1007 (1958). trans-butene-2 show no measurable pickup.
(4) K. H.Geib and P. Harteck, Ber., 66B, 1816 (1933). The analysis of the products of the hydrogenation of
(5) W. J. Moore, Jr., and H. S. Taylor, J . Chem. Phys., 8 , 604 butene-1 and propene, using a mass spectrometer, gave the
(1940). results shown in Table I.
(6) D. J. LeRoy and E. W. R. Steacie, ibid., 10, 676 (1942); 10, The rate a t which atoms impinge on the olefin surface is
683 (1942). proportional to the rate a t which they are formed by dis-
(7) H. W. Melville and J. C. Robb, Proc. R o y . SOC.(London),8196, sociation of H
z on the hot ribbon. This in turn is governed
494 (1949). by the rate of arrival of hydrogen molecules a t the ribbon
(8) B. de B. Darwent and R. Roberts, Dis. Faraday SOC.,14, 65 (determined by the pressure) and the ribbon temperature.
(1953). The rate of hydrogen uptake by butene-1 as a function of the
(9) W. J. Moore, Jr., and L. A. Wall, J . Chem. P h y s . , 17, 1325 tungsten ribbon temperature was measured. The rates
(1949). were taken as the reciprocal of the time required for the
(10) B. S. Rabinowitch. 8. G. Davis and C. A. Winkler, Can. J . pressure to decrease from 31 to 25 p . The results are
Rse.. B21, 251 (1943). shown as an Arrhenius plot in Fig. 1.