P 011528Z OCT 08
FM SECSTATE WASHDC
TO AMEMBASSY CANBERRA PRIORITY
AMEMBASSY LONDON PRIORITY
AMEMBASSY PARIS PRIORITY
INFO MISSILE TECHNOLOGY CONTROL REGIME COLLECTIVE PRIORITY

C O N F I D E N T I A L STATE 104822 
 
 
PARIS FOR EST: HELEN SMITH 
LONDON FOR CHRIS PALMER 
CANBERRA FOR CAROL HANLON 
 
E.O. 12958: DECL: 10/01/2033 
TAGS: MTCRE ETTC KSCA MNUC PARM TSPA FR UK AS
 
SUBJECT: MISSILE TECHNOLOGY CONTROL REGIME (MTCR): THE 
PERCHLORATE FAMILY OF CHEMICALS 
 
Classified By: ISN/MTR Director Pam Durham. 
Reasons:  1.4 (B), (D), (H). 
 
¶1. (U)  This is an action request.  Please see paragraph 2. 
 
¶2. (C)  ACTION REQUEST:  Department requests Embassy Paris 
provide the interagency cleared paper "The Perchlorate Family 
of Chemicals" in paragraph 3 below to the French Missile 
Technology Control Regime (MTCR) Point of Contact (POC) for 
distribution to all Partners.  Department also requests 
Embassy London provide paper to the MTCR Information Exchange 
(IE) Co-Chair (John Andrews), and Embassy Canberra provide 
paper to the Australian MTCR Plenary Chair for 2008/2009 
and/or appropriate staff.  Info addressees also may provide 
to host government officials as appropriate.  In delivering 
paper, posts should indicate that the U.S. is sharing this 
paper as part of our preparation for the Information Exchange 
that will be held in conjunction with the MTCR Plenary in 
Canberra (November 3-7).  NOTE:  Additional IE papers will be 
provided via septels.  END NOTE. 
 
¶3. (C) BEGIN TEXT OF PAPER: 
 
(CONFIDENTIAL REL MTCR) 
 
 
       The Perchlorate Family of Chemicals 
 
Perchlorate is the chemical name used for the salts of 
perchloric acid.  All perchlorates are strong oxidizing 
agents, and as such, they have found application in energetic 
formulations to include propellants, explosives, and 
pyrotechnics.  Numerous perchlorate salts exist.  However, 
this paper will only deal with ammonium perchlorate (NH4ClO4, 
AP), potassium perchlorate (KClO4, KP, or PP) and sodium 
perchlorate (NaClO4, NaP, or SP) because of either their 
energetic properties or their potential use in creating more 
energetic perchlorates.  AP is the most important perchlorate 
in terms of solid propellants for ballistic missiles and is 
controlled specifically by the Missile Technology Control 
Regime (MTCR).  Neither KP nor NaP is controlled specifically 
by the MTCR.  KP has limited value in solid propellants for 
ballistic missiles, although it may be used in a mixture for 
igniters.  There is no known use of NaP directly in solid 
propellants for ballistic missiles.  However, both NaP and KP 
can be converted to 
 AP. 
 
This paper will discuss the preparation of perchlorates, the 
use of perchlorates in energetic formulations with emphasis 
on solid propellants for ballistic missiles, and the current 
MTCR controls on perchlorates. 
 
Preparation of Perchlorates 
 
Almost all commercial perchlorate preparation-including that 
of AP and KP-involves the oxidation of sodium chloride to 
sodium perchlorate.  Sodium perchlorate is most often 
converted to the other more widely used perchlorate salts 
including AP and KP, but can also be used itself in some 
applications. 
 
Complete preparation of perchlorates can be costly in terms 
of resource consumption and technical expertise.  Both 
processes, oxidation to sodium perchlorate and conversion of 
sodium perchlorate to other perchlorate salts, require some 
degree of technical know-how and equipment.  The oxidation 
process is a larger technical challenge and requires more 
specialized equipment.  On the other hand, conversion of 
sodium perchlorate to AP or KP is much simpler, and the 
purchase of sodium perchlorate may be more attractive to 
programs of concern since it avoids the expense and 
difficulties of the sodium perchlorate oxidation process. 
Therefore, the lack of MTCR control on sodium perchlorate 
allows for the potential for a country/entity to make AP with 
less investment in equipment, facilities, and process 
engineering. 
 
