Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Save to My Library
Look up keyword
Like this
1Activity
0 of .
Results for:
No results containing your search query
P. 1
40387212-PETN-Solubility

40387212-PETN-Solubility

Ratings: (0)|Views: 201|Likes:
Published by lmajoris

More info:

Published by: lmajoris on Jan 28, 2011
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

01/28/2011

pdf

text

original

 
August,
1958
SOLUBILITY
F
PENTAERYTHRITOL
ETRANITRATE
1009
SOLUBILITY
OF
PENTAERYTHRITOL TETRANITRATE'
BY
ROBERT
.
ROBERTS
ND
ROBERT
.
DINEGAR
University
of
California, Los
Alamos
Scientijk
Laboratory,
Los
Alamos,
New
Mexico
Received
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
solutionsrelating the tem erature coefficient
of
solubility with the heat of solution
of
the solute. The heat
of
!usion of PETN hasbeen estimated
Lorn
these experiments
as
23-24
kcal. mole.-'
IntroductionPentaerythritol tetranitrate, PETN, is an ex-plosive organic nitrate ester that has been knownfor more than fifty years.
It
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
of
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.
It
is thus evident that for purification reasonsalone precise solubility data on PETN are desirable.An investigation of the available literature brings
to
light that this problem has been investigated
at
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.
140.1°),6
was added to the solvent' in
a
solution
flask
connected by an immersion filter
to
a
weighing bottle.The entire apparatus was then thermostated and the solutionstirred magnetically until equilibrium was attained.8Afterthe given time
a
portion
of
the solution was transferred tothe weighing bottle by means of
a
hand
as
irator.Afterremoving the entire apparatus from the tfermostat, thereceiving
flask
was detached and the weight
of
PETN perwei ht of solvent was found in the following manner.8eighing
of
the sample ffask enabled the weight of soluteplus solvent to be determined. Distilled water8 was then
(1)
Thia
work
was done under the auspices
of
the Atomic Energy
(2)
L.
Vignon and
F.
Gerin.
Compt.
Tend.,
188,
690
(1901).
(3)
W.
Fredrick and
W.
Brun.
Be?.,
63,
2681
(1930).
(4)
T.
Urbanski and
B.
Kwiatkowski,
Roczniki Chem.,
18,
741
(6)
J.
Tranchant,
Mcm.
Poudres,
84,
117
(1962);
P.
Aubertein,
(6)
Original commercial product was obtained from Trojan Powder
(7)
Analytical reagent grade,
used
without further purification.
(8)
t was found that after several hours equilibrium was est,ab-lished. All solutions mentioned in this report were held
at
constanttemperature for
at
least
8
hours
before analysis of the Bolution tookplaoe.Commission.
(1933).
Mem.
POUdTe8,
84,
107
(1962).Company, Allentown,
Pa.
added to the flask and the entire sample heated to constantweight at about
90O.10
The weight
of
solid PETN
was
thendetermined and the solubility easily calculated.
Discussion
of
Experimental ResultsThe solubility of PETN in g. PETN/kg.
sol-
vent, for the solvents acetone, aqueous acetone,ethyl acetate, benzene and ethyl alcohol,
is
given inTables
I
and
11.
TABLE
Temp.,
A.
288.2293.2298.2303.2313.2323.2293.2303.2313.2323.2293.2303.2313.2323.2333.2293.2303.2313.2323.2333.2
Solubilityg. PETN/&.solvent
Acetone
208.10f0.10248.40
f
.50305.60f0.50345.30f0.20449.20
f
.20587.603t3.70106.19f2.07140.62
f
.15185.00f0.23241.93f0.43
Ethyl acetateBenzene
2 75f0.154.96
f
.088.34
f
.1814.48f0.3125.89f0.03
Ethyl alcohol
1.25 0.012.13
f
.013.78f 0.02
6.57
i
.18
11.96It0.06
It
easily can be demonstrated that a plot
of
thenatural logarithm of the mole fraction of solutedissolved (In
Nz)
versus
the reciprocal of the abso-lute temperature is a straight line for all the
sol-
vents investigated. Their slopes, the temperaturecoefficients of solubility, differ, however, and areshown in Table
111.
In general, they are observed
to
decrease with an increase
in
solubility.'l
(9)
The addition
of
water is neoessary whether
it
be miscible
with
the aolvent (aoetone, ethyl alcohol, ethyl acetate) or
not
(benzene)to prohibit the occlusion
of
solvent as the sample approaches dryness.
(10)
Drying temperatures above
90°
cannot be used due to decom-position
of
solid PETN.
(11)
The chance that
a
change in molecular weight of the dissolvedPETN contributed
to
the various values
of
the slopes obtained waaobviated by measuring the apparent molecular weight by the methodof Lhe elevation
of
the aolvent boiling'point. The value obtained
for
PETN in all four solvents was
318
zt
1-a
figure less than
1%
dif-ferent
from
the monomeric
PETN
value
of
316.
It
is
evident that
no
appreciable assooiation, dkaociation, etc.,
oocura
in these solvents.
 
