ESL-TR-84-18

ATMOSPHERIC DISPERSION OF HYPERGOLICLIQUID ROCKET FUELS, (VOLUME I OF III

W.R. HAAS, and S. PRINCE

MARTIN MARIETTA AEROSPACEDENVER. COLORADO 80201

NOVEMBER 1984 JFINAL REPORT oJUNE 1982 - DECEMBER 1983

DTICELECTE 1

JAN 2 4- ']

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:1artin Marietta Aerospace HQ AFESC/RDV`

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62601F 1900 90 13l~.L~BjE ff~r~W~t~piHYPERGOLIC LIQUID

ROCKET PUEUS IVLM of j ____)_____

2.PERSONAL AUTHORI(SIWillardR. Haas; Stephen Prince

13a.TPEO REPORT 13b. TIME COVERED ~ 14- DATE OF REPORT fY,.. Mo.. Day) p16. PIGE COUNT

Final IFROM Jun 82 TO Detc 83 L 1984 November 13216. SUPPLE ME NTARY NOTATION

Availability of this report is specified on reverse of front cover.

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CflILo GROUP Sue OR Atmospheric Dispersion Modeling Nitrogen Tetroxide21 Lj 09 01 Hydrazine Toxic Hazard Corridor-09 I 02 IHypergolic Fuels

-* 19 ABSTRACTI COntRIIAU onl iV~lers OfROICOSPy and identify by blocit nu~mbtr

Titan II weapons systems are charged with hypergolic liquid rocket propellants (hydrazinefuel and nitrogen tetroxide oxidizer). These same propellants are used in support of other L

*- systems, including the MX missile and the space shuttle. This effort was designed tocharacterize the interactions of hypergolic liquid rocket propellants and to provide infor-mation pertinent to the development of a model to describe the transport and diffusion ofairborne combustion products and unreacted vapors from an accident involving these propel-lants.

* This report is prepared in two volumes. Volume I addresses the reactions between nitrogen -

tetroxide and hydxrazine, including the reaction products and the heat released. This infor-mnation was used to determine the combustion time and the height of the resulting fireballbefore it cools and disperses with the air. Volume II discusses the chemical and physicalinteractions of the combustion products with air, and the dispersion of these products inthe environment./ 1!4_________________.__

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PREFACE

This final report, published in two volumes, was prepared by Martin MariettaAerospace, P.O. Box 179, Denver, Colorado 80201, under Contract F42600-81-D-1379for the Air Force Engineering and Services Center, Engineering and ServicesLaboratory, Tyndall Air Force Base, Florida 32403. Efforts documented in thisreport were performed between June 1982 and December 1983. Major Gary Worley and""21t Glenn Seitchek were the AFESC/RDVS project officers.

This report has been reviewed by the Public Affairs Office (PA), and isreleasable to the National Technical Information Service (NTIS). At NTIS, it

will be available to the general public, including foreign nationals.

This report has been reviewed and is approved for publication.

GLENN D. SEITCHEK, 2Lt, USAF ROBERT F. OLFENBU L, Lt Col, USAF, 8SC

Air Quality R&D Project Officer Chi , E vironics Division

F. THOMAS LUB8YNSIVCapt, USAF, BSC OBERT E. BOYER, ol, USAFChief, Environmental Sciences Branch Director, Enginee n 9'and Services

Laboratory

Aooesiion ?or

NTIS GRAMIDTIC TAB 0r"Unanmounced 0Justificatio n

SEDT IC D _st r ibut i o d/.ELECTS Availability CodesJAN 2 _��. vail andi/o

Dift special

iii(The reverse of this ipaqe is blank.)

TABLE OF CONTENTS

Section Title Page

I Introduction . . . . . . . . . . . . . . . . . . . . . . . . . I

[I Compilation of Background Information ........ ... ............ 3

III The Chemistry of the Hydrazine/Nirrogen TetroxideBipropellant System ............ ....................... 5

A. Free Radical Reaction ......... ................ ... 10

B. Nitrosation Reaction ................. .................. 10

C. Atmospheric Oxidation of Hypergolic Rocket Fuels . . .. 14

1. Hydrazine Autoxidation ..... ............... .. 142. Oxidation of Substituted Hydrazines ........ .. 15

D. Atmospheric Reactions of Hypergolic Rocket Oxidizers . 16

IV Thermochemical Analysis of a Hypergolic Reaction ....... .. 19

A. Adiabatic Flame Temperatures and Chemical CompositionCalculated Under Equilibrium Conditions ........... ... 19

1. Combustion in an Open-Field or Vented Environment 222. Confined Silo Fire with Minimal Explosion Hazard . 223. Open-Silo Hypergollc Explosion ... ........... ... 234. Confined Silo Hypergolic Explonlon ........... ... 26

B. Vaporization of Excess Unreacted Propellants CalculatedUnder Nonequilibrium Conditions ............ ...... 30

1. Excess Fuel Reactions .............. ............... 3)2. Excess Oxidant Reactions ..... .............. .. 37

C. Calctilation of Fireball Size and Quantification ofHeat Flux ............... ....................... .. 39

1. Theory ............. ....................... ... 392. Results .................... ...................... 423. Conclusion ............. .................... .. 44

FI AMIOUSPAGZ&

V

TABLE OF CONTENTS(Contlnued)

Section Title Page

r T,'ac:tions of Hypergolic Propellants with Other Chemicals . . . 47

VI Conclusions ............. ......................... .. 49

References ............... .......................... ... 53

,•ppe,,x A - Computer Output, A-50/NTO Reactions .. ........... .. 59

App.rndfx B - Thermochemical Calculations for NonstoichiometricCombustion of A-50 and NTO ..... ................ .. 86

Appendix C - Computer Output, Reactions of Liquid Rocket PropellantsWith Other Chemicals ............... ................... 110

c.1

vi.

4

9 9 9 9

LIST OF TABLES

Table Title Page

I Reaction Products Identified :n the Aerozine-50Nitrogen Tetroxide Reaction .... .................. 7

2 Vapor-Phase Equilibrium Composition of NitrogenTetroxide and Nitrogen Dioxide ... ............. .. 17

3 Input to SP-273 Computer Calculations for BipropellantAccidents ............................................. 28

"4 Thermochemical Properties for Hypergolic Propellantsand Reaction Products ............... .................. 33

5 C'omputer Input for Reactions of Hypergolic RocketPropellants with Other Chemicals ... ............ .. 48

°v i

°."o":

'vi

r . Ir 'I

9 • • . .•. .•.•: • ,=`• • qr •r* =•=•* • ° ••• •*--. • •*• Ni• • ... "" ""•" ""'"'""'" """:"""-"" " " " """"'''

LIST OF FIGURES

Figure Title Page

I Free Radical Mechanism for React'on of N2 04w'ith llydrazInes ............ ..................... .. 11

2 Nitrosation Mechanism for Reaction of N2 04 twith Hydraziles .............. ..................... ... 12 N.

3 Computer Output for Stoichtometric Mixing of A-50 andNTO .................. ........................... ... 35

4 Radiant Fireball Temperature, O/F - 1.02 .. ........ 43

5 Radiant Heat Flux, O/F - 1.02 ............ .............. 43

6 Radiant Fireball Temperature, O/F = 0.20 .. ........ 45

7 Radiant Heat Flux, O/F - 0.20 ...... .............. .. 45

8 Radiant Fireball Temperature, O/F = 5.1 ........... .. 46

9 Radiant Heat Flux, O/F = 5.1 ....... .............. .. 46

?.1a-,

Lim.

I-

'2a

'iii

- - - - - - - - -. - ... . . .. . . - .- . . .-. . . . . ... .-.. ..

SECTION I

INTRODUCTION

The Titan II Weapons System is deployed at sites in Arizona, Arkansas, and

Kansas. Although these sites were rural when initially deployed in the

1960s, land development and population expansion has gradually encroached

upon many of the current sites. because the Titan II Weapons System is

charged with toxic hypergolic liqufd rocket propellants (hydrazine fuels and "

nitrogen tetroxide oxidizer), the civiliPn popnlation near these sites must

be protected from accidental atmospheric releases of these toxic propellants

in the event of a transportation, handling, or storage accident. In addition,

these same propellants are used in support ot other operational and planned

weapons system (e.g., Minutemen III and M-X missile) and space launch

vehicles (e.g., Space Shuttle).

Procedures for predicting toxic vapor corridors for an accidental release

of either hydrazine fuel or nitrogen tetroxide oxidizer were developed in the

early 1960s by the Air Force Cambridge Research Laboratory. At this time,

the type of release anticipated by the Air Force at these sites was a single

propellant spill, and the predictions of the toxic vapor corridors upon

release into the atmosphere were baced on the evaporation of the single

propellant and on its subsequent dispersion. The techniques developed by the

Air Force Cambridge Research Laboratory to determine these toxic corridors

were incorporated into the operational procedures when the Titan II was

deployed.

In 1980, a Titan I accident occurred near Damascus, Arkansas in which the

scenario was much different than the one for which the toxic hazard corridor

calculation procec.res were developed. Leaking fuel within the silo

eventually made contact with the oxidizer on board a Titan 1I, leading to a

violent explosiorn which sent combustion products and possibly some unreacted

propellant se"'ral Thousand feet in to the air, where the atmospheric

dispersion process began. This effort Is designed to characterize the

interactions f hypergolic liquid rocket propellants and to provide

I1

information pertinent to the development of a model which would describe the

transport and diffusion process of the airborne combustion products and

unreacted propellant vapors resulting from a catastrophic accident involving

hypergolic liquid rocket propellants.

a

°

Lo,

2

4

p

-1 -•-: --.-- •,-,,•r -:, . . . . . . . .... . .. . . - - -.v- - •-•J ".•-- -'`•. ;•~ - -.. ••W :'q'; • • •<7 a

SECTION It

COMPILATION OF BACKGROUND INFORMATION

Information with respect to hypergolic interactions between hydrazine

fuels and nitrogen tetroxide oxidizers was obtained from a variety of

sources. The Air Force Project Officer supplied several literature references

which were invaluable in determining critical fireball parameters such as

fireball size, duration, and thermal energy. Technical reports, documents,

and literature sources relative to the identification of combustion products,

Ie fireball generation, and chemical reaction kinetics in the reaction between

the hypergolic liquid rocket fuels were identified through a NASA-RECON and a

Chemical Abstracts computer search.

Past experiments involving reactions between hydrazine fuels and nitrogen

tetroxide/nitrogen dioxide oxidizers have been identified In the literature

reference articles, including the analysis of the Project Pyro tests. The

results of these experiments have identified vapor phase and condensed phase

reaction products resulting from the mixing of two hypergols and have

generated representative explosive yield characteristics for the hypergolic

reaction. In addition to the established combustion products of aerozine-50

with nitrogen tetroxide (which include nitrogen, carbon dioxide, and water

vapor), approximately 60 additional chemical species resulting from this

hypergolic fuel-oxidizer combustion have been reported in the literature.

While the identification and quantification of all such chemical reaction

products is too exhaustive and detailed for the present task, some of these

chemical species may be important components In the combustion fireball due to

thermal or toxicity considerations. Dimethylnitrosamine (NDMA), for example,

is an expected and confirmed product from the nitrogen tetroxide - diemthyl

hydrazine reaction1 and also is a known carcinogen.

3

Information from past accidents which involved reactions of hypergolic

rocket propellants has also been evaluated with respect to the thermophysical

analysis pertinent to the present effort. Results from the Atlas/Centaur

Launch Hazards Assessment Program and the Titan II accident in 1980 were

included In this evaluation.

- -"I". -m.

%'. 1V

44

a 3 13 a19 VWpr-vr%--A5.

SECTION III

THE CHEMISTRY OF THE HYDRAZINE/NITROGEN TETROXIDE BIPROPELLANT SYSTEM

The hypergolic combination of hydrazine-type fuels (including

hydrazine, monometh)lhydrazine [MMH], 1, 1 - dimethlyhydrazine [UDMHJI, and

aerozine-50 (A-50, a 50:50 mixture of hydrazine and UDMH by weight) with

nitrogen tetroxide [NTOJ oxidizers are used in current propulsion systems such

as thp Titan II Weapon. System and the Shuttle Transportation System. This is

of the high specific impulse imparted to the launch vehicle by the chemical

energy released upon mixing the hypergals in the rocket engine.

