PUKDUE UNIVERSITY

TH IS IS TO CERTIFY THAT THE TH ESIS PREPA R ED U N D E R MY SU PE R V ISIO N

BY______________ I ie s lie Mande v i l l e Addison _________

ENTITLED A Study o f The Vapor Phase N itr a tio n o f Butane w ith

Emphasis on The E f f e c t o f Adding Oxygen_______________________

COMPLIES WITH THE UNIVERSITY REG ULATIO NS O N GRADUATION T H E SE S

AND IS APPROVED BY ME A S FULFILLING THIS PART O F THE REQUIREM ENTS

F O R TH E DEG REE OF

Doctor o f P hilosop hy

P R O F K S SO B IN C H A RG E OF T H E S IS

H ead o p S ohooe or D epartm ent

.19. 4 ^

TO THE LIBRARIAN:----
IS
TH IS T H ESIS m NOT TO B E REGARDED A S CONFIDENTIAL.

PSOFS6SOB m CHABGB

GBA1>. SCHOOLFOKM9—
3-49--XM
A STUDY OF THE VAPOE PHASE NITRATION

OF BUTANE WITH EMPHASIS ON

THE EFFECT OF ADDING OZYGEN

A T h e s is

S u h m itte d t o th e F a c u lty

of

Purdue U n iv e rs ity

hy

Le s l i e Mand e v i l l e A ddison

In P a r t i a l F u lf illm e n t o f th e

Eeq.uirem ents f o r th e D egree

of

D o cto r o f P hilosophy

November^ 19^9
 ProQuest N um ber: 27712202

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uest
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 ACKNOWLEDGMENT

C r e d it f o r th e c o D cep tio r and i n i t i a l d i r e c t i o n o f t h i s

r e s e a r c h goes to D r. H. B. H ass. F o llo w in g th e te r m in a tio n o f h i s

a s s o c i a ti o n w ith th e problem^ D r. G. B. Bachman provided, much

c o u n s e l and w ise g u id a n c e . In p a r t i c u l a r ^ h i s s u g g e s tio n s r e l a t i n g

t o th e t h e o r e t i c a l a s p e c ts o f th e problem have been m ost v a lu a b l e .

T h is r e s e a r c h was supported, in p a r t by fu n d s provided, by

Commercial S o lv e n ts C o r p o r a tio n .
 EFFECT OF OZYG^ ON THE VAPOE PEASE NITRATION OF

BUTANE AND TEE MECHANISM OF THE NITRATION REACTION

AN ABSTRACT

SUMMARY

The optimum c o n v e rsio n in th e vapor phase n i t r a t i o n o f h u te n e

may he in c re a s e d s u b s t a n t i a l l y hy th e a d d itio n o f orygen to th e r e a c ­

t io n m ix tu re . Under o rd in a ry c o n d itio n s , t h i s a d d itio n o f oxygen

d e c re a s e s g r e a t ly th e u ltim a te y ie ld based on h y d ro ca rb o n . However,

in c r e a s in g th e r a t i o o f s u r f a c e to volume in th e r e a c t o r ms.kes p o s s ib le

s l i g h t l y h ig h e r c o n v e rsio n s based on n i t r i c a c id and p ro d u ces s t r i k i n g

improvem ents in th e y ie ld based on b u tan e consumed. The use o f steam

a s a d i lu e n t in th e p re se n c e o f oxygen a ls o m it ig a t e s th e h a rm fu l

e f f e c t o f th e oxygen and a id s in r a i s i n g th e c o n v e rsio n s t i l l f u r t h e r .

A more com plete mechanism f o r vapor phase n i t r a t i o n i s p r e s e n te d . T h is

p o s tu l a te s th e p ro d u c tio n o f f r e e a l k y l r a d i c a l s by an o x id a tiv e a t t a c k

on th e hydrocarbon by deco m p o sitio n p ro d u c ts o f th e n i t r i c acid.; combina­

t io n o f th e s e r a d i c a l s w ith NOp to produce n i t r o p©,rs.ffins and a l k y l

n i t r i t e s ; d ecom position o f th e n i t r i t e s to produce a ld e h y d e s and low er

a l k y l r a d i c a l s which a ls o undergo n i t r a t i o n . The p ro d u c tio n o f o l e f i n s

i s accounted, f o r by th e decom position o f a p a r t o f th e f r e e a l k y l

ra d ic a ls .

INTRODUCTION

In an i n v e s t ig a l io n o f th e e f f e c t s o f v a rio u s g a se s on th e

vapor phase n i t r a t i o n o f propane. Hass and A lex an d er ( 4 ) , d isc o v e re d

 2.

t h a t th e a d d itio n o f oxygen to th e r e a c ti o n m ix tu re caused, an i n c r e a s e

in th e c o n v e rsio n o f n i t r i c acid, to n i t r o p a r a f f i n s . The p ro d u c tio n

o f oxygenated, b y -p ro d u c ts was noted, b u t no d e te rm in a tio n was ma.de o f

th e ty p e compounds produced o r o f th e am ounts o f each form ed. In f a c t ,

in a l l p re v io u s s tu d ie s o f vapor phase n i t r a t i o n , a t t e n t i o n has been

d ir e c te d a lm o st e x c lu s iv e ly to an i n v e s t ! g a l lo n o f th e ty p e and q u a n tity

o f n i t r o p a r a f f i n s pro d u ced . The la c k o f d a ta on th e n a tu r e and y i e l d s

o f b y -p ro d u c ts has ma.de an e lu c id a tio n o f th e d e t a i l e d mechanism o f th e

r e a c ti o n im p o s s ib le . S in c e oxygen in c r e a s e s th e p ro d u c tio n o f th e s e

b y - p ro d u c ts , a stu d y o f them becomes im p o rta n t from an economic s ta n d ­

p o in t a s w e ll a s d e s ir a b le from th e t h e o r e t i c a l v ie w p o in t.

B utane was chosen f o r t h i s in v e s t ig a t io n s in c e i t has n o t

been given th e same amount o f a t t e n t i o n accorded th e low er h y d ro carb o n s.

I t i s i n t e r e s t i n g to n o te t h a t d a ta by Hass and Hodge ( 5 ) show t h a t a s

th e homologous s e r i e s o f norm al p a r a f f i n s i s ascended from m ethane to

b u ta n e , n i t r a t i o n becomes e a s i e r .

APPARATUS

The a p p a ra tu s c o n s is te d o f a m e te rin g sy ste m f o r th e r e a c t a n t s ,

a gas p r e h e a te r , a r e a c t o r , and a c o n d en sin g sy stem . The flow c o n tr o l

f o r th e buta.ne and oxygen was p ro v id e d by o r i f i c e ty p e flow m e te rs

o p e ra te d w ith th e r a t i o o f upstream to dow nstream p r e s s u r e above th e

c r i t i c a l p ressu re r a t i o . Thus th e flow was in d ep e n d e n t o f sm a ll p r e s ­

s u re f l u c t u a t i o n s in th e r e a c t o r . N i t r i c a c id was fo rc e d from a l i q u i d

r e s e r v o i r th ro u g h a c a lib r a te d , j e t in to th e p r e h e a te r by a c o n tr o lle d

p ressu re o f n itro g e n .
 3.

The p r e h e a te r c o n s is te d o f a c o i l o f 10 mm. I .D . p y rex g la s s

tu b in g 250 cm. lo n g w ith an opening 60 cm. from th e o u t l e t f o r th e

i n j e c t i o n o f th e n i t r i c a c id .. T his was immersed in a s a l t b a th ms.in-

ta in e d a t a te m p e ra tu re o f 26^*0 . by s t a i n l e s s s t e e l s t r i p h e a t e r s .

Two r e a c t o r s were u se d . The f i r s t c o n s is te d o f a c o i l o f 10

mm. pyrex g la s s tu b in g , 880 cm. lo n g , and h a v in g a d ia m e te r o f 20 cm.

The second was ms.de so t h a t i t could be packed f o r s tu d i e s on th e e f f e c t

o f th e s u rf a c e to volume r a t i o under c o n d itio n s o f c o n sta.n t h e a t t r a n s ­

fer. I t c o n s is te d o f th r e e 90 cm. le n g th s o f 20 mm. I .D . p y rex g la s s

tu b in g . Each was b e n t i n to th e form o f a U and th e t h r e e were connected

in s e r i e s by tu b e s sealed, n e a r th e to p o f each l e g . P a c k in g was i n t r o ­

duced th ro u g h th e ends o f th e tu b e s which w ere s e a le d o f f b e fo re o p e ra ­

t io n . The t h r e e p a rk in g s u sed were 3/1 6 and I /8 in ch p y rex g la s s

h a l i c e s and pyrex gla.ss w ool. The h e a tin g o f b o th r e a c t o r s was

accom plished, by use o f a s a l t b o th provided, w ith im m ersion h e a te r s

o p e ra te d by an a u to m a tic te m p e ra tu re c o n t r o l l e r .

The e x i t g a se s were cooled by pa.ssa.ge th ro u g h a w a te r con­

d e n s e r to remove th e m a jo r ity o f th e l iq u i d p ro d u c ts end th en th ro u g h

a dry i c e - t r i c h l o r o e t h y l e n e t r a p to remove gaseous p ro d u c ts and e x c e ss

b u ta n e . Any g a se s re m a in in g uncondensed were p assed th ro u g h a w et t e s t

gas m eter to E ra su re t h e i r volume and were th en c o lle c te d , o v er w a te r o r

vented a s d e s ir e d .

PRODUCT ANALYSIS

The t o t a l l i q u i d p ro d u c t was e x tr a c te d w ith e th e r to s e p a r a te

th e aqueous and non-aqueous m s b e r ia l s . The a ld e h y d e s p r e s e n t in each

 4.

l a y e r were determ ined by th e hydroxy lam ine h y d ro c h lo rid e m ethod. The

e th e r l a y e r was e x tr a c te d w ith s o d iu m -b ic a rb o n a te to remove a c i d i c

m a te ria ls . The n i t r o p a r a f f i n s re m s tn in g in th e e th e r l a y e r were

d eterm ined by a n itr o g e n a n a ly s i s on an a l i q u o t p o r tio n .

Propene and b u te n e , e th y le n e , carbon monoxide and carbon

d io x id e were determ ined, by an O rs a t a n a ly s i s on a sam ple o f th e e x i t

g ases.

C onversions were based on th e f r a c t i o n o f th e n i t r i c a c id

charged, which ap p e are d a s n i t r o p a r a f f i n s . Y ie ld s a r e based on th e

b u ta n e which r e a c t e d .

NITRATION OF BUTANE 'MITHOCT OXYGEN

E a r l i e r work on th e n i t r a t i o n o f b u tan e was o f an e x p lo r a to r y

n a tu r e . Hence a stu d y o f th e e f f e c t o f oxygen, d i f f e r e n t s u r f a c e to

volume r a t i o s , and d i l u e n ts r e q u ir e d f i r s t an i n v e s t ig a t io n o f th e

r e s u l t s o b ta in a b le w ith n i t r i c a c id a lo n e . S in c e th e c o n ta c t tim e ,

mole r a t i o o f hydrocarbon to n i t r i c a c id and p r e s s u r e had. been

a r b i t r a r i l y chosen to conform t o e a r l i e r s t u d i e s , th e one re m a in in g

v a r ia b le was te m p e ra tu re .

E xperim ents c a r r ie d o u t a t 405*C. , 425®C., and 439*C. s e rv e d

to d e te rm in e th e optimum te m p e ra tu re . The data, from th e s e e x p e rim e n ts

a r e given in T able I . A p l o t o f co n v e rsio n a g a in s t te m p e ra tu re

(F ig u re l ) shows t h a t th e b e s t r e s u l t s a r e o b ta in e d a t a te m p e ra tu re

o f 425®C.

From th e a c t u a l q u a n t i t i e s o f m a te r ia ls produced a s l i s t e d , in

T able I , i t can be seen t h a t te m p e ra tu re has a marked e f f e c t on th e

 F ig u re s r e f e r r e d to in th e a b s t r a c t a r e i d e n t i c a l w ith

th o se h a v in g th e same number in th e t h e s i s p r o p e r.
p ro d u c tio n o f n i t r o p a r a f f i n s . T h is r e a c h e s a mximum and s u b s e q u e n tly

d e c re a s e s w ith te m p e ra tu re . No s u b s t a n t i a l v a r i a t i o n s a r e n o ted in th e

p ro d u c tio n s o f th e v a rio u s b y -p ro d u c ts .

The optimum te m p e ra tu re e f f e c t observed in th e p ro d u c tio n o f

n i t r o p a r a f f i n s has p re v io u s ly been e x p la in e d in two w ays. One i s t h a t

a s th e te m p e ra tu re i s in c r e a s e d , deco m p o sitio n o f n i t r o p a r a f f i n s b eg in s

to tak e p la c e , th u s re d u c in g th e amount found, in th e p ro d u c t. However,

T a y lo r ( l4 ) found t h a t th e h a l f - l i f e of n ltro m e th a n e a t 420*0. i s 4

m in u te s. Even assum ing a much g r e a t e r deg ree o f i n s t a b i l i t y f o r th e

h ig h e r members o f th e s e r i e s , p y r o ly s is should be n e g l i g i b l e a t a con­

t a c t tim e o f 1 .6 se co n d s. Hence t h i s e x p la n a tio n seems in a d e q u a te to

a c co u n t f o r th e f a c t s .

A l t e r n a ti v e ly i t has been su g g e ste d th a ,t com peting s id e r e a c ­

tio n s w ith h ig h e r a c tiv a .tlo n e n e rg ie s and in v o lv in g o rg a n ic m a te r ia ls

become more prom inent a t th e h ig h e r te m p e ra tu re s . Such r e a c ti o n s would

be expected, to produce in c r e a s in g amounts o f b y -p ro d u c ts a s th e tem pera­

tu r e in c r e a s e s . T h is i s n o t th e case how ever. I t may be c a lc u la te d

from T able I t h a t th e change w ith te m p e ra tu re in th e amounts o f o l e f i n s ,

c a rb o n y l compounds and carbon o x id e s p ro d u ced , when c a lc u la te d on th e

b a s is o f grams o f carbon in v o lv e d , does n o t compare w ith th e change in

b u tan e consumed. A c tu a lly th e d e c re a se in m oles o f n i t r o p a r a f f i n s pro­

duced i s a p p ro x im ate ly e q u a l to th e d e c re a s e in m oles o f b u tan e r e a r t i n g .

I t may be concluded t h a t a d e c re a s e in c o n v e rsio n by com peting s id e

r e a c tio n s in v o lv in g o rg a n ic m a t e r i a ls , which become pronounced a t th e

h ig h e r te m p e ra tu re s , i s n o t su p p o rte d by e x p e rim e n ta l e v id e n c e .

NITRATION QE BUTANE NITH OXYGEN

The i n i t i a l e x p e rim e n ts w ith oxygen were perform ed a t th re e

d i f f e r e n t te m p e ra tu re s to d e te rm in e th e v a r i a ti o n in optimum te m p e ra tu re
 T able I

N i t r a t i o n o f B utane W ithout Oxygen

E f f e c t o f T em perature

(C o n ta c t Time = 1 .6 Seconds; 10 mm. I.D . C o il R e a c to r)

Bun No. 42 10 41 Hodge*

(^4%o/BNOg 1 5 .0 1 2 .3 1 5 .0 1 4 .0

T em p eratu re, *C. 405 42^ 435 420

% C onversion** 15 36 22 37

Moles Formed***

BNOg 0 .1 0 0 .2 9 0 .1 4

> c=o 0 .0 6 0 .0 6 0 .1 0

C3H5 + 0 .1 0 0 .1 1 0 .1 4

CpHt 0 .1 0 0.18 0 .1 2

CO 0 .1 3 0 .0 7 0 .1 3

COg 0 .1 0 0 .2 6 0 .0 7

Butane Consumed. Moles**** 0 .3 1 0 .5 5 0 .4 1

* A pproxim ately 3seconds c o n ta c t tim e .

** Based on n i t r i c a c id c h a rg e d .

*** C o rre c te d to m oles p e r 10 m oles o f b u ta n e ch arg ed .

**** C a lc u la te d from th e carbon c o n te n t o f th e p ro d u c ts .

 7.

a s oxygen was added. The r e s u l t s given in T able I I show a maximum

c o n v e rsio n o f 43 p e r c e n t which r e p r e s e n t s a s i g n i f i c a n t in c r e a s e over

th e c o n v e rsio n o b ta in e d under com parable c o n d itio n s w ith o u t oxygen.

When th e s e c o n v e rsio n s a r e p l o tt e d a g a in s t te n p e r a tu r e (F ig u re l ) i t

i s seen t h a t th e optimum te m p e ra tu re i s s t i l l in th e neigh b o rh o o d o f

425®C .

S ince i t was dem onstrated t h a t th e optimum te m p e ra tu re does

n o t vary a p p re c ia b ly w ith th e a d d itio n o f oxygen, th e rem a in in g e x p e r i- .

ment8 were perform ed a t a te m p e ra tu re o f 42$*C. The d a ta given in

T able I I I show th e e f f e c t s on y i e l d s and c o n v e rsio n s o f v a ry in g th e

amount o f oxygen added to th e n i t r a t i o n m ix tu re .

F ig u re 2, which shows th e r e l a t i o n betw een c o n v e rsio n and th e

amount o f oxygen added r e v e a ls t h a t th e h ig h e s t c o n v e rsio n o b ta in a b le

in t h i s r e a c t o r i s 44 p e r c e n t a t a te m p e ra tu re o f 42$*C. w ith a mole

r a t i o o f b u ta n e /o x y g e n /n itr ic a c id o f I 5 / I . 6 / I .

The y i e l d , based, on th e amount o f b u ta r e consumed, i s shown in

F ig u re 3 to d e c re a s e n e a rly l i n e a r l y w ith th e amount o f oxygen em ployed.

Thus i t i s obvious t h a t th e in c r e a s e in c o n v e rsio n observed upon a d d in g

oxygen i s a t t a i n e d only a t th e s a c r i f i c e o f a c o n s id e r a b le amount o f

-h y d ro c a rb o n th rough s id e r e a c t i o n s . The s e r io u s n a tu r e o f t h i s a s p e c t

i s e v id e n t when i t i s noted, t h a t a t th e oxygen vs.lue f o r ma.ximum con­

v e r s io n , only 26 p e r c e n t o f th e b u tan e r e a c t i n g i s c o n v e rte d to n i t r o

p a ra ffin s .

The a c t u a l amounts o f p ro d u c ts from each r e a c ti o n a r e given in

T able I I I . The fo rm atio n o f c a rb o n y l compounds i s p r o p o r tio n a l to th e

amount o f oxygen added. The o l e f i n s and th e carbon monoxide a.ppear to

 T able I I

N i t r a t i o n o f B utane W ith Oxygen

E f f e c t o f Tem perature

(C o n ta c t Time = 1 .6 Seconds; 10 mm. I.D . C o il R e a c to r)

Run No. 12 11 13

CkHio/MO^ 1 2 .7 1$.$ 1 6 .0

Og/ENO^ 2 2 2

T e m p era tu re , ®C. 411 42$ 4$0

% C onversion* 33 43 27

i Yield. 1 7 .4 24 1 $ .6

Moles Formed.

RNOg 0.26 0 .2 7 0 .1 7

t>C=0 0 .7 3 0 .6 8 0 .4 9

C3E6 + C4E8 0 .73 0 .3 7 0 .6 1

CpHi}. 0 .3 1 0 .2 $ 0 .1 1

CO 0 .1 0 0.4$ 0 .2 6

CO2 0 .3 1 0 .1 7 0 .2 1

B utane Consumed, Moles 1 . 3S 1 .06 1 .0 1

* Based on n i t r i c a c id c h a rg e d .
 9.

in c r e a s e slow ly a t f i r s t , b u t f i n a l l y show an a b ru p t r i s e . I t is

i n t e r e s t i n g to n o te t h a t th e amounts o f carbon d io x id e ps.ss th ro u g h a

minimum a t th e same p o in t where th e n i t r o p a r a f f i n s show a mximum.

T h is mximum in th e p ro d u c tio n curve o f n i t r o compounds in

th e p re se n c e o f in c r e a s in g amounts o f oxygen i s somewhat p u z z lin g

u n le s s i t i s assumed t h a t vapor phase n i t r a t i o n i s a f r e e r a d i c a l p r o ­

cess. A p o r tio n o f th e a l k y l r a d i c a l s r e a c t w ith th e n i t r a t i n g a g e n t

to produce n i t r o p a r a f f i n s . However, th e r e a c ti o n o f a l k y l r a d i c a l s

w ith oxygen a ls o o ccu rs w ith extrem e e a s e . Thus when th e oxygen con­

t e n t o f th e r e a c ti o n m ix tu re i s in c r e a s e d , a p o r tio n o f th e f r e e r a d i c a l s

p r e v io u s ly a v a il a b l e f o r n i t r a t i o n a r e removed, by r e a c ti o n w ith oxygen

and a r e c o n v e rted to b y - p r o d u c ts .

The p re se n c e o f o l e f i n s in th e e x i t g a ses r e g a r d le s s o f th e

oxygen c o n te n t o f th e r e a c ti o n m ix tu re i s ev id e n c e o f th e p re se n c e o f

fre e a lk y l r a d ic a ls . The fo rm a tio n o f o l e f i n s from s a tu r a te d hydro­

carbons by^ a f r e e r a d i c a l p ro c e ss i s a w e ll known phenomenon and in

t h i s case in d ic a te s t h a t a c e r t a i n number o f th e f r e e r a d i c a l s und.ergo

o l e f i n fo rm a tio n b e fo re an e f f e c t i v e c o l l i s i o n w ith a n i t r a t i n g a g e n t

can ta k e p la c e . I t i s r e a d i l y seen t h a t i f th e number o f f r e e r a d i c a l s

i s in c re a s e d w h ile m a in ta in in g th e same c o n c e n tra tio n o f n i t r a t i n g

a g e n t, th e fo rm a tio n o f o l e f i n s should become g r e a t e r . The e f f e c t o f

oxygen i s p o s tu la te d , a s a f r e e r a d ic a l- f o r m in g p r o c e s s , s.nd i t ms.y be

n o ted t h a t th e p r e d ic te d r i s e in o l e f i n p ro d u c tio n does o ccu r upon

in c r e a s in g th e amount o f oxygen added.

The t o t a l amount o f b u tan e consumed, in th e e x p erim en ts con­

d u c te d a t v a rio u s te m p e ra tu re s w h ile u s in g a r e a c tio n m ix tu re h a v in g a

b u ta n e /o x y g e n /n itr ic a c id r a t i o o f I 5/ 2/ I a r e given in T able I I . An

 10,

T ab le I I I

N i t r a t i o n o f Butane

E f f e c t o f Oxygen a t C o n sta n t Tem perature

(C o n ta c t Time = 1 .6 Seconds; 10 mm. I.D . C o il R e a c to r)

Run No, 10 16 11 14

CI1H10/SNO3 1 2 .3 13.5 1 5.5 1 3 .2

O2/BNO3 0 1 2 3

T em p eratu re, *C. 425 42$ 42$ 42$

^ C onversion 36 42 43 26

io Y ield 48 32 24 10

Moles Formed

RNOg 0 .2 9 0 .3 2 0 .2 7 0 .2 0

>C =0 0 .0 6 0 .3 7 0 .6 8 0 .9 6

C3 ÏÏ5 + Cij.ES 0 .1 1 0 .3 3 0 .3 7 1 .1 6

CpEij. 0 .1 8 0 .1 6 0 .2 $ 0 .3 1
CO 0 .0 7 0 .$ 1 0 .4 $ 0 .7 8

CO2 0 .2 6 0 .0 $ 0 .1 7 0 .3 8

Butane Consumed, Moles 0.55 0 .9 3 1 .0 6 1 .9 3

 11.

e x am in atio n o f th e s e f ig u r e s shows t h a t th e t o t a l amount o f r e a c ti o n

a g a in d e c re a s e s w ith in c r e a s in g te m p e ra tu re a s was observed p r e v io u s ly

in th e c o rre sp o n d in g e x p erim en ts w ith o u t oxygen. In t h i s c a se no ma.jcl-

mum i s o b se rv e d , a lth o u g h one m ust ap p ear a t low er te m p e ra tu re s th an

th o se s tu d ie d s in c e o b v io u sly i f a s u f f i c i e n t l y low te m p e ra tu re were

ch o sen , th e amount o f m a t e r i a l r e a c ti n g could be ma,de a s sma.ll as

d e s ir e d . The d e c re a s e in b u tan e consumed i s p ro b ab ly a tt r ib u t a .b l e

h e re to a g r e a t e r e x te n t o f ch ain te rm in a tio n in th e oxygen r e a c ti o n a t

h ig h e r te m p e ra tu re s .

EFFECT OF O T f W ON THE NITRO PARAFFINS PRODUCED

The n i t r o p a r a f f i n s formed in Runs 11 and 12 were d r ie d and

f r a c ti o n a te d in a f o u r f o o t colim n packed w ith a. n i chrome w ire s p i r a l .

As can be seen in T able IV, when th e Og/HNO^ r s .tio i s changed from zero

to two, th e amounts o f th e n itr o b u ta n e s formed a r e d e c re a sed s i g n i f i ­

c a n tly , w h ile th e amounts o f th e n itro m e th a n e and n itr o e th a n e a re

in c re a s e d by a f a c t o r o f two. The data, from Runs 11 and 12 show t h a t

te m p e ra tu re has l i t t l e , i f an y , e f f e c t on p ro d u ct d i s t r i b u t i o n .

These r e s u l t s show very c l e a r l y t h a t carbon to carbon bond

f i s s i o n i s in c re a s e d in th e p re se n c e o f oxygen. I t w i l l be shown in a

fo llo w in g s e c tio n on mechanism t h a t t h i s r e s u l t i s to be e x p e c te d .

EFFECT OF SURFACE ON NITRATION

S h e c h te r (6) f i r s t m entioned th e p o s s ib le in flu e n c e on th e

n itr a .tio n r e a c ti o n o f th e s u rf a c e to volume r a t i o in th e r e a c t o r . How­

ever h is s o le concern was a p p a re n tly w ith h e a t t r a n s f e r . I f one views

th e n i t r a t i o n r e a c ti o n a s a f r e e r a d i c a l p ro c e s s which in th e p re se n c e
 12.

T able IV

N i t r a t i o n o f Butane

E f f e c t o f Oxygen on Type o f N itr o P a r a f f in s

Run No. Eodge* 11 12

C2j.Hio/HN03 14 1 5.6 1 2 .7

Og/SNOg 0 2 2

T em p eratu re, ®C. 420 42$ 411

Mole P e r Cent

CE^N02 10 22 19

C2H^ 0 2 13 30 32

1-C3HYNO2 8 5 11

2-Cij.H9N02 45 27 21

1-C jj^H^N02 24 16 17

* D ata tak en from Hodge ( l l )

 13.

o f oxygen in v o lv e s c e r t a i n c h ain m echanism s, then i t becomes obvious

t h a t extended s u rf a c e could be im p o rta n t f o r s t i l l o th e r re a s o n s .