 
Oxidization of Sodium Chlorate and Sodium Perchlorate 
 
The oxidation of sodium chloride to sodium perchlorate is 
conducted in two stages.  Sodium chloride (NaCl) is first 
oxidized to sodium chlorate (NaClO3) and then to sodium 
perchlorate (NaClO4).  Both oxidation stages are electrolytic 
(electrochemical) processes conducted in aqueous solution. 
Water is the source of oxygen incorporated into the chloride 
to make the chlorate and perchlorate species.  Sodium 
chloride is the best starting material for the synthesis of 
chlorates and perchlorates by this process because all of the 
sodium salts (chloride, chlorate, and perchlorate) are 
readily soluble in water. 
 
The oxidation of sodium chloride to sodium chlorate and 
sodium perchlorate normally requires two steps and requires 
specialized equipment (electrolytic cells and anodes) and 
substantial technical knowledge to engineer the process and 
to make and maintain the equipment.  The oxidation steps also 
require significant electrical power input, and the cost of 
the electrical power must be reasonably inexpensive to make 
low-cost perchlorate.  The second stage of the oxidation 
process requires substantially more electric power because it 
becomes more difficult to add the fourth oxygen atom to the 
molecule in the conversion of chlorate to perchlorate. 
 
At the completion of the second oxidation stage, sodium 
perchlorate, typically in the form of its monohydrate (NaClO4 
with one H2O) can be obtained from the aqueous solution by 
concentration, precipitation, and filtration.  However, since 
sodium perchlorate has only limited uses, the aqueous 
solution of sodium perchlorate is more often used in the 
preparation of other perchlorates such as AP and KP. 
 
Conversion of Sodium Perchlorate to AP and KP 
 
Both AP and KP are less water soluble than NaP.  Therefore, 
they can readily be precipitated from an aqueous solution of 
NaP by addition of the appropriate ammonium or potassium 
salt.  For example, to make AP, ammonium chloride can be 
added to precipitate AP and leave the very soluble sodium 
chloride in solution.  Conversely, to make KP, potassium 
chloride is added to precipitate KP and leave sodium chloride 
in solution.  Both AP and KP can be isolated in good yield by 
concentration, precipitation, and filtration.  The isolated 
perchlorate (either AP or KP) is typically recrystallized 
from water to obtain the desired purity and particle size 
before further use. 
 
The process equipment used to convert sodium perchlorate to 
AP or KP is not specialized and involves relatively low 
technology.  It is an ordinary assemblage of steel, tanks, 
pumps, heat exchanger, and piping. 
 
 
Other Conversion Processes for KP to AP 
 
Processes to convert KP to AP have been reported in the 
chemical literature and several patents exist.  These 
processes will not be discussed in detail, however, as they 
generally involve non-aqueous solvents and/or ion exchange 
resins.  The use of these types of organic materials with 
perchlorates poses increased safety risks (fire and 
explosion) compared to the aqueous process used in the 
conversion of NaP to AP.  Furthermore, we are not aware of 
the large-scale, commercial demonstration of any of the 
processes for converting KP to AP.  However, the existence of 
these potential processes for conversion of KP to AP must be 
acknowledged.  These processes could be used by a 
country/entity that needs AP, but lacks the ability to 
make/obtain NaP and has access to KP. 
 
Uses of AP, KP, and NaP 
 
AP is the most widely used oxidizer in solid propellant 
formulations.  AP can also be used in explosive and 
pyrotechnic formulations.  Typical composite propellants 
contain 60 to 70% AP.  Solid rocket motors used in the 
various stages of ballistic missiles are loaded with 
thousands of kilograms of propellant.  Therefore, large 
quantities of low-cost, high-quality AP are required to make 
a substantial number of ballistic missiles of any type. 
 
