THE TOXIC BREAKDOWN CHEMICALS OF UDMH AND HYDRAZINE
Titan II nuclear missile fuel and oxidizer-hypergolic reaction.
Aerozine 50-50
50% Unsymmetrical Dimethylhydrazine ,UDMH, CAS number 57-14-7
50% Hydrazine
Oxidizer-Inhibited Red Fuming Nitric Acid, IRFNA, no CAS number
Breakdown chemicals after fuel leaks (decomposed o-rings or actual corroded pin holes in the missile skin) to atmosphere in the underground work/living area, contact with copper, and water dilution during spills.
Nitrogen dioxide, NO2, CAS number 10102-44-0
Nitric Oxide, CAS No. 10102-43-9
Nitric Acid, (HNO3) CAS No. 7697-37-2
N-Nitrosodimethylamine, NDMA, CAS number 62-75-9
Formaldehyde dimethylhydrazone, FDH, CAS 2035-89-4
Ammonia (NH3)
Dinitogen Tetroxide (N2O4)
Methylamine, (CH3NH2 )
Cyanic Acid (CHNO)
Carbon Dioxide (CO2)
Carbon Monoxide (CO)
Hydrogen cyanide (HCN)
Tetramethyltetrazene (C4H12N4)
Formaldehyde hydrazone(C7H6N4O4 ) CAS number 1081-15-8
Methanol
Dimethylamine; N-Methylmethanamine; (CH3)2NH or C2H7N) CAS number 124-40-3
Methylamine
After researching many USAF and NASA articles the most probable chemicals we encountered in the silo after a missile re-fueling and leaks of Aerozine 50 were Formaldehyde, Hydrogen cyanide and N-nitrosodimethylamine (NDMA). Unfortunately, the NIOSH ceiling limit (C) (maximum exposure for a 15 min period) for Formaldehyde was a mere 0.1 ppm. N-nitrosodimethylamine (CH3)2 NH... (NDMA) had a zero ppm exposure limit. The toxic chemicals lasted for 6 weeks after release to atmosphere. We had no detection device for these chemicals. These toxic chemicals were worse than the original UDMH/Hydrazine fuel itself.
The exact quote from the USAF 392d Medical Group at Vandenberg AFB on page 113:
“After a recent spill, in which some three gallons of UDMH-hydrazine mixture was dumped and diluted with water, after six weeks' elapsed time, UDMH and hydrazine were still present, as were formaldehyde and hydrogen cyanide. Even after neutralization and oxidation with hydrogen peroxide, while the concentrations of UDMH and hydrazine had been reduced effectively to zero, the concentration of formaldehyde was still high. The point here is, that even though it is possible to remove UDMH and hydrazine by oxidation, the by-products may be as offensive as the compounds themselves. Suppose, for a moment, that instead of three gallons, the spill had been three hundred gallons -- or three thousand!”
USAF 392d Aerospace Medical Group document from 1962 (attached at bottom) there are eight extra toxic chemicals from the release of UDMH or Aerozine 50 to atmosphere caused by spilled fuel from refueling or leaky missiles:
Formaldehyde (HCHO)
Hydrogen Cyanide (HCN)
Ammonia (NH3)
Dinitrogen Tetroxide (N2O4)
Methylamine, (CH3NH2 )
Cyanic Acid (CHNO)
Carbon Dioxide (CO2)
Carbon Monoxide (CO)
N-nitrosodimethylamine (CH3)2 NH
Another quote from the 392d Aerospace Medical Group at Vandenberg Air Force Base in 1962 on Page 112 of the document. Full article listed in the left column of the website home page.
“UDMH and Hydrazine, however, with or without N2O4 cause a more severe problem. They are not only toxic in themselves, but many of their degradation products are also toxic; hence, it is not sufficient merely to destroy the hydrazine and UDMH: solutions resulting from their reaction with soil, air and water must be brought within tolerance limits of every degradation product; this may be a large order.”
TABLE II (page 112 of 392d doc)
Toxicities and Limits known breakdown products of the system
N204 - UDMH, N2H4 (1962).
Webmaster note: Notice the word HUMAN on this table from 1962. This is important to anyone contacting the VA for help as you will hear the VA say there are few human studies connecting these fuels with health issues.
