jn. nitrate salts of hydrazine - apps.dtic.mil · a cerdx t -c4-hgi ass spectranctcr th a i&...
TRANSCRIPT
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
Preparcd for SPACE AND MISSILE SYSTLMS ORGANIZATIONAIR FORCE SYSTEMS COMMAND
LOS ANGELES AIR FORCE STATIONLos Angeles, California
APPROVED FOR PUBLIC RELEASE:DISTRIBUTION UNLIMITED
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______ ___ A
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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
C 9b 01.4CR RC.G1A7 NO'S Air wtho r s tha, -v be a~t'.I th#epot
SAN-SO-TR-7Z-63
Approvec ;or publir release; distribution unlimited
-. " U~PL~rNA~-t Tt. rPO"SORIP.G MILITARY ACTuvs?
Space and Missile Systems OrganizationIAir Force S':stems CcmmandILos Angeles, Caliicrnia
3- Ae. AC
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.
tip FORM 143UNC Lt\SSIFIED
FSecurstv Ulasiictin
UNCLASSIFIEDSecurity Classification
14
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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