AIR FORCE REPORT NO. AEROSPACE REPORT NO.SAMGO-TR-72.6-3 TR-0172 (-Z2'.1O)-3

JN.

K' Vacuum Thermal Decompositions of theNitrate Salts of Hydrazine

Prepared by

AERODYNAMICS and PROPULSION RESEARCH LABORATORY

72 JAN 31 i

Laborarory OperationsTHE AEROSPACE CORPORATION

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Z REPORT -r-ILE

VACUUM THERMAL DECOMPOSITIONS OF THE NITRATESALTS OF HYDRAZINE

4OeCR*BP*-VE NROTESf2(TYPO of repoti Pd nlut W~va dute*)

t U T;;ftS- Mrst. name. atid [J initial. Is3*! n&~~)

Hide-oH. Takimoto, Peter Breisacher, Genevieve C. Denault,4

wrjlujm A. Hicks

t ! OR AF 76 TOTAL NO. OF PAGES 7b NO, or ftrCV

7_ _ __ _ _ __ _ _ __ _ _ 169

4&S=;"CtOR GQA14INO 9. 0GIN~AIOR$S lqFORT N~UL-1.ao's)

1704701-71-C-0172

P A Z t'tT j TR-0!72f2210-1Q)-3

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The vacuum zhi-nal decompositions of the combustion intermediatesfrom the reac;t.on of N 20 with N 1-1 have been investigated. Theidentity and conCentrations of the evolved gaseous products from -nono-nitrate and dinitrale salts of hydrazine as well as amnmoniumi nitrate wereIdetermined at successive temperatures until the thermolyses werecompleted, vith a mass spectrometer and differential thermial analiyzer.

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KEY WORDS

Thermal DecompositionMass Spectral AnalysisBiprope~lant Combustion Residue

Hydrazinium Nitrates

Distributicn Statement (Continued)

Abstract (Continued)

UNlCASSIFIEDSecurity Cla ificition

Air Force Report No. Aero'pace Report No.SAMSO-TR-72-63 TR-0172(2210-10) -3

VACUUM THERMAL DECOMPOSITIONS OF THE

NITRATE SALTS OF HYDRAZINE

Prepared by

Aerodynamics and Propulsion Research Laboratory

A71 DEC 31

Laboratory Operations

THE AEROSPACE CORPORATION]

Prepared for

SPACE AND MISSILE SYSTEMS ORGANIZATIONAIR FORCE S1 STEMS COMMANDLOS ANGELES AIR FORCE STATION

Los Angeles, California

Approved for ptiblic release;distribation unlimited

ili-i

FOREWORD

This report is published by The Aerospace Corporation, El Segurdo,

California, under Air Force Contract F04701-71-C-0172. The authors

are H. H. Takimoto, P. Breisacher, G. C. Denault, and W. A. Hicks

of the Aerodynamics and Propulsion Research Laboratory.

This report, which documents research carried out from March

through August 1971, was submitted on 25 January 1972 to Capt Karl

J. Hoch, SYAE,. for review and approval.

Approved

W. R. Warren, Jr., DirectorAerodynamics and Propulsion

Research Laboratory

Publication of this report does not constitute Air Force approval of

the report's firdings or conclusions. It is published only for the exchange

and stimulation of ideas.

Karl J. Hoch, pt, USAF -3

Project Officer

oii -

ABSTRACT

-The vacuum thermal decompositions of the combustion

intermediates from the reaction of N20 4 with N2 H4 have been

investigated- The identity and concentrations cf the evolved

gaseous products from mononitrate and dinitrate salts of

hydrazine as well as amynoniurn nitrate were determined at

successive temperatures until the thermolyses were com-

pleted, with a mass spectrometer and differential thermal

analyzer.

-1il -

r CONTENTS

ABSTRACT. ...................... .. .. ...

L INTRODUCTION .

IL MATERLJALS AND PROCEDURE . . *

HlL RESULTS AND DISCUSSION ....... ........ 9

REFER.ENCES . . ......... ............. !3

FIGURES

II.Vacuumn differential ther.-ogram and produxct profile for

hydrazinium nitrate .. .................... 6

2. Vacuunm differential therxnogram, and product profile for

hydrazinium 'linitrate -

3. Vacuum differential thermogram and product profile for

ammonium ni'trate........... .. ............

