The Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide NASA technical manual was developed at the NASA Johnson Space Center White Sands Test Facility. NASA Technical Memorandum TM-2004-213151 covers topics concerning high concentration hydrogen peroxide including fire and explosion hazards, material and fluid reactivity, materials selection information, personnel and environmental hazards, physical and chemical properties, analytical spectroscopy, specifications, analytical methods, and material compatibility data. A summary of hydrogen peroxide-related accidents, incidents, dose calls, mishaps and lessons learned is included. The manual draws from art extensive literature base and includes recent applicable regulatory compliance documentation. The manual may be obtained by United States government agencies from NASA Johnson Space Center and used as a reference source for hazards and safe handling of hydrogen peroxide

Baker, David L.

Frazier, Wayne

Greene, Ben

NASA Technical Reports Server

Source of Acquisition 
NASA Johnson Space Center 
NASA HYDROGEN PEROXIDE PROPELLANT HAZARDS TECHNICAL MANUAL* 
Ben Greene 
Honeywell Technology Solutions, Inc. 
NASA Johnson Space Center White Sands Test Facility 
Las Cruces, New Mexico 
David L. Baker 
NASA Johnson Space Center White Sands Test Facility 
Las Cruces, New Mexico 
Wayne Frazier 
NASA Headquarters 
Washington, D.C. 
ABSTRACT 
The Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide NASA technical manual 
was developed at the NASA Johnson Space Center White Sands Test Facility. NASA Technical 
Memorandum TM-2004-213151 covers topics concerning high concentration hydrogen peroxide including 
fire and explosion hazards, material and fluid reactivity, materials selection information, personnel and 
environmental hazards, physical and chemical properties, analytical spectroscopy, specifications, 
analytical methods, and material compatibility data. A summary of hydrogen peroxide-related accidents, 
incidents, dose calls, mishaps and iessons learned is inciuded. The manual draws from art extensive 
literature base and includes recent applicable regulatory compliance documentation. The manual may be 
obtained by United States government agencies from NASA Johnson Space Center and used as a 
reference source for hazards and safe handling of hydrogen peroxide. 
BACKGROUND 
After green propellant and improved propulsion systems performance initiatives identified hydrogen 
peroxide (HP) as a candidate propellant for propulsion and power systems, NASA Johnson Space Center 
(JSC) White Sands Test Facility (WSTF) began to develop a hydrogen peroxide reference document. 
The purpose of this document was to provide a central source of information to enable the user to assess 
HP hazards. While there are several excellent sources of HP hazards assessments documents, they are 
dated before 1970, and therefore may not utilize data and other information necessary for modern 
materials selection processes or adequately address recent concerns and current regulatory 
requirernent~.'-~ Recognizing these issues, an effort was initiated to produce a more up-to-date HP 
hazards manual. Earlier presentations discussed the status of this program in 2003 and 2004.6" 
OBJECTIVE 
The objective of this paper is to describe the HP hazards manual, its use, and its availability. 
APPROACH 
LITERATURE SURVEY 
First, representative literature was obtained and reviewed. Next, several key-word search engines 
were used, and relevant papers were found and obtained. Much of the literature came from journals, 
books, conference proceedings, Department of Defense (DoD) agencies, NASA, other government 
agencies including the Department of Transportation (DOT) and the Occupational Safety and Health 
Approved for public release, distribution is unlimited. 
https://ntrs.nasa.gov/search.jsp?R=20070020160 2019-08-30T01:14:02+00:00Z
Administration (OSHA), the Chemical Propulsion Information Agency (CPIA), advisory agencies including 
NIOSH and ACGIH, NFPA, and HP manufacturers. The literature was cataloged and organized by 
subject in the general organization of a draft manual. 
PREPARATION, REVIEW, AND ISSUE 
WSTF materials scientists, chemists, physicists, and mechanical engineers, knowledgeable in the 
subject and active in testing and data analysis, participated in preparation of the draft manual. The draft 