The stoichiometric reaction between aerozine-50 and nitrogen tetroxide

(the bipropellant system used in the Titan 11 Weapons System) may be

represented by the following eqitation2 :

.6522 N2 H4 + .3478 C2 HsN2 + O/F (1.0217) N2 04

- Products -2.245 (1)

where 0/F is the oxidant-fuel mass ratio (2.24' for stoichiometric combustio,)

and the products of combustion consist primarily of water vapor (H 2 0),

nitrogen gas (N2 ), carbon monoxide (CO), carbon dioxide (C02 ), hydrogen

gas (H2), and hydroxide radical (OH). The available chemical energy from

reacting one gram mole of aerozine-50 (.6522 mole hydrazine + .3478 mole UDMH)

with 1.02 moles of nitrogen tetroxide at 25 0 C (298 0 K) is approximately

1.54 X 105 calories (6.63 X 103 BTU per pound aerozine-50 reacted). This

value was calculated from the standard heats of formation of chemical

reactant3 and gaseous reaction products for the stoichiometric hypergolic

reaction referenced at 298°K, and will be discussed in more detail in

Section IV.

I5I

.'I

In addition to the formation of the gaseous combustion products described

above for a stoichiometric reaction between aerozine-50 fuel and nitrogen

tetroxide oxidizer, several competing side reactions occur upon mixing of the

two hypergols, and over 50 chemical species have been isolated and

identified either as chemical intermediates or condensed phase reaction

products in the A-50/NTO hypergolic reaction.

A list of reported secondary chemical reaction products that result from

the interaction of Aerozine-50 fuel and nitrogen tetroxide oxidizer Is

included in Table I. Some of these side products (such as hydrazine nitrate

and hydrogen azide) have been identified as the reaction condensates

responsible for the "hard start- and "popping" phenomena characteristic of

hydrazine-NTO pulsed rocket engines 3 ' 4 ' 5 While these particular chemical

residues affect engine performance and ignition threshold, the instability of

these compounds at elevated temperatures suggests their absence in a p3hypergolic fireball resulting from a propellant accident during transportation

or handling. The hydrazine nitrates and azides; therefore, are not seen to be

airborne toxins in an accidental hypergolic explosion. Other chemical

reaction products are more stable,especially at lower temperatures (5000K),

and the presence of these compounds in a hypergolic fireball may significantly

impact the toxic vapor corridors for a hipropellant accident scenario. The

chemical species in this category include dimethylnitrosamine (NDMA), methyl

amine, dimethyl amine, formaldehyde, hydrogen cyanide, ammonia, and

formaldehyde dimethylhydrazone (FDH). In addition to these reaction products,

unreacted propellant vapors (hydrazine vapor, UDMH vapor, nitrogen dioxide)

resulting from incomplete combustion and volatilization of excess propellant

will also pose a health hazard upon atmospheric dispersion, since both the

hydrazine fucl and nitrogen tetroxide oxidizer are extremely toxic, in both

the liquid and vapor states.

Most of the reaction products cited in the literature and listed in

Table I can be accounted for by one or more of the following chemical reaction

liechanisms.

6L

6V

TABLE I

REACTION PRODUCTS IDENTIFIED IN THE AEROZINE-50

NITROGEN TETROXIDE REACTION

No. Compound Name Molecular Formula Reference

I nitrogen N 1,3,6.4b

- 2 hydrogen H2 3,6

g3 water H 20 3,6

4 oxygen 02 3,6

5 carbon dioxide CO2 1,3.4

6 carbon monoxide CO 1,36.

7 ammonia NH3 1,3,6

8 nitrogen dioxide NO2 1,3

9 nitrous oxide NO 3,6

10 nitric oxide NO 3,6

11 hydroxide OH 2

12 monatomic hydrogen H 2

13 monatomic oxygen 0 2

14 nitrogen trioxide N2 03 2

15 nitric acid HNO 3 3,6

16 nitrous acid HNO 3,6

17 hydrogen azide HN3 3

18 hydrazine azide N2 H N3 3,5

19 methanol CH3 OH 1,320 methyl amine CH3 NH2 1

21 dimethyl amine (CH 3 ) 2 NH2 I

3)2

7',S

4.

TABLE I (Continued)

S..REACTION PRODUCTS IDENTIFIED IN THE AEROZINE-50

NITROGEN TETROXIDE REACTION

No. Compound Name Molecular Formula Reference

22 formamide CNH 0 1

23 formaldehyde CH2 0 3

24 nitrosamine NH 2 NO 3,6 ° i

25 dimethylnitrosamine (CH3 ) 2 NNO 1,3

26 dimethylformamide (CH 3 ) 2 NCO 1

27 methylnitrosamine HCH3NNO 1

28 hydrazine nitrate N2 H5 NO3 1,3,4,7

29 hydrazine dinitrate N2 H42HNO 3 3,5

30 hydrazine nitrite N2 HsNO2 3,5

3.1 dimethylhydrazine nitrate (CH3 ) 2 NH3 NO3 1,3

32 ammonium nitrate NH4NO 3 3,6

33 ammonium azide NNt4 N3 3

34 ammonium nitrite NH4 NO2 3

35 formaldehyde dJmethylhydrazonc CH2 NN(CH3 ) 2 3

36 tetramethyl tetrazine (CH3 ) 4 N4 3

37 tetrazine H4 N4 338 formaldehyde monomethylhydrazone CH2NNHCH3 3

39 triazine H3 N3 3

40 azine H2 NNNH 3

41 monomethylhydrazine CH3 HNNH2 3

42 methyl azide CH3 N3 3

3 3i

8

Aim'

A

TABLE I (Concluded)

REACTION PRODUCTS IDENTIFIED IN THE AEROZINE-50

NITROGEN TETROXIDE REACTION

No. Compound Name Molecular Formula Reference

43 nitromethane CH3 NO2 3

44 methyl ammonium nitrate CH3 NH3 NO3 3

45 nitrosohydrazine N2 H3 NO 3

46 diazomethane CH2 N2 3

47 tetramethylhydrazine (CH3 ) 4 N2 8

48 methyl nitrite CH3 NO2 3

49 methane CH4 3

50 ethane C2 H6 3

51 propane C3 H8 3

52 acetylene C2 H2 3

53 hydrogen cyanide HCN 3

54 formic acid HCOOH 3

55 cyanic acid HOCN 3

56 butadiene C4 H6 3

57 ethyl azide C2H5 N3 3

58 ethylene C 2H 4 3

59 nitrilohydrazine CNN2 H5 3

9

-. .. . .. .. . . . . . . .. S - - . -. . . . . • . . _. .

*!

A. FREE RADICAL REACTIONIo

The oxidant, N2 04 , or more precisely the monomer NO2 is a molecule

with an unpaired electron and is thus capable of forming free radicals. The

NO2 free radical can dimerize, add "o double bonds, abstract hydrogen, and

"*activate" other chemical species for further chemical reactions. Figure 1

details a reaction mechanism between hydrazine type fuels and nitrogen

tetroxide oxidizer through a NO2 -free radical intermediate.

For the hydrazine reactant A (R - H, R' - H), the intermediate products

. are ammonia (E), nitrosamine (F) and ammoniun nitrate (G).

For the monomethyl hydrazine reactant A (R - H, R' - CH3 ) the

intermediate products are monomethyl amine (E), methylnitrosamine (F), and

methyl ammonium nitrate (G).

For the 1, 1-dimethylhydrazine reactant A (R - CH3 , R' CH3 ), the

Intermediate products are dimethyl amine (E), dimethylnitrosamine (F), and

dimethyl ammonium nitrate (G).

Note that only dimethylnitrosamine is stable upon the oxidation by

N2 04 . Nitrosamine readily decomposes to water and nitrogen, and

monomethylnitrosamine decomposes to methanol and nitrogen.

B. NITROSATION REACTION

Figure 2 shows a postulated mechanism and reaction products resulting from

the nitrosation of hydrazlnes by nitrosonium ton (NO+), formed from the

ionization of nitrogen tetroxide which is promoted by donor solvents such as

aminen and hydrazines.

10

• . . . . . . . , . . . . . • . . o . • . - . . • . .. - . .• ., . . . • . . .. .. . . -. . - . • . . ,

N 204 2 . NO2

N02R'RN - N, =1--% R'RN + HONO

(A) 2 (B)

R'RN -NRRN N 4141(C) '.NO2 L D)

'RNH

"R'RN-NO + H20 (or H4+ R'RN-NO + R'RNH NO(F) 2 (G)2 3

if R' - CH3 and R - H, then

N-NO I CH OH + N

H (F) C 3 + 2

I if R R' H, then

H "--N-NO - H 0 + N

H (F) 2 2

Figure 1. Proposed Free Radical Mechanism for Reaction of N204

with Hydrazine (Reproduced from Reference 1)

11

ON- NO2 ONONO2 No + NO;

2 2

R'RN- Nil + NO+ - A R'RN N ~ + H4

(A) 2 (1) 'N

R'RN- N - NOH R'RNHH + NO20(J) (E) 2

+RN + R'OH R'RNNO + H

(K) 3 L) (F)

.NO + NON3 NON 3 R'R,,N(Ht) 2c• (N) 2

NO0 N2 2

R'RN. NH +• 4+ N0_- R'RN -NH,+ NO

(A) 2 H)3

t.

Po

Figure 2. Proposed Nitrosation Mechanism for Reaction of N2 04

with Hydrazines (Reproduced from Reference 1)

12

This reaction also accounts for the formation of substituted amines

(products E + N), nitrosamines (product F) and methanol or water (product L).

It also indicates the formation of nttrosohydrazine (product I), the azides

(methyl and hydrogen, product K) and methyl nitrate or nitric acid (product

M). The substituted hydrazinium nitrates (product H) are formed from the

reaction of substituted hydrazines with nitric acid.

Several of these species may also form via a simpler mechanism. Since

water is a reaction product of the hydrazine/nitrogen tetroxide reaction, the

water generated by this hypergolic reaction may react with unreacted nitrogen

totroxide to form nitrous acid and nitric acid, which may subsequently react

with the substituted hydrazines to form azides, nitrosamines, and hydrazinium

nitrates.

RRN - NN + N - CO2 + H2 0 + N2 (2)', -N2 2 N24 2

+ other products

H2 0

N2 3 4 a 2NO2 ' HNO2 + HNO3 (3)

R'RN -NH 2 + wo R'RNNO + RR'NH + N20+ HO (4)

(A) (F) (E 2

for R' - R - H,

H2N - NH3 + HNO 2 - HN3 + H2 0 + II+ (5)

R'RN - NH + NO R'RN - NH NO NO (6)

(A) 2 3 OtH) 3 3

The occurrence of the other reaction products in the aerozine-50/nitrogen

tetroxide reaction can be best explained by the oxidation of methanol by 1J0 2

(or N2 04 ) which produces formaldehyde. The formaldehyde can further react

to form acetic acid, formamide or an N-substituted formamide, formic acid, arid

formaldehyde dimethyl hydrazone

13

I I~ . -n. -

"U"

In general, the appearance and relative composition of the reaction

prodlucts described above depend on the oxidizer/fuel ratio, reaction

temperature, reaction pressure, degree of mixing of oxidizer and fuel, aad

ge.imetric and temporal mixing conditions (such as surface area and wall

effects, as welt as propellant addition rates). As will be subsequently

described, few of these secondary reaction products are predicted by chemical

equilibrium considerations; most products identtfied in a reaction mixture

therefore are frozpn in a nonequilibrium state due to kinetic barriers. -A

Since activation energies for the various reaction pathways are not readily

.jjailahle, prediction of the absolute amounts of these secondary products In a

given hypergolic reaction is difficult at hest.

C. ATMOSPHERIC OXIOATION OF HYPERGOLIC ROCKET FUELS [Hypecgolic liquid rocket fuel (hydrazine, MMH, UDMH) will react with

.itmospheric oxygen to produce some of the same oxidation products identified .

in the fui/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 !dentified as a minor

oxidation product or intermediate in the UDMH/NTO reaction but as the major

oxidation product In the UDMII/air reaction. Thene air oxidation products are

important in catastrophic accidents In which unreacted liquid fuel or fuel

vapors ire exposed to the air, particularly upon atmospheric dispersion of '

unreacted fuel vapors.