L LNTRODUCTI&Y

Hydnazin-e and alkylated drvtesin cornbiiation riliN 2 OD. have

been used for some t"-'e in liquid bipropralban± rocket motortS The

propulsion systemns utilizing these propellants bave, at fints entoumtered

difficulty 4urizng rapid start and restart zond-iions u-nder "-pressure

enironrnen s: where cofl3ee comnbustion of the ftuel does not occur-

Partially oxidized fuel is acccrnzklted in- the corbssion clatbbe-r nifl

and nozzle area- As a result, the occurrence of abnormnally large, igntion

overapreasures during pulse -node flringn74 hav.e a deletnri-Oas efect, j;-

engine perforinance- The expulsio'n of these combustion intexrmediates-

with the exhaust proeducts can also lead to conamarination of the svacec raft

vehicle surfaces. Previvus work, bas established thatv the m-ajor con-su D-

uents among the residues from the cora-bust'in reactions between N-ps

and hydrazine derivatives are, the nitrate salts of the fruel !"i 23-

Ea>rlier work in our laboratory investigated the therm-ral decominnositi'on

of mononitrate an~d dinitrate salts of monomethy.1h-drazine (IMMTH) -4%7

which are th),e residues resultinge from the incomnplete combustion of N,0.

and MNM. Simultaneous rras s spectr'..vetric diff ercntial therinal analyses

of these cornwounds resulted in the evolution of 1 I identifiable sP-ci.s

This study has been. extenided to int-lude the thermal decornuosition of

nitrate salts of 1-ydra-tine.

rhe itaen of the fnel wce repared by a carefusl lizxation of

an ice c-.$d solution o freshhy distillead Mnrai -fta.~renM

eeuxvziet- iz==fltv of d-ilue -:rick acid- rre wate ws ca-%AtZocmslv reu4-ored

aner recIuced pressure. and! tize rnazooniz-ate -,as curie bv rtte

-=~~~~B theouao I nDc .norinxa:c and dinitrate salt were

White trrsalin slids- hirin-- en".2 zneI, hrgroscvric nro-cnies. T1hbse

c,-,,znmds were slared i;n a dcsi;,cauer and userd imnanediatch afte zc'~

Cation.