manual was reviewed internally at WSTF, and then reviewed externally. Comments received back were 
incorporated as appropriate and a signature copy was prepared for NASA WSTF management signature. 
Once reviewed and approved, the manual was issued internally as a WSTF Reference Document and 
distributed on-site and to other NASA centers. 
The next phase was to issue the document as a NASA Technical Memorandum. This was 
accomplished through coordination with the Publications section at NASA JSC. JSC provided the support 
necessary to complete the formatting in accordance with NASA Technical Manual guidelines. 
The manual contains material that is restricted to government agencies; it is not available in the public 
domain. 
USE OF THE MANUAL FOR HAZARDS ANALYSIS 
NASA's Safety Policy requires the use of an organized and systematic approach to identify and 
control hazards. Hazards analysis approaches for HP are provided. These analysis procedures are 
based on a method used successfully to evaluate fire hazards in oxygen components and systems and 
with hydrazine, MMH, and NTO hypergol systems. Use of the procedures is demonstrated by working 
through simple scenarios. The procedures can also be used as failure analysis tools. 
ASSESSMENT EXAMPLES 
Accident avoidance is a primary goal of the assessment examples. Examples are designed to assist the 
user in evaluating hazards and mitigating risks, using data provided or referenced in the manual. 
CONTENT 
The Fire, Explosion, compatibility and Safety Hazards of Hydrogen Peroxide NASA Technical 
Memorandum contains the following primary subjects: 
e 
e 
e 
e 
e 
e 
e 
e 
0 
e 
HP Hazards Introduction 
Fire and Explosion Hazards 
Materials and Reactivity 
Personnel and Environmental Hazards 
Chemical, Physical, and Thermodynamic Properties of HP Propellants 
Analytical Spectroscopy of HP 
HP Specifications 
Quantitative Determination of HP 
HP Accidents, Close Calls, and Lessons Learned 
Compatibility Tables from FMC Bulletin 104 
Beginning with a discussion of HP as a propellant, the manual presents a historical review of HP 
propellant uses and issues. Introductory concepts of HP as a green propellant are addressed. The 
introduction also outlines the structure of hazard assessment procedures. 
Descriptions of the fire parameters, hypergolic behavior of HP mixtures, HP explosion parmeters, 
and an expanded guide to HP fire and explosion hazards assessments are presented. Liquid and vapor 
detonations, explosive oxidation reactions, and detonations of mixtures of HP with combustible materials 
are addressed. Selected graphs from the early literature were remastered and are presented with the 
appropriate references and disclaimers. Example exercises for fire and explosion hazards assessments 
complete this section. 
Next, the manual examines materials reactivity and compatibility issues, including data treatments 
and stability calculation, active oxygen loss (AOL), and decomposition rates. Materials selection criteria, 
including that for metals, non-metals, and lubricants, are discussed. Incompatibility topics, such as 
hazards identifications, contamination, reactivity, anatytical and physical testing classification systems 
(e.g. Class I -4), and results criteria are then outiined. Stabiiity and reactivity determinations, including 
AOL and microcalorimetry, are discussed, compared, and contrasted. Considerations are given to the 
use of historical AOL data and more recent microcalorimetric data to predict decomposition rates in HP 
systems. Surface effects and passivation are discussed. Compatibility data tables adapted from the 
literature are also presented. Assessment examples include calculation of HP concentration based on 
decomposition rate, AOL, and pressure increases in containers. 
The manual progresses to a discussion of personnel and environmental hazards associated with 
exposures to or releases of HP. Exposure rules, recommendations, and guidelines are presented, 
including those of the American Conference of Governmental Industrial Hygienists (ACGIH), 
Occupational Health and Safety Administration (OSHA), and the National Institute of Occupational Safety 
and Health (NIOSH). Exposure routes including contact to the skin and eyes, inhalation, ingestion, and 
injection and their consequences are discussed, along with general health effects. Handling and storage 
precautions are reviewed, with guidelines for selection and use of personal protective equipment and 