KP can be used as an oxidizer in solid propellant 
formulations, but it is inferior to AP in terms of 
performance.  The theoretical specific impulse values of 
KP-based formulations are approximately 15% lower than 
corresponding AP-based formulations. The low performance 
compared to AP is the principle reason KP is not widely used 
in ballistic missiles. However, in the past KP has been used 
in some solid rocket motors for ballistic missiles and 
battlefield rockets. 
 
KP cannot be used as a direct substitute for AP, and any 
substitution would require a complete redesign of the solid 
propellant rocket motor.  In addition to lower specific 
impulse performance, formulations containing KP have higher 
density values (KP is denser than AP), different burning 
characteristics (burning rate, pressure exponent, temperature 
sensitivity), and signature (KCl is a combustion species) 
than formulations containing AP, all of which are key factors 
for solid rocket motor design. This replacement of oxidizers 
would most likely require significant design changes and a 
motor requalification effort. 
 
KP is widely used as the oxidizer in explosive and 
pyrotechnic formulations.  The Merck Index lists other uses 
for KP in photography, analytical chemistry, and in at least 
some medical treatments. Most of the explosive formulations 
with KP are used for commercial purposes since military 
explosives typically contain high energy explosives such as 
PETN, HMX, and RDX.  Furthermore, the use of KP and other 
perchlorates in commercial explosives has diminished recently 
due to environmental concerns over groundwater contamination 
by perchlorates.  The pyrotechnic formulations with KP 
include automotive airbag inflation units, fireworks, flares, 
and initiation/ignition materials. 
 
Sodium perchlorate has only limited uses, and is used 
primarily as a precursor to the other perchlorate 
salts-especially AP and KP.  The use of sodium perchlorate in 
energetic formulations is hampered significantly by its 
tendency to pick up moisture.  The fact that its most stable 
crystalline form is a monohydrate also makes it less 
attractive in energetic formations.  Like KP, sodium 
perchlorate has been used in explosive and pyrotechnic 
formulations and to treat hyperthyroidism, although such uses 
do not appear to be widespread. 
 
Current MTCR Control of Perchlorates 
 
The MTCR Technical Annex contains several items dealing with 
perchlorates in general as well as specific perchlorates. 
 
MTCR Technical Annex item 4.C.3 controls any perchlorate when 
it is mixed with powdered metals or other high energy fuel 
components.  Binary mixtures of a perchlorate with a powdered 
metal or a high energy fuel component would be expected to be 
extremely dangerous to handle.  Therefore, this section of 
the MTCR Technical Annex deals with complete formulations or 
sub-mixes where sufficient other ingredients are present to 
make the combination safe to handle.  Complete formulations 
are often shipped in ignition devices or some other smaller 
component of a ballistic missile. 
 
Specific perchlorates are mentioned in MTCR items 4.C.2.b.16 
(hydrazinium perchlorate), 4.C.2.b.17 (hydrazinium 
diperchlorate), and 4.C.4.b.1 (ammonium perchlorate).  Of 
these specifically controlled perchlorates, AP is the most 
important to solid propellant formulations for ballistic 
missiles. 
 
Sodium perchlorate and potassium perchlorate are not 
specifically controlled by the MTCR.  Individually, neither 
sodium perchlorate nor potassium perchlorate can be directly 
used in the manufacture of solid propellant formulations used 
in ballistic missiles.  However, both sodium perchlorate and 
potassium perchlorate are of concern -- SP to a greater 
degree -- and both can be used as precursors for AP 
production. Therefore, a country/entity that desires AP for 
use in ballistic missiles but lacks the ability to oxidize 
chlorides to perchlorates could obtain sodium perchlorate or 
potassium perchlorate and convert it to AP. 
 
END TEXT OF PAPER. 
 
¶4.  (U) Please slug any reporting on this or other MTCR 
issues for ISN/MTR.  A word version of this document will be 
posted at www.state.sgov.gov/demarche. 
RICE 
 
 
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