The packed r e a c t o r d e s c rib e d above was used to i n v e s t ig a t e

th e s e e f f e c t s u s in g v a ry in g amounts o f oxygen and s u rf a c e to volume

r a t i o s o f 20, 28, and 300. W hile th e h e a t t r a n s f e r a r e a was c o n s ta n t

in t h i s s e r i e s o f e x p e rim e n ts, i t was c o n s id e ra b ly low er than t h a t

a .v a ila b le in th e e a r l i e r e x p erim en ts in th e 10 mm, I .D . c o i l r e a c t o r .

C o n seq u en tly , no d i r e c t com parison may be ms.de betw een th e two s e t s o f

d a ta .

The r e s u l t s from t h i s ex p erim en ts a r e given in T able 7 . A

com parison o f th e c o n v e rsio n s o b ta in e d w ith o u t oxygen w ith S/V r a .tio s

o f 2 0 , 2 8 , and 300 shows t h a t co n v e rsio n a c tu a ll y d e c re a s e s a s th e

amount o f s u rf a c e i n c r e a s e s . T hat t h i s i s n o t due to th e fa v o r in g o f

some o th e r r e a c tio n over n i t r a t i o n i s dem onstrated by com paring th e

t o t a l amount o f b u tan e consumed in each c a s e . T his v a lu e d e c re a s e s

from 0 .5 1 m oles to O.32 m oles w h ile th e c o n v e rsio n d e c re a s e s from 27

p e r c e n t to 20 p e r c e n t . I t w i l l be noted t h a t th e v a lu e o f 27 p e r

c e n t obts.ined w ith an s / v r a t i o o f 20 in th e packed r e a c t o r i s much

low er th an th e 36 p e r c e n t c o n v e rsio n re p o r te d f o r th e 10 mm. I.D .

c o il re a c to r. S in c e , in th e l a t t e r c a se th e s /V r a t i o i s 4 / l , a p o r­

t io n o f t h i s d e c re a s e must be due to th e s u rfa c e e f f e c t . However, i t

i s f e l t th a.t to some e x te n t th e p o o re r h e a t t r a n s f e r in th e packed,

r e a c to r i s r e s p o n s ib le .

In each c a s e , a s oxygen was added, th e c o n v e rsio n r o s e to a

maximum va.lue th en f e l l o f f . These r e s u l t s a r e given g r a p h ic a lly in

F ig u re 4. The maximum v a lu e s were 42.$ p e r c e n t a t s / v r a t i o s o f 20

and 28, and 44 p e r c e n t w ith S/V r a t i o s o f 3OO. Hence no s i g n i f i c a n t

in c r e a s e s in ms.ximum c o n v e rsio n in th e p re se n c e o f oxygen a re noted w ith

a change in s u r f a c e . On th e o t h e r han d , a marked change in th e q u a n tity

 14.

o f oxygen r e q u ir e d to g iv e th e optimum co n v e rsio n i s n o te d .

I t would be ex p ected t h a t a d e c re a s e in th e amount o f oxygen

would, in c r e a s e th e y ield , based on h y d ro c a rb o n . F ig u re $ shows a com­

p a ris o n o f th e y ie ld s o b tain e d by v a ry in g th e r a t i o o f oxygen w ith th e

th r e e p a c k in g s. C o n sid e ra b le d if f e r e n c e s a r e noted betw een th e y i e l d s

a t s / v r a t i o s o f 20, 28, and 300. The peak y ie ld o b ta in e d when th e s / v

r a t i o i s 3OO i s q u ite u n u s u a l. I t i s th e f i r s t c a se in which an a c t u a l

in c r e a s e in y ield , o f n i t r o p a r a f f i n s was o b ta in e d upon ad d in g oxygen

and a ls o th e f i r s t case in which mxims. in b o th th e y ie ld s and con­

v e rs io n s occu rred w ith e q u a l amounts o f oxygen. In th e pe.st th e c h ie f

o b je c tio n to th e use o f oxygen has been t h a t th e maximum y ie ld s were

o b tain e d a..t d i f f e r e n t oxy-gen/hydrocarbon r a t i o s th an were th e maximum

c o n v e rs io n . E v id e n tly a la r g e S/V r a t i o b rin g s th e s e two maxima,

to g e th e r a t th e same oxygen c o n te n t o f feed g a s .

"While th e e x a c t mechanism by which s u r f a c e e x e r c is e s i t s

e f f e c t i s somewhat o b s c u re , c e r t a i n c o n c lu s io n s ms.y be drawn from an

exam ination o f th e q u a n t i t i e s o f p ro d u cts o b ta in e d in th e above e x p e r i­

ments (s e e T able V) . A r a t h e r la r g e p o r tio n o f th e b u ta n e i s c o n v erted

to b u ten e s and propene th u s mahing t h i s one o f th e g r e a t e s t s o u rc e s o f

lo s s . F ig u re 6 shows how t h i s lo s s v a r ie s w ith oxygen f o r each packing.

In each c a se th e r e i s a g ra d u a l in c r e a s e in l o s s u n t i l th e Og/ENOg r a t i o

re a c h e s approxim s.tely one. A t t h i s p o in t th e r a t e of in c r e a s e in t h i s

l o s s becomes much le .r g e r. T his same e f f e c t was n o tic e d , when u sin g th e

10 mm. c o i l r e a c t o r . I t p ro b ab ly i n d ic a te s th e a b i l i t y o f ihe n i t r a t i n g

a g e n t to u t i l i z e a r e l a t i v e l y h ig h p o r tio n o f th e f r e e a lk y l r a d i c a l s

formed by o x id a tiv e a t t a c k u n t i l a c e r t a i n c o n c e n tra tio n of th e s e

r a d i c a l s i s re a c h e d . A f te r t h a t p o in t, a much l a r g e r p e rc e n ta g e o f

th e s e r a d i c a l s sim ply undergo decom position to form o l e f i n s . I t can be

se en t h a t s. h ig h e r s/v r a t i o ce n se s a g e n e r a l d e c re a s e in l o s s e s es
 15

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 16.

o le fin s . R e f e r r in g now to F ig u re 7, i t i s seen t h a t th e t o t a l amount

o f b u tan e r e a c t i n g in c r e a s e s w ith oxygen, h u t t h a t th e in c r e a s e i s l e s s

th e g r e a t e r th e s /V r a t i o . I t has p re v io u s ly been proposed t h a t such a

d e c re a s e in th e amount o f b u tan e r e a c ti n g i s due to c h a in s to p p in g w ith

l e s s t o t a l p ro d u c tio n o f f r e e r a d i c a l s . Hence th e d e c re a se in o l e f i n

fo rm atio n observed upon I n c r e a s in g th e s u rf a c e i s sim ply a r e f l e c t i o n

o f a low er r a t e o f f r e e r a d i c a l fo rm a tio n .

The d a ta given in T able V show t h a t p ro d u c tio n o f n i t r o

p a r a f f i n s goes th ro u g h a maximum w ith in c r e a s in g oxygen. These maxiroa,

a r e th e same h e ig h t r e g a r d le s s o f th e s/V r a t i o b u t o ccur w ith l e s s

oxygen a s th e s / v r a t i o in c r e a s e s . S in ce th e t o t a l number o f f r e e

r a d i c a l s p r e s e n t i s d ecreased by more su rfa .c e , th e f a c t t h a t th e same

number o f f r e e r a d i c a l s a r e c o n v e rted to n i t r o p a r a f f i n s must mea.n

t h a t t h e i r re a .c tio n to form oxygenated, m a te r ia ls i s a c h a in r e a c ti o n

which i s hin d ered by s u r f a c e . Such a r e a c ti o n would presum ably in v o lv e

■OH o r -OpH r a d i c a l s as chain c a r r i e r s which would be stopped on th e

w a lls . A l a t e r s e c tio n w i l l p r e s e n t a, mechanism based on th e s e con­

c lu s io n s .

THE USB OF STEAM AS A DILUENT

In th e fo re g o in g s e c tio n i t was p o in te d o u t t h a t an e x c ess o f

f r e e ra d ie s .I s i s formed when oxygen i s added to th e n i t r a t i o n m ix tu re to

th e e x te n t o f two m oles f o r each mole o f n i t r i c a c i d .

The f a c t t h a t co n v e rsio n does n o t in c r e a s e g r'e a tly under

th e s e c irc u m sta n c e s in d ic a te s than a.n i n s u f f i c i e n t amount o f th e

n i t r a t i n g a g e n t i s p r e s e n t a.t th e tim e th e e x tr a f r e e r a .d ic a ls a re

a v a .lia b le . T his could stem from, e i t h e r o f two f a c t o r s : ( l ) decom posi­

tio n o f n i t r i c a c id in o th e r w ays, or (2) p ro d u c tio n o f f r e e ra.dica.ls

 17.

o v e r such a s h o r t period, o f tim e t h a t th e a c t u a l n i t r a t i n g a g e n t ( p r e ­

sumably NOp) i s n o t form ed f a s t enough to u t i l i z e them b e fo re th ey

undergo o th e r change. The obvious s o lu tio n to th e d i f f i c u l t y in th e

l a t t e r c a se would, be to add. an i n e r t d i lu e n t to th e m ix tu re s in c e t h i s

would e f f e c t i v e l y d e c re a s e th e r a t e a t which th e f r e e r a d i c a l s a r e

form ed. I t would, n o t , how ever, in flu e n c e m s .te ria lly th e t o t a l q u a n tity

o f them fornfâd b e fo re th e end o f th e n i t r a t i o n tu b e i s re a c h e d . The

m ost l i k e l y c h o ic e o f d i lu e n t would seem to be steam . I t is in e rt,

cheap, has a h ig h h e a t c a p a c ity and i s a lr e a d y b e in g in tro d u c e d a s

w a te r in th e 70 p e r c e n t n i t r i c a c id .

Work by E ib sh m n ( 7) on th e n i t r a t i o n o f e th a n e w ith o u t

added oxygen shows t h a t in c r e a s in g th e d i l u t i o n o f th e n i t r i c a c id has

an a d v e rse e f f e c t on c o n v e rs io n . Under th e s e c o n d itio n s , how ever, th e

r a t i o o f f r e e r a d i c a l s to n i t r a t i n g a g e n t does n o t re a c h an optimum

vs.lue. Hence, a d i lu e n t which d e c re a s e s th e r a t e o f f r e e r a d i c a l forma.-

t io n would n o t be ex p e cte d to in c r e a s e b u t r a t h e r to d e c re a s e th e con­

v e rs io n . W ith e x c ess oxygen p r e s e n t, how ever, th e r a t i o o f f r e e r a d i c a l s

to n i t r a t i n g a g e n t ms,y exceed th e optimum v s .lu e . A d i lu e n t p r e s e n t in

s u it a b le amounts would, d e c re a s e t h i s r a t i o to th e optimum va.lue and

th e re b y le a d to in c re a s e d c o n v e rs io n s .

To t e s t t h i s re a s o n in g , two e x p erim en ts were c a r r ie d o u t

u s in g eq u im o lar amounts o f hydrocarbon and. steam . In each case th e

b u tS D e /o x y g e n /n itric a c id r a t i o was I 5/ 2/ 1 . One was p erform ed in th e

10 mm. c o i l which has an s/V r s ,tio o f 20. O ther p e r t i n e n t in fo rm a tio n

a lo n g w ith th e r e s u l t s a r e given in T ab le V I. A lso in c lu d e d f o r com­

p a ris o n a r e Runs 11 and. 2$ which a r e e q u iv e .le n t in a l l r e s p e c ts e x c e p t

th e y were perform ed w ith o u t added steam . A s t r i k i n g improvement in

b o th co n v e rsio n and y ie ld was o b ta in e d a s a r e s u l t o f th e a d d it io n of

 18.

s te a m . I n c r e a s in g th e s/V r a ,tio caused a f u r t h e r improvement in y ie ld

a lth o u g h th e c o n v e rsio n was n o t a p p re c ia b ly a f f e c t e d .

An ex am in atio n o f th e p ro d u c ts shows t h a t th e steam in c r e a s e s

th e amount o f a ld e h y d e s produced b u t t h a t th e t o t a l amount o f o l e f i n s

formed, d e c re a s e s . T his d e c re a s e , w h ile s m a ll in th e S/V = 4 r e a c t o r ,

becomes c o n s id e ra b le when th e s/V r a t i o i s r a i s e d to 20. In e i t h e r case

th e a c t u a l number o f m oles o f n i t r o p a r a f f i n s produced shows a sub-

s t a .n t i a l r i s e which i s g r e a t e r than th e in c r e a s e b ro u g h t ab out by any

0t h e r s in g le v a r ia b le .

MECHANISM

E vidence t h a t vapor phase n i t r a t i o n p ro ceed s by a f r e e r a d i c a l

mechanism i s fu rn is h e d by th e fo llo w in g f a c t s :

(1) B arton (2) n i t r a t e d o p t i c a l l y a c ti v e 3 -^6 th y Ih ex an e and,

o b ta in e d racem ic 2 - n it r o b u t a n e . T his in d ic a te d t h a t th e secondary b u ty l

group p a s se s th ro u g h a c o n f ig u r a tio n a lly u n s ta b le form in th e n i t r a t i o n

p ro ce ss. The m ost l i k e l y assum ption i s t h a t t h i s in te r m e d ia te i s th e

c o rre sp o n d in g f r e e r a d i c a l .

(2) B l i c k e n s ta f f ( l ) s u c c e s s f u lly n i t r a t e d th e b rid g e h e ad carbon

in b ic y c lo ( 2 ,2 ,1 ) h e p ta n e . T h is would r u l e o u t th e re p la c e m e n t o f

hydrogen by a rea rw a rd a t ta n k and would i n d ic a te in s te a d a forw ard

a t t a c k w ith th e p ro b a b le fo rm a tio n o f a f r e e r a d i c a l i n te r m e d ia t e .

( 3) Hass and S h e c h te r (6 ) found n i t r a t i o n to le a d to th o se n i t r o

p a r a f f i n s c o rre sp o n d in g to a l l p o s s ib le a l k y l r a d i c a l s which can be

formed by b re a k in g only one carbon to carbon bond, in th e o r i g i n a l hydro­

carb o n . MeC le a ry (lO ) a.lso showed th e fo rm a tio n o f o l e f i n s c o rre sp o n d in g

to a l l of th e a l k y l r a d i c a l s p r e s e n t in n i t r o p a r a f f i n s . T h is in d ic a te s

t h a t a l k y l f r e e r a d i c a l s me,y be p r e s e n t , s in c e th e y a r e known to decom­

po se r e a d i l y and r a p i d l y to o l e f i n s ,
 19

T a b le VI

N i t r a t i o n o f Butane in th e P re se n c e o f Oxygen

Use o f Steam a s D ilu e n t

(C o n ta c t Time = 1 .6 Seconds)

Run No. 11 25 17 20

s / v R a tio 4 20 4 20

c 4810/ 32*03 1 5 .6 1 3 .3 1 4 .6 1 4 .0

O2/BNO3 2 2 2 2

O4810/ 82O 9 .6 9 .6 1 1

^ C onversion 36 42 55 54

i Yield. 24 22 30 35

Moles Formed.

RNOg 0 .2 6 0 .28 0 .3 6 0 .3 9

>C=0 0 .6 8 0 .$ 8 0 .8 2 0 .8 8

^3^6 0483 0 .3 7 0 .$ 9 0 .4 1 0 .2 $

C2H4 0.2$ 0 .2 0 0 .1 0 0 .0 8

CO 0 .4 $ 0 .3 9 0 .4 7 0 .4 1

CO2 0 .1 7 0 .1 0 0 .1 0 0.0$

Butane Consumed, Moles 1 .0 6 1.18 1 .1 2 1 .0 2

 20.

(4) McCleary was a ls o a b le to form n i t r o p a .ra ffin s by th e r e a c ­

tio n betw een t e t r a e t h y l lee.d and n i t r i c a c id in th e vapor p h a se . T etrs.-

e th y l le a d has been shown by P aneth ( l l ) to form e th y l r a d i c a l s when

h e a te d under dim in ish ed p r e s s u r e . I f th e sajne b e h a v io r ms.y be assumed

a t a tm o sp h eric p r e s s u r e , th e n i t r o p a .ra ffin s probably came from th e

union o f an e t h y l r a d i c a l w ith th e n i t r a t i n g a g e n t.

T his p r e s e n t work d is c lo s e s two o th e r f a c t s o f s ig n i f ic a n c e :

(5) The p re se n c e o f in c re a s e d s u rfa c e c a u se s a d e c re a se in th e

t o t a l amount o f hydrocarbon r e a c t i n g . T his may be a s c r ib e d to d e s tr u c ­

t io n o f f r e e r a d i c a l in te r m e d ia te s by s u rfa c e r e a c ti o n s ( 9 )•

(6) The in c re a s e d p ro d u c tio n o f o l e f i n s a s w e ll a s n i t r o :para.ffins

when oxygen i s added to th e n i t r a t i o n m ix tu re s u g g e sts f r e e a lk y l radica.1

in te r m e d ia te s s in c e th e s e a r e known to be formed in o x id a tio n s under com­

p a ra b le c o n d itio n s ( 19) .

Much has been s a id a b o u t th e s o - c a lle d a g e n t of n i t r a t i o n .

T his i s d e fin e d a s th e m a te r ia l which r e a c t s w ith th e a l k y l f r e e r a d i ­

c a ls to produce n i t r o p a r a f f i n s . I t i s w e ll known t h a t n i t r i c a c id i s

u n s ta b le a t 425*C. and t h a t th e p ro d u c ts o f th e decom position a r e

n itr o g e n d io x id e , n i t r i c o x id e , oxygen, and w a te r (3)* U n fo rtu n a te ly ,

no d e ta i le d no d e ta ile d , mechanism has been worked o u t f o r t h i s r e a c ti o n .

These p ro d u c ts (e x c e p t f o r th e w ater) may, how ever, be accounted f o r by

th e fo llo w in g r e a c t i o n s :

(1) HOUÛ2 — > HO- + -EOg

( 2) 2 ■WO2 9 2N0 • + O2

Of th e f r e e r a d i c a l s shown, th e HO- r a d i c a l i s th e l e a s t s ta b l e and th e

most r e a c t i v e . Hence i t would be expected, to I n i t i a t e th e fo rm a tio n o f

f r e e r a d i c a l s from hydrocarbons in th e n itr a .tio n p r o c e s s .

( 3) HO * + E H E - -f HOH
 21.

The f r e e a l k y l r a d i c a l s so produced co u ld th e n u n ite w ith -ilOg r a d i c a l s

( ^) *E + -W02 —-4^ RHOg

p ro d u cin g n i t r o p a r a f f i n s . N i t r a t io n th e r e f o r e i s a f r e e r a d i c a l p r o ­

c e ss h u t i s n o t a c h ain r e a c t i o n . I t should he n o ted t h a t any o th e r

c o n c u rre n t p ro c e ss le a d in g to th e fo rm a tio n o f r e a c ti v e f r e e r a d i c a l s

would he expected to c o n tr ib u te t o th e n i t r a t i o n p ro c e ss by in c r e a s in g

th e c o n c e n tra tio n o f a l k y l f r e e r a d i c a l s and hence th e p e r pa.ss con­

v e rs io n s to n i t r o p a r a f f i n s . I t has been shown t h a t t h i s can be done

w ith oxygen. E v idence t h a t n i t r a t i o n i s n o t a ch ain r e a c tio n i s found

in th e f a c t t h a t increa.sed s u rf a c e in th e r e a c t o r tu b e does n o t a l t e r

th e y ie ld s o f p ro d u c ts s u f f i c i e n t l y to be in agreem ent w ith th e r e s u l t s

expected o f a c h a in r e a c ti o n o f any c o n s id e ra b le le n g th ( 9 ) •

On th e b a s is o f th e proposed mechanism th e n i t r a t i n g a g e n t

i s a c tu a ll y -NOg. However, -NOp n i t r a t e s n o t hydrocarbon m olecules

d i r e c t l y b u t a l k y l r a d i c a l s d e riv e d from them , and th e l a t t e r a r e

g e n e ra te d more e f f e c t i v e l y by HO- r a d i c a l s th an by -NOg r a d i c a l s . T his

e x p la in s th e f a c t t h a t -HOg a lo n e i s l e s s e f f e c t i v e th a n n i t r i c a c id a s

a n i t r a t i n g a g e n t in th e vapor ph ase.

A n o th er ad vantage to th e assum ption t h a t e q u a tio n (^ ) r e p r e ­

s e n ts th e c h ie f vapor phase n i t r a t i o n p ro c e ss i s th e ease w ith which

i t may be adapted, to an e x p la n a tio n o f th e f o r m t i o n o f o th e r p ro d u c ts

o f th e r e a c t i o n . The -NOg r a d i c a l i s a re so n a n c e h y b rid whose c h ie f

c o n tr ib u tin g form s p ro b ab ly in c lu d e :

(-)(+)
:0 : N ::0 : - - ^ :0 ::N :0 :

I II
 22.

I f an a l k y l r a d i c a l r e a c t s w ith -NOg in Form I th e p ro d u c t i s a n i t r o

p a r a f f i n , h u t i f in Form H th e p ro d u c t i s an a l k y l n i t r i t e . The

heha.vior o f a l k y l n i t r i t e s under th e c o n d itio n s o f vapor phase n i t r a ­

tio n i s th e r e f o r e im p o rta n t to a more com plete u n d e rs ta n d in g o f th e

n itr a tio n p ro cess.

A lk y l n i t r i t e s a p p e ar to he ex tre m e ly u n s ta b le a t e le v a te d

te m p e ra tu re s . B ice (12) decomposed e th y l n i t r i t e a t k2^**C, in th e p r e ­

sence o f b u tan e a s a d i l u e n t . Ik d e r such c o n d itio n s th e r e i s s l i g h t

chance t h a t th e decom position p ro d u c ts w i l l c o l l i d e w ith u n rea c te d

n i t r i t e m o le c u le s, and th e decom position pro ceed s a s fo llo w s :

( 5) CH3CH2ONO - —> CE^CEgO. + NO

(6 ) CE^CEgO - — ECHO + CE3

The m ethyl r a d i c a l s were I d e n t i f i e d a s t e l l u r i d e s . I f n o t removed from

th e r e a c ti o n m ix tu re th ey re a c te d , w ith n i t r i t e m o lecu les as fo llo w s :

( 7) CE3* + CE3CH2ONO — CEb + CH3ÇHONO

(8 ) CE3ÇHONO — ». CE3CHO + -NO

Kornblum and O liv e to (8) have shown t h a t i f a h ig h e r c o n c e n tra tio n o f

n i t r i t e i s p r e s e n t, th e a lk o x id e r a d i c a l s f i r s t produced r e a c t as

fo llo w s :

(9 ) CH3CHgO- + CÏÏ3CH2ONO — -V CE3CH2OH + CH3CHONO

(1 0 ) CH3ÇHONO — - > CH3CHO + -NO

I t i s e v id e n t from th e s e e q u a tio n s t h a t any n i t r i t e s produced

in th e n i t r a t i o n p ro c e ss would decompose to low er h y d ro ca rb o n s, a ld e ­

hydes and n i t r i c o x id e , a l l o f which a r e observed p ro d u c ts o f n i t r a t i o n .

The low er a lk y l r a d i c a l s a ls o produced ac co u n t in p a r t a t l e a s t f o r th e

lower n i t r o p a r a f f i n s obtained, in th e n i t r a t i o n p r o c e s s . Lower a lk y l

ra d ic a ls a r e a ls o formed from th e d i r e c t d eco m position of h ig h e r a lk y l

r a d i c a l s ( I 3) • T h is a c c o u n ts f o r th e rem ain d er o f th e low er n i t r o

p a r a f f i n s p ro d u ced .
 23.

The above e x p la n a tio n o f th e o r ig in o f th e low er n i t r o

p a r a f f i n s and b y -p ro d u c ts o f th e n i t r a t i o n r e a c tio n i s more s a t i s ­

f a c to r y th an th e assum ption o f sim ple th e rm a l c ra c k in g as a s o u rc e o f

th e s m a lle r a l k y l r a d i c a l s . As a m a.tter o f f a c t th e p ro d u c tio n o f

m eth y l, e t h y l , and p ro p y l r a d i c a l s from b u tan e i s n e g li g ib l e a t th e

optimum te m p e ra tu re and c o n ta c t tim e f o r th e n i t r a t i o n o f b u ta n e .

F u rth e rm o re , s u b sta n c e s such a s iro n s a l t s , which c a ta ly z e th e c ra c k ­

in g o f C-C bonds in h y d ro ca rb o n s, d e c re a se m arkedly r a t h e r th an in c re a s e

th e y i e l d s o f n i t r o p a r a f f i n s o b ta in e d . I f th e rm a l c ra c k in g were c h ie f ly

r e s p o n s ib le f o r th e fo rm a tio n o f low er n i t r o p a r a f f in s i t would be

expected, t h a t cyclohexane would y ie ld c o n s id e ra b le amounts o f 1 ,6 -

d in itro h e x a .n e on n i t r a t i o n .

CHp CHp CHp

I 2 I I I
CHp /C H p CHp / C H p

^C H p- ^GHgEOg
CEg CHp CHg CEgNOg
I I 2 -N02 I I
CHg /C E p ............. CHg ^ C H g
'^CEg ^CEg

S h e c h te r '8 work on cyclohexane showed t h a t t h i s was n o t th e c a s e . He

o b ta in e d o nly n itro c y c lo h e x a n e and a n o th e r p ro d u c t which c o n ta in e d

n itr o g e n b u t decomposed, r e a d i l y on w arm irg to form a t a r . T h is r e s u l t

would, be expected,, i f i t i s assiumed, t h a t f i s s i o n o c c u rs th ro u g h th e

n itrite . Such a r e a c tio n m ight le a d to a n i t r o aldehyde which would be

q u ite r e a c t i v e .
 24,

CHg CHOWO CEg CEO-

I 1 > I I + -NO
CEp /C E p C E p /C E p

/.C E p /-C E p-
CEp ^CEO- CEp CEO
I I > I 1
CEp /C E p CEp /C E p

/C E p /.CEpNOp
CEp CEO CEp CEO
I 1 I I
CEp /C E p CHp / C E p
^ CHp \ CHp

F o llo w in g th e above re a s o n in g , th e vapor phase n i t r a t i o n o f

b u tan e should p ro ceed a s fo llo w s :

D ecom position o f n i t r i c a c id :

(11) HÏÏO3 — ^ HO - + *NOp

Forms.tion o f a lk y 'l r a d i c a l s :

r — y CEgCEpCEpCEp - + EpO
(12) CHoCHpCHpCHo + H0 - (
'• — ?> CH3CH2ÇECH3 + EpO

D ecom position o f a l k y l f r e e r a d i c a l s :

> CS3CEpCH=CEp + -H
( 13) CEoCEpCEpCEp'C
> CE3CH2’ + CEp=CEp

r —^ CH3CH=CHCH3 + H--
(14) CE3CEpCBCH3(
> CE3 - + CEp=CECE3

R e a c tio n of a l k y l r a d i c a l s w ith NOp:

CE3CH2CE2CH2NO2
( 15) CEjCEpCSpCEp" + -N O /
> CEgCEpCEpCEpONO
 25.

