Crystallized HS2O7NO was obtained by reacting excess NO2 gas with liquid HSO3Cl. Stable to a melting point of approximately 105 deg, this reacted with nitrates from about 25 deg and formed M2S2O7, with an acid disulphate intermediary. Excess NO2, whether liquid or gas, reacted with HS2O7NO to five (NO)2S2O7

Heubel, J.

Wartel, M.

English

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NASA TM
-75110
ON THE ACID DISULPHATE (PYROSULPHATE) OF NITROSYIE
Michel Wartel and Joseph Heubel
(NASA -T?^-7517C)
	 CN TH?? ACIC LISOLPPATE
	 N78-17175(PYRCS'JLPHAT F) CF N ITFCSYLE (Paticnal
'eronautics dnd S F aC,1  Affir.istcdt-ion)
	 G p
ifC AG;/4F AOt
	 CSCL C71)
	 Onclas
3/25 054 U4
Translation of: "Sur le disulfate (pyrosulfate) acide de
nitrosyle," Comptes Rcndus Hebdomadalres des Seances de
1'Academie des Sciences, Vol. 261, 1965 1 pp. 5509-5511
luATIONAL AERONAUTICS AND SPACE AlIaNISTRATION
4ASHINGTON, D. C. 205+6	 OCTO1iMR 1977
I
STAN( ARC TITLE PAGE
r '.
i
1.	 Report No. rnment Accession Me. ?.	 Recipient's Ceteleg me.
'1M-75170
4.	 Title end Subtitle
)N `I'ID: ACID DISULPHATE (PYRosuL'lIAm) 02'
S.	 Rep rt D.
ca r 	 1y'/'^.(S tooTe  
6.	 Performing orjenrsebon Code
6.	 Performing orgoni,o,ion Report No.
7'MrMY
7.	 Avthor(s)
lie u:l iraitel and Joseph ZIeubel
10.	 Work Unrt No.
9.	 Performing O'yon sot on Nomo and Address 11. Cnypito r P,gj) No.
-^	 I
:1Ciri^^AN
13.	 Type of Report and Period Covore-4P. o r	 ik)x 5456
ante?iarhara, CA	 () 3108 Iran: Iation
12.	 Sponsoring Agency Nome end Address
";lLt lunal Aeronautics and Space A(Imi ni strati nn
14.	 Sponsoring Agency Code
liington,	 P.	 C.	 20546
15.	 Svpislementory Notes
Translation ni':	 "Sur le dlsuli'ate (pyrosulfate) aside de nitrof:yle,'
Comptes Rendus Hebdomadaires des Seances de 1'Acadernie des Sciences,
Vol. 261, 196 , ph .	 5509-5511
16	 Abat'oct	 —
17.	 Key Words (Selected by Author(,)) 	 18.	 Distribution Statement
Uneiassified - Unlimited
19.	 Secvrlty Clessif. (of this report)	 20.	 Security Closnl. (of th s pope) 21• No. of Popes	 22.
Uncl.a—	 . i_ed	 Uriclasi3ified t,
NASA 11Q
L
ON THE ACID DISULPHATE (PYROSULPHATE) OF NITROSYLE
Michel Wartel and Joseph Heubel
ABSTRACT
By reacting excess NO 2 gas with liquid HS0 3C1, we obtain crystal-
lized HS 20 7 NO. Stable up to the melting point of about 105 1 , this
reacts with riitrates from about 25 0 to form M2S 20 7 , probably with an
acid disulphate intermediary. Excess NO.,, whether liquid or gas,L
reacts with HS 20 7 NO to five (NO)25207'
Within the framework of a systems tic study of the derivatives of
S0 3
 and tri- and pentavalent nitrogen, we have studied the reaction
of chlorosulfonic acid and nitrogen dioxide NO2.
A priori we can conceive of a reaction of the type
(I) HS03C1 + N 2 0 4 -^ f'SO 4 NO + NO2C1
or even
(II) HS03CI + N 20 4 -+HNO 3 + NOS03C1,
as this latter compound has recently been prepared in the pure form
(ref. 1).
In fact, in 1929 Jones, Price, and Webb (ref. 2) by reacting; HS03C1
(ClS0 20H in English) and N 2 0 4 in stoichiometric proportions, obtained
the acid sulphate and the chloride of nitrosyl. This seems to give
credence to a reaction of the type (1), where nitrogen has a valence
of +3 (NOC1). Lacking specifics about the experimental conditions, and
since the presence of nitrosyl chloride could not be explained simply,
we have repeated these experiments using a technique applied in other
analogous reactions; passing N 20 4
 gas through HS0 3C1 at 0 0
 kept in cal-
cination by dry nitrogen under pressure.
We immediately observe hydrogen chloride being liberated, then nitryl
chloride, easily characterized by its infrared spectrum. At the same
time, some nitrosyl chloride is also formed, which can be explained by
1	 ORIGINAL PAGE IS
OF POOR OUAI,I'I'I'
the simultaneous formation of the reducing agent. HC1 (ref. 3).
The liquid on the - alcine becomes more and more viscous, and after
a few I:ours a slight precipitate is formed which accumulates slowly.
The excess liquid is for the most part eliminated by filtration. The
1iqutd vesidue that permeates the crystals I.; evaporated under vacuum
at room temperature and collected at low temperatures. The process
+Scr	 too•	
^	
r
Io
1b
Am
^'9
Fi gur e 1
lasts several days. A vary hygroscopic white crystal IIne powder- remains
that does not "smoke" in air, except for Cl - . It I.; hydrolysed by a
concont.rated sodium solut ton. The concentrat.ton depends on the total
amount of nitrofen, reducing nitroron and sulphur, and the acidit:,y.
DeFpite a slir^ht shortage of nit ,ogee 3, explained by tho violence
of the hydrolysis reaction which gives rise to the formation of a small
amount of NO 2
 from rnitror;en 3, t-hc^ quantitative arralysl:; and the massG
balance are in af,reemenr. wI t h the HS 2 0 7 NO formula. To our krrowledfe
this compound has never before been prepared. The overall reaction can
therefore be written as
(ITT)	 2 HSO 3 M + N 2 04 ---* tiS 2 0 7 NO + NO 2 C1 + 11C1
This simple form noes not pretend to represent all of the Intermediary
mechanisms, which, from s +
 -idles presently underway, seem to be fairly
complicated, ever; more so si:ice NO 2C1 seems to react with HSO 3C1 also.
It is possible that, them as an HSO 4 No intermedlnry. We found some
proof or' this h •ypothesic; by enrryint,
 out a reaction between HSO 3C1 and
HSO 4 NO. Quantitatively this trives HS 
207 NO with the release of IiCl as
it '.
follows:
	
