ON THE FORMATION OF THE THIN SOLID PELLICLE OF NITRIC OXIDES ON THE LIQUID OZONE SURFACE IN THE ATMOSPHERE OF SMOULDERING DISCHARGE IN NITROGEN

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ON THE FORMATION OF THE THIN SOLID PELLICLE OF NITRIC OXIDES ON THE LIQUID

OZONE SURFACE IN THE ATMOSPHERE OF SMOULDERING DISCHARGE IN NITROGEN

S. Temko, S. Kuzmin, M. Hadgy-Ogly, T. Iagodovskaia

To cite this version:

S. Temko, S. Kuzmin, M. Hadgy-Ogly, T. Iagodovskaia. ON THE FORMATION OF THE THIN

SOLID PELLICLE OF NITRIC OXIDES ON THE LIQUID OZONE SURFACE IN THE ATMO-

SPHERE OF SMOULDERING DISCHARGE IN NITROGEN. Journal de Physique Colloques, 1979,

40 (C7), pp.C7-433-C7-434. �10.1051/jphyscol:19797210�. �jpa-00219191�

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JOURflAL DE PHYSIQUE CoZZoqw 6'7% ...s_upp Ldrnent au n07, Tome 40, JuiZZet 2979, page C7- 433

THE F-ORMAllCW ,QF THE THIN SOUD PEUICLE OF MfRlC OXIDES ON THE UQUID

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S.W. Temko, S.K. ~uzmin', M.R. ~ a d ~ ~ - ~ g l ~ " and T.V. 1agodovskaia8*.

. # O S C ~ GeoZogicaZ Plrospeeting I n s t i t u t e (MGPI) Marx Plrospect 18, Moscuw K-9, U . S. S . R.

Acadeniy o f Science U.S.S.R., Moscow

''~aboratorg of PZasm Chemistry, FacuZ t y o f Chemistry, MGU, Moscow, U. S. S. R.

The p r e s e n t r e p o r t i s about p r o c e s s e s o f n i t r o g e n o x i d a t i o n i n smouldering d i s c h a r - g e on t h e l i q u i d ozone s u r f a c e by t h e tem- p e r a t u r e

-

196OC. R e s u l t s of t h e experiment demonstrate, t h a t t h i n s o l i d p e l l i c l e of N205 i s formed on t h e l i q u i d ozone s u r f a c e observing t h e y i e l d of t h e r e a c t i o n pro- d u c t e s we d i s c o v e r two s t a d e o f p r o c e s s : I ) . t h e immediate c o n t a c t of smouldering d i s c h a r g e w i t h t h e l i q u i d ozone s u r f a c e ; 2 ) , t h e d i f f u s i o n of ozone through t h e t h i n s o l i d p e l l i c l e of

N

0

,

which h a s been formed on t h e l i q u i 8 asone s u r f a c e and co- v e r s t h i s s u r f a c e . We make experiments i n t h e vacuum d i s c h a r g e i n s t a l l a t i o n . The i q i t i a l Qzone and t h e r e a c t i o n productes can- dense i n t h e e a t c h , which i s been c o o l e d down t o t h e l i q u i d n i t r o g e n tmnperature -196OC. The c o n s t r u c t i o n of t h e d i s c h a r g e i n s t a l l a t i o n a l l o w s t o r e a l i z e t h e immeu- a t e c o n t a c t o f t h e n i t r i c plasma w i t h t h e S u r f a c e of t h e l i q u i d ogone pel1icle.Theae e x p e r i m e n t i a l i n v e s t i g a t i o n s have been

ma-

d e f o r t h e firs* t i m e and a r e i n t e r e s t i n g f o r u s i n g of plasma t o g e t new o x i d i z e r s 4 The t h e o r e t i c a l e x p l a i n a t i o n t h e p r o c e s s e s of f o r m a t i o n t h e t h i n s o l i d p e l l i c l e of n i t r i c o x i d e s by i n t e r a c t i o n of d i s s o c i a - t e d n i t r o g e n w i t h t h e l i q u i d ozone p e l l i c - l e h a s been made by t h e a u t h o r s . To do t h i s we u t i l i z e d t h e o p t i m i z a t i o n method been developed f o r c l o s e d and open system@

l l - 6 1 and proposed t h e p h y s i c a l model o f t h e process, The t h i n s o l i d p e l l i c l e of n i t r i c o x i d e s i s considered a s an open li- m i t e d system, f o r which d i s s o c i a t e d n i t r o - gen ,and l i q u i d ozone a r e environment. In- t e r a c t i o n between molecules i s d e s c r i b e d by Morse p o t e n t i a l i n t h e p r l l i c l e

$ 7 3

and by Lenard-Gones p o t e n t i a l s l 8 i n g a s and l i q u i d mediuma. The g a s atmosp