/--> CH0CÏÏ2CÏÏCÏÏ3
(16) CH3CH2CHCH3 + -NOp^ NOp
^ CH3CEpCECE3
ÔNO

(IT ) CE3CE2' + -NOp — CEÿEpNOp + CH3CE2OEO

(iB ) CE3' + -NOp —-> CH3NO2 + CH3ONO

D ecom position o f n i t r i t e s :

(19) C3E.JCH2ONO — -NO + C3EYCSPO. > C3HY' + ECHO

y - —> CpEr ' + CEoCEO

(20) CPH5ÇHCE3 — > -NO + CpE^ÇBCEo
6nO "0 > CE3* + CpE^CEO

Now i t w i l l be observed t h a t th e m eth y l, e th y l , and. p ro p y l f r e e

r a d i c a l s produced in ( 13) , ( l 4 ) , ( 19) , and (20) ma,y r e a c t w ith -NOp

j u s t a s th e o r i g i n a l f r e e r a d i c a l s did in ( 15) and ( 16) . T his would

ac co u n t a t l e a s t q u a l i t a t i v e l y f o r th e low er n i t r o p a r a f f in s o b tain ed

e x p e rim e n ta lly and would, a ls o r e s u l t in th e form a.tion o f a d d it io n a l

f r e e r a d i c a l s w ith one l e s s carbon atom . The o l e f i n s ob serv ed in th e

p ro d u c ts a p p a re n tly come from d.ecom position o f th e f r e e r a d i c a l s by

( 13 ) and ( l4 ) and. a ls o from :

(21) 2CE3 ' > CEp=CEp + 2E-

R e a c tio n s (19) and (20) account f o r th e a ld e h y d e s . The la r g e

amount o f carbon monoxide a p p a re n tly r e s u l t s from th e w e ll known

p y r o ly s is o f a ld e h y d e s ( l 5 ) •

400^*0.
(22) ECHO > RE + CO

In s u p p o rt o f t h i s i s th e f a c t t h a t b o th hydrogen and methane

a re found in th e e x i t g a ses a s would be ex p ected from th e decom position

o f form aldéhyde and a c e ta ld e h y d e , No t e s t s were c a r r i e d o u t f o r ethane

o r p ro p an e. The o rg a n ic a c id s o b ta in e d r e s u l t from th e f u r t h e r o x id a tio n

 26.

o f th e a ld e h y d e s .

S in ce only s m l l amounts o f a lc o h o ls a r e form ed, th ey can w ell

he acco u n ted f o r hy th e fo llo w in g decom position o f a t y p i c a l a lk o x y l

r a d i c a l a s i l l u s t r a t e d hy e q u a tio n (9 )• In a d d itio n , a w a ll r e a c tio n of

th e fo llo w in g ty p e may a ls o occu r:

s u rfa c e
(2 3 ) E ' + -OH ---------- -> EOH

The mechanisms p resen ted , above may e a s i l y be extended to cover

th e e f f e c t o f oxygen on th e n i t r a t i o n p ro c e s s . A ccording to "Walsh ( I 5 );

th e low te m p e ra tu re (below 500®C.) o x id a tio n o f b u tan e w ith oxygen p ro ­

ceeds a s fo llo w s :

(2 5 ) CH3CH2CE2CH3 + ‘OE — ->• CE3CH2CHCE3 + EpO

(2 5 ) CE3CH2ÇHCH3 + Op — CE3CH2ÇECH3

( 26 ) CH3CH2ÇBCH3 + CbEpo > CH3CH2ÇHCH3 + CbH^-

6' ÔE

(2 7 ) CÏÏ3CH2CHCE3 - —>- CH3CH2ÇECH3 + -OS

Ô Ô•
Os
(2 8 ) CH3CH2ÇBCH3 - —V- CpE^- + CEOCEO

The same ty p e s o f r e a c tio n s would be expected to r e s u l t from an i n i t i a l

a t t a c k on a prim ary hydrogen e x cep t the.t forms,Idehyde would s p l i t o f f

in s te a d o f a h ig h e r a ld e h y d e . In e i t h e r c a s e , th e a l k y l f r e e r a d i c a l s

so produced would, be a v a ila b le f o r f u r t h e r r e a c tio n w ith oxygen or w ith

•NOp. I t w i l l be noted t h a t th e above o x id a tio n p ro ce ss in v o lv e s a

ch ain r e a c tio n which would be h in d ere d by in c re a s e d s u rfa c e due to

d ecom nosition o r r e a c tio n o f b o th -OE and. -R r a d i c a l s on i t (9) ■

 27.
s u rfa c e
( 29) 'E + *E ------ —— EE

s u rfa c e
( 30) -OH + -OH ---------- ^ EgOp

A lc o h o l f or ma.t Ion could a ls o occur by r e a c tio n ( 23) .

I f th e o x id a tiv e s e r i e s o f r e a c tio n s le a d in g to th e f o r m t i o n

o f f r e e a l k y l r a d i c a l s ru n s c o n c u rre n tly w ith th e n i t r a t i o n , then th e

p ro d u c tio n o f n i t r o p a r a f f i n s should in c re a s e due to th e e x is te n c e o f a

h ig h e r c o n c e n tra tio n o f a lk y l r a d i c a l s . In a d d it io n , th e r a t i o o f

low er to h ig h e r m o le c u la r w eight n i t r o p a r a f f in s should a ls o in c r e a s e

due to a g r e a t ly in c re a s e d c o n c e n tra tio n o f th e low er m o le c u la r w eight

a lk y l r a d i c a l s to g e th e r w ith t h e i r g r e a t e r s t a b i l i t y . I t has been p r e ­

v io u s ly shown t h a t th e s e p r e d ic tio n s a r e borne o u t by ex p erim en t.

 23.

KSFSRMCSS

1 . B l i c k e n s t a f f , E . T. , and Hs,ss, H. B ., J . Am. Chem. S o c . 6Q, 14-31

(1 9 4 6 ).

2. B u rto n , T, M., P r iv a te Communication.

3 ' F o rs y th e , W. E . , and G ia rg u e , W. F . , J . Am. Chem. Soc. $0, 3216-21

(1 9 2 8 ).

4 . H ass, ÏÏ. B ., and A le x a n d er, L. B ., In d . Eng. Chem. 2266-70

(1 9 4 9 ).

5 ' H ass, H. B ., Hodge, S . B .. and V a n d e rb ilt, V. M., In d . Eng. Chem.

2 8 . 339-44 ( 1936) .

6 . B aas, H. B . , and S h e c h te r, H ., In d . Eng. Chem. 39; 817 (1947).

7 . Bibshman, H. J . , P ie rs o n , E. H ., and B ass, B. B ., In d . Eng. Chem.

32, 427-9 (1 9 4 0 ).

8 . Kornblum, N ., and O liv e to , E . P ., J . Am. Chem. Soc. 71 226-8 (1949)

9 . L ew is, B ., and von E lb e , G .. "Com bustion, Flames and E x p lo sio n s o f

G a se s", Cambridge U n iv e rs ity P r e s s , Cambridge (1 9 3 8 ).

10. McCleary , E . F . , and D egering, Ed.. F . , In d . Eng. Chem. 64-7

( I 93B).

11. P a n e th , F. A ., and H o fe d ity , ¥ . . B er. 62E, 1335 (1929); 64, 2702

( 1931) .
12. E ic e , F . 0 . , and Eodowskas, E. L ., J . Am. Chem. Soc. 57, 350-2

( 1935) .
1 3 . E ic e , F. 0 . , "The A lip h a tic F ree R a d ic a ls " - Johns Hopkins P r e s s ,

B a ltim o re (1935)•

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( 1935) .

1 5 . W alsh, A. D ., T ra n s. Faraday Soc. 297 (1947) -

A. STUDY OF THE YAPOE PHASE NITRATION

OF BTJTAflE WITH EMPHASIS ON

THE EFFECT OF ADDING OZYŒN

A T h e s is

S u b m itted to th e F a c u lty

of

Purdue U n iv e rs ity

L e s li e Man d e v i l l e Addison

In P a r t i a l F u lf illm e n t o f th e

R equirem ents f o r th e D egree

of

D o c to r o f P h ilo so p h y

November „ 194-9
 TABLE OF CONTENTS

Page

I n tr o d u c tio n ........................................................................................................................ 1

D is c u ss io n o f R e s u l t s ........................................................................................................... 7

N i t r a t i o n o f M ethane.................................................................................................. 9

N i t r a t i o n o f Butane in th e 10 mm. C o il R e a c to r .......................................11

W ithout Oxygen ............................................................................................. 11

W ith Oxygen.........................................................................................................13

E f f e c t o f Oxygen on P ro d u c t D i s t r i b u t i o n ....................................................17

E f f e c t o f S u rfa c e on N i t r a t i o n ..........................................................................l3

Use o f Steam a s a D i l u e n t ...................................................................................22

N i t r a t i o n o f P ro p a n e ................................................................................................24-

N itro g e n B alance - Forma.tion o f N itro g e n G as..............................................27

M e c h a n ism ......................................................................................................................30

E x p e r i m e n t a l ....................................................................................... 4-2

A p p aratu s and T e c h n iq u e s.......................................................................................4-2

P ro d u c t A n a ly s is ........................................................................................................ 4-7

N itr o P a r a f f i n s . . 47

A c id s ......................................................................................................................49

A ld e h y d e s.............................................................................................................$0

G a s e s ......................................................................................................................50

Chemica,ls U sed......................................................... 54-

T ab les o f Da,ta .............................................................................................................. 55

Sumirery 56

B ib lio g rap h y ....................................................................................................................... 53

 LIST OF TABLES

T ab le Pa.ge

I V a r ia tio n o f Maximum C onversion on N itra .tio n o f an

Homologous S e r i e s ......................................................... 4s

II N i t r a t i o n o f M ethane........................................................................................ 9&

III N i t r a t io n o f Butane W ithout Oxygen - E f f e c t o f T em p eratu re. . 12a

IV N i t r a t i o n o f Butane W ith Oxygen - E f f e c t o f T em perature . . . l4 a

V N i t r a t i o n of Butane - E f f e c t o f Oxygen a t C o n sta n t

T e m p e r a tu r e ............................................................................................................. l4 b

VI N i t r a t io n o f Butane - E f f e c t o f Oxygen on Type o f N itro

P a r a f f i n s ................................................................................................................. 17a

V II N i t r a t io n of Butane - E f f e c t o f Oxygen a t a Surface/V olum e

o f 2 0 .......................................................................................................................... 19a

V III N i t r a t io n o f B utane - E f f e c t o f Oxygen a t a Surface/V olum e

o f 2 8 ..........................................................................................................................19b

IX N i t r a t io n o f B utane - E f f e c t o f Oxygen a t a Surface/V olum e

of 3 0 0 ....................................................................................................................... 19c

X N i t r a t io n o f Butane U sing Oxygen and Steam a s a D ilu e n t . , . 23a

XI N itra tio n of Propane in th e Packed R e a c to r ........................................25a

X II L oss o f N i t r i c Acid to N itro g e n G a s .......................................................27a

X III A nalyses f o r N itro g e n G a s ....................................................................... 26a

E x p e rim e n ta l D ata ........................................................................................ 5 5 a ,b ,c

 LIST OF FIGURES

F ig u re Page

1 E f f e c t o f T em perature on th e N i t r a t io n o f B u ta n e ............................. 12b

2 V a r ia tio n o f C onversion w ith Oxygen..... .................................................... l4 c

3 V a r ia tio n o f Y ie ld w ith Oxygen. ..............................................................l4d

4 V a r ia tio n o f C onversion w ith Oxy^gen U sing D iffe re n t

Surface/V olum e R a t i o s .......................................................................................19d

5 V a r ia tio n o f Y ield w ith Oxygen U sing D if f e r e n t

Surface/V olum e R a tio s ..................................................................................... 19e

6 E f f e c t o f Oxygen on th e P ro d u c tio n o f O le fin s U sing

D i f f e r e n t Surface/V olum e R a tio s ............................................................... 20a

7 E f f e c t o f Oxygen on th e T o ta l Amount o f Butane R e a c tin g . . . 21a

 INTRODUCTION

The p urpose o f t h i s i n v e s t ig a t io n was to d e te rm in e th e in flu e n c e

o f oxygen gas upon th e vapor phase n i t r a t i o n o f b u tan e w ith n i t r i c s-cid.

In view o f th e la r g e amount o f e x p e rim e n ta l work t h a t has been done on

vapor phase n i t r a t i o n , a b r i e f rev iew o f th e r e l e v a n t p o r tio n s w i l l

se rv e to c l a r i f y th e s t a t u s o f th e problem and p la c e th e p r e s e n t work

in i t s p ro p e r p e r s p e c tiv e .

The vapor pha.se n i t r a t i o n o f b u tan e w ith n i t r i c a c id was f ir s t-

perform ed by Hod.ge ( l l ) in 1936. T h is work, conducted a t appro x in n .tely

th r e e seconds c o n ta c t tim e and a t a te m p e ra tu re o f 420®, gave a c o n v e r­

s io n to n i tr o p a ,r a f f i n s o f 37 p e r c e n t based on th e n i t r i c a c id charg ed .

McCleary ( 1 5 ), in 1938, performed, th e same n i t r a t i o n a t v a rio u s tem pera­

t u r e s b u t a t u n d isc lo s e d c o n ta c t tim e s . U n fo rtu n a te ly he used a r a t h e r

low mole r a t i o o f hydrocarbon to n i t r i c a c id and obtained, somewhat-

e rra tic r e s u lts . His d a ta a r e u s e f u l , c h ie f ly in t-hs.t he i s o l a t e d and

i d e n t i f i e d th e dibromo d e r i v a ti v e s o f th e o l e f i n s p r e s e n t in th e e x it

gases. In t h i s wa.y he was a b le to show t h a t th e o l e f i n s formed c o r r e ­

sponded. to each o f th e rad ic e ,Is (e x c e p t m ethyl) a p p e a rin g e,s n i t r o -

p a re ffin s .

O ther i n v e s t i g a t o r s , w orking la r g e ly w ith m ethane, determ ined

th e e ffe c t- o f p r e s s u r e , mole r a t i o , c o n c e n tra tio n o f n i t r i c a c i d . con­

t a c t tim e , and te m p e ra tu re . S h e c h te r (22) found tha.t In c re a se d p re s s u re

had no n o tic e a .b le e f f e c t on c o n v e rsio n b u t sh o rte n e d th e optimum c o n ta c t

tim e f o r a given te m p e ra .tu re . Hedge ( l l ) n i t r a t e d Iso b u te n e a t mole

r a t i o s o f from two to tw en ty , and showed t h a t c o n v e rsio n in c r e a s e s w ith

mole ra .tlo b u t ap p roaches a s y m p to t-ic slly a maximum v a lu e which i s mu.ch

l e s s than 100 p er c e n t. Hlbshmsn (9) used n i t r i c a c id o f s tr e n g th

v a ry in g from 40 to JO p e r c e n t and. found t h a t c o n v e rsio n d e c re a sed as

th e c o n c e n tra tio n o f a c id was lo w e re d , Boyd (3 ) ; who in v e s tig a .te d th e

optimum c o n d itio n s f o r th e n i t r a t i o n o f m ethane, found t h a t th e r e i s

an optimum c o n ta c t tim e f o r each te m p e ra tu re and t h a t th e r e i s a s l i g h t

v a r i a ti o n o f co n v e rsio n betw een d i f f e r e n t te m p e ra .tu re s . Thus th e p ro ­

p e r m atching o f c o n ta c t tim e w ith te m p e ra tu re w i l l g iv e a good, c o n v e r­

s io n , b u t th e r e i s an optimum co n v e rsio n which may be o b ta in e d a t one

p a r t i c u l a r te m p e ra tu re and c o n ta c t t im e .

A lexander ( l ) , w h ile i n v e s t i g a t i n g i n t e r n a l h e a tin g o f th e

n i t r a t i o n r e a c ti o n by th e i n tr o d u c tio n o f a lim ite d , amount o f a i r to

burn p e r t o f th e h ydrocarbon, d isco v ered , a s u r p r i s i n g in crea.se in con­

v e rs io n to n i t r o compounds. T h is was tra c e d to th e oxy:gen c o n te n t o f

th e a i r , and su bsequent e x p erim en ts on th e n i t r a t i o n of m ethane and

propane w ith oxy'gen added gave an in c r e a s e in co n v e rsio n from 23 to "jG

p e r c e n t w ith p ro p an e. The r o l e o f oxygen was p o stu la .ted to in v o lv e

th e form a,tion o f f r e e r a d i c a l s th ro u g h o x id a tiv e a t t a c k on th e hydro­

carbons p r e s e n t, a lth o u g h no d i r e c t e v id e n c e was o ffe re d to s u p p o rt t h i s

c o n c lu s io n . I t was pointed, o u t t h a t an e a r l i e r s u g g e s tio n by Hass (7)

t h a t oxygen m ight aid, th e r e a c ti o n by o x id iz in g th e n i t r i c o x ide produced

to n itro g e n d io x id e which could, a c t a s a n i t r a t i n g a g e n t was u n lik e ly

b o th from a k i n e t i c and thermodyna.mic s ta n d p o in t. At any te m p e ra tu re

t h i s re a .c tio n i s slow compared to th e exposure tim e o f 1 .6 seconds used,

in th e s e n i t r a t i o n s , and th e e q u ilib r iu m m ix tu re a t 400®C. in a system

c o n s is tin g o f 15 m oles i n e r t ga,s, 2 m oles w a te r , one mole oxygen, and,

one mole o f NO + NOy would conta,in 50 p e r c e n t n i t r i c o x id e .

In a l l th e work m entioned above w ith th e e x c e p tio n o f t h a t of

M cCleary, th e only dependent v a r i a b le s studieg^ were c o n v e rsio n o f n i t r i c

 3-

a c id to n it r o p a r a ff in s , a c id it y o f th e a queous p o r t i o n o f th e p ro d u c t

and th e r a t i o o f gas o u t to r e a c t a n t s f e d . M c C le a r y ' s d a ta , a lth o u g h

o b ta in e d u n d e r u n s ta te d c o n d it io n s , do g iv e an i d e n t i f i c a t i o n o f th e

o le f in s fo rm e d and a j ^ a r t i a l d e te r m in a tio n o f th e am ounts p r e s e n t. In

no case was e c o m p le te d e te r m in a tio n o f th e b y - p r o d u c ts m ade. C onse­

q u e n tly no data, a re a v a i l a b le r e l a t i v e t o th e y i e l d o f n it r o p a r a ff in s

based on th e am ount o f h y d ro c a rb o n consumed, i n th e r e a c t i o n . T h is

omi.Gsion ste m s fr o m th e lo w c o s t o f gaseous h y d ro c a rb o n s w h ic h p r e v a ile d

a t th e tim e when vapor phase n i t r a t i o n s t u d ie s o r ig in a t e d , . H ow e ver, i t

is o b v io u s t h a t a tte m p ts t o f o l l o w th e c o u rs e o f th e r e a c t io n more

c lo s e ly 8.8 w e l l a s p r e s e n t day c o s t c o n s id e r a t io n s make a s tu d y o f b y ­

p r o d u c ts m a .n d a to ry. T h is becomes o f p rim e im p o rta ,n c e i n th o s e p ro c e s s e s

i n v o l v i n g oxygen b ecau se o f th e la r g e am ounts o f o xyge na te d, m a .te ri8 .l8

fo rm e d .

The p r e s e n t s tu d y o f th e n i t r a t i o n o f b u ta n e w i t h n i t r i c a c id

and oxyge n i s a d i r e c t s e q u e l t o A le x a n d e r ’ s w o rk on znethane end pro pa ne .

A lth o u g h b u ta n e has s e v e r a l d is a d v a n ta g e s as a raw ra s .te ria .l fr o m a com­

m e r c ia l s t a n d p o in t in t h a t i t i s more e x p e n s iv e , y i e l d s le s s o f th e

d e s ir a b le lo w e r n i t r o p a r a f f i n s , and i s somewhat le s s a v a i l a b l e , th e r e

a re s e v e r a l fan t o r s w h ic h le n d i n t e r e s t t o such a. s tu d y . In o r d in a r y

n it r a tio n s u s in g only th e h y d ro c a rb o n and n i t r i c a c id , b u tan e a p p e a rs

to g iv e a h ig h e r c o n v e rs io n th a n propane w h ic h in tu rn g iv e s s u p e r io r

c o n v e r s io n s t o e th a n e . M ethane i s so d i f f i c u l t to n it r a t e t h a t i t was

th o u g h t im p o s s ib le f o r a. number o f y e a rs u n t i l la n d on ( I 3) i n 1939 ; d is ­

c lo s e d a w o rk a b le p ro c e s s . T h is d i f f i c u l t y is illu s t r a t e d i n p a r t by

data, fr o m H odge’ s t h e s i s w h ic h a re i n t e r e s t i n g in t h a t th e y show th e

r e s u lt s o f n i t r a t i n g th r e e d i f f e r e n t h y d ro c a .rb o n s u n d e r th e same c o n d it io n s
 4.

(420®C., mole r a t i o o f 3 -5 , end c o n ta c t tim e o f a p p ro x lim te ly 3 seconds).

H ydrocarbon C o n v e rsio n , 5

Methane 0

E thane 9

Propane 21

Butane 29

Of p erhaps g r e a t e r s ig n if ic a n c e a re th e optimum c o n v e rsio n s f o r th e

fo u r low er norms.l p a r a f f i n s a s l i s t e d in T able I. I t w ill be noted

th a .t th e maximum c o n v e rsio n s in c r e a s e w ith th e m o le c u la r w eight o f th e

hy d rocarbon. S in c e a d d in g oxygen in th e n i t r a t i o n o f propane gs.ve such

marked improvements in th e c o n v e rsio n s to n i t r o p a r a f f i n s , b u tan e would

be expected, to show even more fa v o r a b le r e s u l t s .

The use o f g a se s such a s b u tan e f o r th e p ro d u c tio n o f

oxygenated chem icals by d i r e c t o x id a tio n in th e C elan ese C o rp o ra tio n

p la n t a t B ishop, T exas, s u g g e s ts t h a t th e b y -p ro d u c ts from n i t r a t i o n

in th e p rese n c e o f oxygen mi.ght be im p o rta n t from an economic v iew p o in t.

A side from such c h a r a c t e r i s t i c s which mi.ght be p e c u lia r to b u ta n e , th e

la c k o f p re v io u s d a ta would make such a. stu d y v a.lu ab le,

S h e c h te r noted th e im portance o f r e a c t o r d e s ig n s on con­

v e rs io n s and c ite d t h i s a s s re a so n f o r th e d iv e rg e n c e betw een h is

r e s u l t s and th o se o f Boyd f o r th e n i t r a t i o n o f rnethsne. Boyd used a.

r e a c t o r ma.de o f 25 mm. O.D. pyrex tu b in g and obtained, a maximum con­

v e rs io n o f 12.2 p e r c e n t a.t 46l®C. end a, c o n ta c t tim e o f 0 .42 seco n d s.

S c h e c h te r ’s r e a c t o r , made o f 5 mm. O.D. tu b in g , allow ed a co n v e rsio n o f

l 9 .7 p e r c e n t a t 435®C. and a c o n ta c t tim e of 1 .4 9 seco n d s. He s t a t e s

t h a t th e e f f e c t i s due to th e la r g e r a t i o o f s u rf a c e to volume which

g iv e s e x c e lle n t h e a t t r a n s f e r end te m p e ra tu re c o n tr o l . A lexander p o in te d

o u t t h a t h is p o s it i v e r e s u l t s in th e use o f oxy gen as a. n i t r a t i o n a i d ,

 4a.

T a b le I

V a r ia tio n o f Maximum C onversion Upon

A scending an Homologous S e r ie s

Hydrocarbon CHb C3S8 n-CqHj_o

I n v e s tig a to r * S h e c h te r Hibshms.n A lexander Addison

C o n ta c t Time, S ec. 1 .4 7 0 .2 1 1 .6 1 .6

Mole Ee.tio 1 2.5 12.5 1 1.0 12.3

T em p eratu re, ®C. 435 470 410 425

Maximum C o n v ersio n , 19 25 28 36

* A ll r e s u l t s tak en from th e Purdue Ph.D . th e s e s by th e inve s tig a .to r s

named
In c o n tra s t to s i m i l a r u n s u c c e s s fu l e x p e rim e n ts p e rfo rm e d by H odge,

w e re due to im p ro v e d h e a t t r a n s f e r o b ta in e d in th e s m l l e i ' d ia m e te r'

t u b in g .

On th e o th e r hand.. Pease ( l ? ) fo u n d t h a t e x te n d e d g la s s s u r ­

fa c e s s u p p re s s th e hom ogeneous, n o n - e x p lo s iv e r e a c t io n betw e en p ro p a n e

and oxygen w h ic h i s n o r m a lly c o m p le te a t 375 * 0 . U nder th e s e c o n d it io n s

th e r e a c t i o n does n o t b eg in u n t i l th e te m p e ra tu re re a c h e s 500®C. and

th e p r o d u c ts , in s te a d o f b e in g m o s tly carbon m o n o x id e , c o n s is t o f

la r g e a.mounts o f o l e f i n s , a ld e h y d e s , m ethane and h y d ro g e n . He a ls o

fo u n d t h a t a t h i n c o a t in g o f p o ta s s iu m c h lo r id e r a i s e s th e re q u ire d

te m p e r a tu r e an a d d i t i o n a l h u n d re d d e g re e s . T h is c o r r e la t e s w e l l w it h

th e o b s e rv B .tio n o f Hodge ( lO ) t h a t p o tassiu m n i t r a t e re d u c e s th e e f f e c t

o f oxygen on n i t r a t i o n .

S i m i l a r e x p e rim e n ts by Pease end M unro (iS ) d is c lo s e th e

f o r u m t io n o f s i g n i f i c a n t c u a n t i t i e s o f h y d ro g e n p ero x id e end a l k y l

h y d r o p e r o x id e s . These r e s u l t s f e l l lo g ic a lly in to th e p r e s e n t ly

s.cce p te d m echanism f o r th e o x id a t io n o f h y d ro c a rb o n s in th e absence

o f fla m e , w h ic h p o s tu l a te s f r e e r a d i c a l s as i n t e r m e d ia t e s .

¥hen th e above e f f e c t s of s u r fa c e a re n o te d and when i t is

r e c a ll e d t h a t extended s u r fa c e s s to p f r e e r a d i c a l s th u s e n d in g c h a in

r e a c tio n s , it is c le a r t h a t th e s u r fa c e t o volum e r a t i o may have

e ffe c ts o th e r th a n th o s e due to h o s t tr a n s fe r e ffic ie n c y . C e r t a in ly

th e d a ta i n hand a re i n s u f f i c i e n t t o a llo w c o n c lu s io n s to be d ra w n . It

w o u ld be m ost i n t e r e s t i n g t o have r e s u l t s fr o m e x p e rim e n ts w here th e

s u r fa. ce to volum e r a t i o hs.d been \a .r ie d u n d er c o n d it io n s o f c o n s ta n t

hee.t t r a n s f e r .