(TV)	 HS03C1 + fiSO4NO .P IM + f{S207NO.
Hence, by assuming the intermediary formation of hSO 4 NO, we have a
condensation reaction with the elimination of HC1. It is perhaps by a
reaction of the same type that it, is possible to explain the formation
of NOC1 in the reaction of S0 2C1 2 and NO 2 (ref. 4).
HS 20 7 NO metls at 105 + 2 0 and this melting point was reproducible
In several trials even though we could detect a slight decomposition
beginning at this temperature. The liquid obtained is viscous and is
easy to keep supercooled, especially after several trials. Thermo-
gravimetric analysis with a heating rate of 100 0 /hour shows that the
decomposition starts around 115 0 in the dynamic mode (curve 1, in Figure
1). The decomposition accelerates rapidly. All trace of the condensed
phase disappears around 3201.
Reacting the acid disulphate of nitrosyl with sodium nitrate, or
better yet, with the potassium nutrate-sodium nitrate eutectic, we
find that the mass loss and the release of NO 2 is noticeable from 250,
which shows that the nitrosyl group reacts with the NO 3 ion.
If the nitrate/disulphate ratio in moles is equal to 1 (curve 2)
we find that the reaction is followed by the decomposition of excess
HS 20 7 NO. On the other hand, if we use a ratio of 2, we get the metal-
lic disulphate.	 For this reaction to be complete it; is desirable to
proceed above an isotherm with thoroughly homogenized mixture (Curve 3a).
Therefore the nitrate attacks both the NO group and the H-end of the
I
	
	
acid, with the formation of NO 2 on the one hand, and of nitric acid
on the other. Both are titrated effectively in the volatile phase.
It is possible, and this remains to be proved, that the reaction
may proceed two ways:
	
(V)	 Hs207NO + MNO3  	 ^1 204 + HS207M2
	
(VT)	 HS207M + MNO
3
 ---^. HNO 3 + M2S207
The second is slower at the temperature at which (5) takes place.
Be that as it may, by .1sing the molecular ratio of sodium/disulphate
equal to 2, the phase remaining after proceeding along an isotherm at
85 0
 is pure sodium disulphate (x = ray pattern).
Furthermore, by reacting this residue with 2NO 3 , using; the K
eutectic of NaNO 3 , around 170 0
 we find an abrupt loss nf rinss whtoh
ORIGINAL PAGE IS
3	 OF POOR Qt;AI,I'I'Y
spunds t.3 the IIbevatIon cif' N,0
the role of an 04- donor v 1 S-:i-v ; 3 tht
(curve? 3b); tho nitrate plays
d t:;ulphate ( ref. 5) .
(V r 7 1	 MLS20 + "' IhINO 3 --W ?M ISO 4 + N,O 1^ --w .'NO 2 + 1/2 011
On the same t?raph wo show the cut've re: ult ing from the react-ion of
Na,S.,0 7 + eutectic NaNO^ + KNO 3 (curve 4). They overlap.
~ Theret'ore, by re pot in 1^, excess N 2 0 4 araci 1'" 3 C1 we obtain HS,07NO
vary probably through an JJSO 11 N0 intermediary. Other reactions present l,^
being studled at the I,abor:atory lead to tlae S:ame pr0dta4t, part 1cul.at'ly
tile rt'act ion or litluld SO-^ and 11SO 11 NO.	 By react ins* 11,lutd N-,0 11 and
HS.,O 7 NO at 20 1
 for several drays, we obt:ttrt, after ellminatlnt>, ntt.rlc
aeid and NO) , a cr'y stalltne oubst:ance whose formula approximates
(NO) .,S, O 7 , obtalned off votively by tre:it It1r, the ,ame sulphate' by
..
raseous NO 2 at 60 0 . We can ask ou1'SelVeS further whether Junes
(ref'. .') hasn't in 1':1.'t obtained tills product which has the Same
+ r:ttic , a: I{SO11NO.
REFERENCES
( 1 ) B. Vandorpe and J. Hebbel , complex renduS, .'00, 1 0 0", p. 661 o.
(2) C. W. H. Jones, W. J. Price arut H. W. Webb, J. Chom. Sc c. (hondon)
lq ca. p. 312
(3) h'. ,t. Co111s, F. P. Glatt
	 D. H. k3oddar'd and A. E. Hebdon, J. Chem.
, (Londorl) , 1 ^5 y , p. 443.
(4) K. : I topporkn rid P. Grove, Z. Chum, 5, No. 3, 1965, E'I'. 1.11-1111
(5) G. Delarue, Oommunication to the analytical chemistry sw, , tlon of tht,
French Chemical. Society, June 15, 1962.
4
I


On the acid disulphate (pyrosulphate) of nitrosyle

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