Chemical process for study of thermodynamic and kinetic behavior of electrically activated reaction

Yeh, G. C.

English

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K I N E T I C  STUDY OF ELECTRICALLY ACTIVATED REACTING SYSTEMS 
AT RELATIVELY LOW TEMPERATURE LEVELS 
Progress R e p o r t  S u b m i t t e d  t o  
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION 
O f f i c e  of G r a n t s  and R e s e a r c h  C o n t r a c t s  
Washington 2 5 ,  D. C.  
GPO PRICE $ 
CFSTl PRICE(S) $ 
// 60 P R I N C I P A L  INVESTIGATOR Hard copy (HC) 
Microfiche (M F) /m NGR- 39 - 0 2 3- 0 0 2 
ff 653 July 65 GEORGE C. YEH 
Professor of C h e m i c a l  E n g i n e e r i n g  
G e o r g e  C. Y e h  
Professor of C h e m i c a l  E n g i n e e r i n g  
_.- . , *  /k ' . ~ I .,, ' 
H e n r y  T. ' K o o h c e ,  D i r e c t o r  
R e s e a r c h  and D e v e l o p m e n t  
PERIOD COVERED: September 1965 - March 1966 
_RESEARCH AND DEVELOPMENT D I V I S I O N  
V I  LLANOVA UNIVERSITY 
VILLANOVA. PENNSYLVANIA 
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https://ntrs.nasa.gov/search.jsp?R=19660014305 2020-03-16T19:52:57+00:00Z
A complete, c r i t i c a l  review of t h e  thermodynamic and k i n e t i c  
behaviors  of twenty-six r e a c t i o n s  h a s  been c a r r i e d  o u t  and t h e  fo l -  
lowing four teen  r e a c t i o n s  have been s e l e c t e d  f o r  f u r t h e r  i n v e s t i -  
ga t ion .  
1. 
2. 
3. 
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7 .  
8. 
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1 2 .  
13. 
14 , 
.-- H2 + I 2  *----- 2 H I  
N2 + 2 C  S C2N2 
2 N 0 2  + H20:--- 2HNO3 + NO 
NO2 + 03 h-- NO3 + 0 2  
NO + NO3 .+< 2 N 0 2  
2 N 0 2  + 0 2  2 N 0 3  
NO3 + NO2 z-2 N 2 0 5  
0 3  + NO F L x  NO2 + 0 3  
NO + C 1 2  -e NOC 1 
CO + NO2 %d NO + C 0 2  
co + 0 2  z = =  2 c 0 2  
CO + 0 3  - 2 c 0 2  
N 2  + €32 "3 ( U n c  a t a ly zed ) -- H2 + NO2 v NO + H 2 0  
The o t h e r  r e a c t i o n s  w e r e  r e j e c t e d  f o r  t h e i r  undes i rab le  
k i n e t i c  behaviors ,  fiavirig either iuncertain mechanisms or uncon- 
t r o l l a b l e  r a t e s ,  Among t h e  above four teen  r e a c t i o n s  t h e  f i r s t  
I . t h r e e  have been c l a s s i f i e d  f o r  t h e  next  phase of t h i s  study s i n c e  
t h e i r  k i n e t i c  behaviors  under n o r m a l  r e a c t i o n  cond i t ions  show t h a t  
I t h e  a p p l i c a t i o n  of t h e  proposed a c t i v a t i o n  techniques  may gene ra t e  
very va luable  da ta  needed f o r  t e s t i n g  and analyzing t h e  t h e o r e t i c a l  
a s p e c t s  of t h e  proposed technique. 
I 
The complete experimental  planning has  been made and t h e  
I 
necessary  equipment i s  being constructed f o r  t h e  f i r s t  r e a c t i o n ,  
I 
I 
I 
H2 + I 2 T = 2 H I .  The flow shee t  of t h e  process  i s  a t tached .  
Iod ine  c r y s t a l s  a r e  vaporized a t  a cons t an t  r a t e  (1) and measured 
( 2 ) ,  t hen  t h e  vapor i s  preheated (3 )  t o  a temperature  no t  above 
6OOOC b e f o r e  e n t e r i n g  t h e  r e a c t o r  ( 7 ) .  All t h e  s u r f a c e s  t h a t  t h e  
I 2  gas  stream touches w i l l  have t o  be hea ted  above 185OC, b.p. o f  
The temperature of  I2 gas stream a t  t h e  i n l e t  of t h e  r e a c t o r  I20 
w i l l  be measured by potent iometer  and thermocouples. The I 2  gas  
w i l l  be s u r f a c e  charged negat ive ly  by t h e  porous e l e c t r o d e  (4)  
made of s t a i n l e s s  s t e e l  wool t o  which high vo l t age  s t a t i c  nega t ive  
charge i s  appl ied  using a DC power supply ( 1 2 ) .  S i m i l a r l y ,  H2 g a s  
w i l l  be suppl ied  from a s tandard gas  cy l inde r  (16)  and t h e  flow 
r a t e  w i l l  be r e g u l a t e d  wi th  a needle va lve  and measured wi th  a 
ro tameter  (15 ) .  The H2 gas  i s  then preheated (14) t o  a temperature  
n o t  above 6OOOC be fo re  e n t e r i n g  t h e  r e a c t o r .  A t  t h e  i n l e t ,  t h e  H2 
. 
gas  w i l l  be su r face  charged p o s i t i v e l y  by t h e  porous e l e c t r o d e  ( 5 )  
using a s e p a r a t e  power supply ( 1 3 ) .  A wel l -def ined and uniform 
f i e l d  w i l l  be e s t a b l i s h e d  between t h e  two e l e c t r o d e s ,  and t h e  