T h is i n v e s t lg e t io n hes shown t h a t c m oderate in c r e a s e in con­

v e rs io n i s o b teln ed in th e n i t r a t i o n o f b u tan e in th e p rese n c e o f oxygen

U nder th e s e c o n d it io n s , th e m a jo r b y -p ro d u c ts a r e o l e f i n s end a ld e ­

hydes. The h e a t t r a n s f e r a re a pi e se n t in th e r e a c t o r ap p e a rs t o have

q u it e an im p o r te n t e f f e c t on th e maximum c o n v e r s io n ,

It has been fo u n d th e t th e s u r fa c e to volum e r a t i o he.s en

e f f e c t a p e r t fr o m b e e t t r s n s f e r . T h is he s been a s c r ib e d to a, c h a in

s to p p in g m e c h a n is m ‘whi.ch causes e more even r a t e o f p ro d u c tio n o f alley 1

f r e e r a d i c a l s th ro u g h o u t th e r e a c t o r . Steam as a. d i l u e n t hs.s been fo u n d

to e x e r t a s im ila r in f lu e n c e .

I n a d d itio n , a. m echanism has been w orked o u t w h ic h a c c o u n ts

f o r a l l o f th e known f a c t s c o n cern in g n i t r a t i o n . T h is p o s t u la t e s ib e

fo r m a tio n o f allQ -l f r e e r a d i c a l s , t h e i r r e a c t i o n w it h n it r o g e n d io x id e

t o p ro d u c e n i t r o p a r a f f i n s end a .lk y 'l n i t r i t e s , end th e s u b s e q u e n t decom­

p o s itio n o f th e n i t r i t e s to a ld e h y d e s and lo w e r alky 1 i & d i c a l s . F is s io n

p r o d u c ts a re a c c o u n te d f o r by a s i m i l a r s e r ie s o f r e a c ti o n s w i t h th e s e

a lk y l r a d ic a ls -
 7.

DISCUSSION OF RESTITS

The s e le c t io n o f th e ty p e o f a p o e .ra iu s and th e c o n d it io n s

u n d e r w h ic h i t was t o he o p e ra te d w ere g overned hy tw o f a c t o r s : fir s t,

th e d e s ir e to e lim i.n a te e x tra n e o u s " v a r ia h le s and s e c o n d , th e n e c e s s ity

f o r c o r r e l a t i n g r e s u l t s w i t h th o s e o f po.st i n v e s t i g a t o r s . S in c e Hodge

has shown t h a t c o n v e rs io n a p p ro a c h e s a zmximimi v a lu e as th e mole r a t i o

is in c r e a s e d , w it h n e g l i g i b l e e f f e c t s sh ove h y d r o c s r h o n / n i t r i c a c id

r a tio s o f l 4 , a r a tio o f Ip was chosen f o r t h i s work. A le x a n d e r , who

p e rfo rm e d th e p r e v io u s w o rk w i t h o x y g e n , o p e ra ted a t a c o n ta c t tim e

o f 1 .6 se con ds end a t te m p e r a tu r e s betw een 350 *C . and. t 35 ®C. Hence

a c o n ta c t tim e o f 1 .6 seconds was used u n ifo rm ly - in a l l th e s e e x p e r i ­

m ents and w hatever iem pere.ture r e q u ir e d to g iv e ms.xlinum c o n v e r s io n .

The i n i t i a l w o rk was done i n an a p p a ra tu s p a tte r n e d a f t e r A le x a n d e r ’ s ,

u s in g a r e a c t o r c o n s i s t i n g o f 7 nm. O .D . p y re x t u b in g . C heck r u n s on

m ethane c o u ld he ma.de s e t i s f e . c t o r i l y in t h i s sp p -e .ra tu s, b u t i t p ro v e d

u n s u it a b le f o r b u ta n e w h ic h has a much h ig h e r v i s c o s i t y , th u s g iv i n g

e xtre m e ly - h ig h p re s s u r e d ro p s and r e q u i r i n g v e ry la r g e i n l e t p re s s u r e s .

H o d g e 's work on b u ta n e was done i n a r e a c t o r c o n s tr u c te d o f 1 C mm. I . D .

tu b in g , hence a d u p lic a te o f t h i s r e s e t o r was made f o r th e work on

b u ta n e . L a t e r work on th e e f f e c t o f th e s u r fa c e t o vo lu m e r a t i o (s/V
r a tio ) was done i n a r e a c t o r m d e o f 22 mm. O .D . t u b in g so d e v is e d t h a t

it c o u ld be ps.cked w i t h v a r io u s s iz e s o f p y re x h e lic e s o r g la s s w o o l in

o rd e r to v a ry th e am ount o f s u r f a c e . A re a c to r o f t h is ty p e has

r e la t iv e ly p o o r h e a t t r a n s f e r c h a r a c t e r is t ic s , , a lt h o u g h th e s e e re c o n ­

s ta n t, th u s e l i m i n a t i n g h e a t t r a n s f e r es a v a r i a b l e .

The m e te r in g o f th e r e a c t a n t m a t e r ia ls by a. new , improved

m ethod a llo w e d e x c e l l e n t c o n t r o l o f fe e d c o m p o s itio n and r a t e . T h is

is d e s c r ib e d more c o m p le te ly u n d e r Api^arn t u s . The m ethod o f a n e ly s is

f o r p r o d u c ts o f e x p e rim e n ts 1 -1 2 was th e same as t h a t used by A le x a n d e r .

F o r th e re m s .in d e r o f th e w o rk , n i t r o a n a ly s e s w ere p e rfo rm e d by e

m o d if ie d K j e ld e h l m ethod w h ic h e l i m in â te s u n c e r t a in a s s u m p tio n s

f o r m e r ly me,d e . A ls o a s y s te m o f a n a ly s is f o r th e p r i n c i p a l b y - p r o d u c ts

( n a m e ly , o l e f i n s , a ld e h y d e s , a c id s , n it r o g e n o x id e s and carbon o x id e s )

was a d o p te d . T h is added g re e .tly to th e u t i l i i y o f th e d a ta o b ta in e d

end made p o s s ib le a c a lc u l a t i o n o f y ie ld based on th e hydrocarbon c o n ­

sumed. D e t a i l s o f th e a n a l j t i c e l p ro c e s s e s a re g iv e n u n d e r F x p e i'im e n ta l

P ro c e d u re .
 I. N itr a tio n o f M ethane

A c c u r a te , c u a n t i t e t i v e s t u d ie s on ve.por phase n i t r a t i o n of

h y d ro c a rb o n s a re a b ra n c h o f e x p e r im e n ta l o r g a n ic c h e m is try r e q u i r i n g

e s p e c i a l te c h n iq u e . T h is i s am ply illu s t r a t e d by th e work o f B oyd,

S h e c h te r, end A le x a n d e r on th e n i t r a t i o n o f m e th a n e . A l l th r e e w orked

e t a tm o s p h e ric p re s s u r e o r s l i g h t l y above u s in g c o m p a ra b le te m p e r a tu r e s ,

c o n t a c t tim e s , and m ole r a t i o s . N e v e r t h e le s s , th e ms.ximum c o n v e rs io n s

o b ta in e d w ere 1 2 . P p e r c e n t , l B . 7 p e r c e n t, end 1 7 -1 p e r c e n t , r e s p e c ­

tiv e ly . W h ile much o f th e T 's r ia t io n me.y be tr a c e d t o th e d ia m e te r o f

th e r e a c t o r used (1 0 mm., 5 mm., and 7 mm., r e s p e c t i v e l y ) , o th e r

v a r ia b le s su ch as th e m e te r in g s y s te m end m ethod o f p r o d u c t a n a ly s is

a re in v o lv e d . The im p o rta n c e o f t h i s la t t e r fa c to r is apT^arent fr o m

c o m p a ris o n s o f th e r e s u l t s o f H at c h e r ( 6 ) w it h th o s e o f A le x a n d e r and

S h e c h te r a t 100 p s i . The fo r m e r i n v e s t i g a t o r o b ta in e d a c o n v e rs io n o f

2 7 .1 p er c e n t a t e, te m p e ra tu re o f . end 0 .7 5 se con ds c o n ta c t tim e .

The l a t t e r w o r k e r s , u s in g en i d e n t i c a l a p p a ra tu s and th e same c o n d it io n s ,

g o t a, c o n v e rs io n o f 2 1 .1 p e r c e n t.

In v ie w o f th e above data., i t was th o u g h t e s s e n t i a l t o demon­

s tra te a b ilit y to ch e ck p r e v io u s r e s u l t s . C o n s e q u e n tly , e x p e rim e n ts 1-6

w ere p e rfo rm e d u s in g m ethane as th e h y d r o c a rb o n . The r e s u l t s a re l i s t e d

in T a b le I I a lo n g w i t h c o rr e s p o n d in g e x p e rim e n ts fr o m th e w o rk o f

A le x a n d e r . E x p e rim e n ts 1 and 4 have been o m i.tte d ina sm u ch as th e p r o ­

d u c t a n a ly s e s f o r th e s e w ere extrem ely d o u b t f u l . I t w i l l be n o te d th a t

th e c o n v e rs io n s In Runs 2 end 3 do n o t c h e c k very c lo s e ly w ith th e

c o r r e s p o n d in g c o n v e rs io n s o b ta in e d by A .le x a n d e r ( 1 1 -A and y -A ) . H ow e ver,

if th e r e s u l t s fr o m Runs 2 and 3 e re c o r r e c te d to uhe seme c o n d itio n s as

 T able I I

N itra .tio n o f Methane

Run No. 2 3 5 6* 5 -A ** 11 - A * *

C o n ta c t Tim e, S ec. 1 .2 3 1 .4 7 1 .0 1 .6 1 ,6 1 .7

CEp/mOg 12 .3 1 1 .0 1 5 .0 1 5 .0 1 5 .3 1 6.0

O g/m o^ 1 .5 6 0 0 1 .5 6 0 1 .3

°!q C onversion*** 1 8.0 1 4 .1 1 7 .2 1 7 .6 2 3 .4

iü C o rre c te d C onversion**** 2 1 .0 1 7 .0 1 7 .2 -- 1 7 .6 22 .0

Rea.ctor D ia m e ter, mm. 7 7 10 10 7 7

* R e s u lte d in an e x p lo sio n

** A le x a n d e r's d a ta .

*** P er c e n t o f n i t r i c a c id charge which i s co n v erted to n i t r o

p a ra ffin s .

**** C orrected, to a c o n ta c t tim e o f 1 .6 seconds and a mole r a t i o o f

15.
 10.

1 1 -A and 5 -A a c c o r d in g to c o r r e l a t i o n s f o r m ole r a t i o and c o n t a c t tim e

d e te rm in e d by A le x a n d e r th e a g re e m e n t i s s e tls fs c to r y . Runs p snd 6

w ere made i n th e 10 mm. I . D . r e a c t o r p re p a re d f o r b u ta n e . E x c e l le n t

a g re e m e n t was o b ta in e d between 5 and p - A , b u t i t wss fo u n d th a .t

e x p e rim e n t 6 i n w h ic h oxygen was added c o u ld n o t be c o n t r o l l e d . The

d if f ic u lt y was e p p e r 'e n tly due t o in a d e q u a te h e a t t r a n s f e r w i t h its

s tte n d e .n t p o o r te m p e r a tu r e c o n t r o l .

As a r e s u l t o f th e s e e x p e rim e n ts , it was d e c id e d t h a t th e

m ethod fo llo w e d fo r n it r a tio n was s a t i s f a c t o r y and t h a t s u f f i c i e n t

te c h n ic u e had been m a s te re d t o e .llo w i n v e s t i g a t i o n o f b u ta n e .

 11.

I I . N i t r a t i o n o f Butane In th e Ten M illim e te r R e a c to r

N i t r a t i o n W ithout Oxygen

P re lim in a ry a tte m p ts to n i t r a t e b u tan e in th e 7 inm. r e a c t o r

■were u n s u c c e s s fu l because th e la r g e p r e s s u r e drop th ro u g h th e r e a c t o r

under h ig h r a t e s o f flow m d e th e vapor p r e s s u r e o f b u tan e I n s u f f i c i e n t

to im, in t a i n th e p ro p e r c o n ta c t tim e . W hile work could have been p e r ­

formed w ith th e c o n ta c t tim e o b ta in a b le ^ i t was th o u g h t t h a t th e 1 .6

second m lu e used by A lexander would be ad'vantageous to m a in ta in in

t h a t com parisons could be ms.de more r e a d ily . I t would have been

p o s s ib le to a tts .in t h i s r e s u l t e i t h e r by s h o rte n in g th e 7 mm. r e a c t o r

o r by u s in g a. c o i l o f l a r g e r d ia m e te r. The l a t e r d e v ic e was adopted

s in c e th e form er would have meant u s in g a low er th ro u g h p u t w ith a

lo n g e r p e rio d o f o p e ra tio n and would have in g e n e ra l a ffo rd e d a l e s s

f l e x i b l e a p p s .ra tu s . The o n ly f o re s e e a b le d e f e c ts in th e 10 mm. r e a c to r

were i t s p o o rer h e a t t r a n s f e r c h a r a c t e r i s t i c s . However^ D r. Hodge o f

Commercial S o lv e n ts was o f th e o p in io n t h a t t h i s r e a c t o r would be

s a t i s f a c t o r y f o r b u tan e s in c e t h i s hydrocarbon has a l a r g e r h e a t

c a p a c ity than m ethane. D r. Hass p o in te d o u t t h a t th e r e s u l t s w ith

methane o b ta in e d in t h i s r e a c t o r in Run No. 5 gs,ve ev id en ce o f s u it a b le

o p e r a tin g c h a r a c t e r i s t i c s in a s much as th e n i t r a t i o n o f methane has

p re v io u s ly been shown to r e q u ir e e x c e lle n t h e a t t r a n s f e r .

A. r e a c t o r c o n s is t in g o f 25 f e e t o f 10 mm. O.D. pyrex tu b in g

b e n t in to a 18 cm. O.D. c o i l was i n s t a l l e d . A t th e same tim e i t was

found p o s s ib le to use a j e t ty p e o f gas flow m eter which g r e a tly improved

th e e a se o f o p e ra tio n and a c c u ra c y o f th e n i t r a t o r . I t was n e c e s s a ry to

r e p la c e th e dry ic e t r a p s and w a te r s c ru b b e r used by A lex an d er w ith a

r e f l u x condenser capa.ble o f c o n d en sin g a l l th e u n rea c te d b u tan e in

o rd e r to g e t s a t i s f a c t o r y remo-va.l o f a l l n itr o p a .r a f f in s from th e ga.s stre a m .
 12.

T able I I I g iv e s th e r e s u l t s from th e n i t r a t i o n o f b u ta n e a t

th r e e d i f f e r e n t te m p e ra tu re s b u t a t a c o n s ta n t c o n ta c t tim e o f 1 .6

s e c o n d s. A r e s u l t o b ta in e d by Hodge ( l l ) i s a ls o in c lu d e d f o r com­

p a r is o n . U n fo rtu n a te ly , on ly an e s tim a te d c o n ta c t tim e i s a v a il a b l e

f o r h is work b u t i t can be seen t h a t th e r e s u l t s a re s u b s t a n t i a l l y

d u p lic a te d by th e p r e s e n t work. A graph o f th e s e c o n v e rsio n s ag a ,in st

te m p e ra tu re (F ig u re l ) shows t h a t optimum r e s u l t s a re a tt a i n e d a t a,

te m p e ra tu re o f ^25*C.

A t t h i s p o in t i t was decided t h a t th e n i t r a t i o n d a ta would

be more u s e f u l i f th e y in clu d e d q u a n tita b iv e d e te rm in a tio n s o f m s.te ria ls

o th e r th an n i t r o p a r a f f i n s produced. T h is would in c lu d e propene, b u te n e ,

e th y le n e , ald e h y d e s carbon monoxide and carbon d io x id e . O ther o x id a ­

tio n p ro d u c ts a r e produced, b u t th e q u a n t i t i e s a r e sm a.ll, an d , due to

th e d i f f i c u l t y o f a n a l y s i s , th e y a r e n o t c o n s id e re d . T h is new in fo rm a­

tio n perm i.ts th e c a lc u la tio n o f y i e l d s of each p ro d u ct based on th e p e r

c e n t o f th e b u ta n e r e a c t i n g .

Such d a ta from th e fo re g o in g e x p erim en ts a t ^05®C., 4 2 5 ^ 0 .,

and . a re a ls o given in T able H I . I t can be seen t h a t in th e

m o d erately narrow te m p e ra tu re ran g e re p o r te d h e r e , te m p e ra tu re has a

marked e f f e c t on th e q u a n tity o f n i t r o p a r a f f i n s produced.. T h e ir p ro ­

d u c tio n re a c h e s a maximum and s u b se q u e n tly d e c re a s e s w ith in c r e a s in g

te m p e ra tu re .

The optimum te m p e ra tu re e f f e c t observed in th e p ro d u ctio n o f

n i t r o p a r a f f i n s has p r e v io u s ly been e x p la in e d in two ways. One i s t h a t

a s th e te m p e ra tu re i s in c r e a s e d , d ecom position o f n i t r o p a r a f f i n s begins

to ta k e p la c e th u s re d u c in g th e amount found in th e p ro d u c t. However,

T a y lo r (2k) found tha.t th e h a l f - l i f e o f n i t r o methane a t 420*0. i s fo u r

m in u te s . Even assum ing a much g r e a t e r d egree o f i n s t a b i l i t y f o r th e

 12s,

T able I I I

N i t r a t i o n o f Butane W ithout Oxygen

E f f e c t o f T em perature

; 10 mm. I.D . C o il R e a c to r)

Run No. 42 10 41 Hodge*

Ci,Hio/HH 03 15.0 12.3 15.0 1 4 .0

T em p eratu re, ®C. 405 425 435 420

$ C onversion** 15 36 22 37
M oles Formed***

RNOg 0 ,1 0 0.29 0 .1 4

J> 0 = 0 0 .0 6 0 .06 0 .10

C^Hg+CgHg 0.1 0 0 .1 1 0 .14

0.10 0.18 0.12

CO 0.13 0 .0 7 0.13

COg 0 .1 0 0 .26 0 .0 7

Butane Consumed., Moles**** 0 .3 1 0.55 0.41

* A pproxim ately 3 seconds c o n ta c t tim e .

** Based on n i t r i c a c id ch arg ed ,

*** C o rre c te d to m oles p e r 10 moles o f b u tan e c h a rg e d .

**** C a lc u la te d , from th e carbon c o n te n t o f th e p ro d u c ts .

 yz b

FIGURE I

EFFECT OF TEMPERATURE ON THE NITRATION

OF BUTANE AT ( . 6 CECONOC CONTACT TIME

(RATIO C)4H,q/HN0-,. = I5 ; 10 MM. I.D . REACTOR)

O 2 MOLES Og/MOLE HNOg

□ - NO OXYGEN

4o

>20

10

0
400 %^0 440

TEMPERATURE,
 13.

h ig h e r iDembers o f th e s e r i e s , l y s i s should he n e g li g ib l e a t a con­

t a c t tinie o f 1 .6 se co n d s. Hence t h i s e x p la n a tio n seems in a d e q u a te to

a c c o u n t f o r th e f a c t s .

A l t e r n a t i v e l y i t has been s u g g e ste d t h a t com peting s id e r e a c ­

t io n s •with h ig h e r a c tiv s -tio n e n e rg ie s becomes more prom inent a t th e

h ig h e r te m p e ra tu re s . Such r e a c ti o n s -would be expected to produce

in c r e a s in g siaounts o f b y -p ro d u c ts a s th e te m p e ra tu re in c r e a s e s . T his

i s n o t th e case ho-wever. I f th e to-ts.l number o f m oles o f b u tan e which

r e a c t a re c a l c u l a t e d , i t can be seen t h a t th ey in c r e a s e up to a c e r t a i n

te m p e ra tu re and then d e c re a s e . Hence th e d e c re a se in y i e l d s o f n i t r o

p a r a f f i n s observed above th e optimum te m p e ra tu re cannot be th e r e s u l t

o f com peting s id e r e a c t i o n s . A c tu a lly th e d e c re a se in m oles o f n i t r o

p a r a f f i n s produced i s a p p ro x im a te ly e q u a l to th e d e c re a se in m oles o f

b u tan e r e a c t i n g . Hence i t may be concluded t h a t th e assum ption o f

com peting s id e r e a c ti o n s which occur a t th e h ig h e r te m p e ra tu re s i s n o t

su p p o rted by e x p e rim e n ta l e v id e n c e .

The d e c re a s e in y i e l d s o f n i t r o p a r a f f i n s can be e x p la in e d

more sim ply and in b e t t e r acco rd w ith th e d a ta assem bled in th e fo llo w ­

in g way. The n i t r a t i o n would a p p e a r to be a f r e e r a d i c a l r e a c t i o n . As

such i t should be s e n s i t i v e to f r e e r a d i c a l s to p p in g m echanism s. If

th e s e mechanisms a r e assumed to become more and more prom inent a s th e

te m p e ra tu re r i s e s , i t fo llo w s th a.t th e y ie ld s o f n i t r o p a r a f f i n s should

d e c re a s e c o rre s p o n d in g ly . T h is i s b e lie v e d to c o n s t i t u t e e-vldence f o r

th e f r e e r a d i c a l mechanism o f n i t r a t i o n which i s proposed in a l a t e r

s e c tio n .

N i t r a t i o n o f Butane W ith N i t r i c Acid and Oxygen

I t was concluded from an exam in atio n o f A le x a n d e r 's d a ta t h a t

th e a d d itio n o f oxygen would n e c e s s i t a t e th e use o f a low er te m p e ra tu re

 14.

to a tts .in optimum r e s u l t s . A r e a c ti o n m ix tu re c o n s is tin g o f b u ta n e ,

oxygen, and n i t r i c a c id in a r a t i o of 15: 2 :1 was used a t th r e e d i f f e r e n t

te m p e ra tu re s . The r e s u l t s , given in Table IV, show a maximum c o n v e rsio n

o f 43 p e r c e n t. However, when th e s e co n v e rsio n s a r e p lo tte d a g a in s t

te m p e ra tu re (F ig u re l ) , i t i s seen t h a t th e optimum te m p e ra tu re i s s t i l l

in th e neighborhood o f 425*C.

S in c e th e in c r e a s e in co n v ersio n w ith t h i s amount o f oxygen

was n o t very g r e a t , f u r t h e r ex perim ents were c a r r ie d o u t to determ in e

th e e f f e c t o f v a ry in g th e amount o f oxygen added (T able V ). In itia lly ,

i t was th o u g h t t h a t a te m p e ra tu re o f 425®C. would be s a t i s f a c t o r y s in c e

th e r e was no change in th e optimum tem p e ra tu re when th e oxygen r a t i o

was changed from zero to two. Ifh ile i t was su sp ected t h a t th e d e c re a se

no ted w ith an oxygen r a t i o of th r e e m ight have been caused by u n d e s ir ­

a b le e f f e c t s r e s u l t i n g from too hig h a t e n p e r a t u r e . Run No. 15, p e r ­

formed a t 8 te m p e ra tu re o f 405*C. a ls o showed a d e c re a se in c o n v ersio n

to 21 p e r c e n t. Hence th e h ig h e r tem p e ra tu re can n o t have been th e

dom inant f a c t o r in re d u c in g th e y i e l d ,

F ig u re 2, which shows th e r e l a t i o n betw een con v ersio n and th e

amount o f oxygen added, r e v e a ls t h a t th e h ig h e s t con v ersio n o b ta in a b le

in t h i s r e a c t o r i s 44 p e r c e n t a t a te m p e ra tu re o f 425*0. w ith a mole

r s .t i o o f b u ta n e :o x y g e n :n itr ie a c id o f 15/ I . 6/ I .

The y i e l d , based on th e amount o f b u tan e consumed, i s shown

in F ig u re 3 to d e c re a se n e a rly l i n e a r i l y w ith th e amount o f oxygen

employed. Thus i t i s obvious t h a t th e in c r e a s e in co n v ersio n upon

ad d in g oxygen i s a tt a in e d only w ith th e s a c r i f i c e o f c o n s id e ra b le

amounts o f th e h y d ro ca rb o n . The s e rio u s n a tu re o f t h i s a s p e c t i s

e v id e n t when i t i s noted t h a t a t th e oxygen v alu e f o r ms.ximum conversion .

 l4 a

T able IV

N i t r a t io n o f B utane With Oxygen

E f f e c t o f T em perature

(C o n ta c t Time = 1 .6 Seconds; 10 mm. I.D . C o il R e a c to r)

Eun No. 12 11 13

C4H10/BNO3 1 2 .7 15.5 1 6 .0

O2/ÏÏNO3 2

T em p eratu re, ®C. 4 ll 4-25 450

io C onversion* 33 43 27

io Y ield 1 7 .4 24 I5 .6

Moles Formed

ENOg 0 .2 6 0 .2 7 0 .1 7

> C =0 0 .7 3 0 .6 8 0 .4 9

C^HG+C^^ 0-^3 0 .3 7 0 .6 1
C2H4 0 .3 1 0 .2 5 0 .1 1

CO 0 ,1 0 0 .4 5 0 .2 6

COg 0 ,3 1 0 .1 7 0 .2 1

Bu ta n e Con s umed, Mol e s I.3 S 1 . 06 1 .0 1

* Ba.sed on n i t r i c a c id c h a rg e d .
 141,

T able V

E f f e c t o f Oxygen a t C o n sta n t T em perature

(C o n tac t Time = 1 .6 Seconds; 10 ram. I.D . C o il R e a c to r)

Run No. 10 16 11 14

Ci^Eio/mOq 12.3 13.5 15.5 13.2

Og/SNOg 0 1 2 3

T e m p era tu re , *C. 425 425 425 425

^ C onversion 36 42 43 26

i Y ie ld 48 32 24 10

M oles Formed

ENOg 0 .2 9 0 .3 2 0 .2 7 0 .20

> c=o 0 .0 6 0 .3 7 0.68 0 .9 6

CqB^+CAHg 0 .1 1 0 .3 3 0 .3 7 1.16

CgEi), 0 .1 8 0 .1 6 0.25 0 .3 1

CO 0 .0 7 0 .5 1 0.45 0.78

COg 0 .2 6 0.05 0 .17 0.38

Butane Consumed, Moles 0.55 0.93 1.06 1.93

 /4

FIGURE 2

NITRATION OF BUTANE

VARIATION OF CONVERSION WITH OXYGEN AT k 2 y c .

(RATIO C^Hjo/HNOq OF I 5 ,

CONTACT TIME 1.6 SECONDS; 10 MM. I.D . REACTOR)

40

X
fe
z
o

W
y

i 2 3
MOLES OXYGEN PER MOLE NITRIC ACID
 FIGURE 3

NITRATION OF BUTANE

VARIATION OF YIELD WITH OXYGEN AT

(RATIO Ci.Hjq/HNO^ OF I 5 ,

CONTACT TIME = I . 6 S E C O N D S 10 MM. I.D . REACTOR)

ÜJ

w 20

LÜ

2 3
MOLES OXYGEN PER MOLE OF NITRIC ACID
 15.

o n ly 26 p e r c e n t o f th e b u ten e r e a c ti n g i s con v erted to n i t r o p a r a f f i n s .

The a c t u a l amounts o f p ro d u c ts from each r e a c tio n a r e given in

T able V. The form a.tion o f c a rb o n y l compounds i s a s t r a i g h t l i n e fu n c tio n

o f th e oxygen added. The b u te n e s p lu s propene and th e carbon monoxide

a p p e a r to in c r e a s e s lo v ly a t f i r s t , b u t f i n a l l y show an a b ru p t r i s e . It

i s i n t e r e s t i n g to n o te t h a t th e amounts o f e th y le n e and carbon d io x id e

seem to pa,ss th ro u g h a minimum a t th e same p o in t where th e n i t r o p a r a f f i n s

show a raa.ximum.