Hydrazine Autoxidation°'A

Hydrazine reacts wrth atmospheric oxygen to produce nitrogen and water

accordi.ng to Equation (7).

N2 H4 + 02 . N2 + 2H20 (7)

14

A sLde product of this air oxidation of hydrazine vapor is gaseous

amnmoola, and the rate of the main reaction, as well as the side reaction

producing ammonia ias been determined to he strongly dependent on surface area9and geometric factors

Hydcazine may also decompose in the absence of air to form ammonia,

nitrogen, and hydrogen according to several pathwayq, 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 6 10 Thus, unreacted hydrazine va~or:i 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 reazion or explosion.

2. Oxidation of Substituted Hydrazines

The major oxidation products identified in the MMH/air reaction are

formaldehyde monomethyl hydrazone (FNH), methane, methanol, nitrogen, and

water 1 1 . The reaction between UDMH and air produces FDH, nitrogen, andwater according to the stolchiometry in Equation (10).

3 (CI1 3 ) 2 NNH9 + 202>2(CH3)2NNCH2 + N2 + 41120 (10)

Diazomethane, dimethylamine, ammoniaand NUMA h:ive been identified as

minor products In the UDNHH/air reaction

15

J

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 nirrogen dioz.ide vapors. The proportion of nitrogen tetroxide to nitrogen

dioxide in the vapor rihase is controlled by the equilibrium constant K forp

the reaction:

2 NO K K p N2 04 (11)2 N20 4 p 2(p NO2 )

Where p N20 4 = partial pressure N204 vapor at equilibrium

p NO2 - partial pressure NO2 vapor at equilibrium

The equilibrium constant K for the association of two molecules ofp

nitrogen dioxide gas into one molecule of nitrogen tetroxide gas is

rnmperature-dependent and can be calculated by the Gibbs free-energy function

for the association reaction [Equation (11)]:

LGO - -RT In K = -13600 + 412.6 T (12)p

Where R = gas constant (1.987 cal/mole OK)

K - association equilibrium constant (1/atm)p

T = gas temperature (OK)

AGO - Gibbs free energy (calories/mole)

The equilibrium mole fractions of nitrogen tetroxide gas and nitrogen

dioxide gas as a function of temperature as calculated from Equations (11) and

(12) are presented in Table II. In this case, the mole fractions of nitrogen

16

I

oxide vapors (NO2 or N2 04 ) are equal to the partial pressures of the

vapors at one atmosphere total pressure. The percent of dissociation of

aitrogen tetroxtde dimer to nitrogen dioxide monomer,as defined in Equation

(13),is also presented in Table It. Thus, above lOO°C (371°K), unreacted

nitrogen tetroxide gas is virtually completely dissociated into nitrogen

dioxide gas 1 2 .

p NO2 X 100Percent Dissociation __(13)

p NO2 + 2p N2 04

TABLE II. EQUILIBRIUM COMPOSITION OF NITROGEN TETROXIDE AND NTTROGENDIOXIDE IN THE VAPOR PHASE AS A FUNCTION OF ABSOLUTETEMPERATURE

(PTota1 = I Atmosphere)

Mole Mole

Temperature Fraction Fraction Percent

K N2 04 NO2 Dissociation

298 .698 .302 18

333 .539 .461 30

323 .426 .574 40

373 .066 .934 88

1.1,

17

4

Oxidizer vapors evolved during a hypergolic propellant accident, which

iill Include both N2 0 4 and NO2 gases, will react with the atmospheric

components of air during EirebaLl generation and aerial dispersion. These

vapors are expected to react with molecular oxygen to produce a mixture of

nitrogen oxides (NOx) which may include nitrogen trioxide (NO 3 ; x - 3),

dinitrogen trioxide (N 2 0 3 ; x = 3/2) and dinitrogen pentoxide (N 2 0 5 ;

-52). They will also react with atmospheric water vapor to produce both

nitrous acid (INNI0 2 ) and nitric acid (ITO 3 ). The latter phenomenon is

Ynown .-i t'he acid ra n effect. Vaporized rocket oxidizer may also react with

su-y hydrocarbon pollutants in the atmosphere, and these interactions are

,:,tailed 'n Reference 13.

18

. . . . . . .. . . . . . .

SECTION IV

THERMOCHEMICAL ANALYSIS OF A HYPERGOLIC REACTION

L,-on mix~ng of the hypergolic rocket propellant (A-50 and NTO) during an

accidental spill or missile tank rupture, the chemical energy of the

propellants is converted into thermal energy used to heat the hypergolic

combustion products, to vaporize excebs unreacted propellant, and to heat the

surroundings in the vicinity of the accident. The thermal energy of the

resultant fireball, as well as it measure of the time-dependent energy release

of the fireball (heat fluy) upon fireball generation and lift-off, are

important in the quantification of the release height of the chemical

components contained in the fireball and the subsequent deposition pattern

upon aerial dispersion.

Thermochemical analysis for hypergolic fireballs were calculated for three

separate cases: (1) Fireball combustion products were identified and

adiabatic flame temperatures were calculated, using theoretical thermodynamic

combustion properties of the hypergolic propellants and the gaseous reaction

products; (2) Where the oxidizer to fuel ratio was far removed from

stoichiometric combustion, the chemical reaction was treated as a

nonequilibrium condition, in which the resultant thermal energy of the

fireball was used to heat and vaporize the excess propellant; and (3) The

time - temperature profile of a hypergolic fireball was calculated, assuming

radiative heat transfer to the environment. These analyses, as well as the

determination of the fireball size, are detailed in the sections that follow.

A. ADIABATIC FLAME TEMPERATURE AND CHEMICAL COMPOSITION CALCULATED UNDER

EQUILIBRIUM CONDITIONS

Quantification of equilibrium chemical species and calculation of fireball

adiabatic temperatures resulting from stoichiometrtc and nonstoichiometric

19

reactions of aerozine-50 with nitrogen tetroxide were accomplished using a

computer program tcj calculate complex chemical equilibrium composition (NASA

SP-273) 1 4 . The program solves equations by reiteration to minimize the

Gibbs free energy of the chemical reaction products and maintain a mass

balance between the chemical reactants (hypergolic propellants) and chemical

products (combustion products, oxidation products, and unreacted

propellanta). This particular program has been routinely used at Martin

Marietta to calculate rocket performance parameters for Titan launch vehicles

employing hypergolic propellants. The program employs approximately 60

possible reaction products resulting from a particular hypergolic propellant

combination.

Flame temperatures of hypergolic fireballF 4ere calculated by this prggram

for an adiabatic condition, i.e., conductive, convective, and radiative heot

losses to the environment are negligible. In this case, the heat of reaction

of combining (a) moles of A-50 with (b) moles of NTO at 25 0 C (298 0 K) was

used to heat the resultant chemical species in the fireball from 25 0 C to the

final flame temperature TF.

For the hypergolic chemical reaction:

a C. 6 9 6 H5 39 N2 + bN2 04 -=-•* njpj + /Hreaction (14)

where:

a - number of moles of A-50 reacted

b - number of moles of NTO reactedn= number of moles of combustion product P

Hreacton heat evolved from chemical reaction

(calories/mole or BTU/pound)

20

The adiabatic flame temperature (TF) is calculated for the hypergolic

reaction as follows:

Alreaction aA llf (A-50) + hA Hf (NTO) - .pf (P)

J298 nj CpjdT (15)

For unreacted propellant vapors (PK) which may be hydrazine vapor, U1MH

vapor, NTO vapor or NO2 vapor depending on the relative amounts of fuel and

oxidizer involved in the hypergolic accident (O/F mole ratio is 1.02 for

stoichiometric combustion), the enthalpy change from 2980 K to TF Includes

a phase tranRition, therefore the final thermochemical equation which includes

both gaseous combustion products and vaporized propellant may be written

(a + a,) Hf (A-50) + (b + bh)A Hf (NTO)- g n A Hf (Ps)

S9jCp dT + n C dT + nk Hva (PkS dT jj k pk y ap k

2998 9

+ 4" k Cpk dT (16)

Where:

aI a number moles excess A-50 vaporized

bI a number moles excess NTO vaporized

AHf = the standard heat of formation of the liquid rocket propellants

(A-50 or NTO); or the standard heat of formation of the jth

gaseous combustion product

p - the constant pressure heat capacity for the jth gaseois

combustion product

n the number of moles of kth unreacted vaporized propellant

21

• r -d

CpI . the constant pressure heat capacity for the k th unreacted

propellant at the temperature Interval of Interest U_

Tv temperature (°K) at phase transttion

&H latent heat of vaporization at Tv oK .va0p

Computer calculations were performed for oxidizer-to-fuel (O/F) mole

ratio& between 0.0102 and 510.0. The O/F molb ratio for -ito~chlometric

combustion is 1.02, and the O/F mole ratio for the full inventory of

h'ypergolic propellant conLained in the Titan It missile (104,609 pounds .1

aerozine-50 and 207,560 potindc nitrogen tetroxide) is approxmately 0.90. The

calculations were also performed at several reaction pressures intended to

sinmi•are different accident scenarios:

1. Combustion in an Open-Field or Vented Environment

P1 - 1.0 atm

The hypergolic reaction pressure was defined as 1.0 atmosphere (14.7 p3ia)

for pcopellant accidents: in which the gaseous combustion products were allowed

to 2xpon'I and release in an unconfined space. This analysis would be

,'epresentative of an open-field propellant spill, or a silo spill in which the

blant cover door was removed or vented.

2. Confined Silo Fire with Minimal Explosion Hazard

P2 - 12.56 atm

This jlrtiation Is intended to represent a bipropella-it accident in a

confined Titan II missile silo (700-ton horizontal silo door intact) in which

the propellant leak rate is too slow to allow any overpressure conditions in

the silo due to deflagrition or detonation of the combined hypergolic rocket

propellanr.s. In this case, the silo pressure will slowly rise until the 700

22

. -. . . . . . .. . . . . . . . . . . . . . . . ..

i

ton blast door will be ejected, and the resultant fireball will he

subsequently released from the opened silo. The pressure at fireball lift-offtime can be calculated from the force required to remove the horizontal silo

door as follows:

P2= Pressure required to eject silo cover -

Weight Silo Door (Pound) + 4X Shear Force T-Lock RestraintExposed Surface Area Silo Door (17)

66S1.4 X 10- Lb + 4(5.5 X 10 Lb) 2.45 X 104 Lb/Ft2P2

954 Ft 2

P2- 185 psia - 12.56 atmospheres

3. Open Silo Hypergolic Explosion

P3 - 1.0 atmosphere + Pover

This analysis is performed to estimate a large-scale propellant spill in

which the propellants spill out of missile tankage and mix in an open silo.

In this case the spill and mixlng rates of the hypergollc propellants are

large enough to initiate a chemical explosion. Detonation reacttons between

%idrazine-type fuftIs and nitrogen tetroxide oxidizer have been previously

documented in the literature1 5,16. The analyses for the detonation shock

front resulting from the accidental explosion has been calculated,using the

gesetric conditions present In the Titan II launch tube. The area available

for expansion of the shock front In this case Is equal to twice the

cross-sectional area of the launch tube (expansion in two directions) minus

the void cross-sectional area of the missile. This is

2( rrR2 ) frR2 946 Ft2 (18)

23

I I I

where:

R -radius of launch tube a 2 2 Feet

R' radius of missile - 5 Feet

Many different factors can affect the severity of the shock

overpressure . The most significant of these are:

a. Total propellant weight

b. Propellant type pC. TNT equivalent yield .

d. Geometry of surroundings.

The relevant geometry for an in-silo explosion resulting from the mixing

of the two hypergolIc propellants has been defined above.

The TNT equivalent yield is a measure of the explosive potential of the

detonation reaction, i.e., the TNT yield is the weight fraction of the

explosive substance which Is equal to the same weight of TNT. In hypergolic

explosions between A-50 fuel and NTO oxidizer, a 0.5 percent TNT equivalent yield

conservative maximum can be expected from Project Pyro test data1 6 .