1,

^{e r e}

c o n s i s t s of atomic and molecular n i t r o g e n and molecular oxygen 0

,

which i s , educed by t h e r e a c t i o n . The 3 n t e r r a c t i o n w i t h e l e c t r o n s , i o n s can be d i s r e g a r d e d , becam u s e d e r g e e s of i o n i z a t i o n a r e n e g l i g i b l e i n consequence of low t e m p e r a t u r e -196OC and comparat e v l y low p r e s s u r e 0.4-0.6 t o r . To w r i t e t h e s t o i c h i o m e t r i c e q u a t i o n s of t h e chemical r e a c t i o n s t h e i n i t i a l combi- natrkons, t h e i n t e r m e d i a t e and u l t i m a t e p r o d u c t e s of t h e r e a c t i o n s a r e t o be con-

s i d e r e d . The i n i t i a l combinations t h e i n - t e r m e d i a t e ' and u l t i m a t e p r o d u c t e s of t h e r e a c t i o n s a r e c a n s i s t of t h e next compo- n e n t s : 1, N2, 0 3 , 0 2 , NO, N02, NO3, N205*

We a r e t o d i s c o v e r such t h e d i s t r i b u t i o n of a l l t h e components which s a t i s f i e s t h e c o n d i t i o n s of 'Inon-hard normali z i n g w and g i v e s t h e minimum of t h e f r e e energy of t h e t h i h s o l i d p e l l i c l e of 'ni-t;rie e x i d e s ,

The c o n d i t i o n s of "non-hard n o r m a l i z i n g n c o n s i s t of t h e s t o i c h i o m e t r i c e q u a t i o n s of t h e chemical r e a c t i o n s and t h e c o n d i t i o n of b a l a n c e of g e t t i n g - i n and g e t t i n g - e u t n i t r o g e n .

The method of s o l u t i o n , To d i s c o v e r t h e v e c t o r - d e n s i t y of d articles yve n e t from t h e e q u i l i b r i - k u c o n d i t i o n s t h e h a 1 i n t e - g r a l Fredholm e q u a t i o n s of t h e f i r s t kind, which a r e t o be s o l v e d j o i n t l y w i t h t h e n o r m a l i z i n g c o n d i t i o n s f6r t h e a l l t h r e e mediums. The i n t e g r a l equations of t h e f i r s t k i n d t a k e i n t o account t h e i n t e r i n - f l u e n c e between t h e t h i n s o l i d p e l l i c l e of n i t r i c o x i d e s and i t s environment. To s o l - ve t h e e q u a t i o n s we u s e F o u r i e r c o n v o l u t i - on h a s been done we do expansion i n s e r i e s by t h e Legendre o r Gegenbayer polynomials.

A t r e s u l t we g e t t h e G i l b e r t g e n e r a l i z e d problem

f

9 , l O J f o r t h e c o e f f i c i e n t s of

$he g o t t e n s e r i e s , , The v e c t o r - d g n s i t y of p a r t i c l e s i n t h e p e l l i c l e of n i t r i c o x i d e s and i t s environment i s t h e s o l u t f o n of t h e problem. Having known t h e v e c t o r - d e n s i t y of t h e p a r t i c l e s we a r e d i s c o v e r i n g t h e p h y s i c s v a l u e s c h a r a c t e r i z i n g t h e s t a t e of t h e s o l i d t h i n p e l l i c l e of n i t r i c oxi- d e s , t h e g a s and l i q u i d mediums.

The r e s u l t s . T h e e x p e r i m e n t i a l r e s u l t s [ l

I]

i n c l u d e t h e dependence of y i e l d N205 from t h e t i m e of i n t e r a c t i o n of t h e n i t r i c plasma w i t h t h e p e l l i c l e of l i q u i d ozone.

We have discovered f o u r s e r i e s . of t h e dependence of y i e l d N,O, f o r d i f f e r e n t i n i -

.= 2

t i a l q u a n t i t i e s of l i q u i d ' o z o n e O3 ( Fig.

1 ),The analogous dependences f o r t h e r e - mainder of non-reacted ozone have been

d i s c o v e r e d ( Fig. 2 ). The computation g i v e s t h e p i c t u r e o f t h e d i s t r i b u t i o n of t h e d e n s i t i e s o f t h e components i n t h e t h r e e mediums: t h e t h i n s o l i d p e l l i c l e of n i t r i c o x i d e s , t h e g a s and l i q u i d mediums.

The c o n c l u s i o n s . The e x p e r i m e n t i a l inve- s t i g a t i o n s demonstrated, t h a t t h e r e a c t i - on of o x i d a t i o n of a c t i v e n i t r o g e n i n t e - r a c t i n g w i t h t h e p e l l i c l e of l i q u i d ozone by t h e t e m p e r a t u r e -196OC and t h e pressu- r e 0.4-0.6 t o r t a k e s place. The u l t i m a t e proddct of o x i d a t i o n i s N ⁰

.

Having been proposed b e f o r e by t h e d t % o r s 11-6jthe

s t a t i s t i c t h e o r y of l i m i t e d c l u s t e r s i s a p p l i e d t o d e s c r i b e t h e p r o c e s s e s i n open systems. The comparison t h e experimental and t h e t h e o r e t i c r e s u l t s d e m o n s t r a t e s i t s good co-ordination.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19797210

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5

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