T h is ma.ximum p ro d u c tio n o f n i t r o compounds i s somewhat p u z z lin g

u n le s s i t i s a.ssumed t h a t vapor phase n i t r a t i o n i s a f r e e r a d i c a l p ro c e s s .

A p o r tio n o f th e alk j^l r a d i c a l s r e a c t w ith th e n i t r a t i n g a g e n t to produce

n itr o p a ra ffin s . However, th e r e a c tio n o f a lk ^ 1 r a d i c a l s w ith oxygen a ls o

p ro ce e d s w ith extrem e ea.se. Thus when th e oxygen c o n te n t o f th e r e a c tio n

m ix tu re i s in c r e a s e d , a. p o r tio n o f th e f r e e r a d i c a l s p re v io u s ly a v a ila .b le

f o r n i t r a t i o n a re removed by r e a c tio n w ith oxygen.

The p re se n c e o f o l e f i n s in th e e x i t gases r e g a r d le s s o f th e

oxygen c o n te n t o f th e r e a c ti o n m ix tu re i s ev id en ce o f th e p rese n c e of

f r e e alky^l r a d i c a l s . The fo rm a tio n o f o l e f i n s from s a tu r a te d hydro­

carbons by a f r e e r a d i c a l p ro c e ss i s a w e ll known phenomenon end in

t h i s case i n d ic a te s t h a t a c e r t a i n number o f th e f r e e r a d i c a l s undergo

o l e f i n fo rm a tio n b e fo re an e f f e c t i v e c o l l i s i o n w ith a n i t r a t i n g a g e n t

can ta k e p la c e . I t i s r e a d i l y seen t h a t i f th e number o f f r e e r a d i c a l s

i s in c re a s e d w h ile ma. in ta. in in g th e same c o n c e n tra tio n o f n i t r a t i n g a g e n t,

th e f o r m t i o n o f o l e f i n s should become g r e a t e r . The e f f e c t o f oxygen is

p o s tu la te d s,s a f r e e r a d ic a l- f o r m in g p ro c e s s , and i t may be no ted t h a t th e

p r e d ic te d r i s e in o l e f i n p ro d u c tio n does occur upon in c r e a s in g th e amount

o f oxygen a d d e d .
 16.

The t o t a l amount o f b u tan e consumed in th e e x p erim en ts con­

ducted a t v a rio u s te m p e ra tu re s w h ile u sin g a r e a c tio n m ix tu re h aving a

buta,n e /o x y g e n /n itr ic a c id r a t i o o f I 5/ 2/ I a re given in Table I I I . An

ex am ination o f th e s e f ig u r e s shows t h a t th e t o t a l amount of r e a c tio n

aga.in d e c re a s e s w ith in c r e a s in g te m p e ra tu re a s was observed p re v io u s ly

in th e c o rre sp o n d in g ex p erim en ts w ith o u t oxygen. In t h i s case no ma.xi-

mum i s o b s e rv e d . I t i s obvious t h a t i f a s u f f i c i e n t l y low tem p e ra tu re

were chosen, th e amount o f m t e r i a l . r e a c tin g could be ma,de as sm a ll a s

d e s ir e d . The te m p e ra tu re r e q u ir e d f o r the d e c re a se would l o g i c a l l y be

ex p ected to be low er in th e p re se n c e o f oxygen. The d e c re a se in b utane

consumed i s a ttr lb u t a .b l e h e re t o th e same e f f e c t as b e fo re : nam ely, a

g r e a t e r e x te n t of ch ain te rm in a tio n a t h ig h e r te m p e ra tu re s .
 17.

III. E f f e c t o f Oxygen on th e H itro P a r a f f in s Produced

The n i t r o p a r a f f i n s formed in Puns 11 and 12 were d rie d and

f r a c t i o n a t e d in a f o u r f o o t column parked w ith a w ire s p i r a l . A lthough

g r e a t a c c u ra c y was prohahly n o t o b ta in e d , th e r e s u l t s a re q u ite

in te re s tin g .

As can be seen in T able VI, when th e Og/ENOg r a t i o i s changed

from zero to two, th e amounts o f th e n i t r o b u ta n e s formed a r e d e c re a sed

s i g n i f i c a n t l y , w h ile th e n i t r o methane and n i t r o ethane a re In c re a se d bj"

a f a c t o r o f tw o . The r e s u l t s from Buns 11 and 12 show t h a t tem p e ra tu re

has l i t t l e , i f any, e f f e c t on p ro d u c t d i s t r i b u t i o n .

These r e s u l t s show very c le a r l y t h a t carbon to carbon bond

f i s s i o n i s in c re a s e d by th e p re s e n c e o f oxygen. I t w i l l be shown in a

fo llo w in g s e c tio n on mechanism t h a t t h i s r e s u l t i s to be e x p e cte d .

 l? a

T able VI

N i t r a t io n o f Butane

E f f e c t o f Oxygen on Type o f N itro P a r a f f in s

Bun No, Hod ge* 11 12

14 15.6 1 2 .7

O2/MO3 0 2 2

T em p era tu re , *C 420 425 411

Mole P er Cent

CÏÏ3NO2 10 22 19

CgE^NOg 13 30 32

1-CgEyNOg 8 5 11

2-CkEÿîOg 45 37 21

l-Ci^EgNOg 24 16 17

* Data, tak en from Hodge ( l l )

 IS .

IV, E f f e c t o f S u rfa c e on N itr a tio n

The p o s s ib le in flu e n c e of th e r a t i o o f s u rfa c e to volume in

th e r e a c t o r on th e n i t r a t i o n r e a c tio n was f i r s t m entioned by S h e c h te r

(2 2 ). W hile he p o in te d o u t th e d e s i r a b i l i t y of h av in g a la r g e s/V
r a t i o , h is s o le concern was a p p a re n tly h e a l t r a n s f e r . . However, i f one

view s th e n i t r a t i o n r e a c tio n a s a f r e e r a d i c a l p ro ce ss in v o lv in g c h a in s,

then i t becomes e v id e n t t h a t extended s u rfa c e could r e a d i ly be im p o rta n t

f o r s t i l l o th e r r e a s o n s . An i l l u s t r a t i o n of t h i s i s a ffo rd e d by th e

work o f Pease (iT ) on th e n o n -e x p lo siv e r e a c tio n between oxygen and pro­

pane. Here In c re a se d s u rfa c e cau ses th e minimum r e a e tio n tem p e ra tu re

to be r a i s e d from 375*C. to pOO®C. and changes th e p r in c i p a l p ro d u cts

from carbon monoxide to o l e f i n s , a ld e h y d e s, hydrogen and m ethane.

In o rd e r to i n v e s t ig a t e th e s e s u rfa c e e f f e c t s more c a r e f u ll y ,

a r e a c t o r was c o n s tr u c te d from 22 mm. O.D. pyrex tu b in g which could

r e a d i ly be packed to give v a ry in g amounts o f s u rfa c e w h ile m i n t a i n i n g

th e same w a ll a r e a and n e a rly th e same volume. I t was reco g n ized t h a t a

r e a c t o r made o f tu b in g w ith t h i s la r g e a d iam e te r would have r e l a t i v e l y

poor h e a t t r a n s f e r c h a r a c t e r i s t i c s . N e v e r th e le s s , i f th e s / v r a t i o was

to be i n v e s t i ga.ted as an in d ep en d en t v a r i a b le , th e h e a t t r a n s f e r had to

be k e p t c o n s ta n t r e g a r d le s s o f i t s a c tu a l v a lu e . Hence th e optimum

r e s u l t s should be b e t t e r than th o se h e re in o b tain ed b u t th e e f f e c t of

changing th e s/V r a t i o should be th e same in e i t h e r c a se .

The th r e e p a c k in g s used to vary th e s / v r a t i o were 3 /l6 inch

p yrex h e l i c e s , l / S in ch pyrex h e l i c e s , and g la s s w ool. The s / v r a t i o s

o b ta in e d were 2 0 / l , 2 S / l , and 3OO/I, r e s p e c t i v e l y . I t m ight be p o in te d

out t h a t in th e c a se of th e g la s s wool th e e f f e c t i v e s / v r a t i o was

proba.bly somewhat l e s s than t h a t c a lc u la te d because o f cha.nneling. With

 19.
each p a rk in g , a. s e r i e s o f ex p erim en ts were perform ed u sin g Og/SNOg

r a t i o s o f from zero to t h r e e . In a l l c a se s i t was obvious t h a t f u r t h e r

a d d itio n s o f oxygen would have no b e n e f i c i a l e f f e c t . R e s u lts o b tain e d

under th e th r e e c o n d itio n s o f p a rk in g a re given in T ables V II, V I I I,

and IX.

A com parison o f th e c o n v e rsio n s o b tain ed w ith o u t oxygen w ith

s / v r a t i o s o f 20 , 28 , and 300 shows t h a t th e con v ersio n a c tu a ll y d e c re a s e s

a s th e amount o f s u rf a c e in c r e a s e s . T hat t h i s i s n o t due to th e fa v o rin g

o f some o th e r r e a c tio n over n i t r a t i o n i s dem onstrated by com paring th e

t o t a l amount o f b u ta n e consumed in each c a se . This v a lu e d e c re a s e s from

0 .5 1 mole to 0 .3 2 mole w h ile co n v ersio n changes from 27 per c e n t to 20

p e r c e n t. I t w i l l be noted t h a t th e v alu e o f 27 p er c e n t o b tain e d w ith

an s / v r a t i o o f 20 in th e packed r e a r t o r i s much low er than th e 36 per

c e n t c o n v ersio n r e p o r te d f o r th e 10 mm. I.D . c o i l r e a c t o r . S ince in the

l a t e r c a se th e s/V r a t i o i s 4 / l , a p o rtio n o f t h i s d e c re a se must be due

to th e s u rf a c e e f f e c t . However, i t i s f e l t t h a t to some e x te n t th e pocr

h e a t t r a n s f e r in th e packed r e a c t o r i s r e s p o n s ib le . C e r ta in ly t h i s i s

to be expected from th e work on methane u s in g v a rio u s ty p e s o f a p p a ra tu s

a s d isc u s s e d on pa.ge 9-

In each c a se a s oxygen was added, th e c o n v e rsio n ro s e to a

maximum v a lu e th en f e l l o f f . These r e s u l t s a re given g ra p h ic a lly in

F ig u re k. The ms.ximum v a lu e s were 42.5 p er c e n t a t s/V r a t i o s o f 20 and

28 , and 44 p e r c e n t w ith S/V r a t i o s o f 3OO. Hence no s i g n i f i c a n t

in c r e a s e s in maximum co n v e rsio n in th e p rese n c e o f oxygen a re noted with

a change in s u r f a c e . On th e o th e r hand, a marked change in th e q u a n tity

o f oxygen re q u ir e d to g iv e th e optimum co n v ersio n i s n o te d .

I t would be expected t h a t a d e c re a s e in th e amount o f oxygen

would a f f e c t th e y ie ld based on h y d ro carb o n . F ig u re 5 shows a comparison

 19a

T able VII

N i t r a t io n o f Butane

E f f e c t o f Oxygen a t an s/v R a tio of 20

(T em perature = 425®c,. ; C o n tact Time = 1 .6 Seconds)

Run No. 13 21 25 22
C4H10/ENO3 1 2.0 16.0 14.3 15.9
O2/BNO3 0 1 2 3
C o nversion, 27 33 42 39
Y ie ld , 33 30 22 13
M oles P roducts***

RNOg 0 .2 1 0.21 O .2S 0.25

> c=o 0 .1 4 0.32 0.58 0 .9 0

^ 3^ 6+Fi(-H8 0.15 0.2 1 0.59 0.93

0 .03 0.13 0 .20 0.5 1

CO 0 .3 3 0 .30 0 .39 0 .6 7

COg 0.03 0 .0 6 0.10 0 .0 7

Butane Consumed , Ploles 0 .5 1 0 .6 4 1.13 1.76

* Based on th e amount o f n i t r i c a c id charged.

** Ba,sed on b u tan e consumed.

*** C o rre c te d to a t o t a l bu tan e flow o f 10 m o les,

 19b,

T able V III

N i t r a t io n o f Butane

E f f e c t o f Oxygen a t an s/V R a tio o f 28

(T em perature = 425*0.; C ontact Time = 1 . 6 Seconds)

Run No. 31 30 28 29
C4H10/BNO2 16.2 1 5.6 13.8 1 4.1
Og/SNOg 0 1 2 3
C o n v ersio n , 25 39 39 30
Y ie ld , 44 36 23 12

Moles P roducts***

RNOg 0.16 0.25 0.28 0 .21

C=0 0.09 0 .3 0 0 .58 0 .8 1

C3H6+Ci|.H8 0.09 0 .2 1 0.48 0.82

C2% 0 .06 0.12 0.28 0.59

CO 0 .1 4 0 .2 9 0.43 0.63

COg 0 .0 6 0 .0 4 0.1 1 0.07

B utane Consumed, Moles 0 .3 4 0.68 1.13 1 .67

* Ba.sed on th e amount o f n i t r i c a c id c h a rg e d .

** Based, on th e bu tan e consumed.

*** C o rre c te d to a t o t a l . b utane flow of 10 m o les-

 19c

T ab le IX

N i t r a t i o n o f Butane

E f f e c t o f Oxygen a t an S/V R a tio o f 3OO

(T em perature = 4 2 5*0.j C o n ta c t Time = 1 .6 Seconds)

Run No. 34 35 32 36 33

C4B10/BNO3 1 5.6 15.5 15 .7 14.8 14.6

O2/HNO3 0 0 .5 1 1.25 2

C o n v ersio n , 20 33 44 41 34

Y ie ld , 37 46 45 38 20

Moles Formed***

RNOg 0.13 0 .2 1 0.28 0.2 8 0 .2 4

>C=0 0.05 0.18 0 .3 2 0 .4 1 0.63

C3ÏÏ5+Cij.BB 0.10 0.09 0 .1 4 0.18 0 .4 4

C2H4 0 .0 7 0.05 0 .0 3 0 .1 2 0 .2 9

CO 0 .2 4 0.18 0 .2 3 0.28 0 .4 9

COg 0 .0 4 0 .0 9 0 .1 2 0 .0 6 0 .0 7

Butane Consumed, Moles 0 .3 2 0.42 0 .58 0.68 1 .07

* Baaed on th e amount o f n i t r i c a c id c h a rg e d .

** Baaed on th e b u tan e consumed..

*** C o rre c te d to a t o t a l . b utane flow o f 10 moles

 FIG U RE 4

EFFECT OF OXYGEN ON CONVERSION

W IT H D IF F E R E N T SU RFACE/VO LU IC R A TIO S

(TEMPERATURE = 4 Z 5 ° C . , CONTACT TIM E = I .6 SECONDS)

0- s /v “ 20} s /v = 28; D - C /V = 3OO

on
9
i 30

U!

MOLES 0 - PER MOLE HNO

 FIGURE 5

NITRATION OF BUTANE

EFFECT OF OXYGEN ON YIELD

WITH DIFFERENT SURFACE/VOLUME RATIOS

{TEMPERATURE = 4 2 ^ * 0 , , CONTACT TIME = ( .< SECONDS)

O- s /v = 20; 6- s /v = 28; D- S /V = gOO

0 2 3
MOLES OXYGEN PER MOLE OF N IT R IC AC I
 20.

o f th e y ie ld s o b ta in e d by V8.rying th e r a t i o o f oxygen w ith th e th r e e

p a c k in g s . I f th e curve f o r th e 2 0 / l s/V r a t i o i s compared w ith th s.t

given in F ig u re 3 f o r th e 10 mm. c o i l , i t w i l l be seen t h a t th ey a re

s u b s t a n t i a l l y e q u iv a le n t. T h is proba.bly r e s u l t s fr*om, com pensation f o r

th e d e c re a s e in h e a t t r a n s f e r a r e a by th e in c r e a s e in s u r f a c e . On th e

o th e r hand, c o n s id e r a b le d i f f e r e n c e s a r e noted between th e y i e l d s a t

s / v r a t i o s o f 20, 28, and 300- The peak o b ta in e d when th e s / v r a t i o i s

300 i s q u ite u n u su a l. I t i s th e f i r s t experim ent in which an a c t u a l

in c r e a s e has been o b ta in e d upon a d d in g oxygen. In a d d itio n t h i s v a lu e

i s e q u iv a le n t to th e b e s t y ie ld p re v io u s ly o b tain e d w ith b u ta n e , w hich,

i t w i l l be r e c a l l e d , was g o tte n in th e 10 mm. c o i l w ith o u t oxygen. In as­

much a s a p p ro x im a te ly th e same amount o f oxygen i s r e q u ir e d under th e s e

c o n d itio n s f o r rte.ximum y ie ld and c o n v e rs io n , th e use o f oxygen a s a.

n i t r a t i o n a id would be f e a s i b l e from an economi.c s ta n d p o in t. S in c e th e

d e c re a s e in y ie ld caused by oxygen was th e c h ie f com m ercial draw back to

t h i s p ro c e s s in th e p a s t , i t i s f e l t t h a t th e b e n e f i c i a l e f f e c t o f th e

p ro p e r amount o f s u rf a c e c o n s t i t u t e s a m ajor c o n tr i b u ti o n . I t should be

a g a in p o in te d o u t t h a t th e s e r e s u l t s pro b ab ly do n o t r e p r e s e n t th e b e s t

o b ta in a b le . A more s u it a b ly designed r e a c t o r , based on th e d a ta h e re in

p r e s e n te d , should g iv e c o n v e rsio n s t h a t a re s u b s t a n t i a l l y h ig h e r w ith

no d e c re a s e in y i e l d . I t w i l l be shown in a fo llo w in g s e c tio n t h a t

th e s e same c o n c lu s io n s a re a p p lic a b le to propane.

W hile th e e x a c t mechanism by which s u rfa c e e x e r c is e s i t s

e f f e c t in somewhat o b sc u re , c e r t a i n c o n c lu s io n s me.y be drawn fi'om an

exa.m ination o f th e q u a n t i t i e s o f p ro d u c ts o b ta in e d in th e above e x p e r i­

m ents. A r a t h e r la r g e p o r tio n o f th e b u tan e i s c o n v e rted to b u te n e s and

propene th u s making t h i s one o f th e g r e a t e s t s o u rc e s o f l o s s . F ig u re 6

 FIGURE 6

EFFECT OF OXYGEN ON FORMATION OF

PROPENE ANO BUTENES WITH

VARIOUS s u r f a c e / vo lu m e RATIOS

(CONTACT TIME = 1 .6 SECOriF;S; C};H;r)/HNOg = l|))

O- s /v = 20; s /v = 28; O- S /V = 300

.0

CO
w
z
L-J
H-
g

a!
w
z
w
CL
O
cc
CL

o
CO
ÜJ

2
MOLES OXYGEN PER MOLE N ITR IC ACID
 21.

shows how t h i s quaxitity v a r ie s w ith oxygen f o r each p a c k in g . In each

c a se th e r e i s a, g ra d u a l in c r e a s e u n t i l th e Og/ENO^ r a t i o re a c h e s a p p ro x i-

ma.tely one. At t h i s p o in t th e r a t e o f in c r e a s e becomes much l a r g e r .

T h is same e f f e c t was n o tic e d when u s in g th e 10 mm. c o i l r e a c t o r . It

p ro h ah ly i n d ic a te s th e a b i l i t y o f th e r e a c tio n m ix tu re to u t i l i z e a

r e l a t i v e l y h igh p o r tio n o f th e f r e e a lk y l r a d i c a l s formed by o x id a tiv e

a t t a c k u n t i l a c e r t a i n c o n c e n tra tio n i s re a c h e d . A f te r t h a t p o in t, a

much l a r g e r p e rc e n ta g e o f th e s e r a d i c a l s undergo decom position to form

o le fin s . I t can be seen t h a t a h ig h e r s / v r a t i o ca u se s a g e n e ra l low er­

in g o f th e curve w ith o u t a l t e r i n g i t s b a s ic sh a p e. R e f e r r in g now to

F ig u re 7 , i t i s seen t h a t th e t o t a l amount o f b u tan e r e a c ti n g in c r e a s e s

w ith oxygen, b u t t h a t in c re a s e d s u rf a c e d e c re a s e s th e amount o f t h i s

in c r e a s e a t any given oxygen r a t i o . I t has p r e v io u s ly been assumed t h a t

such a d e c re a s e in th e amount o f b u tan e r e a c ti n g i s due to ch ain s to p p in g

w ith l e s s t o t a l p ro d u c tio n o f f r e e r a d i c a l s . Hence th e d e c re a s e in o l e f i n

fo rm a tio n observed upon in c r e a s in g th e s u rfa c e i s sim ply a r e f l e c t i o n of

a low er r a t e o f f r e e r a d i c a l fo rm a tio n .

The d a ta given in T a b le s V II, V TII, and IZ show t h a t pro d u c­

t io n o f n i t r o p a r a f f i n s goes th ro u g h a ma.ximum w ith in c r e a s in g oxygen.

These maxima, a r e th e sa,me h e ig h t r e g a r d le s s o f th e s/v r a t i o b u t occur

w ith l e s s oxygen a.s th e r a t i o i n c r e a s e s . S in c e th e t o t a l number o f fre e

r a d i c a l s has been d e c re a se d by s u r f a c e , th e f a c t t h a t th e same number a re

c o n v e rted i n to n i t r o p a ra .ffin s must mean t h a t t h e i r r e a c ti o n to form

oxygéna,te d m a t e r i a ls i s a c h a in r e a c ti o n which i s h in d e re d by s u r f a c e .

Such a r e a c ti o n would presuma,bly in v o lv e HO o r HOp r a d i c a l s a s chain

c a r r i e r s and would be stopped on th e w a lls . A l a t e r s e c tio n w i l l p r e ­

s e n t a mechanism based on th e s e c o n c lu s io n s .
 EFFECT OF OXYGEN ON AMOUNT OF BUTANE

REACTING USING VAR IOUS'SURFACE/VOLUME RATIOS

(CONTACT TIME 1.6 SECONDS,

Ci^H,o/HN03 = 1 5 , TEMPERATURE = 4 2 $ T . )

O - s / v = 20; A - s / v - 28; O - S /v = 300

X
u
E3
y

w
0_

i
y

2 3
MOLES OXYGEN PER MOLE OF NITRIC AC in
 22.

V. The Use o f Steam a s a D ilu e n t

In the fo reg o in g s e c tio n i t was p oin ted out th a t an e x c e s s o f

f r e e r a d ic a ls are formed when oxygen i s added to the n itr a t io n m ixture

to th e e x te n t o f two moles fo r each mole o f n i t r i c a c id .

The f a c t th a t conversion does not in c re a se g r e a tly under these

circum stances in d ic a te s th a t an in s u f f i c i e n t amount o f th e n it r a t in g

agent i s p resen t a t the time the ex tra f r e e r a d ic a ls are a v a ila b le . This

could stem from e it h e r o f two fa c to r s : ( l ) decom position o f n i t r i c a c id

in oth er ways, or (2) production o f fr e e r a d ic a ls over such a sh ort

p erio d o f tim e th a t the a c tu a l n it r a t in g agent (presumably NO2) i s n ot

formed f a s t enough to u t i l i z e them b efore they undergo oth er change.

The obvious s o lu tio n to the d i f f i c u l t y in the l a t t e r case would be to

add an in e r t d ilu e n t to the m ixture sin c e t h is would e f f e c t i v e l y

d ecrease the r a te a t which the fr e e r a d ic a ls are formed. I t would n o t,

however, in flu e n c e m a te r ia lly the t o t a l q u an tity o f them formed b efo re

the end o f the n itr a t io n tube i s reached. The mast l i k e l y ch oice o f

d ilu e n t would seem to be steam. I t i s in e r t , cheap, has a high heat

c a p a c ity and i s alrea d y bein g introduced to some e x te n t a s water in the

70 per cen t n i t r i c a c id .

Dr. Bass p o in ted out th a t work by Hibshman (9 ) on the n it r a ­

tio n o f ethane w ithout added oxygen show th a t in c r e a sin g th e d ilu tio n

o f th e n i t r i c a c id has an adverse e f f e c t on co n v ersio n . Ifeder th e se

c o n d itio n s , however, th e r a t io o f fr e e r a d ic a ls to n it r a t in g agent does

n o t reach an optimum v a lu e . Hence, a d ilu e n t which d ecrea ses the r a te

o f fr e e r a d ic a l form ation would not be expected to in c re a se but r a th er

to decrease the con version . With ex c ess oxygen p r e se n t, however, the

r a t io o f fr e e r a d ic a ls to n it r a t in g agen t exceeds the optimum v a lu e . A

 23.
d ilu e n t p resen t in s u ita b le amounts would, decrease t h is r a t io to the

optimum value and thereby le a d to in crea sed co n v ersio n s.

To t e s t t h i s rea so n in g two experim ents were c a r r ie d out

u sin g equim olar amounts o f hydrocarbon and steam. In each case the

b u ta n e /o x y g e n /n itr lc a c id r a t io was I 5/ 2/ I . One was performed in the

10 mm. c o i l which has an S/V r a t io o f h and the other in the packed

r e a c to r w ith an s /T r a t io o f 20. Other p e r tin e n t in fo r n a tio n alon g

w ith the r e s u lt s are given in Table X. A lso included fo r comparison

are Buns 11 and 25 which are e q u im le n t in a l l r e sp e c ts excep t they

were performed, w ithout added steam. A s tr ik in g improvement in both

conversion and y i e l d was obtained, a s a r e s u lt o f the a d d itio n o f steam.

In c r ea sin g the s / v r a t io caused, a fu rth er improvement in y ie ld ,

alth ou gh the conversion was not ap p reciab ly a f f e c t e d .

An exam ination o f the prod.ucts shows th a t the steam in c r e a se s

the amount o f aldehydes produced but th a t the t o t a l amount o f o le f in s

formed d e c r ea se s. This d ecrease w h ile sm all in the 8/7= 4 r e a c to r ,

becomes c o n sid era b le when the s / 7 r a tio i s r a is e d to 20. In e ith e r

ca se the a c tu a l number of moles o f n itr o p a r a ffin s produced shows a

s u b s t a n t ia l r i s e which i s g r e a te r than the in crea se brought about by

any other s in g le v a r ia b le .

I t i s f e l t th a t the g r e a te s t p o s s i b i l i t y o f e f f e c t in g improve­

ments in the vapor phase n itr a t io n process l i e s in the use o f steam as a

d ilu e n t in a p rocess u sin g oxygen and a la r g e amount o f su r fa c e . From

the r e s u lt s given here i t i s obvious th a t s t r ik in g improvements can be

made p a r t ic u la r ly in view o f the f a c t th a t no attem pt was made to d eter­

mine optimum c o n d itio n s .