The static peak overpressure for the detonation blast wave is the measured

air pressure in the shock front, and is related to the total propellant

weight, TNT equivalent yield and reduced distance ( ) by the following

equation:

log P -- 2.349 logy + 3 (19)over

where Pover a the static peak overpressure (psig) and X. - the reduced

distance.

24

A

In theory, a given overpressure will occur at a distance from an explosion

proportional to the cube root of the energy yield or to the cube root of the

explosive weight. Full-scale tests indicate that this relation between

distance and energy released holds for explosive yields into the megaton

range: 1 5

* ~r .(20)

(%W)

where r = equivalent silo hemisphere radius

I? (946/2#") 1'/ 2 - 42.3 Feet

and percent W = Equivalent explosive weight involved in hypergolic reaction.+ (O .

not include unreacted vaporized propellant).

Equation (19), which was valid for 1000-pound Project Pryo test data for

reduced distances ( ) between 1.0 and 10.0, can be combined with Equation

(20) to give the final static overpressure equation:

* 12.3log P - -2.349 log +3 (21)

over (.005 Wb)/3

Where W b the total liquid propellant weight (pounds) involved in the

hypergolic reaction.

From Equation (21), hypergolic reactions involving large quantities of %

mixed propellants are more catastrophic in nature, resulting in higher static Lpeak overpressures and explosive detonation. As the total propellant weight

involved in the hypergolic reaction (Wb) decreases, the peak overpressure

decreases and the accident scenario more closely resembles a nonexplosive

chemical combustion.

25

For an accident involving the full inventory of rocket propellant in a

properly fueled Titan II missile (Wb - 3.122 X 105 Lb) the equivalent

yield is 1.56 X 10 Lb TNT, and the calculated peak overpressure is 872 pstg

(60.3 atmospheres). This pressure was therefore used to calculate the

theoretical thermody-iamic combustion products and adiabatic flame temperatures

-esulting from a catastrophic ac,. tdent Involving the full Inventory of liquid

rocket propellant contalied in the Titan I1 missile (Stage I and Stage 2).

4. Confined Silo Hypergolic ExplosionP4 0 12.56 atmosphere + Pover

Tho 'ituation in whicr a catastrophic hypergolic accident occurs in a

closed missile silo has been approximated by a.3u.uaIng an initial slow pressure

buildup followed by an explosive detonation of mixed propellants. In this"-ase, the maximum silo prt,;sure before ejection of the 700-ton horizontal Rilo

door woule be the pressure required to eject the silo cover (12.56

r.nm.spheres) plus the static peak overpressure resulting from the hypergolic

exLplos~on. For a catastrophic accident involving the mixing of the full

propellant load in a sealed Titan 1I missile silo, the maximum pressure

calculated Is 12.5.5 atm + 59.3 atm overpressure - 71.9 atmospheres total

pressure. This preassure is considered a worst-case explosive condition. In

accIdents which involve the accidental mixing of hypergolic propellants in a

;ea'ed silo, the atiial silo pressure will depend on the rate of propellant

mix.:ng, and on the configuration of the missile and silo prior to the

;icc.dctt. For example, peak overpressures would be diff,!rent for conditions

in which Stages I and (I are confined in the silo than for those conditions

which result In the :i;cputsion of Stage I and/or II, plus the reentry vehicle

(RV) from the silo. The latter case was typical of the accident scenario near

Dam-isos, Arkan,;as. The total pressure in the sealed silo prior to fireball

lift-off is therefore hounded by the minimum pressure to eject the silo door

(12.56 atm) and ti'e mixitnum pressure due to a hypergolic explosion

(12.56 atm + P ).

2;,

p

b4

Fifteen computer calculations were performed for various hypergolic

combinations simulating an in-silo mixing accident (silo door open or closed)

or an open-field accident. A description of the computer input pertinent to

these 15 calculations is presented In Table III. Results of these

15 computer runs, referenced by their respective case numbers are found

in Appendix A. The first five runs are calculated for an O/F sole ratio of

.902 (the ratio used in the fueling and firing of a Titan II misaile). These

calculations were also performed, assuming thermal interaction of the air

present in the silo (125,000 Ft 3 air). The total propellant weight was

decreased from 3 X 105 pound in Run I to 3 X 102 pound in Run 5, while the

O/F mole ratio (.90) and weight of silo air (9,475 pound) were held constant.

27

Tn. .1V~t _1VTW_7_-Z11or

TABLE III. INPUT TO SP-273 COMPUTER CALCULATIONS

FOR BIPROPELLANT ACCIDENT'S

0/F 0/F Weight Weight WeightRun Case Kale Weight A-5O NTO Air P1 P2 P3 P4No. No. Ratio Ratio Pounds Pounds Pounds atm atm atm atm

5 31 1 .902 2.076 1.046x105 2.076x105 9.475x103 1 12.56 60.3 71.9

2 2 .902 2.890 l.046x101 2.076xlu 9.475xlIJ 1 12.56 --- --

3 3 .902 11.04 1.0464103 2.076x103 9.475x103 1 12.56 --- --

4 4 .902 92.57 1.046x102 2.076x102 9.475x10 3 1 12.56 ---- ----

5 5 .902 907.8 10.46 20.76 9.475x]0 3 1 12.56 --- --

6 6 1.02 2.348 9.247x104 2.076x105 9.475x103 1 12.56 59 70.6

7 19 1.02 2.245 9.247x10 4 2.076x10 5 0 1 12.56 ---- --

8 32 0.51 1.122 9.247xl10 4 1.0384105 0 1--- --

9 20 0.204 4.49xl0 1 9.247x104 4.152x104 0 1--- ---1 4 04

* 10 21 0.102 2.25x10 9.247410 2.076x1001--- --

* 11 23 0.010 2.25x102 9.247x104 2.076x103 0 1--- --

12 33 2.04 4.49 4.623x10 4 2.076x10 5 0 1--- --

13 26 5.1 1.123x40 1.849x104 2.076x105 0 1-----------

14 23 51.0 1.123x102 1.849x103 2.076x10O 0 1--- --

15 30 51.0 1.123x10 3 1.84qx10 2 2.076x10 5 0 1- ---------

j ~51*Results for the full inventory of liquid rocket propellant (3x10 pounds) Indicate

adiabatic flame temperatures of 29160K, 31800K, 33400K, and 33570K for silo

pressures of 1 atmosphere, 12.56 atmospheres, 60.3 atmospheres, and 71.9 atmospheres

respectively. The major fireball constituents for this reaction were carbon monoxide,

* carbon dioxide, hydrogen gas, water vapor, nitric oxide, nitrogen gas, hydroxide radical,

anid oxygen gas, the proportion of which varied according to the reaction (silo) pressure.

As the total propellant weight decreased, the thermal energy of the combustion products was

used ro heat the silo air. Thus In Case 5% which employed a 1/1000 propellant load (3x102

* pound), the adiabatic flame temperature was reduced to 3230K at 1 atmosphere pressure and

also 3230K at 12.56 atmospheres pressure. The exact quantity of silo air which will

* interact with the hypergolic rocket fuels will depend on the extent of mixing and fireball

glift-off time.

28

Run number 7 (Case 19) details the computer results for a stoichiometric

mixing of hypergolic rocket propellants (O/F - 1.02) in the absence of

interacting air. The resulcs of this analysis, presented in Figure 3, will be

used in thermochemical calculations to be described in subsequent sections.

Since no air was allowed to interact with the liquid rocket fuel, the

calculated adiabatic flame temperature of 2917°K is independent of the total

propellant weight, Wb, as long as the O/F ratio remains constant.

Hypergolic spills which involve an excess of A-50 fuel (Computer Runsj 8-11) indicate that the calculated equilibrium chemical species contained in

the fireball would be carbon blavk 1C), methane gas (CH 4 ), hydrogen gas

(H 2 ), and nitrogen gas (N2 ).

Spills which involve an excess of NTO oxidizer (Computer Runs 12-15)

contain mostly nitrogen gas and oxygen gas as equilibrium fireball components

with very small amounts of other chemical species present.

These computer results which involve nonstoichiometric mixing of A-50 fuel

and NTO oxidizer are accurate for ideal thermodynamic conditions, i.e., when

the Gibbs free energy of the reaction products is minimized. Unfortunately,

not all chemical reactions occur naturally and within a reasonable time frame

to produce the thermodynamically stable product.

-As an allotropic form of carbon, graphite is thermodynamically more stable

than a diamond. A diamond, however, does not spontaneously revert to

the graphite without extremes of temperature. The difference between

the actual chemical composition and the thermodynamically predicted com-

positions may be attributed to the kinetic barrier or energy of activation

for the reaction. Since the nonstoichiometric calculations described above

for a mixing of hypergolic fuel and oxidizer do not account for kinetic

effects, a more realistic approach to fuel-rich or fuel-lean combustion

reactions is presented in the following section.

29

I t

L

B. VAPORIZATION OF EXCESS UNREACTED PROPELLANTS CALCULATED UNDER

NONEQUILIBRIUM CONDITIONS

Because the NASA SP-273 computer program did not predict propellant

vaporization due to kinetic factors, an approach was formulated which allows

the vaporization of excess liquid rocket propellant and calculates the final

adiabatic flame temperature of the resulting fireball under nonstoichiometric

conditions.

In general, the fuel and oxidizer reacted stoichiometrically, according to

Equation (I) in Section III, and the thermal energy resulting from this

chemical reaction was used to vaporize any excess unreacted propellant. The

fireball chemical species for nonstoichiometric conditions, therefore,

contained the combustion products calculated for Computer Run 7 (Case 19) and

the vaporized excess propellant. Because the chemical thermal energy released

from the hypergolic reaction was used to vaporize and heat excess propellant,

final adiabatic temperatures were significantly lower than those reported in

Section A.

Calculations are provided in this section for the following vaporization

conditions:

1. All excess fuel (hydrazine + UDMH) vaporized

2. All excess oxidizer (N2 04 ) vaporized

3. UDMH selective evaporation

4. Hydrazine monodecomposition and UDMH evaporation

5. Oxidizer evaporation and dissociation into NO 2

The exact vaporization condition depends strongly on the nature of the

hypergolic accident. Condition 4, for example, would be a more likely result

than Condition 1 in cases in which the accident involves an explosion, since

the decomposition of hydrazine to ammonia occurs catalytically and rapidly

when explosively initiated. Condition 5 is the preferred mechanism for oxidizer

30

vapor release at temperatures above 3730K (refer to Table II - Section D).

UDMH selective evaporation may occur during tank rupture because the vapor

pressure of UDMH liquid is significantly higher than hydrazine liquid.

The mathematical development of the thermochemical equation required to -

predict fireball temperatures and chemical compositions in hypergolic

reactions Involving an excess of A-50 fuel or NTO oxidizer is presented below:

Define:1 I # moles hydrazine liquid reacted

a2 a # moles UDMH liquid reacted

a3 M # moles nitrogen tetroxide liquid reacted

a4 = # moles carbon dinoxide (CO) formed by combustionI

a4 W # moles carbon monoxide (CO) formed by combustion

a6 a # moles hydrogen radicxi (H) formed by combustion

a7 # moles hydrogen gas (1 2) formed by combustion

a8 M # moles water vapor (H120) formed by combustion

ag = # moles nitric oxide (NO) formed by combustion

2) formed by combustion

a10 W # moles hydroxide radical (OH) formed by combustiona 1 2 # moles oxygen gas (02) formed by combustion

a 1 3 a # moles hydrazine vaporized

14 - # moles UDMH vaporized

2a15 # moles NO2 formed from a15 moles N2 04

a 1 6 M# moles NH3 formed from hydrazine decomposition3decomposition

a 17 a # moles H2 formed from hydrazi.nedeopstna,, W # moles N2 formed from hydrazine decomposition

a1g M # moles N2 04 vaporized

0( Oxidizer/Fuel mole ratio

- Percent Mixing (Fraction of excess propellant vaporized)

X - moles of excess fuel (A-50)

Y moles of excess oxidizer (NTO)

f fraction excess N2 04 (g) dissociated into 2NO 2 (g) at

temperature T(°K)

31

IZ~S%,,.,... ..... ...............