Pniie 2 HXNO 3 mn"IiA.ft E v ie t

corrlesno-G 2-* -tothe c-c rvsta5 1 nc form. Wie- ctdni~v t ec:-

pacted in a -r-mi tk -v tube. t maeia ±eofl

NH.- 2fO i neftd&t 1OI--3 0 C (Et- vanlu IGC -6 when

heated ravidvy- A siow- rae ohafn resni:.ed it abblint and dCtLoann-0

T-heaanc used in tMhis nza-,ss serrer. ~frta hr

analyses studwa described in oujr n~rev--.*as repbon t: The- -s-I.rne

em nplayed a w e.1-regulated eprur-prtnndfraecosrtd

Of a silver 1tazzig b'oik andz ramtched =a;-. o-f thS k0s'tmmfesflor -cont-t

the temerature. Faanic rteronia of z:-:-' d_- '- os s-cits frccn the

funace am* quick insject-ion into teinan source of w- ass srdec-trcwnetcr

wre achieved by operating under Ions Pre~ssues. Use of ..hcancz or-'rz-e

with rapd P.-flPPfl2 minimmized the nossihilit of soiid-ts reacios <wcn-r -

ngbetween the ofl ipodncrs and the dopsn eiu.Fra~o

th- F Et Wemo-.cr u, raH4-Ia4 A A

~neraa it unaAL-nUfl2 premn laid ===e ered 3 wpi=n By redwtioc of

iht~r~'Crcsr-mm to r.-= Do uzcx &Z-7 -4o_ a4

-cnresidene t ofe a! -- pwo~ct easee in bc s.zn- sy.stem ttrc

A cerdx t -C4-hgi ass spectranctcr th a i& sysen cc~

=*seed essire;y oi giass a=& stailless STeel was- te ar :t nin off *t-

70r0speaet The prssnr-e is- zeSp~ecrrmer was27C1) t

izif.and ewen dnerirmg the peak ezzatcrn- dIi zt =ctee- I W

= ~santaks Pin a ncrr c-c onm a ihl4 sumfie ~ r~nar

She~-auandA -- ss -spectr-aliart. :Be c=o-t--

!ran=-re- data proEz~ts of the ewhed sn -- were constrrcteii A

-:a=ty of ato n±-- - leaked i"o he nnra se for re-fereczs-

afH pea-k I eswdama Ia~ imrn s

-atyiar--:- 65 =g of ate nzte saalt lwas akz-ed arecvy i=0 a

b-fss sanine RDt de, terezlbar thaCaccAznetir rm.Ac

ate piass tu-be =as inserted izlo a cavity of ti-aC beatig- Blk-c ~ni~e

was3 cutcassed- Sor a snintanl pericd Of :imne and zbe mmass s-pccnia bac-

wt:--h recordm off th-ssscui ear etigrt f2C

~~~an ~ ~ 1 axiascni. aeofaot 0sc corer"- tie =assZ ratecp I

--as us-c £zc fl errcor-e on C toe to-rernvn ama tte mass

-4-j

be --- .iq- t- c l- - '-W=be

r=ecLthe cpCafl.SM rai r1Xe& Mt aflre Sat e AMr~i fI'z'~atew

ti ats CE 224- -ab ak apinn ara f wer wa ze&T s

aen4 3wa vfv be ca~etlw less tztl at - a cezCa abe 5=be wert

awas Csen rlrWe a C

CEri tie ae ra (5&zI ~ )a~ae t

C)X-

C) _ _ _ _ _ _ _ _ _ _

'2 H 0i/12.j

8-N 0 N

w6N 2I-r_-~

U)

2- 2-

0 50 100 150 200 250 300TEMPERATURIE, 0C

Figure 1. Vacuum differential thermogram and productprofile for hydraziziurn nitrate

_ )

LU _

12 H 0 ~~ I

CI-002

HN3m.U6- N20

-J

02-\'

0 50 10 15V0 5 00 50 tOO 150 200 5 0TEMPERATURE, 0

Figure 2. Vacuum differential thermogram andproduct profile for hydrazinium dinitrate

-7-

~LLJ

-4

C)

20 H2I

N22

!6H 2 0 - 4 I

_ NO

1I2i NH3L I N 2W

, 1L )/ \a/J- 1/

0 50 100 150 200 250 300TEMPERATURE, 'C

Figure 3. Vacuum differential thermogram andproduct profile for ami-, onium nitrate

-3- !~ ~

I4

IIL RESULTS AND DISCUSSION

The differential thermograms and the zompositions of the evolved

gases versus temperature during the thermal decompositions of N- 4.

HNO 3 , N2 H7 " .HNO5 , and NH4NO 3 are plotted in Figs. 1-3. Identical

temperature scales are used for both graphs. The terminal exotherm

in the differential thermograms obtained in the decomposition at ambient

pressure was replaced by a large endotherm iii vacuum similar to that

reported for MMH" HNO 3 salts. The observed effect is the net result of

the heat released during thermolysis and heat - bsorbed upon volatilization

of the products. Apparently, the heat of vaporization of the substantial

amounts of water formed is the dominating factor in determining the shape

of the thermogram.

In Fig. 1. it can be seen that the major products evolved were water,

NO, and N 2, with evolution starting at approximately L09 C. Consider-

ation of only thes-- major kpecies indicates that the decomposition of

N2H4 - HNO 3 may be described by the following equation, which had

previously been proposed by Hodgkinson r7l:

4N 2 H4 " N0 3 5N 2 + ZNO 1C 1H O

Among the minor products found were N 20, NO 2, NH 3 , HN 3 , H2 , and 02.

A barely detectable quantity of hydrazine (not shown it Fig. 1) was obtained

in some of the runs. This is probably due to the dissoc-ation of the nitrate

salt. Further evidence for the occurrence of hydrazinium nitrate dissoci-

ation can be seer by a small spectral peak appearing at a mass number of

-9-