 23 a

T able X

N i t r a t i o n o f B utane in th e P re se n c e o f Oxygen

Use o f Steam a s D ilu e n t

(C o n ta c t Time = 1 .6 Seconds)

Bun N o. 11 25 17 20

s /v k 20 4 20

Ci^Eio/ENOq 1 5 .6 13.3 1 4 .6 14.0

Og/SNOg 2 2 2 2

9 .6 9 .6 1 1

C o n v ersio n , ^ 36 42 55 54

Y ie ld , i 2k 22 30 35

Moles Formed:

RNOg 0 .2 6 0.28 0 .3 6 0 .39

>0=0 0 .6 8 O.5B 0 .8 2 0.88

0 .3 7 0 .59 0 .4 1 0.25

CgBh 0 .25 0.20 0 .1 0 0.08

CO 0 .4 5 0.39 0 .4 7 0 .4 1

COg 0 .1 7 0 .1 0 0 ,1 0 0.05

B utane Consumed, Moles 1 .0 6 1.18 1 .1 2 1.02

 2k.

VI. N itr a tio n o f Propane

The e f f e c t o f oxygen on conversion obtain ed in t h is in v e s tig a ­

tio n was s m l l e r than th a t rep orted by Alexander fo r propane. A s e r ie s

o f con version s ob tain ed in the in v e s tig a tio n s w ith propane u sing various

O2/HNO3 r a t io s a t two d iff e r e n t tem peratures are given below:

O2/M O 3 0 0 .9 1 .9 3-5

io Conversion at 395‘*C. 20 38 53 76

^ Conversion at 4lO®C. 28 49 53 62

These experim ents were conducted in a 7 mm. 0, D. c o i l r e a cto r w h ile the

experim ents w ith butane were performed e ith e r in a 10 mm. I . D. c o i l

r e a c to r or in a 22 mm. O.D. packed r e a c to r . One d iffe r e n c e between the

two c o i l r e a c to r s i s th e S/V r a t io which i s 8 in the case o f the former

and 4 w ith the l a t t e r . However, i t has been shown th a t v a r ia tio n s in

t h is r a t io do not cause s ig n if ic a n t v a r ia tio n s in the maximum conversion

o b ta in a b le w ith butane. The only other fa c to r s which could be r e sp o n sib le

fo r the d iffe r e n c e are: ( l ) a d iffe r e n c e in the heat tra n sfe r area pre­

se n t in the two c o i l s , or (2) a d iffe r e n c e in the chem ical behavior o f

the two hydrocarbons

In view o f the in t e r e s t in g e f f e c t o f the su rface to volume

r a t io on y ie ld (based, on hydrocarbon) in the case o f butane, i t was

deemed im portant to d isco v e r whether th ese e f f e c t s could be observed

w ith propane. S in ce a complete d u p lica tio n o f the work already done

was im p o ssib le , i t was decid ed to check on ly a few d iff e r e n t experim ents.

I f a c lo s e correspondence between butane and. propane was obtained in

th e se then I t would be assumed, th a t d u p lic a tio n could, probably be

obtained, under oth er c o n d itio n s . I t would a ls o fo llo w th a t butane

would g iv e s im ila r r e s u lt s to those obtain ed w ith propane by Alexander

i f a d u p lic a te apparatus were used.

 The e x p erim en ts l i s t e d in T ab le XI were perform ed w ith p r o ­

pane in th e pa,cked. r e a c t o r u sin g s / v r a t i o s o f 3OO and 28. I t w i l l be

noted. th a ,t th e c o n v e rsio n s and y ie ld s given in Runs 38 , 3 9 , and 40 a r e

th e same o rd e r o f m agnitude a s th o se o b tain e d w ith b u tan e in Runs 33;

32, and 28, r e s p e c ti v e ly . W ith b u tan e in th e s/v= 300 r e a c t o r , th e

c o n v e rsio n and y ie ld b o th d e c re a sed a s th e O2/HNO3 r a t i o was changed

from one t o two. T h at th e co n v e rsio n did n o t d e c re a s e w ith propane

under th e same c o n d itio n s shows t h a t propane r e q u ir e s s l i g h t l y more

oxygen f o r maximum c o n v e rsio n under th e s e c o n d itio n s . The d a ta would

i n d ic a te a co n v ersio n w ith propane a t an O2/M O 3 r a t i o o f 1 .5 t h a t

would be compa,rable to th e v alu e o f 44 p e r c e n t o b ta in e d in Run 33

w ith b u ta n e .

S in c e A lex an d er worked a t a c o n s id e ra b ly low er te m p e ra tu re .

Run 40 was conducted a t 400*C. I t was found t h a t w ith th e parked

r e a c t o r , t h i s m erely caused a d e c re a se in c o n v e rsio n . Hence i t i s n o t

p o s s ib le to a s c r ib e th e d if f e r e n c e s in co n v ersio n to te m p e ra tu re . It

becomes obvious t h a t d i f f e r e n t optimum te m p e ra tu re s a s w e ll a s co n v er­

s io n s a r e shown by d i f f e r e n t r e a c t o r s .

A f i n a l check was provided by Run 43 which was ma,de w ith an

s / v r a t i o o f 28 and on O2/HNO3 r a t i o o f tw o . The c o n v ersio n o b tain e d

was s l i g h t l y b e t t e r th a n t h a t o b ta in e d w ith b u ta n e . The y ie ld o f 33

p e r c e n t for th e n i t r a t i o n o f propane was s i g n i f i c a n t l y h ig h e r than th e

23 p e r c e n t v a lu e f o r b u ta n e . I t ms.y be concluded then t h a t propane

w i l l show th e same e f f e c t w ith in c re a s e d s u rfa c e in th e p re se n c e of

oxygen that b u tan e d o e s. From th e d a ta f o r Run 43, i t would ap p ear

p o s s ib le to a c h ie v e even more s t r i k i n g e f f e c t s . T h is r e s u l t i s n o t

p a r t i c u l a r l y s t a r t l i n g in t h a t propane i s more r e s i s t a n t to o x id a tio n

 25a

T able XI

N i t r a t i o n of Propane in th e Packed R e a c to r

(C o n ta c t Time = 1 . 6 Seconds)

Run N o. 33 39 40 43

CgEg/mOg 1 5 .0 15.8 14.6 1 3.0

O2/HNO3 1 2 2 2

Tem pera,ture, ®C . 425 425 400 425

s / v R a tio 300 300 300 26

C o n v ersio n , ^ 33 39 16 44

Y ie ld , i 37 24 31 33

Moles o f P ro d u c ts :

RNO2 0 .2 6 0 .2 4 C.13 0 .3 4

t> C=0 0 .3 4 0.6 2 0 .0 3 0 .6 4

0 .1 6 0 .2 0 0 .1 0 0.18
C3B6
0 .0 6 0.07 0.05 0.08
C2%
CO 0 .2 8 0 .3 4 0 .2 9 0.35

C02 0 .0 8 0.10 0 .08 0.1 5

Propane R e a c tin g , Moles 0 .6 5 0 .9 6 0 .3 9 0.93

 26..

t h a t b u tan e and p ro p y l r a d i c a l s sh o u ld show l e s s tendency to decompose

in to o le f in s . Hence i t i s th e o p in io n o f t h i s a u th o r t h a t w ith th e

p ro p e r S/V r a t i o , th e n i t r a t i o n o f propane w ith oxygen could be ma.de

to g iv e c o n v e rsio n s ap p ro a c h in g th o se o b ta in e d by A lexander b u t w ith

y i e l d s o f th e same o rd e r a s th o se o b ta in e d w ith no oxygen. The use o f

steam a s a d i lu e n t would be s tr o n g ly a d v is e d .
 27.
V II. N itro g e n B alance

D ata re p o rte d by Hodge ( l l ) and H atcher (8) i n d ic a te t h a t

5 p e r c e n t o r l e s s of th e n i t r i c a c id charged i s co n v erted to m o lecu lar

n itr o g e n . However, th e s e f ig u r e s a r e a t v a ria n c e w ith th e 20 p e r c e n t

l o s s o b ta in e d in com m ercial n i t r a t i o n a c c o rd in g to v e rb a l in fo rm a tio n

from a Commercial S o lv e n ts r e p r e s e n t a t i v e . T h is f ig u r e i s q u ite

im p o rta n t com m ercially s in c e i t r e p r e s e n ts u n rec o v e rab le n itro g e n

w hereas th e n i t r i c oxide and n itro g e n d io x id e may be rec o v e red as

n itr ic a c id .

U n fo rtu n a te ly , t h i s d isc re p a n c y was n o t n o ted u n t i l n e a r th e

end o f t h i s i n v e s t i g a t i o n . S in ce a n a ly s e s had been ms,de r e g u l a r l y f o r

n i t r i c o x id e , n itr o g e n d io x id e and n i t r o p a r a f f i n s , i t should, have been

p o s s ib le to e stim s.te n itr o g e n l o s s by d i f f e r e n c e . However, a s e rio u s

e r r o r was p r e s e n t in a l l d e te rm in a tio n s o f n i t r i c oxide p r io r to Run 26.

T h is had r e s u l te d from a la c k o f a p p r e c ia tio n o f th e s o l u b i l i t y o f

b u tan e in th e f e r r o u s s u l f a t e re a g e n t used f o r a b s o rb in g th e n i t r i c oxide

A lso th e n itr o g e n d io x id e v a lu e was p ro b ab ly somewhat low in most ca se s

becau se o f l o s s e s due to i t s s o l u b i l i t y in th e r e t a i n i n g s o lu tio n used

in sam p lin g . However. th e p e rc e n ta g e n itr o g e n l o s t a s c a lc u la te d in

t h i s m n n e r i s s e m i- q u a n tita tiv e ly a c c u r a te . Such v a lu e s a s could be

o b ta in e d a r e given in T able X II.

The la r g e a p p a re n t in c r e a s e in n itro g e n l o s s on going from

th e c o i l r e a c t o r to th e peeked r e a c t o r w ith an s/V r a t i o o f 28 could

be due e i t h e r to a d e c re a s e in h e a t t r a n s f e r o r to an in c r e a s e in s u rfa c e

S in c e a f u r t h e r in c r e a s e in th e s/V r a t i o to 3OO caused a sm a ll f u r t h e r

d e c re a s e in l o s s , i t i s f e l t t h a t poor h e a t c o n tr o l m ust be r e s p o n s ib le

f o r th e d i f f e r e n c e . T h is p o in t i s , o f c o u rs e , s u b je c t fco q u e s tio n and

i t would be d e s ir a b le to o b ta in more p o s it i v e e x p e rim e n ta l evidence to

 27 a,

T able X U

L oss o f N i t r i c A cid to N itro g e n Gas

( A ll E xperim ents a t 425®C., 1 .6 Seconds C o n tact Time and

Ci^Hio/HNO, R a tio o f I 5 )

s / v R a tio

4* 23 300

Og/SNOg P e r Cent Loss to Ng**

0 20 30 33

1 -- 27 24

2 0 24 7

3 — 11

* E xperim ents in th e 10 mm. I.D . c o i l .

** C a lc u la te d by d if f e r e n c e betw een n i t r i c a c id charged and

recovered. NO, NOg, and RNOg.
 23.

c o n firm i t . N e v e rth e le s s th e i n d ic a tio n t h a t s u rfa c e has no d e t r i ­

m en ta l e f f e c t i s e n c o u ra g in g in l i g h t o f th e a d v an tag es shown hy t h i s

f a c t o r in im proving hydrocarbon co n v ersio n to n i t r o p a r a f f i n s .

The e f f e c t o f oxygen a p p e a rs to be q u ite d e f i n i t e and f a v o r ­

a b le . No mechanism i s o f fe r e d f o r th e n itr o g e n l o s s so t h a t i t i s

im p o s s ib le to e x p la in j u s t why th e a d d itio n o f oxygen should p re v e n t

it. However, i t should, be recognized, t h a t th e c o n v e rsio n o f n i t r i c

a c id to n itr o g e n i s a r e d u c tio n , and t h a t th e a d d itio n o f oxygen would

be expected, to m inim ize such a p ro c e s s .

In o rd e r to o b ta in a check on th e v a l i d i t y o f th e above

m easurem ents, a method, o f a n a ly s is was worked out and a p p lie d to s e v e r a l

e x p e rim e n ts. S in c e even a r e l a t i v e l y la r g e n itr o g e n l o s s would r e p r e ­

s e n t only a sm s.ll p o r tio n o f th e ga.seous p ro d u c ts , i t was found n e c e ssa ry

t o remove a l a r g e p o r tio n o f th e condensable m s.te ria ls in a dry ic e t r a p ,

An a l i q u o t p o r tio n o f th e rem ainder was s u b je c te d to th e r e g u la r ga,s

a n a ly s i s p ro ce d u re to remove carbon d io x id e carbon monoxide, o l e f i n s

axd n i t r i c o x id e . The rem s-inder o f th e b u tan e was absorbed, in kero sen e.

Oxygen was added and th e m ix tu re was burned over h o t copper o x id e . From

th e d e c re a s e in volume upon com bustion a lo n g w ith a m easure o f th e carbon

d io x id e produced . i t was determ ined th a.t hydrogen and methane were p r e ­

s e n t. The o r i g i n a l r e s id u e l e s s th e q u a n ti ti e s o f th e s e m a te r ia ls gs.ve

th e amiount o f m o le c u la r n itr o g e n . A q u a l i t a t i v e t e s t was perform ed on

t h i s m s b e ria l by a llo w in g i t to r e a c t w ith h o t ms.gnesium to form th e

n itrid e . S ubsequent h y d r o ly s is gave th e odor o f ammonia.

The r e s u l t s o f t h r e e such a n a ly s i s a r e given in T able X H I.

I t w i l l be observed, t h a t rough checks a r e o b ta in e d between th e measured

 28a

T able X III

A n aly ses f o r N itro g e n Gas

Bun N o. 36 38 4l

H ydrocarbon Butane Propane Butane

s / v R a tio 300 300 4

O2/M O 3 1 .2 5 1 0

T em p eratu re, ®C . 425 425 425

M easured N itro g e n * L o s s , ^ 19 23 24

E stim a te d N itro g en * * L o s s , ^^ 13 28 31

Moles Hp 0 .0 2 0 .0 1 0 .01

Moles CHi|_ 0 .0 3 0.02 0.02

* Measured, by gs.s a n a ly s is and. re p o r te d a s mole fb o f th e

n i t r i c a c id c h a rg e d .

** E stim a te d by method used in T able X.

 29.

v a lu e and t h a t c a lc u la t e d hy d if f e r e n c e . As would he expected from th e

low v a lu e s f o r NOg, th e m easured n itro g e n l o s s i s g e n e ra lly low er th an

th e c a lc u la t e d v alu e and i s p ro b ab ly more a c c u r a te .

T able X I I I a ls o l i s t s th e a c t u a l q u a n ti ti e s o f hydrogen and

m ethane formed W hile s m a ll, th e s e v a lu e s do giv e a d d it io n a l ev id en ce

o f th e p re se n c e o f a f r e e r a d i c a l p ro c e ss inasm uch a s th e methane m ust

have been formed, by th e a t t a c k o f a m ethyl r a d i c a l on a n o th e r h y d ro ­

carbon m o le c u le .

In g e n e ra l, th e n , i t would ap p ear t h a t l o s s o f n i t r i c a c id

to m o le c u la r n itr o g e n i s a s e r io u s problem in vapor phase n i t r a t i o n .

F u rth e rm o re , i t i s aggrava.ted by poor h e a t c o n tr o l. On th e o th e r hand,

th e p re s e n c e o f oxygen in th e n i t r a t i o n m ix tu re and perhaps a la r g e s/V

r a t i o a p p e a r to red u c e th e lo s s c o p s id e r a b ly .
 30.

MECHMISM

S p e c u la tio n s c o n c ern in g th e mechanism o f vs,por phase n i t r a ­

t io n have been r i f e . I t was in v e s tig a te d , d i r e c t l y by McCleary and.

D egering ( I 5 ) . Hass e t a l ( 6 ) s ta te d , c o n c lu sio n s drawn from examina­

tio n o f t h e i r e x p e rim e n ta l data,. The c o n c lu sio n s reach ed ms,y be sta b e d

a s fo llo w s :

(1) N i t r a t i o n p ro ce e d s th ro u g h a f r e e r a d i c a l p ro c e s s .

( 2) A lk y l f r e e r a d i c a l s a r e formed, by an o x id a tiv e a t t a c k on

th e hydrocarbon by n i t r i c a c i d .

( 3) These f r e e r a d i c a l s a t t a c k a n i t r i c a c id m olecule w ith th e

fo rm a tio n o f a n i t r o p a r a f f i n m olecule and an -OH r a d i c a l .

(4 ) Lower m o le c u la r w eight n i t r o p a r a f f i n s r e s u l t from a lk y l

r a d i c a l s produced d i r e c t l y from th e hydrocarbon.

(5 ) The form s,tion o f o x id iz e d ro a,terial i s th e r e s u l t o f r e a c tio n

betw een th e hydrocarbon and n i t r i c a c i d .

(6 ) Some d ecom position of n i t r o p a r a f f in s o ccu rs by r e a c tio n w ith

n itr ic a c id .

W hile such a view o f th e sechanism ms,y n o t be in h e r e n tly

w rong, i t does l i t t l e more than s u g g e st th e n a tu r e s o f th e r e a c tio n s

ta k in g p la c e . I t is how ever, p o s s ib le , w ith th e a id o f o ld e r data,

and th e newer d a ta assem bled in t h i s t h e s i s to propose a s e r i e s o f

e q u a tio n s which a c c o u n t f o r m ost o f th e observed p ro d u c ts and f o r th e

v a r i a t i o n s in th e s e p ro d u c ts which r e s u l t from c e r t a i n changes in condi­

t io n s and in th e mole r a t i o s o f th e r e a c t a n t s . The p roposed mechanisms

in v o lv e r e a c t i o n s , which f o r th e most p a ,rt, have been o b serv ed to occur

p re v io u s ly under s i m i l a r c o n d itio n s .
 31.

E vidence t h a t n i t r a t i o n pro ceed s by a f r e e r a d i c a l mechanism

i s fu rn is h e d by th e fo llo w in g f a c t s :

(1) B urton (4) n i t r a t e d o p t i c a l l y a c ti v e 3-m ethylhexane and

o b ta in e d racem ic 2 - n it r o b u t a n e . T his in d ic a te s t h a t th e secondary

b u t y l group p a s se s th rough a c o n f1g u r a tio n a lly u n s ta b le form in th e

n i t r a t i o n p ro c e s s . The most l i k e l y assum ption i s t h a t t h i s i n t e r ­

m ed iate i s th e c o rre sp o n d in g f r e e r a d i c a l .

(2) B l i c k e n s ta f f (2) s u c c e s s f u lly n i t r a t e d th e b rid g eh ead carbon

in b ic y c lo (2 2 .1 ) h e p ta n e . T h is would r u l e out th e rep la ce m e n t o f

hydrogen by a rea rw a rd a t t a c k and would in d ic a te in s te a d a forw ard

a t t a c k w ith th e p ro b a b le form a,tion o f a f r e e r a d i c a l in te r m e d ia te .

( 3) S h e c h te r (22) found n i t r a t i o n to lead to th o se n i t r o p a r a f f in s

c o rre sp o n d in g to a l l p o s s ib le a lk y l r a d i c a l s which can be formed, by

b re a k in g only one carbon to carbon bond in th e o r i g i n a l h y d ro ca rb o n .

M cCleary (15) a l s o showed th e fo rm atio n o f o l e f i n s c o rre sp o n d in g to

a l l o f th e a l k y l r a d i c a l s p r e s e n t in n i t r o p a r a f f i n s . T his in d ic a te s

t h a t a l k y l f r e e r a d i c a l s may be p r e s e n t s in c e they a re known to decom­

pose r e a d i l y and r a p i d l y to o l e f i n s .

(4) M cCleary was a ls o a b le to form n i t r o pa.rs,ffin s by th e r e a c ­

t io n betw een t e t r a e t h y l le a d and n i t r i c a c id in th e vapor p h a s e .

T e t r a e th y l le a d has been shown by P aneth ( I 6 ) t o form e th y l r a d i c a l s

when h e a te d under d im in ish ed p r e s s u r e . I f th e same b e h a v io r ms.y be

assumed a t a tm o sp h eric p r e s s u r e , th e n i t r o p a .ra ffin s probably came

from th e union o f an e th y l r a d i c a l w ith th e n i t r a t i n g a g e n t.

T h is p r e s e n t work d is c lo s e s two o th e r f a c t s o f s ig n if ic a n c e :

(5 ) The p re s e n c e o f in c re a s e d s u rf a c e cau ses a d e c re a se in th e

t o t a l amount o f hydrocarbon r e a c ti n g . T his ms,y be a s c r ib e d to d e s tr u c ­

t io n o f f r e e ra ,d ic a l in te r m e d ia te s by s u rfa c e r e a c tio n s (1 4 ).
 32.

( 6) The in c r e a s e d p ro d u c tio n o f o l e f i n s a s w e ll a s n i t r o p a r a f f in s

when oxygen i s added to th e n i t r a t i o n m ix tu re s u g g e sts f r e e a l k y l r a d i c a l

in te r m e d ia te s s in c e th e s e a r e known to he formed in o x id a tio n s under

c o m p a ralle c o n d itio n s ( 25) .

Much has been said, s h o u t th e s o - c a lle d a g e n t of n i t r a t i o n .

T h is i s d e fin e d a s th e n e .te r ia l which r e a c t s w ith th e a l k y l f r e e r a d i c a l s

t o produce n i t r o p a r a f f i n s I t i s w e ll known t h a t n i t r i c a c id i s

u n s ta b le a t 425*C . and t h a t th e p ro d u c ts o f th e decom position a re

n itr o g e n d io x id e , n i t r i c o x id e , oxygen and w ater ( 5 )• U n fo rtu n a te ly ,

no d e ta i le d mechanism has been worked out f o r t h i s r e a c t i o n . These pro­

d u c ts (e x c e p t f o r th e w a te r) may. how ever, be accounted f o r by th e

fo llo w in g r e a c ti o n s :

(1 ) HONOg ———
^ HO* + 'NO2

(2) 2 "NO2 2N0 • + Og

Of th e f r e e r a d i c a l s shown, th e HO- r a d i c a l i s th e l e a s t s ta b l e and

th e m ost r e a c t i v e . Hence i t would be ex p ected to i n i t i a t e th e form a­

tio n o f f r e e r a d i c a l s from hydrocarbons in th e n i t r a t i o n p ro c e s s .

(3 ) HO" + EH — > E- + HOH

The f r e e a lk y l r a d i c a l s s o produced could th en u n ite w ith -NOg r a d i c a l s

(4) "E + *NOg — ^ ENOg

p ro d u cin g n i t r o p a r a f f i n s . N i t r a t io n t h e r e f o r e i s a f r e e r a d i c a l p ro ­

c e s s b u t i s n o t a c h a in r e a c t i o n . I t should be n o te d t h a t any o th e r

c o n c u rre n t p ro c e s s le a d in g to th e fo rm a tio n o f r e a c ti v e f r e e r a d i c a l s

would, be expected to c o n tr ib u te to th e n i t r a t i o n p ro c e ss by in c r e a s in g

th e c o n c e n tra tio n o f a l k y l f r e e r a d i c a l s and hence th e p e r pass con­

v e rs io n s to n i t r o p a r a f f i n s . I t has been shown t h a t t h i s can be done

w ith oxygen. E vidence t h a t n i t r a t i o n i s n o t a chain r e a c tio n i s found

in th e f a c t t h a t in c re a s e d s u rf a c e in th e r e a c t o r tu b e does n o t a l t e r
 33.
th e y i e l d s o f p ro d u c ts s u f f i c i e n t l y to he in agreem ent w ith th e r e s u l t s

ex p ected o f a c h ain r e a c ti o n o f any c o n s id e ra b le le n g th ( l 4 ) .

On th e b a s is o f th e proposed mechanism, th e n i t r a t i n g agœ t

i s a c t u a ll y -NOg. However, -NOg n i t r a t e s n o t hydrocarbon m olecules

d i r e c t l y b u t a lk y l r a d i c a l s derived, from them end. th e l a t t e r a re

g e n e ra te d more e f f e c t i v e l y by HO- r a d i c a l s than by -NOg r a d i c a l s . T his

e x p la in s th e f a c t t h a t -NOg a lo n e i s l e s s e f f e c t i v e than n i t r i c a c id as

a n i t r a t i n g a g e n t in th e vapor ph ase.

A nother ad v an tag e to th e assum ption t h a t e q u a tio n (4) r e p r e ­

s e n ts th e c h ie f vapor phase n i tr a .tio n p ro c e ss i s th e e a se w ith which i t

may b e a d a p te d to an e x p la n a tio n o f th e f o r m t i o n o f o th e r p ro d u c ts o f

th e r e a c t i o n . The -NOg r a d i c a l i s a reso n an ce h y b rid whose c h ie f con­

t r i b u t i n g form s probably^ in c lu d e :

(-)(+)

:0: N : : 0 : <--> :0::N:0:

I II

I f an a lk y l r a d i c a l r e a c t s w ith -NOg in Form I th e p ro d u c t i s a n i t r o

p a r a f f i n , b u t i f in Form I I th e p ro d u c t i s an a lk y l n i t r i t e . The

b e h a v io r o f a l k y l n i t r i t e s under th e c o n d itio n s o f vapor phase n i t r a t i o n

i s th e r e f o r e im p o rta n t to a more com plete u n d e rsta n d in g o f th e n i t r a t i o n

p ro ce ss.

A lk y l n i t r i t e s a p p e a r to be extrem ely u n s ta b le a t elevabed

te m p e ra tu re s . E ic e (20) decomposed e th y l n i t r i t e a t 425®C. in th e p r e ­

sence o f buta.ne a s a d i l u e n t . Under such c o n d itio n s th e r e i s s l i g h t

chance t h a t th e d ecom position p ro d u c ts w i l l c o ll id e w ith unr e a c te d

n i t r i t e m o le c u le s . and th e d eco m position p ro ceed s a s fo llo w s :

(5) CH3CH2ONO > CE3CH2O ' + NO

(6) CHgCHgO - —-> ECHO + CE3 -

 34,
The m ethyl r a d i c a l s were i d e n t i f i e d a s t e l l u r I d e s . I f n o t removed from

th e r e a c ti o n m ix tu re th ey re a c te d w ith n i t r i t e m o lecu les a s f o llo w s ;

( 7) CH^- + CH3CH2ONO — -> CSij, + CH3ÇHONO

(S) CH3CHONO — ^ CH3CHO + -NO

Kornhlum and. O ilv e to (12) have shown t h a t i f a h ig h e r c o n c e n tra tio n o f

n i t r i t e i s p r e s e n t, th e a lk o x id e r a d i c a l s f i r s t produced r e a c t as

fo llo w s :

(9) CÏÏ3CH20- + CH3CH2ONO — CH3CE2OH + CE3ÇÏÏONO

( 10) CE3ÇHONO — ^ CH3CHO + -NO

I t i s e v id e n t from th e s e e q u a tio n s t h a t any n i t r i t e s produced

in th e n i t r a t i o n p ro c e s s would decompose to low er h y d ro carb o n s, ald eh y d es

and n i t r i c o x id e , a l l o f which a r e observed p ro d u c ts o f n i t r a t i o n . The

low er a l k y l r a d i c a l s a ls o produced account in p a r t a t l e a s t f o r th e

low er n i t r o p a r a f f i n s o b ta in e d in th e n i t r a t i o n p r o c e s s . Lower a lk y l

r a d i c a l s a r e a ls o formed from th e d i r e c t decom position o f h ig h e r a lk y l

r a d i c a l s (19) • T h is a c co u n ts f o r th e rem ain d er o f th e low er n i t r o

p a r a f f i n s produced.