For an adiabatic process.

rl

H reactants - AHf products + 0 C dT (products)-298 P

where T. adiabatic flame temperature

0

C = low pressure heat capactZy of productspr

for C A + BT + CT2 + DT3 jC in cal/mole OK

then upon integration: AHo• reactantsf

B 2 C 3 D 4AH° products + AT + T + T + T + E (22)

f F F F F2 3 4

where E = -A(298) - (298) (298) D (2984

2 3 4

The low-pressure heat capacities for fireball reaction products, as well

•s the standard free energies of formation for reactants and products, were

obtained from a variety of sources 14 ' 1 7 , 1 8 and are presented in Table IV.

",he vapcr-phase heat capacity for UDMH was not readily available 1.n the19literature so it was estimated by using Dobratz's Equation

Note that the sensible and latent heats for propellant vaporization are

'iot required In this analysis, since these heats are already included in the

h,,ats of formation of the propellant vapors at 298K ( AH for speciesfp

13, 11,, ind 19).

3.

32

TABLE IV. THERNOCHEMICAL PROPERTIES FOR HYPERGOLIC PROPELLANTS

AND REACTION PRODUCTS

Temp•. Coef- o Rangeficient Species* AHf OK A B 102 C 105 D 109 E 10-3

a, N2 H4 (1) 12054

a2 VDMH(1) 12339a 3 N2 04 (1) -4676 .....

a4 CO -26416 273-3700 6.480 0.1566 -. 0239 0 -1.998

a5 CO2 -94052 273-3700 6.393 1.0100 -. 3405 0 -2.324a6 H 52094 1000-5000 4.968 0 0 0 -1.480aT,a17 H2 0 273-3700 6.424 0.1039 -. 0078 0 -1.960

a8 H2 0 -57798 273-3700 6.970 0.3464 -. 0484 0 -2.227a9 NO 21600 273-3700 6.462 0.2358 -. 0770 .0873 -2.024

alo,a 18 N2 0 273-3700 6.529 0.1488 -. 0227 0 -2.010

I]a OH 9625 1000-5000 5.785 0.1906 -. 0386 .0273 -1.805

a12 02 0 273-3700 6.732 0.1505 -. 0179 0 -2.071

a 1 3 N2H4 22434 1000-5000 10.12 1.85 -. 6680 1.119 -3.780

a 1 4 UDIH 20705 0-2000 4.06 6.54 -2.18 0 -3.921

a 1 5 NO2 7960 273-1500 5.481 1.366 -. 842 1.88 -2.170

a16 NH -11040 273-1500 6.586 0.6126 .2366 -1.598 -2.253a19 N2 04 2114 273-1500 7.945 4.46 -2.71 0 -4.109

AH• - heat of formation (calories/mole)

2 3C - A + BT + CT 4 DT (calories/mole OK)p

*Species are gaseous unless otherwise noted by (1).

33

511it I

For example:4o

iýH hydazine vapor (2980K) iH hydrazine liquid (298) (23)•f

H H29 8

Yap

and SH298 AHNBP + C1 (T -298) - Cv (TB - 298) (24)vap yap p B p

therefore

10 HAO ( 9) NB? v(T 284f (298,v) " •Hf (298,1) +p (TB -298) + • N1vap P (TB- 2 9 8 )

where 1 - liquid phase

v - vapor phase

NBP = normal boiling point

TB - temperature at boiling

Coefficients for a stoichiometric reaction of A-50 fuel and NTO oxidizer

were determined from Equation (1), Section III for the reactants (hydrazine,

UDMfI, and NTO), and from the computer output for stoichiometrtc combustion

(Figure 3) for the normal combustion products. These coeff -ts are:

81 : .6522 a2 - .3478 a3 - 1.0217a4, - .3807 a5 _ 34 a6 = 15

.a149 .1755a 7 - .3570 a8 - 2.087 a 9 - .0726

a10 - 1.985 all - .3267 a12 - .59

Only the major combustion species were included In this analysis, and

Soxygen (a 1 2 ) was used to provide a mass balance for the chemical reaction.

34

-- - Q -"

3U 8

0 /

SI~

z 0 2

3--

4 " 4

-•0 •;. -,, .

el l y

2 - 4

Of MO

U0 fM 0

0q ..... '.2

Poob.Lavialecp

The coefficients for mnreacted vaporized propellb.ts were determined from

the O/F mole ratio ( O) and vaporization condition-as follows:

1. Excess Fuel Reactions

Define o< - 1.02171 +X

X , 1.0217 - ""

Cas'3 1. All excess hydrazine and UDMH vaporized

a1a 1 3 - moles hydrazine vaporizee [(.6522X) * 0(.6664 - .6522-o)/c"

a 1 4 * moles UDMH vaporized -

.3478X) - (.3553 - .3478CV)/'c r

a a a a a15, 16, 17, 18, 19 - 0

Ca e 2. IJI)DH selective vaporization

a14 Q (.3553 - .3478V)/o<

a1 3 a15, a16, a 1 7 , a1 8 , 19-0

Case 3. Hydrazine decomposition and UDMH vaporization

N2 H4----'- NH3 + 1/2N2 + 1/2H2

a 1 4 - 0(.3553 - .34780)/0(

a,6 - t (.6664 - .(,5220')/o,

a 1 7 - 0 (.3332 - .3261J')/o¢"

al 8 -, (.3332 - .3261o0)/or

a13, S, 9 - 0

36

'je

2. Excess Oxidant Reactions

Define t - 1.0217 + y

14

y - 0-1.O217

y a • (0-1.0217)

815 # I moles excess N2 H4 Q • ( 0-1.0217)

S2a15, # moles vaporized NO 20f (OC -1.0217)a19- # moles vaporized N2 04 0 (l-f) Q(09-1.0217)

a13, 14, '16, 817, 818 - 0

Upon mztttplicatLon by known coefficients, integration of the heat

capacity function, and collection of terms, the final thermochemical equation

for nonstoichiometric hypergolic propellant reactions is:

7375.6 + (a13 + a16)(12054) + a14(12339) + (a15 + a19)(-4676)

- -. 1595x10 5 + 41.49T + 8.007xlO- 3 T2 - 1.063x1O- 6 T3 + 3.807x10"12T4

+a13( .186x10 5 + 10.12T + 9.25x10- 3 T2 - 2.227x10' 6 T3 + 279.8x1O- 1 2T 4)

+a 1 4 ( .186x10 5 + 4.06T + 32.7x10- 3 T2 - 7.267x1O- 6 T3 + O.0T4

+2a 5 - 12 415( .058x10 + 5.48T + 6.83xlO-T - 2.807xlO 6 T3 + 4 70x10 T)+a5-3 2 -63 -12 416(- .133x10 5 + 6.59T + 3.06xlO T + .788xlO T + -399.5xlO1 T)

+a 1 7 (- .020x10 5 + 6.42T + .52xlO- 3 T2 - .026xlO- 6 T3 + 0.O04 )

+a1 8 (- .0260x1O5 + 6.53T + .74xlO- 3 T2 - O76xlO- 6 T3 + O.OT4 )

+a19(- .020x10 5 + 7.95' + 22.3-O13T2 _ 9.03xlO-6 T3 + O.OT )

(26)

37

Adiabatic Flame Temperatures and Fireball Compositions were calculated forvarious O/F ratios, vaporization conditions, and mixing conditions and orepresented In Appendix B. Note that when a13 , a14, a1S, a 16 , a17,

a18, and a19 are zero, Equation (26) reduces to a stoichiometrlc

combustion, and yields an adiabatic flame temperature of 2979°K. This".14

temperature !s approximately 2 percent higher than that predicted by the NASASP-273 program because not all the combustion products were considered in this

analyaos and because the heat capacity data used In this analysis were

different than the data used in the computer program.

For a fourfold exceas of A-50 fuel (O/F - .204, Analysis 5) the adiabatic

flame temperature erops to 1046 0 K, and the mole fractions of hydrazine vapor

and UDMII vapor contained In the fireball ore 0.25 and 0.14, respectively. The

"Nalance of the chemical constituents in the fireball include primarily water

vapor (mole fraction .20) nitrogen gas (mole fraction .19), and oxygen (mole

fraction .06): with trace amounts of the remaining combustion products. When

calculated for hydrazine decomposition with the same fourfold excess of fuel

(O/F - .204, Analysis 6), the calculated fireball temperature is 1523°K

(increase 'n temperature due to thermal stability of ammonia vapor over

hydrazine vapor) and the major fireball species are hydrogen gas, w;ater vapor,

nitrogen gas, UDMH vapor, and ammonia gas.

For a fourfold excess of NTO oxidizer (O/F a 5.1, Analysis 15), the final

calculated adiabatic fireball temperature is 810 K and the fireball

composltIoa consists primarily of NO2 gas (mole fraction .57), nitrogen gas

(mole fraction .14) aid water vapor (mole fraction .14).

The fireball temperature for the oxidizer-rich reaction is much lower than

for the fuel-rich reaction, because energy is required to vaporize excess

S204 liquid ( L H N 04 - 6790 cal/mole NTO) and to dissociate the

vaporized N2 04 molecules into two molecules of nitrogen dioxide gas

*( A ll N2 04 - 13,600 cal/mole NTO). As described previously, b-th of

these heats aIre accounted for in the standard heat of formation of NO2 gas

;1L 298"K (coefficient a1 5 in Table IV).

38p

Note that excess propellant vaporization Is not predicted for

oxilizer/fuel ratios larger than 17.7 or smaller than .06 in cases in which

both propellant species are 100 percent mixed. In these cases, the heat of

r,.actton is sufficient to raise the exces;s propetlant Liquid temperature

(sensibln heat) but not sufficient to vaporize the excess propellant (heat of

vapou izat ion).

C. CALCULATION OF FIREBALL SIZE AND QUANTIFICATION OF HEAT FLUX

Mie fireball size and heat flux calculations presented here are based on

the mathematical description presented by Sandia Laboratories. 7 This

free-field model uses black-body radiation heat losses and continuous

expaision of the fireball volume. The convective heat losses and mixing of

the reactants and products with the enviro:%ment ar- conqidered negligible

during the fortation and Initial lift-off of the fireball.

1. Theory

The calculations for the fireball. formatrion, usi'ng this Sandia

Laboratories model, represent the reaction time, tb, based on a sphertcal

*. fireball and a hydrodynamic flow model as

tb - 0.6 Wb (27)

The reaction time Is the time necessary for the ma4s of hypergolic propellant,W'b, to mix and react to completion. The reaction time, tb, is also

eqitralent to the fireball lift-off time. The radius of the fireball, rb,was determined from the spherical gas volume and the average ý.as denqity,

10- P (,W)/R'T,

.38

rb - (3/41' f )1/3 1/3 (28)b Wb

39

1' -ft

The fireball growth ratio was based on the assumption that the propellant

was consumed at a constant rate, R, where

W h b W 1/6 5/6R - /t t /(0.6 ) - Wb /63. (29)

b I.

The radius of the fireball as a function of time, t, was determined, using

Equation (29) to specify the propellent weight and the methodology used to K-

develop Equation (28). This leads to

r - (3 Rt/4fr 1O )1/3 - C t 1/3 (30)

during the time when the propellants are reacting and

r (314b/4 17-)1/ 3 t 1/3

after the reaction has terminated and the fireball has lifted off.

The fireball temperature and rate of energl reioase were determined froman energy balance that equated the enthalpy of the input propellant minus the

energy radiated to the environment to the rate )f charge of internal energy in

the fireball. This can be written as

Rh. - C-0- AT4 = d (Wh)fb/dt (31)

for the pe, lod of time when propellant is being consumed by the reaction and

d (-h)fb/dt - - C-O AT4 (32)

after the reaction is complete.