d i s t a n c e  between t h e  two e l e c t r o d e s  may be v a r i e d  a s  d e s i r e d  by 
moving one o r  bo th  e l e c t r o d e s  toward t h e  cen te r  of t h e  r e a c t o r .  
Thus, t h e  p o t e n t i a l  ac ross  t h e  two e l e c t r o d e s  and t h e  s i z e  of 
t h e  r e a c t o r  can be f r e e l y  v a r i e d  whi le  maintaining a wel l -def ined 
and uniform f i e l d .  The charged spec ies  w i l l  move toward t h e  elec- 
t r o d e  of  oppos i t e  p o l a r i t y  and c o l l i d e  wi th  t h e  charged s p e c i e s  of 
oppos i t e  p o l a r i t y  s i n c e  t h e i r  flows a r e  counter-current .  The de- 
composed I and H atoms may a l s o  r e a c t  and form H I .  The charged 
s p e c i e s  and any p o l a r  spec ie s  w i l l  be o r i e n t e d  o r  even d i s t o r t e d  
according t o  t h e  f i e l d  e s t a b l i s h e d  while  they a r e  t r a v e l l i n g  i n  
t h e i r  c o l l i s i o n  courses .  The temperatures of r e a c t i o n  w i l l  be kept  
c o n s t a n t  below 6OOOC i n  order  t o  avoid t h e  r e v e r s e  r eac t ion .  The 
p r e s s u r e  i n  t h e  r e a c t o r  w i l l  be maintained a t  1 atm. A p a r t  of 
t h e  p roduc t s  w i l l  be drawn ou t  s t e a d i l y  through g l a s s  wool packing 
(8), which promotes t h e  c o l l i s i o n  of any charged spec ie s  t o  n e u t r a i i z e  
them. t o  prevent  any f u r t h e r  r e a c t i o n  between them. Then, t h e  product  
g a s  mixture  w i l l  be passed through a quencher (10)  t o  b r ing  them t o  
t h e  room temperature r a p i d l y  i n  order  t o  prevent  any p o s s i b l e  
f u r t h e r  r e a c t i o n s  before  it i s  accura t e ly  measured f o r  i t s  volume 
and m a s s  and then sampled fo r  analyses.  The product g a s  w i l l  be 
analyzed by t h e  techniques of chromatography and I. R. Spectroscopy. 
The r e a c t o r  having the s i z e  of 2 "  I.D. x 24" i s  being made by 
t h e  Corning Glass  Company and the  temperature  of r e a c t i o n  w i l l  be 
maintained by r a d i a n t  h e a t e r s  i n  order t o  e l imina te  any secondary 
f i e l d s  which may be developed by r e s i s t ance - type  h e a t e r s .  I n  t h e  
quencher ( l o ) ,  t h e  I2 formed w i l l  be removed p e r i o d i c a l l y  and t h e  
remaining gas  w i l l  then  be analyzed f o r  H I .  
The technique descr ibed  above has  been developed based on t h e  
r e sea rch  experience gained by t h e  p r i n c i p a l  i n v e s t i g a t o r  i n  t h e  
l a s t  seven years ,  i n  t h i s  f i e l d .  I t  would permit  s tudying quan- 
t i t a t i v e l y  t h e  e f f e c t s  (1) of i o n i z a t i o n  and of p o l a r i z a t i o n  by 
i o n i z a t i o n ,  ( 2 )  of d i s t o r t i o n  by t h e  irnposed e lectr ic  f i e l d ,  ( 3 )  of 
o r i e n t a t i o n  i n  an e lectr ic  f i e l d ,  (4 )  of ene rg ie s  and f requencies  
of c o l l i s i o n s ,  and o t h e r  e l e c t r o s t a t i c  and electrodynamic i n t e r a c t i o n  
w i t h i n  and between molecules. 
The d e t a i l s  of t h e  r e s u l t s  w i l l  be included i n  t h e  annual 
r e p o r t  due i n  September 1966. 
The summary of some s t u d i e s  j u s t  completed by the principal 
i n v e s t i g a t o r  a s  an i n t e g r a l  p a r t  of t h i s  r e sea rch  program b u t  no t  
. 
. supported by NASA is also shown in the renewal proposal to be 
submitted to NASA in the immediate future. 
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Flow Sheet of H2 + 1 2 < = 2 2 H I  Reaction 
I2 vaporizer 
Rotameter (12) 
Preheater ( 1 2 )  
Negative porous electrode made of stainless wool. 
Positive electrode made of stainless wool. 
Potentiometer and thermocouples for temperature measurement. 
Reaction zone 
Glass w o o l  packing - neutralization zone. 
Radiant heat f o r  temperature control. 
3i- 
A 
10. Quencher. 
11. To Rotameter and then sampling bottles. 
1 2 ,  13. DC power supply, 
14. Preheater ( H 2 )  
15. Rotameter (H2)  
16. Hydrogen bottle. 



Kinetic Study of Electrically Activated Reacting Systems at Relatively Low Temperature Levels Progress Report, Sep. 1965 - Mar. 1966

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