The r e l a t i v e amounts o f NOg r a d i c a l s which r e a c t in Forms I

and I I , r e s p e c t i v e l y , a r e n o t knov/n b u t th e r a t i o m ust be a t l e a s t 3 /1

to a c c o u n t f o r th e r e l a t i v e q u a n t i t i e s o f low er n i t r o p a r a f f i n s produced.

From T able VI i t may be seen t h a t th e p e rc e n ta g e y ie ld s o f n i t r o butanes

b e a r a r a t i o o f 3 /1 to th e p e rc e n ta g e y i e l d s o f low er n i t r o p a r a f f i n s .

The a c t u a l r a t i o i s undoubtedly low er th an 3/ I s in c e a l l of th e n i t r i t e

formed, i s n o t c o n v e rted to low er a l k y l r a d i c a l s b u t i s co n v erted in pa.rt

to a ld e h y d e s , o l e f i n s , and s a tu r a te d hydrocarbons and i s th u s l o s t to

f u r t h e r form s.tion o f n i t r o p a r a f f i n s .
 35.

The above e x p la n a tio n o f th e o r ig in o f th e low er n i t r o

p a r a f f i n s and b y -p ro d u c ts o f th e n i t r a t i o n r e a c tio n i s more s a .tis -

f a c t o r y th an th e assum ption o f sim ple therm s.! c ra c k in g a s a so u rc e o f

t h e s m a lle r a l k y l r a d i c a l s . As a m a tte r o f f a c t th e p ro d u c tio n o f

m e th y l, e t h y l , and p ro p y l r a d i c a l s from b u tan e i s n e g li g ib l e a t th e

optimum te m p e ra tu re and c o n ta c t tim e f o r th e n i t r a t i o n o f b u ta n e .

F u rth e rm o re , su b s ta n c e s such a s iro n s a l t s , which c a ta ly z e th e c ra c k ­

in g o f C-C bonds in h y d ro carb o n s, d e c re a se ma.rkedly r a t h e r than in c re a s e

th e y i e l d s o f n i t r o p a r a f f i n s o b ta in e d . I f th erm al c ra c k in g were c h ie f ly

r e s p o n s ib le f o r th e fo rn e .tio n o f low er n i t r o p a r a f f i n s i t would be

expected, t h a t cyclohexane would y ie ld c o n s id e ra b le amounts o f 1 ,6 - d in i tr o -

hexane on n itr e ,tio n .

^C H p /C E g .
CHp '^CHp CHp CHp
1 I — > 1 ^ 1
CHg ^ CHp CHg
NCHg ^ CHp

CEo CEg CHp CHpNOp

t " 1 ^ 2 -HOj I t
CHp / C S g ^ CEg /C H p
CHp ^CEp

S h e c h te r* s work on cyclohexane showed t h a t t h i s was n o t th e ca,se. Ee

o b ta in e d only n itro c y c lo h e x a n e and a n o th e r p ro d u ct which c o n ta in e d

n itr o g e n b u t decomposed r e a d i l y on warming to form a t a r . T his r e s u l t

would be e x p e c te d , i f i t i s assumed, t h a t f i s s i o n occurs th rough th e

n itrite . Such a r e a c ti o n m ight lea d to a n i t r o aldehyde which would be

q u ite r e a c t i v e .

CHg CHONO CHp XEO-

I 1 —-> ) ) + -NO
CHp ^ CEo CHp .CHp
'-CHg < c E2
 36

^CHp ^CHo
CEp ^CEONO CH., '^CHO-
I I -----> I I + •NO
C ^^^C H g CHg^CHg
^^ C“Eîp
p "^CH' p

y.#»CHp CEg '

CHp '^CEO- CHp CEO
1 I — - 1 I
CHp / C H . CHp /C H p
< c4 CHg

y / CHg / . CEgNOg
CHp CEO -NO. CHp CEO
I I -> I 1
CHg^^CHg ° ^ c -3

F o llo w in g th e above re a s o n in g , th e ■vs.por phase n i t r a t i o n o f

b u tan e should, proceed, a s fo llo w s :

D ecom position o f n i t r i c a c id :

(11) HNOp — HO- + -NOp

F o r m tio n o f a l k y l r a d i c a l s :

(12) y— CEqCHpCHpCHp ' + HpO

CH.CEpCHpCHo + HO- (
CHgCHpCHCEq + HpO

D ecom position o f a l k y l f r e e r a d i c a l s :

( 13 ) CE3CHpCE=CEp + -H
CHpCHpCHpCHp ' (
CHgCHp ' + CEp=CHp

(14) CHpCH=CHCH3 + H*
CHoCHpCHCHn
CEo- + CHp=CBCEq
 37.
R e a c tio n o f a l k y l r a d i c a l s w ith NOg:

( 15 ) y - -> CH.CHpCHpCHpNC p
CH3CE2CÏÏ2CH2 • + -NOp
CEpCEpCHpCEpONO

( 16 ) CEgCEpCECEp
CÏÏ3CH2CECH3 + 'EOp-^ NOp
CE3CE2CHCH3
ONO

(17) CS3CEP - + 'NOg —- > CH3CE2NO2 + CE3CEgOWO

( 18) CE3 " + -NOp CE3NO2 + CE3ONO

D ecom position o f n i t r i t e s :

( 19 ) C3EYCEgONO > 'NO + CpE^CEgO- - - - > C3EY - + ECHO

( 20) y --> CpEz" + CH3CH0

C2H5CHCH3 > -NO + CpSsCECS^(
^ONO "0 CE,- + CgScCSO

Now i t w i l l he observed t h a t th e m ethyl, e th y l , and p ro p y l f re e r a d ic a ls

produced In ( I 3) , ( 1 4 ), (1 9 ), end (20) may r e a c t w ith -NOp j u s t as th e

o r i g i n a l f r e e r a d i c a l s did in ( I 5 ) and ( 16) . T his would account a t

l e a s t q u a l i t a t i v e l y f o r th e low er n i t r o p a r a f f in s o b tain e d e x p e r i­

m e n ta lly and would a ls o r e s u l t in th e fo rm ation o f a d d it io n a l f r e e

r a d i c a l s w ith one l e s s carbon atom . The o le f in s observed in th e p ro ­

d u c ts a p p a r e n tly come from decom position of th e f r e e r a d i c a l s by ( 13)

and ( l4 ) and a ls o from :

( 21) 2CE3 ' CEp=CEg + 2E-

R e a c tio n s (19) end (20) acco u n t f o r th e a ld e h y d e s. The

la r g e amount o f carbon monoxide a p p a re n tly r e s u l t s from th e w e ll

known p y r o ly s is o f a ld e h y d e s ( 25) :
, , 400® C .
(22) RCEO RE + CO
 33.

I n s u p p o r t o f t h i s i s t h e f a c t t h a t b o th hydrogen and

m ethane a r e found in t h e e x i t g a s e s a s would be e x p e c te d fro m th e

d e c o m p o s itio n o f form a.ldehyde and a c e t a l d e h y d e . No t e s t s w ere

c a r r i e d o u t f o r etha.ne o r p r o p a n e . The o rg a n ic a c id s o b ta in e d r e s u l t

fro m th e f u r t h e r o x id a tio n o f th e a ld e h y d e s .

S in c e o n ly s m a ll am ounts o f a lc o h o l s a r e fo rm ed , th e y can

w e l l be a c c o u n te d f o r by t h e f o llo w in g d e c o m p o sitio n o f a t y p i c a l

a l k o x y l r a d i c a l a s i l l u s t r a t e d by e q u a tio n ( 9 ) • In a d d i t i o n , a w a ll

r e a c t i o n o f th e f o llo w in g ty p e ms.y a l s o o c c u r:

(2 3 ) R- + -OH ROE

The m echa.nlsms p r e s e n te d above may e a s i l y b e e x te n d e d t o

c o v e r t h e e f f e c t o f oxygen on th e n i t r a t i o n p r o c e s s . A c c o rd in g to

W alsh ( 2 5 ) , th e low te m p e r a tu re (below 500 ®C.) o x id a tio n o f b u ta n e w ith

oxygen p ro c e e d s a s fo llo w s :

( 24 ) CEgCEgCEpCEg + -OH — CH3CH2ÇHCE3 + EpO

(2 5 ) CH3CE2ÇBDH3 + Op 4^ CH3CH2ÇHCH3

Ô-

(2 6 ) CH3CH2ÇHCÏÏ3 + ^ CH3CH2CHCE3 +

Ô- OE

(2 7 ) CH3CE2CHCE3 - —■> CH3CH2ÇHCE3 + -OH

ÔH

( 28 ) CH3CH2CÏÏCH3 — CgH^* + CH3CHO

0 •

The same ty p e s o f r e a c t i o n s would be e x p e c te d lo r e s u l t fro m an l n i t l a .1

a t t a c k on a prim a.ry h y drogen e x c e p t th a .t form ald eh y d e would s p l i t o f f

i n s t e a d o f a h ig h e r a ld e h y d e . In e i t h e r c a s e , th e slk y 1 f c e e r a d i c a l s

s o p roduced would b e a .v a lia b le f o r f u r t h e r r e a c t i o n w ith oxygen o r w ith

'NOg. I t w i l l be n o te d t h a t th e above o x id a tio n p ro c e s s in v o lv e s a

c h a in r e a c t i o n w hich would be h in d e re d by in c re a s e d s u r f a c e due to

 39-
decom positdon o r r e a c tio n o f b o th -OH and -R r a d i c a l s on i t ( l 4 ) .
(29) -R + .R § B # 8 .ç e ^ pp

(30) "OE + "OS EgOp

A lc o h o l fo rm a tio n could a ls o occur by r e a c tio n ( 23) .

I f th e o x id a tiv e s e r i e s o f r e a c tio n s le a d in g to th e form a,tion

o f f r e e a l k y l r a d i c a l s ru n s c o n c u rre n tly w ith th e n i t r a t i o n , then th e

p ro d u c tio n o f n i t r o p a r a f f i n s should in c r e a s e due to th e e x is te n c e o f a

h ig h e r c o n c e n tra tio n o f a lk y l r a d i c a l s . In a d d it io n , th e r a t i o o f

low er to h ig h e r m o le c u la r w eight n i t r o p a .ra ffin s should a ls o in c re a s e

due to a g r e a t ly in c re a s e d c o n c e n tra tio n o f th e low er m o le c u la r w eight

a l k y l r a d i c a l s to g e th e r w ith t h e i r g r e a te r s t a b i l i t y . I t has been p r e ­

v io u s ly shown t h a t th e s e p r e d ic tio n s a re borne o u t by experim ent (se e

T able Vl) .

An e x c e l le n t t e s t o f t h i s th e o ry i s a ffo rd e d by Robinson *s

( 21) work on th e n i t r a t i o n o f 1 ,1 ,1 - tr if l u o r o p r o p a n e . He found t h a t

th e o n ly n i t r o compounds formed were l - n i t r o - 3 , 3, 3- tr if lu o r o p r o p a n e

and l - n i t r o - 2 , 2 , 2 - t r i f l u o r o e t h a n e . F a ilu r e to produce 2 - n i t r o - 3 , 3, 3-

tr if lu o r o p r o p a n e r e s u lte d from th e h ig h ly n e g a tiv e c h a r a c te r o f th e

tr if lu o r o m e th y l group which prev en ted an a tta .c k in g group from ap p ro ach ­

in g th e 2- p o s i t i o n . C o n seq u en tly , th e o n ly n i t r i t e which could be

formed would be th e l , l , l - t r i f l u o r o - 3 - p r o p y l n i t r i t e . Decom position o f

t h i s could le a d o n ly to th e form atio n o f a 1 , 1 ,1- t r i f l u o r o e t h y l r a d i c a l

a lo n g w ith fo rm ald eh y d e. As was p r e d ic te d , no n itro m e th an e was form ed.

The above o v e r - a l l mechanism f o r th e vapor phase n i t r a t i o n

p r o c e s s , w h ile i t i s n o t com plete nor e n t i r e l y proven, o f f e r s many

a d v a n ta g e s over p r e v io u s ly proposed mechanisms. Among th e s e a r e i t s

im p lic a tio n s a s to p ro ce d u re s f o r inq)rovlng the y ie ld s o f n i t r o p a r a f f i n s

 40.

o b ta in a b le and f o r a l t e r i n g th e r a t i o s o f th e n i t r o p a r a f f i n s p ro d u ce d .

Some o f th e s e im p lic a tio n s a r e l i s t e d below .

(1 ) Any a g e n t which in c r e a s e s th e c o n c e n tra tio n o f a lk y l fre e

r a d i c a l s p r e s e n t in th e n i t r a t i o n m ix tu re w i l l in crea.se th e p e r pass

c o n v e rs io n . T his a g e n t may be a. s u b sta n c e l i k e oxygen which produces

a l k y l r a d i c a l s by an o x id a tiv e a t t a c k o r i t could be a compound s im ila r

to azom ethane o r d im e th y l m ercury which have been shown to low er th e

p y r o ly s is te m p e ra tu re o f h y d ro carb o n s.

(2) Both th e p e r pass co n v e rsio n and th e y ie ld based on h ydro­

carbon ma.y be improved i f th e p ro d u ctio n o f f r e e a lk y l r a d i c a l s i s ma.de

t o ta k e p la c e a t a u niform optimum r a t e which c o rr e ls .te s v/ith th e r a t e

o f p ro d u c tio n o f "NOg r a d i c a l s . T his ma.y be accom plished by adding

oxygen to in c r e a s e th e r a t e o f form a.tion o f a lk y l r a d i c a l s , o r i f

e x c e ss oxygen i s p r e s e n t, by in c r e a s in g th e amount o f s u rfa c e in th e

r e a c t o r t o d e c re a s e th e r a t e o f form a.tion o f a lk y l r a d i c a l s . A d ilu e n t,

such a s steam , w i l l a ls o se rv e to d e c re a se th e r a t e o f a lk y l r a d i c a l

form a.tion . P ro p e r ad ju stm e n t o f th e s e v a rio u s f a c t o r s should le a d to

th e h ig h e s t p o s s ib le p ro d u ctio n o f n i t r o p a .ra ffin s .

( 3) C a re fu l h e a t c o n tr o l i s e s s e n t i a l to ms. in t a in th e v a rio u s

r e a c ti o n s in p ro p e r b a la n c e . W ithout q u a n ti ta t iv e inform a.tion on r a t e

c o n s ta n ts i t i s im p o ssib le to c a lc u la te th e optimum te m p e ra tu re f o r a

given s e t o f c o n d itio n s , b u t i t i s p o s s ib le to p r e d ic t t h a t th e r e w i l l

be an optimum te m p e ra tu re and a ls o how c e r ta in f a c t o r s w i l l in flu e n c e

t h i s te m p e ra tu re .

(4) The use o f a h ig h r a t i o o f hydrocarbon to n i t r i c a c id should

n o t be n e c e s s a ry i f a n o th e r d ilu e n t i s u s e d . The s u b s t i t u t i o n o f a
 41.

d i l u e n t which may e a s i l y he condensed, such a s steam , m ight s im p lif y

th e r e c y c li n g o p e ra tio n and im prove hydrocarbon u t i l i z a t i o n a s w e ll.

(5 ) The y ie ld based on hydrocarbon i s lim ite d b o th by th e decom­

p o s it i o n o f a l k y l r a d i c a l s to o l e f i n s and by th e f i s s i o n p ro c e ss which

i s r e s p o n s ib le f o r th e p ro d u c tio n o f low er n i t r o p8,rs.ffins and v a rio u s

b y - p ro d u c ts . Hence any a tte m p t to in c r e a s e th e p ro d u c tio n o f th e low er

n i t r o p a r a f f i n s a t th e expense o f th e h ig h e r ones w i l l le a d t o a g r e a te r

d e s tr u c ti o n o f hydrocarbon. T h is s u g g e sts t h a t , o th e r f a c t o r s b e in g

e q u a l, th e more e f f i c i e n t p ro c e ss f o r th e p ro d u ctio n o f low er n i t r o

p a r a f f i n s would be to n i t r a t e low er hydrocarbons r a t h e r than h ig h e r

h y d ro c a rb o n s ,

(6) The f i s s i o n p ro c e ss may be fav o red by any means which w i l l

cause a l a r g e r r e l a t i v e p ro d u c tio n o f a lk y l n i t r i t e s or o f a lk y l hydro­

p e ro x id e s . Oxygen has t h i s e f f e c t as i s shown by T able V I. A p ro ce ss

which u se s a h ig h e r c o n c e n tra tio n o f th e n i t r a t i n g a g e n t r e l a t i v e to the

hydrocarbon b u t in th e p rese n c e o f a d ilu e n t to avoid e x p lo s iv e c o n d i­

tio n s sh o u ld have t h i s same e f f e c t .

( 7) W ith regard to a l t e r i n g th e r a t i o s o f n i t r o p a r a f f in s p ro ­

duced, i t should be noted t h a t o x id a tiv e a t t a c k fa v o rs secondary

hydrogens o v er prim ary h y d ro g e n s. Hence b u tan e would be expected to

produce more n i t r o e th a n e th an n i t r o propane s in c e i t has a h ig h e r

r a t i o o f secondary to prim ary hydrogens ( s e e e q u a tio n s (19) sad ( 2 0 ) ) ,

An in c r e a s e in th e o x id a tiv e a t t a c k by added oxygen should cause a,

g r e a t e r in c r e a s e in n i t r o e th a n e p ro d u c tio n w ith b u tan e than w ith p ro ­

pane, On th e o th e r h and, n i t r a t i o n a t h ig h e r te m p e ra tu re s should, cause

an even l a r g e r amount o f p rim ary a t t a c k s in c e a,s th e te m p e ra tu re i s

r a i s e d th e r a t e s o f a t t a c k on prim ary and secondary hydrogens become

more n e a rly th e same ( 25) . W ith propane t h i s would be expected to lead

t o a h ig h e r p e rc e n ta g e o f n i t r o e th a n e in th e n r o d u c t.
 42.

EXPERIMENTAL

I. A p p aratu s and Technique

The a p p a ra tu s used, in t h i s in v e s tig a tio n i s very s im i la r to

t h a t used, hy A lex an d er ( l ) . A com plete d e s c r ip tio n o f many o f th e item s

in v o lv ed would be re d u n d a n t. However, sone improvements have been

e ffe c te d , in th e equipm ent and th e o p e ra tin g pro ced u re has been imde

e a s ie r. A d is c u s s io n o f such p e r t i n e n t f a c t o r s w i l l be g iv e n .

Gas Flow

The a c c u r a te m e te rin g o f th e hydrocarbon and oxygen stream s

employed in n i t r a t i o n s tu d ie s i s d e s ir a b le . O r ig in a lly th e s e flow s

were c o n tr o lle d by a n e e d le v a lv e a.nd th e r a t e measured by th e sim ple

manometer ty p e flow m eter d e s c rib e d by A lex an d er. T his was n o t v ery

s a t i s f a c t o r y inasmuch a s c lo s e c o n tr o l by such v a lv e s a s were a v a ila b le

was d i f f i c u l t . A lso th e r a t e o f flow was in flu e n c e d to a marked degree

by f l u c t u a t i o n s in downstream p r e s s u r e . T his proved p a r t i c u l a r l y

troublesom e in e x p e rim e n ts in v o lv in g oxygen and in one case (Run 6)

caused an e x p lo s io n . A s o lu tio n to th e problem was found in th e use

o f j e t s o f such a s i z e t h a t th e u p stream p re s s u re re q u ire d to m ain tain

th e d e sire d , gas r a t e was a t l e a s t 2 .5 tim es th e downstream p r e s s u r e .

I t should b e n o ted t h a t under th e s e c o n d itio n s , th e mass r a t e o f flow is

c o m p le te ly in d ep en d en t o f th e downstream p r e s s u r e . The c o n tr o l o f th e

p r e s s u r e in f r o n t o f th e j e t was c o n v e n ie n tly accom plished, w ith diaphragm

r e d u c tio n v a lv e s . A s ta n d a rd Hoke re d u c in g v a lv e was used on th e oxygen

c y lin d e r and an a c e ty le n e re d u c in g ga.uge f o r th e b u tan e o r propane

c y lin d e r.

The j e t s th em selv es c o n s is te d o f a p ie c e o f 8 mm. pyrex

tu b in g which was drawn down t o a c a p i l l a r y a t one e n d . Sm oother

 43.

o p e ra tio n •was o t ta in e d when th e c a p i l l a r y p o r tio n was a t l e a s t one in ch

in le n g t h . A s e c tio n o f 10 mm. tu h in g was s lip p e d ov er th e c a p i l l a r y

end. o f th e j e t and r i n g s e a le d to th e c e n te r o f th e 8 mm. tu h in g . In

o p e ra tio n ^ th e 8 ram. tu h in g was connected to th e diaphragm gauge w ith

a heavy w a lle d , ru h h e r tu h in g which was cap ab le o f w ith s ta n d in g 100

pounds o f p r e s s u r e . Such a tu h e w i l l o p e ra te s a t i s f a c t o r i l y a t p re s s u r e s

up to 80 pounds over lo n g p e rio d s o f tim e . The 10 mm. end o f th e j e t

assem bly was connected to th e i n l e t o f th e r e a c t o r hy Tygon tu h in g o f

an a p p r o p r ia te s i z e .

The j e t may he c o n v e n ie n tly c a li h r a t e d e i t h e r s e p a r a te ly or

in p la c e in th e a p p a ra tu s . W ith th e p re s s u re in f r o n t o f i t a d ju s te d

to a, s u i t a b l e v a lu e and a l l o th e r flow s c u t o f f , th e gas is s u in g i s

passed, th ro u g h a wet t e s t m eter f o r a m easured p erio d o f tim e . Flow

r a t e s a r e o b ta in e d in t h i s way f o r s e v e r a l p re s s u r e s and a c a li b r a t io n

curve i s drawn. T here i s a l i m i t to th e v a r ia tio n in r a t e which may he

g o tte n w ith any one j e t w ith o u t u sin g e x c e s s iv e ly h ig h p r e s s u r e s . Hence

th e s iz e o f th e c a p il la r y i s somewhat c r i t i c a l , h u t th e p ro p e r diam eter

i s e a s i l y determ ined, a f t e r some e x p e rim e n ta tio n .

H i t r i c A cid Feed

The n i t r i c a c id i n je c ti o n system used was e x a r tly th e same as

t h a t d escrib ed , in d e t a i l hy A le x a n d er. In g e n e ra l, i t c o n s is te d o f a

one l i t e r round bo tto m f l a s k as th e n i t r i c r e s e r v o i r which was f i t t e d

w ith an i n l e t f o r n itr o g e n ga.s above th e s u rfa c e and. an e x i t tuhe

d ip p in g below th e l iq u i d l e v e l . T his d ip tu h e connected to a c a p il la r y

j e t which was f i t t e d , i n to th e p r e h e a te r . A d i f f e r e n t i a l m n o m eter was

connected, betw een th e n itr o g e n i n l e t and th e p o in t where th e j e t en te red

 44.

th e p r e h e a te r , so t h a t th e p re s s u re a c ro s s th e j e t could be m easured.

A by-pa,ss was provided, a c ro s s th e manometer f o r e a se in s t a r t i n g the

a p p a r a tu s , The p r e s s u r e to th e a c id r e s e r v o i r was c o n tro lle d , by a

diaphragm gauge, and. a b le e d v a lv e was provided, to r e l e a s e p r e s s u re in

o rd e r t o s to p th e a c id flo w . The amount o f n i t r i c a c id used, was

m easured by w eighing th e f l a s k b e fo re and. a f t e r each ru n .

C a lib r a tio n o f th e j e t ha.d to be ma,d.e in s i t u under a c tu a l

o p e r a tin g c o n d itio n s a s th e flow r a t e under a given p r e s s u re was

in flu e n c e d by th e te m p e ra tu re o f th e j e t . I t was found t h a t f lu c t u a ­

t io n s were d e c re a se d c o n s id e ra b ly by p la c in g a fo u r l i t e r su rg e v e s s e l

in th e n itr o g e n l i n e j u s t b e fo re th e a c id f l a s k .

Preheat, e r

A p r e h e a te r was pro v id ed to b r in g th e g ases c lo s e to r e a c tio n

te m p e ra tu re b e fo re e n te r in g th e r e a c t o r and to f u r n is h th e means o f

v a p o riz in g th e n i t r i c a c id . T his c o n s is te d o f l8 0 cm. o f 10 mm. pyrex

tu b in g made i n t o a c o l l 15 cm. in d ia m e te r and. jo in e d by a T to a n o th e r

c o i l 60 cm. lo n g and. 20 cm. in d ia m e te r. The open end o f th e T was

p la c e d v e r t i c a l l y , and th e o u te r s e c tio n o f a b a l l j o i n t s e a le d to i t ,

so t h a t th e j o i n t pi*ojected. above th e c o i l . T his b a l l j o i n t provided, a

s e a t f o r th e n i t r i c a c id i n j e c t i o n j e t . The lo n g e r c o l l was connected

to th e oxygen and. hydrocarbon fe e d system s and th e s h o r te r c o i l led. to

th e r e a c t o r . The whole assem bly was placed, in a s a l t b a th m in ta in e d

a t a te m p e ra tu re o f 265*0.

R e a c to rs

Three r e a c t o r s were used in t h i s i n v e s t i g a t i o n .

R e a c to r 1 . T h is c o n s is te d o f a c o i l o f 7 pyrex tu b in g

would i n to two c o n c e n tric s p i r a l s , 15 and 20 cm. in d ia m e te r, r e s p e c ti v e ly ,

 45.

and had a volume o f 600 m l. The c o i l was an e x a c t d u p lic a te of t h a t

used, hy A lexander and was used only f o r p re lim in a ry experim ents on

m eth a n e . I t was found to g iv e such la r g e p re s s u re drops w ith "butane

t h a t i t could n o t "be used .

R e a c to r 2 . T h is r e a c to r was a ls o o f th e c o i l ty p e and con­

t a i n e d a p p ro x im a te ly 25 f e e t o f 10 ram. I.D . pyrex tu b in g . I t s volume

was 600 m l. in ex p erim en ts 5 -1 2 . At t h i s p o in t i t was r e p a ire d and

th e volume was in c re a s e d to 7OO m l.

R e a c to r 3• T his r e a c to r was d esig n ed f o r a stu d y o f th e

e f f e c t o f th e su rfa c e/v o lu m e r a ,tio . I t c o n sisted , o f th re e 90 cm.

le n g th s o f 22 ram. O.D. pyrex tu b in g . Each was b e n t i n to th e form o f

a U and th e th r e e were connected in s e r i e s . The c o n n e ctin g tu b es were

s e a le d in th e s id e s o f th e la r g e IT-shaped p ie c e s n e a r th e to p . Packing

was in tro d u c e d th ro u g h th e open to p s which were th en s e a l e d . The

a.ssembly was p lac e d v e r t i c a l l y in a s a l t b a th and held th e r e by

w eig h ts a.ttach ed to th e bottom o f th e r e a c t o r .

P ro d u c t Recovery^

The e x i t ga.ses from th e r e a c to r were passed th rough a v e r t i c a l l y

p la c e d , s p i r a l , w a te r condenser i n to a 5OO m l. f l a s k w ith a s id e arm.