40

•- --- - '. .,, - -< '-- '- '- , •- .. . _" .. '" " _" _' .::-:- .. ::.:- =''':' " -- " - " -' -'.- -- " ;---- . . .. .. ... .

i

Equation (31) can be rearranged and simplified using the assumptions and

definitions outlined above to give the following nonlinear differential

equation that was solved numerically for the temperature during the reactiontime Wt'4-C1): i

4 'R 2/3 14/3

dT hi hfb .7b 16 (3

dt' t'Cp

hi * H reactants, enthalpy of reactants0

hfb W [o JCPd]products, enthalpy of products

- 1 (black body radiation)

- Boltzmann's constant

Wb weight of propellant

t t/tb - nondimensional time

R' international gas constant

P 1 atmosphere, pressure of ambient fireball

(MW) a molecular weight of gaseous products

C A + B T + C T2 + D T3 , specific heat of productsP

T a absolute temperature

Equation (32) can also be rearranged to solved for the temperature of the

fireball after the reduction is completed and the fireball lifts off (t' 1).

dT 41"6- [i3 2/3 14/3T (34)

1.66 Wb6 Cp 4 F P (MW)

41

, . . ... ... ... ... . • ... ... .. .......... r . . .. . . ... . ...... . . . . . . . ... . .. .. . . .. ... ...

2. Results

Equations (33) and (34) were integrated numerically, using a Fourth Order

Rtnge - Kutta Method. The tnitial temperature, T(t') - TIO), for the case

durLng the propellant reaction, Equation (33), is the adiabatic flame

teoperature. The initial condition for Equation (34) which describes the

fireball, temperature after lift-off, t'>l, was considered to be the solu:tion

of Equation (12) at t' - 1.

Figure 4 shows the temperature, dimensLonless time relationship for

3•KIO5 pounds of stoichiometric mixture of N1204 and A-50. The initial

"" temperature of the fireball was calculated to be 2979 K and decreased to

- 22430K at t' - 1 which is 4.9 seconds after ignition. The temperature of

thc rising fireball was calculated to decrease to 15180K at t' - 3 or t -

14.7 seconds after ignition.

Figure 5 shows the radiant heat flux from the fireball as function of t'

for Lhis stoichiometric mixture. The initial value is 393 Btu/Sec ft 2 and

decreased to 126 Btu/sec ft 2 at t' = 1 after the lift-off, t' >1, the heat

flux continues to drop off to approximately 27 Btu/sec ft 2 at t' - 3.

42

3000

N..

"2500

S2000

I ° 1500 -"___

C 5 1.0 1.5 2.0 2.5 3._

400

300

i I'0

2oo

u_ C, j

.5 1.0 1.5 2.0 2.5 3.0

Dimensionless Time (t)

Figures 4 and 5. Radiative Fireball Temperature and Heat Loss

514= 3.00 X 10 Pounds

O/F - 1.02

43

L

The aomperature and heat flux from a fireball that results from

1.34 X 105 pound mixture of A-50 and N2 0 4 containing a 4X excess of A-50

are shown in Figures 6 and 7, respectively. The intitial temperature was

1046°K and decreased to 1035°K at lift-off, t' 1, which, for this case,

occurs 4.3 seconds after ignition. The temperature continues to decrease

after itft-ofý and is 10000K at t' - 3 or 12.9 seconds after Ignition. The

initial heat flux for thiA case is 6 Btu/sec ft 2 and decreases to 5.7

Btu/sec ft 2 at t' - 1. At t' a 3, the heat flux has decreased to 4.9 .

Btu/sec ft 2 . The increased energy needed to evaporate and heat the excess

A-50 reduces the energy available to rsise the temperature of the fireball and

radiate to the environment.

Figures 8 and I show the relationships of the temperature and radiant heat

flux vs. time for a 2.3 X 105 pound mixture of A-50 and N2 04 containing

a 4X exces3 of N2 04. The initial temperature of this system is 810°K

and decreases to 804 K at lift-off, t' = I or t - 4.7 seccnds after

ignition. The temperature decreases to 786°K at t' - 3 or 14.1 seconds

.Ifter ignition. Again, the temperiture and heat flux are decreased because of

the energy needed to raise the temperature and vaporize the excess N2 04 "

3. Conc lusion

The equations developed and evaluated in this section of the report are

general and 'an be used to determine the temperature and heat flux from a

homogeneous fireball when the thermodynamic properties of the reactants and

products are known. The maximum temperature and heat flux result from a

stoichionetric mixing of the propellants. Excess N2 0 4 reduce both of

these properties of the fireball more than exceui fuel because of its greater

heat of vaporization and specific heat. This causes more energy to be

consumed by the components of the reacti on fixture; therefore, less energy is

released to the environment.

44

d

--. . . . . . . . .

050

S1030

E

990. ... .. ..

0 1.0 1.5 2.5 .3

6.0

3 .0I

*) b" . ..

•.5 1.0 1.5 2.C 2.5 2.0

Dimensionless Time (t)

Figures 6 and 7. Radiative Fireball Temperature and Heat Loss

Wb - 1.34 X 105 Pounds

O/F - 0.204

810

0 300 -

'.35

.35.

.5 1.0 1.5 2.0 2.5 3.0 .

I -- L

2..2 X15 oud

bA

C.'l

- 5.351

Sb- ,

• .5 1.0 1.5 2.,3 2.5 3.0 r?

Dimensionless Time (t)','

Figures 8 and 9. Radiative Fireball Temperature and Hteat Loss

Wb ,•2.26 X 105 Pounds

0/F - 5.1

46 -

SECTION V

REACTIONS OF HYPERGOLIC PROPELLANTS WITH OTHER CHEMICALS

To characterize the explosive hazards of reacting a hypergolic fuel (A-50

or NTO) with other chemicals that may be encountered in a highway or railway

accident, the NASA SP-273 computer progr-,m was used to predict the theoretical

flame temperatures and combustion products resulting from such an accident.

Calculations were performed, assuming an equal weight of hypergolic fuel and

nonpropellant chemical (O/F weight ratio of 1.0), and were performed at 1.0

atmosphere Lotal pressure which would be indicative of an open-field

accident. Because these calculations only consider ideal chemical

thermodynamic conditions (and not kinetic parameters as discussed in Section

A), the computer output for these reactions contains only the combustion

products which would be present at chemical equilibrium.

The chemical reactants used as computer input for these calculations are

included in Table V. Computer output for the reactions of hypergolic rocket

propellants with these other chemicals are included in Appendix C.

47

ib

TABLE V. COMPUTER INPUT FOR REACTIONS OF HYPERGOLIC ROCKET

PROPELLANTS WITH OTHER CHEMICALS

CaseNo. Fuel* Oxidant*

34 Methylene Chloride NTO

35 Ethylene Gylcol NTO

36 Dichlocoethane NTO

37 Liquid Propane NTO

38 n-Octane NTO

39 Acetone NTO

40 Acetylene NTO

41 Ammonia NTO

42 A-50 Liquid Oxygen (LOX)

43 A-50 Air (g)

44 A-50 Chlorine

45 A-50 Nitric Acid

46 A-50 Hydrogen Peroxide

* All reactants are in the liquid state unless otherwise Inoted. I

4.8

k1

48

.-)

SECTION VICONCLUSIONS

The purpose of this document is to provide engineering data which will be

used to predict the aerial dispersion patterns of chemical reaction products

resulting from catastrophic accidents involving the mixing of hypergolic

liquid rocket propellants. The analysis methods described in this report have

been developed for the A-50/NTO propellant combination, but the general

thermodynamic methods are applicable to any other fuel/oxidizer combination '.

which may be encountered in an accidental hypergolic vapor release. The

salient features of the comr'itational methods described In this report are:

1. Stoichiometric reactions of A-50 fuel and NTO oxidizer have been

successfully characterized using the NASA SP-273 computer program for the

calculation of complex chemical equilibrium and rocket performance.

Reactions have been defined according to the type of propellant accident

(open-field, open-silo, closed-silo, and hypergolic explosion) and

according to the presence of intera:ting air. For a catastrophic accident

involving the full inventory of liquid oxidizer (207, 560 pounds nitrogen

tetroxide) and liquid fuel (104, 609 pounds Aerozine-50) which occurs in

an open Titan II missile silo, the calculated adiabatic flame temperature

is 2916 0 K (5249 0 R) which is consistent with fireball data previously

reported in the literature1 5 . This calculation was performed assuming

thermal interaction of air present in the closed silo (125,000 ft 3

air). The major gaseous combustion products contained in the fireball

were determined to be carbon monoxide, carbon dioxide, hydrogen radical,

hydrogen, water vapor, nitric oxide, nitrogen, hydroxide radical, and

oxygen.

2. For hypergolic combustion under nonstoichlometric conditions (O/F

mole ratio ' 1.02) a calculation methodology is presented in which the

heat evolved from the stoichtometric reaction was used to heat and

vaporize the excess propellant. Major fireball components for the

fuel-rich reaction were hydrazine vapor, UDMH vapor, nitrogen gas and

49

IL I Wwrlý ý

water vapor for accident scenarios which favored A-50 evaporation; and

ammonia vapor, UIMH vapor, nitrogen gas, hydrogen gas, and water vapor for

accidents characterized by A-50 evaporation and hydrazine

monodecomposition. Fuel-lean hypergolic reactions contained both nitrogen

dioxide gas and nitrogen tetroxide gss in the vapor phase of the fireball,

the proportions of which depended upon the adiabatic temperature of the

resultant fireball. Oxidizer to fuel mole ratios above 17.7 and below

0.06 were not characterized in this analysis, because the thermal energies

derived from these hypergolic reactions were not sufficient to vaporize

the excess propellant.

3. *. -neralized scheme for determining time-temperature and heat

flux-temperature profiles for hypergolic fireballs is discussed. The

development of the heat flux equations was based on the assumption that

the major heat loss mechanism during fireball generation and lift-off was

radiative, and conductive and convective heat losses were negligible.

This is consistent with fireball heat transfer mechanisms previously

reported in the literature2 1 . The largest initial heat flux calculated

was for the stoichiometric reaction of A-50 fuel and NTO oxidizer. This

reaction gave an initial heat flux and temperature of 400 Btu/ft 2 second

and 2979 0 K, respectively. The temperature of the fireball for this

stoichiometric combustion dropped to approximately 2240 0° at lift-off

(t' - 1.0). Nonstoichiometric hypergolic combustions yielded much smaller

initial heat fluxes and temperatures

(Q/A = 2.15 Btu/ft 2 second, T - 810°K for O/F - 5.1;

Q/A - 5.98 Btu/ft 2 second, T - 1046°IK for 0/F - 0.20).

As a result, the initial adiabatic flame temperature for these

nonstoichiometric hypergolic reactions did not change appreciably during

fireball generation and lift-off.

4-- - -- - - - - - -

S. 50

I."

V.

4. Fireball sizes were estimated using the theoretical equations:

• ? 1/3 1/3 '

r Wbrb " b."

"

Where rb - fireball radius

Wb - total propellant weight (lbs) in reaction

P density of combustion products

for an ideal gas:

MW avg P

RTF

Where W average molecular weight of combustion gasesavg

P - pressure of gases (14.7 psia under standard conditions)

R - ideal gas constant (10.731 ft 3 - psia/fR - mole)

Tf adiabatic flame temperature (OR)

The calculated fireball radius for an accident involving the full5inventory of A-50 fuel and NTO oxidizer (Wb - 3.12 X 10 pound;

MWavg - 21.9; TF - 5249OR) using this approach is approximately 235

feet which generally corresponds to the fireball radius established

empirically for A-50/NTO reactions20:

0.328i

rb 4.43 W 0 - 281 feetb b

5. Computational methods using the SP-273 computer program were used to

predict the thermal energies and chemical reaction products resulting from

the mixing of a hypergolic liquid rocket propellant with other chemical

51

mo

species that may be encountered in a highway or rail accident. Although

these calculations were performed assuming ideal thermodynamic conditions

for the chemical reactants and products, they are still useful for

estimating fireball temperatures and hazardous vapor envelopes for these

accident scenarios.

In addition to the computational methods described above for the

characterization of critical fireball parameters (e.g., chemical composition,

thermal energy, and geometric size), an exhaustive literature survey was

completed in order to compile existing knowledge in the hydrazine (MMH, UDMH)

- nitrogen tetroxide hypergolic reaction. Over 50 chemical reaction products

resulting from this combination have been described in the literature, and

most of these products can be accounted for by one or more simple chemical

mechanisms. One of these chemical components, nitrosodimethylamine, is of

particular concern in a hypergolic bipropellant accident, because it is a

confirmed product in both the A-50/NTO reaction and in the A-50/air reaction,

and is a known carcinogen.

52

"". . Onia.I . -

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Environmental Protection Subcommittee Meeting. CPIA Publication 348.