63, correspond~ing to HN0 3 Water a-,( N.0 were amnong the first

products evolved at Elie lower temperatures. The decomnposition wvasA

comrplete at about 255 0C.

The~ zecu.lts fr,n- the vacuum differential thermogramr and product

pi-ofile obtained from the decomposition of N~4 ZHNO3 are shown in

Fig. 2. In cfomparison to the mononitrate, water was released at lower

tcpraue tca 150 C) andrpater was manifested in the first endothezm

observed in the thermnogramis. In addition, a convsicerable quantity of

NO 2 was evolved at these temnperatures. In fact, NO., which -..as a mninor

product in NH~4- TINO, decomnposition, bef-ame one of the major species,I

together with water, NO, and N_. A substantially greater amount of iN33-

was also produced, whereas the remaining expected speci-es, N 0, NHi3major~~~~~~~~~ p3dcs h eopoiinratozbrNH'Z 3 myb

H2 *and 0.,, were found as minor pr'- ducts. Again, with the observed

14 written as:

N HAZHNO c+NO+O 3P7

However, the decomposition rca-t'Au oi the double nitrate salt is very

complex, and the minor products can play an important role in detertrmrang

the relative quantity of the major species. Thus, no sin~gle equation can be

vwritten to represent accurately the species produced.A

Among the evolved species from the thermolyses of nitrate salts of -:

hydrazine, a gaseous product having a miass number of 43 was observed

and attributed to hydraz.-ic acid (IN 3) --his product is an extremely

shock- and heat-sensitive energetic compound that may be formed y

-10-

I, the nitrosation of the hydrazine followed by rearrangement and dehydration.

The presence of this explosive compound is consistent with the identification

of m ethylazide discovered in our previous work during the thermcdysis ofI 'mMIi. HNO 3 . These results are also arv~iogous to the resualts obtainedt b

Dauerman, et al r8l where H-N 3 was observed when N 204 cordensed on

N2 H 4 at a 13w temperature was allowed to warm up slovaly. These results

are of particular interest in that HN 3 would aiso be formed during the

operation of N 0/hydrazine bipropellant motors under high-altitude con-

ditions. Although this azide would not be accumulated under a low-pressure

environment, it nevertheless is capable of triggering the detonation of the

nitrate salts accumulated in the combustion chamber walls. Thus, ifJ

szufficient qjuantity of the combustion intermediate had been formed from

previous firings, the resultant effect would be, an abnormally high ign-ition

overpressure. Suach pressure spiking phenonienon had been observed in

the operation of bipropellant motors under a low-pressure environent.

The decomposition of ammon~ium nitrate '9 .7 has been described asI

INH NO N2H 0 1H.

The reaction, howvever, is m uch more complicated, as evidenc'ed by the

rslsshown in Fig. 3. In addition to water and NP, s-.naller amoui.as

0 f NO, N HL and N -mere also obtained. The f ormation of tne latter two

5pecies during thie decomposition of am noniumn nitrate has pre-;iously been

revo-Zed r?~ A small peak at mass nuimber of 63 (HNQ 3 ) was also observed.

No evider'ce for the presence of NO, %.,as found, although a small quantity

may have been present but was undetected since the mass spe--tra is

obscured by interfering compounds.

This study of the combustion intermediates from the reac-tion of

2 0 4 with hydrazine -tas defined the temperature range required forIthe removal oi these 'hvdrazL---e nitrates by thermal degradation. The

identil, of the evolved species and their respective concentrations as

a function of increasing temperature have also been obtained.

M

-12-

REFERENCES

1. Christos, T.; Miron, Y.; James, H.; and Perlee, H.; J. Spacecraft

Rockets, 4 (9), 1224 (1967).

2. Pezlee, H.; Christos, T.; Miron, Y.; and James, H.; J. Spacecraft

Rockets, 5 (2), 233 (1968).

,3. Mayer, -. W.; Taylor, D.; and Schieler, L; Combust. Sci. and

Technol., 1, 119 (1969).

4. Breisacher, P.; Takimoto, .I H.; Denault, G. C.; and Hickr, W. A.;

Combustion and Flame, 14, 397 (1970).

5. Sommer, F., Z. Anorg. Chem., 86., 71 (1914).

6. Sabanejeff, A., Z.Anorg. Chem., 20, 21(1899).

7. Hodgkinson, W.R.E., J. Soc. Chem. Ind., 32, 519 (1913).

8. Ray, A. B.; Koehlier, G.; Selzer, G. B.; and Dauerman, L; AIAA, 6,

2186 (1968).

9. Rosser, W.A.; Inami, S. H.; and Wise, -. ;J. Phys. Chem., 67,

1753 (1963).

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