TABLE II (1962)
A - Asphyxiation
B - Blood Cell damage or alteration
F - Fertilizer in low concentration
I - Irritant to skin, mucous membranes, and organs
K - Kidney damage
L - Liver damage
P - Poisonous in high concentration
In 1984 the USAF was still looking into the toxic reaction of these fuels with just air. Ask yourself, why was the USAF still researching when in 1962 they already new of the problem?
ATMOSPHERIC DISPERSION OF HYPERGOLIC
LIQUID ROCKET FUELS, (VOLUME I OF III)
W.R. HAAS, and S. PRINCE
MARTIN MARIETTA AEROSPACE
DENVER. COLORADO 80201
NOVEMBER 1984
FINAL REPORT
JUNE 1982 through DECEMBER 1983
ENGINEERING AND SERVICES LABORATORY -
AIR FORCE ENGINEERING AND SERVICES CENTER
TYNDALL AIR FORCE BASE, FLORIDA 32403
C. ATMOSPHERIC OXIDATION OF HYPERGOLIC ROCKET FUELS
Hypergolic liquid rocket fuel (hydrazine, MMH, UDMH) will react with atmospheric oxygen to produce some of the same oxidation products identified .
in the fuel/nitrogen tetroxide reactions. Because oxygen is a weaker oxidizer than NTO, the stable oxidation products resulting from the interaction of the
hydrazine fuels with air are intermediates in the hydrazine/NTO reaction. For example, formaldehyde dimethyl hydrazone (FDH) has been identified as a minor oxidation product or intermediate in the UDMH/NTO reaction but as the major oxidation product In the UDMH/air reaction. These air oxidation products are important in catastrophic accidents in which un-reacted liquid fuel or fuel vapors are exposed to the air, particularly upon atmospheric dispersion of un-reacted fuel vapors.
Hydrazine Autoxidation
Hydrazine reacts with atmospheric oxygen to produce nitrogen and water
according to Equation (7).
N2 H4 + 02 => N2 + 2H20
A side product of this air oxidation of hydrazine vapor is gaseous ammonia, and the rate of the main reaction, as well as the side reaction
producing ammonia has been determined to be strongly dependent on surface area and geometric factors.
Hydrazine may also decompose in the absence of air to form ammonia, nitrogen, and hydrogen according to several pathways, the most generally
accepted on is represented in Equation (9).
N2 H4 => NH3 + 1/2 N2 + 1/2 H2 (9)
This reaction, often termed hydrazine monodecomposition, occurs only in the presence of an appropriate catalyst (e.g.,metal surfaces) or upon sparking or detonation of vapor mixtures. Thus, un-reacted hydrazine vapors may be expected to form ammonia, nitrogen, and hydrogen gas with the release of
thermal energy under conditions in which the accidental mixing of hypergolic rocket fuels favors a detonatton reaction or explosion.
2. Oxidation of Substituted Hydrazines
The major oxidation products identified in the MMH/air reaction are formaldehyde monomethyl hydrazone (FMH), methane, methanol, nitrogen, and
water 1 1 . The reaction between UDMH and air produces FDH, nitrogen, and water according to the stolchiometry in Equation (10).
3 (CH 3 ) 2 NNH2 + 202 =>2(CH3)2NNCH2 + N2 + 4H20 (10)
Diazomethane, dimethylamine, ammonia and NDMA have been identified as minor products In the UDMH/air reaction
D. ATMOSPHERIC REACTIONS OF HYPERGOLIC ROCKET OXIDIZERS
Unreacted liquid rocket oxidizer (NTO) may vaporize during an accident involving hypergolic rocket propellants to product nitrogen tetroxide vapors
and nitrogen dioxide vapors. The proportion of nitrogen tetroxide to nitrogen dioxide in the vapor phase is controlled by the equilibrium constant Kp for the reaction: (see attached paper below)
From other references:
Inhibited Red Fuming Nitric Acid IRFNA. Fuming Nitric Acids are unstable releasing nitrogen dioxide, nitric oxide, and nitric acid mist into the atmosphere.
Breakdown chemicals when released or leaked to atmosphere.
1. Nitrogen dioxide ( NO2) CAS number 10102-44-0
2. Nitric Oxide CAS number 10102-43-9
3. Nitric Acid (HNO3) CAS number 7697-37-2