November 1981.

.A

i.

58 ,8 •J_

.1

APPENDIX A

COMPUTER OUTPUT

AEROZINE-50/NITROGEN TETROXIDE REACTIONS

Case O/F Air PressureNo. Mole Ratio Weight Percent Atm Page

1 .90 2.9 1.0 60

1 .90 2.9 12.56 61

1 .90 2.9 60.3 62

1 .90 2.9 71.9 63

2 .90 23.3 1.0 64

2 .90 23.3 12.56 65

3 .90 75.2 1.0 66

3 .90 75.2 12.56 67

4 .90 96.8 1.0 68

4 .90 96.8 12.56 69

5 .90 99.7 1.0 70

5 .90 99.7 12.56 71

6 1.02 3.1 1.0 72

6 1.02 3.1 12.56 73

6 1.02 3.1 59.0 74

6 1.02 3.1 70.6 75

19 1.02 0.0 1.0 76

19 1.02 0.0 12.56 77

32 0.51 0.0 1.0 78

20 0.20 0.0 1.0 79

21 0.10 0.0 1.0 80

23 0.01 0.0 1.0 81

33 2.0 0.0 1.0 82

26 5.1 0.0 1.0 83

28 51.0 0.0 1.0 84

30 510.0 0.0 1.0 85

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APPENDIX B

THERMOCHEMICAL CALCULATIONS FOR NONSTOICHIOMETRIC

COMBUSTION OF AEROZINE-50 AND NITROGEN TETROXIDE

Analysts O/F Percent VaporizationNo. Mole Ratio Mixing Conditions Page

,1, 1.02 100 No Excess Propellant 87

2 0.51 100 H & UDMH Evaporated 88

3 0.51 100 UDMH Evaporated 89

, 0.51 100 UDMH Evaporated & H Decomp. 90

0).O.20 100 H & UDMIH Evaporated 91

0, 0,20 100 UDMH Evaporated & H Decomp. 92

7 J.O to 100 H & UrDAH Evaporated 93

0.10 100 UDMH Evaporated & H Decomp. 94

9 0.06 100 H & UDMH Evaporated 95

0.0A 80 H & UDMH Evaporated 96

11 0.06 60 H & UDMH Zvaporated 97

t2 9.06 40 H & UDMH Evaporated 98

13 0.06 20 H & UDMH Evaporated 9915: 2.04 100 NO2 (g) 1015 52.04 100 NO2 (g) 100

16 7.00 100 NO2 (g) 10217 7.00 80 NO2 (g) 103

15 7.00 60 NO2 (g) 104

16 7.00 40 NO2 (g) 105

21 7.00 20 NO2 (g) 106

21 8.55 100 N204 (g) + NO2 (g) 107

22 13.02 120 N2 04 (g) + NO2 (g) 108

23 i7.72 100 N2 04 (g) + NO2 (g) 109

86

I-

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 1

OXIDIZER/FUEL MOLE.RATIO 1.02

PERCENT MIXING 100

VAPORIZATION CONDITIONS No Excess Propellant

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a1 3 = 0 a14 - 0 a15 0

a16 0 a17 x 0 a18 = 0

aiog 0

RESULTS:

Flame Temperature 2979 OK ( 5363 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .061carbon dioxide CO2 .050hydrogen radical H .028hydrogen H2 .057water vapor H20 .332nitric oxide NO .012nitrogen A .3160hydroxide O .052oxygen 02.094 02Ohydrazine vapor N2 H4 (g) .000UDMH vapor C2H 8 N2 (g) 000

nitrogen dioxide NO2 0.000am moni1a NH3(g) .0

nitrogen tetroxide N204(g) .000

Average Molecular Weight 23.13 lbs/lb-mole

87m

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 2

OXIDIZER/FUEL MOLE RATIO 0.51

PERCEN1T MIXING 100

VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 .6545 a14 2 .3489 al5 = 0

a1 6 = 0 a17 = 0 a18 = 0

-19 0

RESULTS:

Flame Temperature 1975 OK ( 3556 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .052carbon dioxide CO2 .043hydrogen radical H .024hydrogen H2 .049water vapor H60 .286nitric oxide NO .272nitrogen N.04hydroxide 0 .045oxygen 02 .081hydrazine vapor 2 ) .090.048UOMH vapor C8H8NZ(g) 000nitrogen dioxide 2 .000ammonia NH3 (g) .000nitrogen tetroxide N204(g).000

Average Molecular Weight 25.66 lbs/lb-mole

88

4.- • . , -• , ".,' ,,....• . . . . . . .. . '.- ,- - . . .. - • . .

THERMCrHEMICAL DATA SHEET

ANALYSIS NO. 3

OXIDIZER/FUEL MOLE RATIO .51

PERCENT MIXING 100

VAPORIZATION CONDITIONS UDMH Selective Evaporation

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 0 a14 .3489 a15 = 0a16= 02al7 0 al 8 = 0

a 19 0

RESULTS:

Flame Temperature 2402 OK ( 4324 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .057carbon dioxide CO2 .047hydrogen radical H .026hydrogen H2 .054water vapor H20 .314nitric oxide N.01ritrogen Ný .299hydroxide .049oxygen 02 .089

.000hydrazine vapor N2 H4 (g) .053UDMH vapor C2HsN2(g)nitrogen dioxide .000ammonia NH3 ( .000nitrogen tetroxide N0 4(g) .000

Average Molecular Weight 25.02 lbs/lb-mole

89

THERMOCHEMICAL DATA SHEET

S-<,

AIf;P. Lv 7S NO. 4* .'

OXIDIZER/FUEL MOLE RATIO .51

PECEN -T MIXING 100 ,

VAPORIZATION CONDITIONS UDMH Evaporation & Hydrazine Decomposition

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 0 a14 = .3489 a15 = 0 _-._

a = .6545 a17 = .3272 a18 = .3272 .

0

R ES T TS.

Flame Temperature 2239OK ( 4031 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .048carbon dioxide CO2 .040hydrogen radical H .022hydrogen H2 .086water vapor H60 .263nitric oxide N .009

nitrogen N .291hydroxide .041o0xyen 02 .074hydrazine vapor N2 H4 (g)UDMH vapor C28H8N2 (g) .4nitroaen dioxide N2 (.000ammon i a NH3 (g) .082nitrogen tetroxide N204(g) .000

Ave-aae M'olecular Weiaht 23.55 lbs/lb-mole

90

4

......................d 0 Wilm

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 5

OXIDIZER/FUEL MOLE RATIO .204

PERCENT MIXING 100

VAPORIZATION CONDITIONS All Excess Hydrazine t UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 s 2.614 a14 2 1.394 a15 a 0

a16 0 a17 0 a18 = 0

a1 9 a 0

RESULTS:

Flame Temperature ojOK ( _OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .037carbon dioxide CO2 .031hydrogen radical H .017hydrogen H2 .035water vapor H0 .203nitric oxide .007nitrogen N .193hydroxide 0 .032oxygen 02 .057hydrazine vapor N2H4 (g) .254UDMH vapor C2HsN2(g) .135nitrogen dioxide NO2 .000ammonia NH3 (g) .000nitrogen tetroxide N204 g) .000

Average Molecular Weight 30.38 lbs/lb-mole

91

THERMOCHEMICAL DATA SHEET

viLYSIS NO. 6

OxiDI:ER/FUEL XOLE RATIO .204

?ER^.NT MIXING 100

;,'?ORIZATION CONDITIONS UDMH Evaporation & Hydrazine DecompositionCOEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a1 3 = 0 a14 = 1.394 a15 2 0

a!6 2.614 a17 = 1.307 = 1.307

319 z 0

aZ::jLTS:

Flame Temoerature 523 OK ( 2742 OR)

7 ireball Species Formula Mole Fraction

carbon monoxide CO .029carbon dioxide .024

hydrogen radic3l H .014hydrogen H2 .129water vapor H60 .162nitric oxide .006nitrcgen NA .255hydroxide OR .025oxygen 02 .046hydrazine vapor N2H4 (g) .000UDMH vapor C2HsN2 (g) .108nitrooen dioxide :N2 .000ammonia NH3(g) .202

nitrogen tetroxide N20 4 (g) .000

Average M.Iolecular Weight 24.20 lbs/lb-mole

92

:S+

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 7

CXIDIZER/FUEL MOLE RATIO .102

PERCENT MIXING 100

VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 5.881 a14 - 3.136 a1 5 - 0

a16 0 a 17 • 0 a18 0

a 19 = 0

RESULTS:

Flame Temperature 580 OK ( 1045 OR)

Fireball Species Formula Mole Fraction ,

carbon monoxide CO .025carbon dioxide CO2 021hydrogen radical H .011hydrogen H2 .023water vapor H 0 .136nitric oxide NO.005nitrogen NA .130hydroxide 0 .021oxygen 02 .039hydrazine vapor N2 H4 (9) .384UDMH vapor C H6N2 (g) .205nitroaen dioxide N.2 .000ammonia NH3 (g) .000nitrogen tetroxide N204(g) .000

Ave-age Molecular Weight l4.p• lbs/lb-mole

93r

L

4-

93 E

THERMOCHEMICAL DATA SHEET

XNALYSIS NO. 8

CYXDIZEI/FUEL MOLE RATIO .102

PERCE':T MIXING 100

VAPORIZATION CONDITIONS UDMH Evaporation & Hydrazine Decomposition

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:a! 3 = 0 a31 = 36 5 __0___

ai 14 a15______

Sa!6 = 5.881 a7 2.941 al 8 = 2.941

a,o 0

RE LT-S:Flame Temoerature J.IZ6 K ( 2171 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .018carbon dioxide CO2 .015hydrogen radical H .008hydrogen H2 .156water vapor H60 .098nitric oxide N .003nitrogen NA .232hydroxide O .015oxygen 02 .028hydrazine vapor N2H4 (g) .000UDMH vapor C2H8 N2 (g) .148nitrogen dioxide N02 .000ammonia NH3 (g) .278nitrogen tetroxide N204(g) .000

Aver3ge ,Iolecular Weight 24.61 lbs/lb-mole

* 94

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 9

OXIDIZER/FUEL MOLE RATIO .060

PERCENT MIXING 100

VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 •i 10.39 a14 554a = z 0,

a16 f 0 a17 0 a183 0___.o_

al9 0 "

RESULTS:

Flame Temperature 29-8-OK 537 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .017carbon dioxide CO2 .014hydrogen radical H .008hydrogen H2 .016water vapor H0 .094 Pnitric oxide .003nitrogen NA .089hydroxide O .015oxygen 02 .027hydrazine vapor N2H4(g) .468UDMH vapor C6HBN2(g) .249nitrogen dioxide NO2 .000ammonnia NH3 ( .000nitrogen tetroxide N2O4(g) .000

Average Molecular Weight _ _ _ _4_ lbs/lb-mole

95

..................................

