The solubility of pentserythritol tetrsnitrate (PETN) in acetone, aqueous acetone, ethyl alcohol, ethyl acetate and ben-zene has been measured as
function of temperature. The data have been analyzed in terms of the e uations
solutionsrelating the tem erature coefficient
solubility with the heat of solution
the solute. The heat
!usion of PETN hasbeen estimated
IntroductionPentaerythritol tetranitrate, PETN, is an ex-plosive organic nitrate ester that has been knownfor more than fifty years.
is normally preparedby the simple nitration of pentaerythritol, duringwhich process the four hydroxyl groups are replacedby nitrate groups.2The preparation of pentaerythritol, however, bythe condensation of formaldehyde and acetaldehyde, in the presence of Ca(OH)2,has been shownby Fredrick and Bruna to give rise to certain by-products, the most important being dipentaerythri-tol. This latter consists of two pentaerythritolnuclei, formed from two of the methylol groups pro-duced by the reaction of three moles of formalde-hyde with one mole of acetaldehyde and the sub-sequent reduction of the aldehyde group
tri-methylol acetaldehyde by a fourth mole of formal-dehyde, joined by an ether linkage.Dipentaerythritol, DIPE, gives a hexsnitrateupon nitration, DIPEHN, which must be sepa-rated from PETN by its solubility difference inaqueous acetone.
is thus evident that for purification reasonsalone precise solubility data on PETN are desirable.An investigation of the available literature brings
light that this problem has been investigated
least thrice bef0re.~.6 Since these data, however,are not in agreement with each other, a general re-investigation of the problem for certain common,useful solvents was attempted.Experimental Procedure
Excess dried PETN, three times recrystallized from ace-tone, (m.p.
was added to the solvent' in
connected by an immersion filter
weighing bottle.The entire apparatus was then thermostated and the solutionstirred magnetically until equilibrium was attained.8Afterthe given time
the solution was transferred tothe weighing bottle by means of
irator.Afterremoving the entire apparatus from the tfermostat, thereceiving
was detached and the weight
PETN perwei ht of solvent was found in the following manner.8eighing
the sample ffask enabled the weight of soluteplus solvent to be determined. Distilled water8 was then
was done under the auspices
the Atomic Energy
Original commercial product was obtained from Trojan Powder
Analytical reagent grade,
without further purification.
t was found that after several hours equilibrium was est,ab-lished. All solutions mentioned in this report were held
before analysis of the Bolution tookplaoe.Commission.
added to the flask and the entire sample heated to constantweight at about
thendetermined and the solubility easily calculated.
Experimental ResultsThe solubility of PETN in g. PETN/kg.
vent, for the solvents acetone, aqueous acetone,ethyl acetate, benzene and ethyl alcohol,
easily can be demonstrated that a plot
thenatural logarithm of the mole fraction of solutedissolved (In
the reciprocal of the abso-lute temperature is a straight line for all the
vents investigated. Their slopes, the temperaturecoefficients of solubility, differ, however, and areshown in Table
In general, they are observed
decrease with an increase
water is neoessary whether
the aolvent (aoetone, ethyl alcohol, ethyl acetate) or
(benzene)to prohibit the occlusion
solvent as the sample approaches dryness.
Drying temperatures above
cannot be used due to decom-position
The chance that
change in molecular weight of the dissolvedPETN contributed
the various values
the slopes obtained waaobviated by measuring the apparent molecular weight by the methodof Lhe elevation
the aolvent boiling'point. The value obtained
PETN in all four solvents was
figure less than
appreciable assooiation, dkaociation, etc.,
in these solvents.