STUDIES ON RDX AND RELATED COMPOUNDS

IV. THE BACHklANN OR COh,lRINATION PROCESS1

Abstract
,,
r ~ snitric acid a n d ammonium nitrate
I h e eHect oi \.;lrying thc c o ~ l c c ~ i t r a t i oof
on the yield of RDX h a s been tletcrmined a t 35"C., using hesamine, hcsarnirie
rnononitrate, a n d h e s a ~ n i n edinitratc. T h e activation energies for the iormation
o i R D X from hcramine, hesaminc mononitratc, a n d hexalnine dinitrate were
iouncl to be approsimately 11 kcal., 12.5 kcal., and 16.5 kcal., respectively.

Introduction
.A srucl~.of the prodi~ctionof I'lDX' from ammonium nitrate, ~jnraformal-
cleh>.tlc,and acetic anli>.clride, reportecl in a previoi~spaper (2), inclicatetl that
hesamine clinitr-ate ancl nitric acicl were intermediates in t h e reaction. Con-
\.el-sion oi these intermecliates t o RDX presumably corresponcls t o t h e reactions
invol\.ed in the Uachmann process ( l j , in which tlie starting mater-ials are
Iiesaniinc, nitric acicl, alnmoniuni nitrate, and acetic anliyclr-icie in x glacial
acetic acid meclium ancl the reaction temperature is about 70°C.
Stitdies \\.ere therefore continuecl ~rsirig the Baclimann type of reaction
s!.stcm, since this perniittecl appropriate solcttions of Icnown concentrations of
hex;lniine, nitric acicl, ancl animonium nitrate t o be ilsed. T h e present stirdy
\\-as made t o cletermine tlie effect of var->ringtlie concentrations of animoniunl
nitrate ancl nitric acicl a t 3Ei°C., where kinetic studies are possible, ancl t o
determine t h e activation energies associatecl with certain simple steps possible
in the con\.ersion of Iiexar-nine to R D S .

Results and Discussion

T h e apparattls a n d techniqi~csi~secl\vere si~llilarin all essential respects to
K ~ C J clescriljecl
S ~ previously (2j.
Experimerlts t o clctermine the effect of nitric acicl concentration on ).ielcl,
and of ammonii~rnnitrate concentration on rate ant1 1.ielcl of RDX were made
i r ~clilferent types of reaction rneclia. One ol these consistccl of absolute nitric
acicl in acetic anhyclride, and two others contained absolute nitric acicl in
acetic anli!.clride - acetic acid mixtures of which the acetic anhydride contents
were 50% a n d 877;. I n three other analogous reaction systems the acetic
anhydride n a s replaced by propionic anhyclride, and the acetic acid b y pro-
pionic acicl. A few experiments were also m a d e with nitrogen pentoxide in
acetic anhq.clric1e.
1 illanziscri&t received A p r i l 19, 1951.
Co~ztri6zrbio?zf'romthe Physical Chentistry Laboratory, McGill U7tiversity, hfo7ttreu1, QuE.,
with financial assislance fro~tl the National Research Council o j Canada.
 TI'ZLLZAMS AND WZNKLER: STUDIES OF RDX AND R E L A T E D COd1.IPOC.VDS. It' 643

While the clifferent systems diftered in details of behavior with \.ariation of

reactant concentrations, the general t).pe of behavior observecl is iriclicated by
the results shown in Fig. 1. T h e rate and yield values were reprod~iciblclvitliin
about f 5%.

T h e o p t i ~ n a lnitric acid concentration a t 35OC. for various s>stelns st~rclied

are given in Table I. These values remained essentiall) unaltcrecl \\hell the
ammoniurn nitrate concentration was changetl from 1.5 to 3 rnolcs per mole
hesamine. No marked cliffererice in rate of formation or > ielcl of KDX n a s
observed when nitrogen pentoxide rather than absolute nitric acid n a s ilsed.
Some experiments with copper nitrate trihydrate slio~\edt h a t it too could serve
efficientl). as the source of nitric acid.

Optimal nitric acid concelltra~ion,

rnoles/molc hesarni~le
100"'
anhydride anhydride
Acetic anhyclricle
Hexarnine
I-Iexarnine
rnonoilitrate
Hexarnine
dinitrate
Propionic anhydride
Hexarnine
Hexarnine
dinitrate

T h e minimal concelitration of ammonium nitrate lor maximal ).ield of RDX

was found t o be between 5 and 6 moles per mole liexamine or its mono- or
dinitrate, in t h e various media used.
644 CANADIAN JOCXL-AL 01;C H E M I S T R Y . I'OL. 29

Througho~rtthe study, a marl~edsuperiority of acetic over 111-opionicall-

hydride was readily recognized in respect of both rate of prociuction and
yield of R D X (Table 11), a l t h o ~ ~ ginh the general trends ol rate and yield with
variation of nitric acid and ammonium nitrate there was little to clistinguish
the behavior of the two anh>.clrides.