monitoring equipment, along with general safety aspects of engineering design. Applicable National Fire 
Protection Association (NFPA) storage codes and reference to explosive safety standards for quantity- 
distance relationships are also cited in this section. Passivation procedures for various materials and ‘ 
their intended use with HP are also reviewed. Transportation issues governed by the Department of 
Transportation (DOT) and regulatory environmental requirements set by the Environmental Protection 
Agency (EPA), including aspects of waste classification and disposal, are presented and discussed. 
The appendices begin with a presentation of HP physical and chemical properties and their 
reference sources. The content of this section includes: 
0 
0 Units and Conversion Factors 
0 Physical Constants 
0 Thermodynamic Data 
0 
Temperature Dependency Tables for HP Propellant Properties 
General Information for HP Propellants 
Heats of Reaction of HP Propellants with Fuels 
The next topic of discussion is the analytical spectroscopy of HP that includes: 
0 Refractive Index 
0 Ultraviolet Spectroscopy 
0 Visible Spectroscopy 
0 Raman Spectroscopy 
0 Infrared Spectroscopy 
0 Spectroscopic Methods for Trace Components in HP 
The appendices progress to HP specifications. Topics include: 
0 
0 
Introduction and Background including an informative history of specifications 
Specification Requirements including those from inactive, proposed, industry, and current 
military specifications including MIL-PRF-I 6005F “Performance Specification: Propellant, 
Hydrogen Peroxide” and some of the changes it has undergone.’ This section is organized 
so that future changes to specifications can be documented in subsequent revisions to the 
manual with minimum effort. 
The next topic of discussion is the quantitative determination of HP. Topics include: 
Background 
HP Purity (Assay) 
Trace Methods for Determination of HP in Air and Water 
Common Anions 
Ammonium, sodium, and potassium 
HP Stability 
Evaporation Residue 
Total Carbon 
Metals 
Next, a summary of over 80 accidents, close calls, and lessons learned involving HP is presented. 
These were primarily obtained through the course of the literature review and by sources provided in the 
peer review process. This section provides an excellent base of examples that can be used to provide 
increased awareness of HP hazards and the need for appropriate training and controls. 
permi~sion.~ 
Finally, compatibility data tables are presented that were reproduced from FMC Bulletin 104 by 
CONCLUSIONS 
Fire, Explosion, Compatibility and Safety Hazards of Hydrogen Peroxide NASA Technical 
Memorandum NASA/TM-2004-213151 has been prepared. It is intended to be a tool for engineers, 
chemists, field operators, safety and emergency personnel, and others that should be aware of hazards 
of working with or around HP or HP systems. The manual is restricted to government agencies. For 
further information concerning this manual, please contact: 
David L. Baker 
NASA Laboratories Manager 
Dbaker@wstf.nasa.aov 
(505)524-5605 
Ben Greene 
Chemist, Honeywell Technologies Solution, Inc. 
Bareene @ wstfinasa.aov 
(505)524-5761 
Elizabeth Ball 
Technical Editor, L&M 
eball@wstf.nasa.uov 
(505)524-5678 
REFERENCES 
1. Hydrogen Peroxide Handbook. Air Force Rocket Propulsion Laboratory, 
AFRPL-TR-67-144, 1967. 
2. Liquid Propellant Handbook. Chemical Propulsion Information Agency. CPINM4, 1994. 
3. Materials of Construction for Equipment in Use with Hydrogen Peroxide, FMC Bulletin No. 104, 
FMC, Industrial Chemicals Group, Philadelphia, PA 1966. 
4. McCormick, J.C. Hydrogen Peroxide Rocket Manual. FMC Corporation, 1965. 
5. Schumb, W. C., Satterfield, C. N., and Wentworth, R. L. Hydrogen Peroxide. American Chemical 
Society Monograph Series. Reinhold Publishing Corporation, New York, 1955. 
6. Greene, B., Baker, D. L., and Frazier, W. NASA Manual on Fire, Explosion, Compatibility, and 
Safety Hazards of Hydrogen Peroxide. JANNAF Propulsion and Subcommittee Meeting, 
Charlottesville, VA, 2003. 
7. Greene, B., Baker, D.L., and Frazier, W.R. Hydrogen Peroxide Hazards Manual. JANNAF 
Propulsion and Subcommittee Meeting, Colorado Springs, CO, 2003. 
8. MIL-PRF-16005F. Performance Specification: Propellant, Hydrogen Peroxide 
(MlL-PRF-76005F). Defense Energy Support Center, Fort Belvoir, VA. August 2003. 


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