1010
ROBERT
,
ROBERTS
ND
ROBERT
,
DINEGAR
Vol.
62
Temp.,
A.
293.2298.2303.2313.2
TABLE
1
Aqueousacetone
%
wat,e;
by
wt.
6.2312.3018.2223.9935.1155.806.2312.3018.2223.9935.1155.806.2312,3018.2223.9935.1155.806.2312.3018.2223.9935.1155.80
TABLE
11
Solvent
Ethyl acetateAcetoneBenzeneEthyl alcohol
Solubility,
g.
PETN/kg.
solvent
162.91f0.1793.12f0.0552.22f0.1028.68f0.056.80
f
0.030.25
f
.004
19O.86fO0.09114.62f 0.1066.12f0.0836.66f0.059.25
f
.030.38f0.003225.92
f
0.26137.37 f0.2181.83f0.1046.53f0.0412.57 f0.030.57f0.009314.21
f
.03.202.53f0.17126.58f0.2676.60f0.1923.30f0.171.26
f
0.01
A
In
Nz
cal.
mole-1
430049701094511000
Consider the following equation which repre-sents the solubility equilibrium
solid solute
(SZ)
=
saturated solution
(SSz)
(1)
The thermodynamic equilibrium constant
K
interms of activities
(A),
s
AssnlAsn
(2)
Since the activity
(Asz)
of
the pure solute isunity, by definitionor
K
(3)
K
fzNz
I
1
10 20 3040 50 60 70
80
90
Wt.
70
HzO.
Fig,
1.
with
fa
=
activity coefficient
of
the solute in thesaturated solution.
If
one considers the relationship between thetemperature dependence of the Gibbs free energychange and the thermodynamic equilibrium con-stant, the van’t
Hoff
isochore results
d
In
K
AH0
dT
RT’
where
AHo
=
difference in the molal heat contentbetween the standard state
of
reactants (pure
sol-
ute
H)
and products (solution
of
infinite dilution,
HO).
(4)
=-
Substitution
of
K
=
fZNz
n
(4)
ivesSinceEquation
5
becomes
Nowla
Substitution in
(6)
givesand, for any concentration
of
soluteIn generalwith
AH8,,1
=
AHi
+
AH,AHf
=
heat
of
fusion of solute (at the specific conditions)
AHm
=
heat effect
of
mixing liquid solute with solvent
AHf
=
AHf*,
he calorimetric (true) heat
of
fusiononly when there is no interaction between soluteand solvent-and at this point
AH,
=
0,
making,
TABLE
V
wt.
%
0
6.2312.3018.2223.9935.1155.80
water
A
In
N2
4.97
x
108
5.896.998.108.9711.3615.06190.00 23.4
AHt*
simultaneously
AHsOl
=
AHf”.
Thus [d In
Nz/
d(l/T)],,t
is proportional to
aMf*,
a constant, only
(12)
G. N.
Lev&
and
M.
Randall,
“Thermodyasmica,”
McGraw-Bill
Book
OQ.,
Now
York,
W.
Y,,
1823,
p.
W0.
V

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->