RATESos PRODUCTIOS .\KO YIELDS OF RDX AT 35OC. I N ACETIC

AXD P R O P I O S I C .XSII\'DRIDIZ - ACID SYSTEMS

1 50%
anhydride
-
j 87%.
, arthydr~de ,
1 loo 51;
anhydride
x20sin
art11ydricle
) --

-4cetic anhydride
Rate* yo Yield I Rate* 47,Yield
---
Rate* %Yield Rates
- -- I-
Hexamine 6.2 34 5.6 34 6.8 25 5.6 25
Hesamine
dinitrate 6.8 28 1s 65 1 4 56 12,s 51

Propionic anhydride
Hexarnine 2.2 7.9 2. S 14 4.5 16 - -
Hexa~nine
dinitrate 1.1 / I8 3.4 31 5.6 29 - -

* Rates were determined f r o ~ nsr~~ootlred

reaction-tznze curves a n d ore e.vpressed a s per cent RDX
jormed'after 15 min. reactzot~. Bollr rates alrd yields are calcillated on the assrr~~rptiorrthat one
vrolc of ke.xartzine can tlreoreti~allyprodlrce two nloles o j R D X . Opti~n(zlc o ~ ~ c e ~ ~ tofr anitric
t~~r~
acid throzrghozrt.

-.
I he superiority of acetic anhydride may be partly ascl-ibed to a solve~it
effect ( 2 ) , but is probably concerned to a large extent with the production of
the active nitrolyzing agent. T h a t anhydride is i~lvolvedin this ma>-is indi-
cated b y the observation that prolonged azeotropic distillation with benzene
of reaction mixtures containing optimal hexarnine, nitric acid, and arnmoniurn
nitrate concentrations in acetic acid, nitromethane, or nitrobenzene, failed to
yield even traces of RDX. I f , ho~vever,as little as 8% acetic anhj-clricle mas
d d c d to such dried mixtures, appreciable yields of R D X were obtained. It
seems unlikely t h a t the active nitrolyzing agent produced in the presence of
a n h ~ d r i d eis acetyl (or propyl) nitrate (3), but it might be nitrogen pentoside
or a cationic agent resulting from dehj-dration of nitric acid (ci. 4).

Activatio7z Energies for the Conversion of I$e.vamine, I e x a n z i n e ibIono~titrafe,and

Hexamine Dinitrate to R D X
Rates of R D X formation were determined a t different tenlperatures using
hexamine, or one of its nitrates, in the presence of the corresponding optimal
amounts of nitric acid and ammonium nitrate. Initial rates of R D X formation
were used for calculating the activation energies ,with an error estimated to be
of the order f 1.0 kcal.
 I [ . I L L I A I I S A X D I V I N K L E R : S T C D I E S O F RD.Y .4XD R E L A T E D COdfP0Li.VD.S. 11.- ,645

The activation energies obtained in the temperature range 20° to 40°C., from
rates determined a t 5 O interlrals, \\.ere:
Hexamine 11 kcal.
Hexanline monoriitrate 12.5 kcal.
Hexamine cli11it1-ate16.5 kcal.
While therc is probnl,l>- ILO significant difference between the first two values,
the value for hexamine clinitrate was significantly higher. These activatioll
er~crgies\\~oulclseem to indicate that hexamine dinitrate is not an intermediate
in the conversion of hesaminc to RDX by the Bachmann reaction a t 35OC.
There remain the possibilities that neither nitrate, or alternativel!. that the
mononitrate, is involved in this reaction. I t is the intention to present evidence
in favor of the secontl possibility in a subsequent paper dealing with the thermo-
chemistry of the s).stem.

Acknowledgment
Grateful aclino~vledgrnentis made to the committee on Research, McGill
Universit!., for financial assistance in the preparation oi this manuscript.

References
N NE., and SHEL:.HAS,
1. B A Z H ~ I ALV. J. C. J. .Am. Chern. Soc. 71: 1842. 1919.
2. GILLIES, A., WILLILXIS, H. L., ;i~ld\VI!INKLER,C. A. Can. J. Chern. 29: 377. 1951.
3 . McI<.ku,: I n . H., and WRIGIIT,G. F Can. J. Research, U , 27: 462. 1949.
. , R r c ~ ~ o uEI.
F.
4. VROOM,A. Ti. and \YINKLER, C. :I. Can. J. Research, B, 28: 701. 1950.
This article has been cited by:

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Evaluation of Bachmann Process for RDX Synthesis. International Journal of Chemical Reactor Engineering, ahead of print.
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