.......... °

95 A

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 10

OX:D:ZER/FUEL MOLE RATIO .060

ERCE.NT MIXING 80VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = .8.31 a1,a = 4.43 a15 = 0

a 16 = 0 a17 = 0 a1 8 = 0

a19 0

•'E•LLTS:

Flame Temperature 406 0K ( 731 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .020carbon dioxide CO2 .017hydrogen radical H .009hydrogen H2 .019water vapor HsO .100nitric oxideN .004nitrogen .104hydroxide 0 .017oxygen 02 .031hydrazine vapor N2 H4 (g) .437UDMH vapor C2H8 N2 (g)nitrogen dioxide NO2 .000ammonia NH3 (g)00nitrogen tetroxide N204(g) .000

Average Molecular Weight 35.86 lbs/lb-mole

St

96

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. H

OXIDIZER/FUEL MOLE RATIO .060

PERCENT MIXING 60

. VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a-13 6-2-. a14 3.32 815 = 0

.\:.a16 =0a17 = 0a18 "0

a19 0

RESULTS:

Flame Temperature 550 OK ( 991 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .024carbon dioxide CO2 .020hydrogen radical H .011hydrogen H2 .023water vapor H60 .132nitric oxide NO .005nitrogen NA .125hydroxide O .021oxygen 02 .037hydrazine vapor N2 H4 (g) .393UDMH vapor C.210C6H 8N2(g) .0nitrogen dioxide NO2 .00Dammonia NH3 (g) .000nitrogen tetroxide N204(g) .000

Average Molecular Weight 34.39 lbs/lb-mole L

97,

* ~97

THERMOCHEMICAL DATA SHEET

ANriLYSS NO. 12

CYTDIZER/FUEL XOLE RATIO .060

PE7CEjT ',iIXING 40

VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 4.16 a14 = 2.22 a15 = 0

a!.6 = 0 a17 = 0 a18 a 0

RESULTS:

Flame Temoerature 769 OK ( 1385 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .030carbon dioxide CO2 .025hydrogen radical H .014hyydrogen H2 .028water vapor H60 .166nitric oxide N .006nitrogen N 157

hydroxide 0 .026oxygen 02 .047

022hydrazine vapor N2 H4 (g) .328UDMH vapor C2H8 N2 (g) .176nitrogen dioxide NO2 .000ammonia NH3 (g)nitrogen tetroxide N204 (g) .000

Average Molecular Weight 32-62 lbs/lb-mole

98

THERMOCHEMICAL DATA SHEET5

A.AALYSIS NO. 13

OXIDIZER/FUEL MOLE RATIO .060

PERCENT MIXING 20

VAPORIZATION CONDITIONS All Excess Hydrazine & UDMH Evaporated

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 2.08 a14 1.11 a15 z 0

a16 : 0 a17: 0 a18 0

a19 0

RESULTS:

Flame Temperature 1202 OK ( 2164 OR)

Fireball Species Formula Mole Fraction p

carbon monoxide CO .040carbon dioxide C02 .033hydrogen radical H .019hydrogen H2 .038water vapor H0 .220nitric oxide N .008nitrogen Ni .209hydroxide O .034oxygen 02 .062hydrazine vapor N2 H4 (g) .219UDMH vapor C2H8 N2 (g) .117 Pnitrogen dioxide N02 .000ammon ia NH3(g) .000nitrogen tetroxide N204(g) .000

Average Molecular Weight 29.33 lbs/lb-mole

99

- S - . - '. S - .. . .. . . . . .-. -. ,

* .4 .. -

THERMOCHEMICAL DATA SHEET

•1ALYSiS NO. 14

OXid!ZER/FUEL ,OLE RATIO 2.04

PERCH.NT VIXING 100

V'APRIZATIGN CONDITIONS Excess N2.0 (1) 100% Dissociated into NO2 (g)

COEFF!C, ENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 0 al1 = f a15 = 1 02

a16 = 0 a1 7 = 0 a1 3 _

RESULTS:

Flame Temperature 1958 OK (3525OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .046carbon dioxide C02 .038hydrogen radical H .021hydrogen H2 .043water vapor H2 0 .251nitric oxide NO .009nitrogen Ný .238hydroxide O .039oxygen 02 .071hydrazine vapor N2 H4 (g) .000UDNH vapor C2HsN2 (g) .000nitrocen dioxide NO2 .245armonia NH3(g) .000nitrcgeri tetroxide N204(g) .000

>-.r%-,e Molecular Weiqht 28.72 lbs/lb-mole

100

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 15

OXI0IER/FUEL MOLE RATIO 5.1

PERCENT MIXING 100

VAPORIZATION CONDITIONS Excess N2 04 (1)100% Dissociated into NO2 (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 = 0 a14 = 0 a1 5 4.0783

a16 = 0 a17 2 0 a1 8 : 0

a 19 = 0

RESULTS:

Flame Temperature 810 OK ( 1459 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .026carbon dioxide CO2 .022hydrogen rtdical H .012hydrogen H2 .025water vapor H60 .144nitric oxide NO .005nitrogen N4 .137hydroxide 0 .022oxygen 02 .041hydrazine vapor N2H4 (g) .000UDMH vapor C2H8 N2 (g) .000nitrogen dioxide NO2 .565ammonia NH3 (g) .000nitrogen tetroxide N204(g) .000

Average Molecular Weight Ar nl Ibs/lb-mole

ip

101

-4. . . . ° . . . . • . . . . - o - • - ° . - . . . . o . - o • . . °

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 16

OXIDIZER/FUEL MOLE RATIO 7.00

PERCENT MIXINIG 100

VAPORIZATION CONDITIONS Excess N0 4 (1) 100% Dissociated into NO, (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 a14 : alS = 5.98

a1.6 a17 0 a18 " 0

I.ala 0

RESULTS:

Flame Temperature 486 OK ( 875 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .021carbon dioxide CO2 .017hydrogen radical H .010hydrogen H2 .020water vapor H2O .114nitric oxide NO .004nitrogen N .109hydroxide .018oxygen 02 .032hydrazine vapor N2H4(g).000UDMH vapor C2H8N2(g) .000nitrogen dioxide NO2 .656armmon i a NH3 (g) .000nitrogen tetroxide N204(g) .000

Average Molecular Weight 38.07 lbs/lb-mole

K

a 102

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 17

OXIDIZER/FUEL MOLE RATIO 7.00

PERCENT MIXING 80VAPORIZATION CONDITIONS Excess N2 04 (0 ) 100% Dissociated into NO2 (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

"a1 3 = 0 a14= 0 ajS = 4.78

a16 = 0 a17: 0 a 1 8 a 0

a19 = 0

RESULTS:

Flame Temperature 674 OK ( 1214 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .024carbon dioxide C02 .020hydrogen radical H .011hydrogen H2 .023water vapor H60 .132nitric oxide N .005nitrogen N .125hydroxide 0 .021oxygen 02 .037hydrazine vapor N2 H4 (g) .000UDMH vapor C2H8N2(g) .000nitrogen dioxide NO2 .603ammonia NH3 (g) .000nitrogen tetroxide N20 4 (g) .000

Average Molecular Weight 36.91 lbs/lb-mole

I.10

THERMOCHEMICAL DATA SHEET

ANALYSIS '40. 18

OXIDIZER/FUEL MOLE RATIO 7-00

PERCENT MIXING 60 t

VAPORIZATION CONDITIONS Excess N,04 (1).lO0% Dissociated into NO, (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a1 3 = 0 a14 3 0 a15 a 3.59

a 16 = 0 a 17 2 0 a18 * 0

a19 = 0

RESULTS:

Flame Temoerature 920 OK (_1657 OR)

Firebill Species Formula Mole Fraction

carbon monoxide CO .028carbon dioxide CO2 .023hydrogen radical H .013hydrogen H2 .027water vapor H60 .155nitric oxide N .005nitrogen .147hydroxide 0 .024oxygen 02 .044hydrazine vapor N2 He(g) .000UDMH vapor C2HBN2 (g) .000nitrogen dioxide NO2 .533ammonia NH3 (g) .000nitrogen tetroxide N204 (g) .000

Average Molecular Weight 35.25 lbs/lb-mole

104"71

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 19

OXIDIZER/FUEL MOLE RATIO 7.00

PERCENT MIXING 40

VAPORIZATION CONDITIONS Excess N.2 0, (1) 100% Dissociated into NO,, (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 . 0 a14-_ 0 al 5 2.39

a16 0 a17- 0 a18 0

a19-

0

RESULTS:

Flame Temperature 1267 OK ( 2281 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .034carbon dioxide C02 .028hydrogen radical H .016hydrogen H2 .032water vapor H 0 .189nitric oxide NO .007nitrogen NA .179hydroxide O .030oxyaen 02 .053hydrazine vapor N2H4(g) .000UDMH vapor C2H8 N2 (g) .000nitrogen dioxide NO2 .432ammonia NH3 (g) .000nitrogen tetroxide N2 04 (g) .000

Average Molecular Weight 32.97 lbs/lb-mole

105

THERMOCHEMICAL DATA SHEET

A0ALYSIS NO. 20

OYIDIZER/FUEL MOLE RATIO 7.00

DERCENJT 'AIXINIG 20 &

VAPORIZATION CONDITIONS Excess N2 04 (1) 100% Dissociated into N02 (g)

CCEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a03 = 0 a14 2 0 a15 - 1.20

a16 z 0 a 17 a 0 a18 z 0

alo= 0

RESULTS:

Flame Temperature 1840 OK ( 3313 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .044carbon dioxide C02 .036hydrogen radical H .020hydrogen H2 .041

water vapor H60 .240

nitric oxide N.008nitrogen NA .228hydroxide O038.03oxygen 02 .068hydrazine vapor N2H4 (g) .000UDMH vapor C2H6'i 2 (g) .000nitroqen dioxide NO2 .276ammonia NH3 (g) .000nitrogen tetroxide N204 (g) .000

Average -Molecular Weight 29-38 lbs/lb-mole

106

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 21

OXIDIZER/FUEL MOLE RATIO 8.549

PERCENT MIXING 100

VAPORIZATION CONDITIONS Excess NO2 4 (1) 88% Dissociated into NO. (q)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 "a1 4 " n a15 * _ _5 _

a 16 * n a17 = a18 " 0

a19 = _

RESULTS:

Flame Temperature 361 OK ( 650 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .019carbon dioxide C02 .01:5hydrogen radical H .009hydrogen H2 .017water vapor HO0 .102nitric oxideN8 .004nitrogen N .097hydroxide .016oxygen 02 .029hydrazine vapor N2 H4 (g) .000UDMH vapor C2 HSN 2 (g) .000nitrogen dioxide NO2 .646ammoni a NH3 (t) .000nitrogen tetroxide N204?g) .046

Average Molecular Weight 41.06 lbs/lb-mole

4 107

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 22

OXIDIZER/FUEL MOLE RATIO 13.02

PERCENT MIXING 100

VAPORIZATION CONDITIONS Excess N2 04 (1) 40% Dissociated into NO2 (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a 13 = 0 a14- 0 a15 z 4.84

a 16 0 a17 0 a18 0

i a19 = 7.16

RESULTS:

Flame Temperature 319 OK ( 575 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .016carbon dioxide CO2 .0.14hydrogen radical H .008hydrogen H2 .015water vapor H60 .090nitric oxide N .003nitrogen N .086

hydroxide 0 .014oxygen 02 .026hydrazine vapor N2 H4 (g) .000UDMH vapor 41H8N2(g) .000nitrogen dioxide NO2 .418ammonia NH3 (g) .000nitrogen tetroyvde N2 04 (g) .310

Average Molecular Weight 54.04 lbs/lb-mole

108

THERMOCHEMICAL DATA SHEET

ANALYSIS NO. 23

OXIDIZER/FUEL MOLE RATIO 17.72

PERCENT MIXING 100

VAPORIZATION CONDITIONS Excess N2 04 (1) 18% Dissociated into NO, (g)

COEFFICIENTS FOR UNREACTED PROPELLANT SPECIES:

a13 8 0 a14 = 0 al5 a 2.97

a16 = 0 a17 a 0 al8= 0

a19 13.73

RESULTS:

Flame Temperature 296 K (53 OR)

Fireball Species Formula Mole Fraction

carbon monoxide CO .015carbon dioxide CO2 .012hydrogen radical H .007hydrogen H2 .014water vapor H60 .080nitric oxide N .003nitrogen NA .076hydroxide O .013oxygen 02 .023hydrazine vapor N2H4 (g) .000UDMH vapor C2H8 N2 (g) .000nitrogen dioxide NO2 .229ammonia NH3(g) .000nitrogen tetroxide N204(g) .529

Average Molecular Weight 64.80 lbs/lb-mole

109

APPENDIX C

COMPUTER OUTPUT, REACTIOIS OF LIQUID ROCKET PROPELLANTS

WITH OTHER CHEMICALS

Case No. Oxidant Fuel Page

34 Nitrogen Tetroxide Methylene Chloride 111

35 Nitrogen Tetroxide Ethlene Glycol 112

36 Nitrogen Tetroxide Dichloroethane 113

37 Nitrogen Tetroxide Liquid Propane 114

38 Nitrogen Tetroxide Octane 115

39 Nitrogen Tetroxide Acetone 116

40 Nitrogen Tetroxide Acetylene 117

41 Nitrogen Tetroxide Anonia 11842 LOX Aerozine-50 119

43 Air Aerozine-50 120

44 Chlorine Aerozine-50 121

45 Nitric Acid Aerozine-50 122

46 Hydrogen Peroxide Aerozine-50 123

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