Most o f th e liq u i d p ro d u c ts were condensed h e re , b u t some s t i l l rem ained

in th e ga.s s tre a m . Complete rem o m l o f th e liq u i d p ro d u cts was o b ta in e d

by p a s s in g th e g ases which issu e d from th e f l a s k in to a dry ic e condenser

s e t above a one l i t e r f la e k p laced in a dry ic e - e th y le n e t r i c h l o r i d e b a th .

T h is condensed most o f th e butane and a l l o f th e rem ain in g liq u id p r o ­

d u c ts . The i s o l a t i o n o f th e liq u id p ro d u c ts was e f f e c te d by slow evs.pora-

t io n o f th e b u ta n e . The uncondensed ga.ses p a s sin g th rough th e dry ic e

c o n d e n se r, were measured by" s wet t e s t m eter and vented to th e hood .

 46.
O p e ra tio n

The p ro ce d u re fo llo w ed in p e rfo rm in g a n i t r a t i o n ws.s as

fo llo w s :

(1) The n i t r i c a c id fla ,sk was w eighed, connected to th e d e liv e ry

j e t and n itr o g e n c y li n d e r . The h y -p a ss a c ro s s th e d i f f e r e n t i a l manometer

was o p e n e d .

(2 ) The r e g u l a t i n g v a lv e on th e hydrocarbon fe e d system was

a d ju s te d to th e p r e s s u r e r e q u ir e d to g iv e th e d e s ire d flow .

(3) The r e g u l a ti n g v alv e on th e oxygen system was a d ju s te d to th e

p ressu re r e q u ir e d to g iv e th e d e s ire d flow .

(4 ) The by-ps.ss was closed, and th e d e s ire d amount o f n itro g e n

p r e s s u re was adm i.tted to th e n i t r i c a c id fla .sk .

(5) The g a ses from th e r e a c t o r which had been v e n tin g to th e hood

were d ir e c te d th ro u g h th e condensing system and,th e tim j.ng c lo c k was

s ta rte d .

D uring th e c o u rse o f th e ru n , a sam ple o f th e e x i t g8.ses was taken f o r

a n a ly s is . A f t e r s u f f i c i e n t m a t e r i a l had been c o ll e c t e d , th e run was

term i.nated in th e fo llo w in g manner:

(1) The v e n t vs.lve on th e n itr o g e n system was opened to s to p th e

n i t r i c a c id flo w . The c lo c k was stopped and th e gs,s s tre a m was d iv e rte d

to th e hood..

( 2) The oxygen flow was s to p p e d .

( 3) A f t e r p u rg in g th e r e a c t o r f o r one m inute th e hydrocarbon flow

was sto p p e d .

The n i t r i c acid, f l a s k was now re-w eig h ed to determ in e th e amount used .

The p ro d u c ts c o ll e c t e d by th e w a te r con d en ser and th e dry ic e condenser

were weighed and th e wet t e s t m eter r e a d in g was re c o rd e d .

 47.
II. P ro d u c t A n a ly s is

The fo llo w in g methods o f p ro d u ct a n a ly s e s were worked o u t in

c o n ju n c tio n w ith Mr. J . V. H ew ett.

E l t r o P a r a f f in s

The method used, by pa.st i n v e s t i gs,tors f o r th e d e te rm in a tio n of

n i t r o p a r a f f i n s was a s fo llo w s . The t o t a l r e a c tio n p ro d u ct was su b je c te d

to a z e o tro p ic d i s t i l l a t i o n w ith w a te r, r e c y c lin g th e aqueous la y e r u n t i l

o n ly one phase appeared in th e d i s t i l l a t e . T his non-aqueous m a te r ia l

was d r ie d and s trip p e d , o f a l l m a te r ia ls b o i li n g below 80*C. The

rem s.inder was assumed, to be n i t r o p a r a f f i n s . The number o f moles p re s e n t

was estim a.ted from th e av erag e m o lecu lar w eight a s o b ta in e d by a crude

f ra c tio n a tio n . T h is method was used in experim ents 1-12.

I t was rec o g n ize d t h a t th e above method o f a n a ly s is perm itted,

many p o s s i b i l i t i e s f o r e r r o r . Such e r r o r s would in c lu d e incom plete

remova.l o f th e n i t r o p a r a f f i n s from th e r e a c tio n m ix tu re , in c lu s io n o f

oxygenated hydrocarbons in th e is o l a te d non-aqueous m a te r ia l, and th e

in a c c u ra c y o f d e te rm in in g avera.ge m o lecu lar w eights by f r a c ti o n a ti o n in

th e columns a v a i l a b l e . A method was evolved which e lim in a te d th e s e

e r r o r s and ma,d.e th e a n a ly s i s q u ic k e r and e a s i e r .

The t o t a l l i q u i d p ro d u ct was e x tr a c te d r e p e a te d ly w ith e th e r

to remove a l l n i t r o p a r a f f i n s . T his e th e r la y e r was tr e a te d w ith s o lid

sodium b ic a r b o n a te to remove a c id ic m a .te ria ls Inasmuch as some o f th e s e

m ight have been n itr o g e n a c id s . A s tr o n g e r base could, n o t be used a s i t

would have caused r e a c ti o n betw een th e n i t r o compounds and any aldehydes

p r e s e n t. An a l i q u o t p o r tio n o f t h i s e th e r s o lu tio n was an aly zed f o r

n itr o g e n by one o f th e methods p re se n te d below . S ince a l l o f th e

n itr o g e n p r e s e n t was due to n i t r o p a r a f f i n s , t h i s gave d i r e c tl y th e

number o f m oles produced..

 48.

No s im p le , q u ick y e t a c c u r a te method o f a n a ly s i s f o r n i t r o

p a r a f f i n was found, in th e l i t e r a t u r e . A K je ld a h l proceudre given hy

Somers ( 23) looked, p ro m isin g h u t had p r e v io u s ly been found in th e s e

l a b o r a t o r i e s n o t to give re p ro d u c ib le r e s u l t s . However, w ith s u it a b le

m o d if ic a tio n s i t was ms.de to g iv e very a c c u r a te a n a ly s e s on known com­

pounds and was found, to be s u i t a b l e .

Improved. K je ld a h l A n a ly s is f o r N itr o Compounds

A sam ple o f th e compound to be a n a ly z e d , o f s u f f i c i e n t s iz e

to c o n ta in ftom 3 t o 5 1% . o f n itr o g e n , i s introduced, in to a 100 m l.

K J e ld a h l f l a s k c o n ta in in g 2 ml. o f e th a n o l and 1 ml. o f TiClg re a g e n t

(20 p e r c e n t s o lu tio n c o n c e n tra te d h y d ro c h lo ric a c i d ) . One gla.ss bead

i s added and th e s o lu tio n i s b o ile d f o r 2 m in u te s . I f th e p u rp le c o lo r

o f th e T iC lg r e a g e n t i s c o m p letely d e s tro y e d , th e re d u c tio n should be

re p e a te d w ith a sm a,ller sam ple. A f te r c o o lin g , O.5 g- KgSOi^, 5O mg.

CuSOk, 50 log. HgO, and 5 lol. c o n c e n tra te d EpSO^ a re added, and th e

m ix tu re i s d ig e s te d u n t i l th e l iq u i d rem a.ining i s c o lo r l e s s . The

cooled c o n te n ts a r e d i lu t e d w ith 20 m l. o f w ater and th e f l a s k i s

a tta c h e d to an a e r a tio n a p p a r a tu s . An e x c e lle n t d e s c r ip tio n of t h i s

a p p a ra tu s i s given by Somers ( 23) . The a s p i r a t o r i s s t a r t e d and th e

f l a s k i s h e a te d f o r 2 m in u tes to remove a c id ic g a s e s . The r e c e iv e r i s

now f i l l e d w ith 50 m l. o f 2 p e r c e n t b o r ic a c id s o lu tio n to absorb th e

ammonia. The fla ,s k i s then cooled in ic e and '^0 p er c e n t aqueous NaOH

c o n ta in in g 2 .5 g. NapS p e r l i t e r i s added u n t i l th e s o lu tio n tu rn s a

d i r t y brown c o l o r . The ic e b a th i s removed and. b e a t i s a p p lie d to the

d ig e s tio n fla .s k f o r 15 m in u te s . The b o r ic a c i d - f i l l e d r e c e iv e r i s then

removed, and th e ab so rb ed ammonia t i t r a t e d d i r e c t l y u sin g 0 .0 1 N. a c id

and. a mixed brown c r e s o l gr-een-m ethyl re d I n d ic a to r .

 49.

A s e a rc h f o r an a n a l y t i c a l method which would n o t in v o lv e a

K je ld a h l d ig e s tio n has r e s u l te d in a new p ro c e d u re . Inasmuch a s th e

v o l a t i l i t y o f th e am ines c o rre sp o n d in g to th e low er n i t r o p a r a f f in s i s

f a i r l y h ig h and t h e i r b a s i c i t y i s g r e a t e r than t h a t o f ammonia, i t has

been found p o s s ib le to red u c e th e n i t r o p a r a f f in s w ith T iC l^ in hydro­

c h lo r i c a c id , n e u t r a l i z e , d i s t i l l th e am ines in to b o ric a c id and t i t r a t e

them d i r e c t l y w ith a c id . The a d v a n ta g e s claim ed f o r th e method a re

g r e a t e r a c c u ra c y , s im p lic ity and in c re a s e d speed.

S im p lifie d P ro ced u re f o r th e Lower N itro P a r a f f in s

A sample o f th e n i t r o p a r a f f i n o f such a s iz e a s to c o n ta in

2 to 5 iHg- o f n itr o g e n i s weighed in to a 100 m l. K je ld a h l f l a s k c o n ta in ­

in g 1 m l. o f 20 p e r c e n t TiClg in h y d ro c h lo ric a c id and 2 m l. o f e th a n o l.

T h is i s b o ile d f o r 2 m inutes then d ilu te d to 30 m l. w ith d i s t i l l e d w ater

and p la c e d on a E je ld a h l a e r a tio n a p p a ra tu s and 10 ml. o f 50 per c e n t

aqueous NaOH added. The f l a s k i s h e a te d s tro n g ly f o r 15 m inutes and

th e am ines cau g h t in 50 m l. o f 2 p e r cen t b o r ic acid s o lu tio n . They

a re then t i t r a t e d w ith 0 .0 1 N a c id u sin g brom c r e s o l green-m ethyl red

mixed i n d i c a t o r .

A c id ic M a te r ia ls

The above p ro c e d u re f o r h a n d lin g th e liq u i d r e a c tio n p ro d u cts

gave an aqueous p o r tio n and an e th e r e x t r a n t . An a li q u o t p o rtio n o f

each (b e fo re tre a tm e n t w ith sodium b ic a rb o n a te in th e c a se o f th e e th e r

e x tra ,c t) was t i t r a t e d w ith s ta n d a rd b a se to b o th th e m ethyl orange and

p h e n o lp h th a le in e n d p o in ts . The t o t a l number o f m oles o f a c id th u s found

were c a lc u la .te d and, r e p o r te d as su ch . S ince th e q u a n ti ti e s involved

were ex trem ely sm a,ll, no a tte m p t was made to determ in e th e in d iv id u a l

a c id s p r e s e n t . From th e r e la .tiv e amounts o b ta in e d w ith th e two

 50.

i n d i c a t o r s , i t can be seen t h a t a c o n s id e ra b le p o rtio n o f th e a c i d i t y

was due t o o rg a n ic a c id s .

C arb onyl Compounds

An a l i q u o t p o r tio n o f b o th th e w ater and th e e th e r la y e r was

b ro u g h t t o th e m ethyl orange en d p o in t w ith O.5 N b a s e . A few m i l l i l i t e r s

o f a s a tu r a te d s o lu tio n o f hydroxy lam ine h y d ro c h lo rid e was then added to

th e sam ple b e in g a n a ly z e d , which was then a.Howed to stan d f o r 10 m inutes.

Any a ld e h y d e s and k e to n e s p r e s e n t r e a c t w ith th e hydroxy lam ine and

l i b e r a t e h y d ro c h lo ric a c id . The amount o f a c id th u s formed i s a

m easure o f th e c a rb o n y l compounds and m y be determ ined by b rin g in g th e

s o lu tio n back to th e m ethyl orange e n d p o in t w ith s ta n d a rd b a se . The pH

o f th e hydroxylam ine h y d ro c h lo rid e s o lu tio n should be a d ju s te d to a

v a lu e o f 3-4 b e fo re i t i s u sed .

Gas A n a ly s is

An O rs a t ty p e a n a ly s is was used to determ ine th e amounts of

carbon d io x id e , carbon monoxide, n itro g e n d io x id e , n i t r i c o x id e, butenes

p lu s p ro p en e, e th y le n e , b u ta n e , m ethane, hydrogen , and. n i tr o g e n . Because

o f th e tim e consuming n a tu r e o f th e p ro c e s s , th e l a s t fo u r m a te ria ls were

only determ ined in a few c a s e s . The a p p a ra tu s c o n s is te d o f a 100 ml. ga.s

b u r e t t e w ith a t h r e e way sto p c o c k jo in e d to a m anifold to which were

connected s e v e r a l gas a b s o rp tio n p i p e t t e s . Samples f o r th e analy^sis

were ta.ken in g a llo n ju g s by d is p la c e n e n t o f a, s a tu r a te d sodium s u l f a t e

s o lu tio n . The m a te r ia ls removed a.re l i s t e d below in th e o rd e r o f t h e i r

rem oval a lo n g w ith th e a b s o rb e n t used in each c a s e .

( 1) N itro g e n d io x id e . Absorbed in 5O p er c e n t s u l f u r i c a c id ,

u s in g a f r e s h 1 m l. p o r tio n o f th e a b s o rb e n t f o r each p a s s . A s p e c ia .l
 51.

p i p e t t e was used f o r t h i s a b s o rp tio n . A 125 m l. b u lb , parked w ith

g la s s ro d s was s e a le d to th e m anifold th ro u g h a th re e way sto p c o c k . A

l e v e l i n g b u lb was a tta c h e d to th e low er end, and th e assem bly was f i l l e d

w ith m ercury. The o th e r arm o f th e sto p c o c k was s e a le d to a n o th e r th re e

way s to p c o c k . One arm o f t h i s was s e a le d to th e bottom o f a c a lib r a te d

c e n tr if u g e tu b e and th e o th e r was b e n t to d isc h a rg e in to a w aste a c id

fla s k . The c e n tr if u g e tube serv ed as an a c id r e s e r v o i r . In o p e ra tio n ,

1-2 m l. o f acid, was l e t in on to p o f th e mercury and. th e stopcock turned,

to co n n ect t h i s b u lb to th e m an ifo ld . The ga.s was adm itted, by low ering

th e m ercury b u lb and e x p e lle d by r a i s i n g i t . The acid, was then d i s ­

charged by a p ro p e r m an ip u la tio n o f th e sto p co ck s and a f r e s h sample

introduced-.

( 2) Carbon d io x id e . T his was absorbed in 30 per c e n t aqueous KOH

s o lu t i o n , making th r e e ps.sses b e fo re each r e a d in g , u n t i l a c o n sta n t

r e a d in g wan o b ta in e d .

( 3) N i t r i c o x id e . T h is was absorbed in a s a tu r a te d s o lu tio n of

f e r r o u s s u l f a t e in 15 p e r c e n t s u l f u r i c a c id u n t i l a c o n s ta n t re a d in g

was o b ta in e d .

(4) Propene p lu s b u te n e s . E ig h ty -o n e and 38 p er c e n t s u lf u r ic

a c id was used a s an a b s o rb e n t in th e p i p e t t e d e sc rib e d under n itro g e n

d io x id e . A f r e s h 1 m l. p o r tio n was used f o r each pa,ss. The 31 p e r cent

acid, was used u n t i l th e a b s o rp tio n p e r pe.ss was l e s s than O.5 m l. The

88 p e r c e n t was u sed u n t i l th e lo s s p e r p a ss became c o n s ta n t. The sum

o f th e s e c o n s ta n t lo s s e s in th e 83 p e r c e n t a c id , s u b tra c bed from th e

to ta .1 amount ab so rb ed in th e 8l and, 38 p e r c e n t a c id ga,ve th e q u a n tity

o f th e s e o l e f i n s p r e s e n t.

(5 ) E th y le n e . T his was ab so rb ed in 96 p e r c e n t s u l f u r i c a c id

which c o n ta in e d one p e r c e n t s i l v e r s u l f a t e . The a n a ly s i s i s c a r r ie d

o u t in th e sa.me manner a s f o r th e 38 p e r c e n t a c id .
 52.

(6) Carbon m onoxide. Ammonleal cuprous c h lo r id e was used a s

th e a b s o rb e n t and th e a n a ly s is c o n tin u ed u n t i l a c o n s ta n t r e a d in g was

a tta in e d .

(7 ) B utane. K erosene was used as th e a b s o rb e n t. I t wa.s found,

n e c e s s a ry to renew th e a b s o rb e n t once to com plete th e a n a ly s i s , s in c e

th e va.por p re s s u re above a m o derately c o n c e n tra te d s o lu tio n o f butane

in kero sen e i s c o n s id e ra b le .

(8) Hydrogen and m ethane. The r e s i d u a l gas from th e above

a n a ly s e s was mixed w ith a m easured volume o f a i r and burned, over th e

h o t copper o x id e. The i n i t i a l volume l o s s to g e th e r w ith th e lo s s

o b ta in e d by a b s o rp tio n o f th e r e s id u e in aqueous KOH allow ed th e c a l ­

c u la tio n o f hydrogen and m ethane.

(9 ) N itro g e n . O btained by d iff e re n c e between the re s id u e b e fo re

com bustion and th e sum of th e hydrogen and m ethane.

I t i s a b s o lu te ly n e c e ssa ry tha.t th e p o tassiu m hy d ro x id e,

f e r r o u s s u l f a t e , and cuprous c h lo rid e s o lu tio n s be s a tu r a te d w ith

b u tan e b e fo re th e s t a r t o f th e a n a ly s i s . F a ilu r e to observe t h i s p r e ­

c a u tio n w i l l r e s u l t in high v a lu e s f o r carbon d io x id e , n i t r i c o x id e,

and carbon monoxide.

 III. C a lc u la tio n s

C o n ta c t Time

T h is was c a lc u la te d from th e number o f moles o f m a te ria ls

charged on th e b a s is of no change in th e number o f moles d u rin g th e

re a c tio n . O bviously t h i s assum ption i s in c o r r e c t b u t in tro d u c e s no

g r e a t e r r o r in t h a t th e m a jo r ity o f th e m a te r ia l charged i s butane

■which comes th ro u g h unchanged . The mean p re s s u re pre■ vailing in th e

r e a c t o r i s used where th e r e i s a c o n s id e ra b le p r e s s u re d ro p . In a l l b u t

th e e x p erim en ts perform ed in th e 7 mm. r e a c t o r , th e p r e s s u re drop was

n e g li g ib l e and th e p r e s s u r e used was t h a t measured a t th e o u t l e t .

C onversion

T his was c a lc u la te d a s th e mole p e rc e n ta g e o f th e n i t r i c

a c id charged which appeared a s n i t r o p a r a f f i n s .

M oles o f P ro d u c ts

The a c t u a l m olar amounts o f th e v a rio u s p ro d u cts o b tain ed a re

r e p o r te d a s su ch . No e s tim a tio n o f th e w ater produced was ma,de in ■view

o f th e in ac c u ra c y o f such a d e te rm in a tio n . These q u a n ti ti e s were

a d ju s te d f o r th e D isc u ssio n S e c tio n to th e v alu es which would have been

o b ta in e d i f e x a c tly 10 m oles o f bu tan e had been used.

Y ie ld s

By a c o n s id e r a tio n o f th e number o f moles of carbon in each

p r o d u c t, an e s tim a tio n o f th e t o t a l amount o f b utane r e a c tin g wa.s ob tain ed

The number o f m oles o f bu tan e co n v erted to n i t r o p a r a f f i n s , a s computed

on t h i s b a s i s , d.i'vlded, by th e t o t a l moles r e a c ti n g gave th e y ie ld based

on h y d ro carb o n .
 54.

IV. ChemicalB Used.

Met ha,ne

S in ce pure methane in c y lin d e rs i s q u ite expensive and because

i t was to be used only f o r checking th e a p p a ra tu s , i t was prepared from

n a t u r a l g a s. The method o f Boyd ( 3) wan used in which th e gs.s i s scrubbed

w ith c o n c e n tra te d s u l f u r i c a c id , pa.ssed over s o lid c a u s t i c , and then

p assed a t 100 pounds p re s s u re ov er a c tiv a te d c h a rc o a l which a b so rb s th e

h ig h e r homologs o f m ethane.

Propane

T his was o b tain e d from P h i l l i p s P etro leu m Company a s t h e i r

T e c h n ic a l Gra.de and was 95 p e r c e n t p u re.

B utane

T h is was s u p p lie d by P h i l l i p s P etro leu m Company a s t h e i r

P ure Grade and was g u aranteed to be 99 p e r c e n t p u re .

N i t r i c Acid,
B a k e r's C .P . n i t r i c a c id was used a s o b ta in e d . T itr a .tio n s

were made t o check th e s ta te d a ssa y in every ca.se.

Oxygen
Pure oxyrgen, as su p p lie d by th e L inde A ir P ro d u c ts Company in

c y li n d e r s , was u sed .
 55

V. E x p e rim e n ta l Da,t a

The fo llo w in g ta b u la r d a ta (T able Xrv) give th e c o n d itio n s

f o r and r e s u l t s from e x p erim en ts 1-43 on which t h i s t h e s i s i s b a sed .

C a lc u la te d v a lu e s ,s u c h a s c o n ta c t tim e , c o n v e rsio n , and y i e l d , a r e n o t

in c lu d e d inasm uch a s th e y a p p e ar in th e t h e s i s i t s e l f and may be

derived, from th e d a ta p re s e n te d h e r e .

The r e a c t o r used in each case i s designated, by a number

to th e fo llo w in g schem e.

R e a c to r Volume I.D . s/v

No. (m l.) P acking R a tio

1 625 5 None 8

2 600 10 None 4

2a TOO 10 None 4
3a 623 20 3/ 16" h e li c e s 20

3b TOO 20 1/ 8” h e li c e s 28

3c 800 20 G lass wool 300

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 56.

SUMMARY

1 . I t has te e n d em onstrated t h a t an In c re a s e in c o n v e rsio n

o f b u ta n e t o n i t r o p a r a f f i n s from 36 p e r c e n t to 4$ p e r c e n t ms.y be

o b ta in e d by th e a d d itio n o f oxygen to th e n i t r a t i o n m ix tu re .

2 . F u r th e r in c r e a s e in c o n v ersio n may be o b tain ed th rough

th e use o f steam a s a d i lu e n t in th e p rese n c e o f oxygen.

3 . The e f f e c t o f oxygen on b y -p ro d u c ts i s l a r g e ly to

in c r e a s e th e fo rm a tio n of o l e f i n s , a ld e h y d e s, end. carbon monoxide.

4 . In th e p rese n c e o f oxygen, th e m t e r i a l s produced in

l a r g e s t q u a n tity e r e o l e f i n s .

5 . The l a r g e s t p o r tio n o f th e c a rb o n y l compounds formed

i s fo rm eld eh y d e.

6. Oxygen f a v o rs th e fo rm a tio n o f low er m o le c u la r w eight

n itr o p a ra ffin s .

7 . The amounts o f b y -p ro d u c ts r e l a t i v e to n i t r o p a r a f f in s

a re d e c re a sed by th e use o f steam, a s a d i l u e n t , th u s c a u sin g en

in c r e a s e in y ie ld b ased on th e hydrocarbon consumed.

8 . P acking th e r e a c t o r w ith pyrex s u rfa c e d e c re a s e s th e

c o n v e rsio n in th e absence o f oxygen. T h is d e c re a se i s a ls o

accompenied. by a d e c re a se in t o t a l r e a c ti o n .

9 . E xcess s u rf a c e in th e p resen ce of oxygen e x e r ts an

i n h i b i t i n g e f f e c t on th e form a.tion o f o l e f i n s and carbon monoxide

b u t shows l i t t l e e f f e c t on n i t r o p a r a f f in fo rm a tio n . Hence improved

y i e l d s a r e o b ta in e d w ith e q u iv a le n t c o n v e rs io n s.

10. The b e n e f i c i a l e f f e c t o f s u rfa c e i s p o s tu la te d to be

due to a s l i g h t i n h i b i t i n g e f f e c t on th e p ro d u c tio n o f f r e e r a d i c a l s
 57.

by oxygen. T h is ca u se s a more even p ro d u c tio n o f f r e e r a d i c a l s

th ro u g h o u t th e r e a c t o r .

11. The p rese n c e o f an optimum te m p e ra tu re in vapor phase

n i t r a t i o n s i s shown to be due to d e s tr u c tio n o f f r e e r a d i c a l i n t e r ­

m ed ia te s a t h ig h te m p e ra tu re s .

12. The fo rm a tio n o f m o le c u la r n itr o g e n was found to be an

im p o rta n t l o s s o f n i t r i c a c id . T h is l o s s was minimized, by th e a d d i­

tio n o f oxygen to th e r e a c ti o n m ix tu re and. p ro b ab ly by th e p resen ce o f

e x c e ss s u r f a c e .

1 3 . Poor h e a t tra .n s fe r i s r e s p o n s ib le f o r in c r e a s e d lo s s to

n itro g e n .

14. I t was found t h a t c o n c lu sio n s drawn from a stu d y o f butane

may be a p p lie d to p ro p a n e .

1 5 . A d e ts d le d mechanism i s given which a c co u n ts f o r th e

e x p e rim e n ta l f a c t s c o n c ern in g vapor phase n i t r a t i o n . T his shows

t h a t n i t r a t i o n proceeds th ro u g h th e r e a c tio n of a lk y l f r e e r a d i c a l s

w ith n itr o g e n d io x id e to produce n i t r o p a r a f f in s and a lk y l n i t r i t e s .

D ecom position p ro d u c ts a s w e ll as th e low er m o le c u la r w eight n i t r o

p a r a f f i n s come from th e m a te r ia ls produced by p y r o ly s is o f th e n i t r i t e s .

1 6 . The e f f e c t o f oxygen on vs,por phase n i t r a t i o n i s e x p la in e d

on th e b a s is o f th e mechanism. The main e f f e c t was found t o be due to

a low te m p e ra tu re o x id a tio n w ith i t s a tte n d e n t p ro d u c tio n o f a lk y l f r e e

r a d i c a l s w hich ru n s c o n c u rre n tly w ith th e n i t r a t i o n .

 58.

BIBLIOGRAPHY

1 . A le x a n d er, L . G ., A Study o f th e Vapor Phase N i t r a t io n o f P a r a f f in s ,

Ph.D . T h e s is , Purdue U n iv e rs ity (1947)-

2 . B lic k e n s ta .f f , P . T ., and H ass, H. B . , N i t r a t io n o f B ic y c lo ( 2 ,2 ,1 )

H eptane, J . Am. Chem. Soc. 1431 (1 9 4 6 ).

3. Boyd, T ., N i t r a t io n o f M ethane, Ph.D. T h e s is , Pu.rdue U n iv e rs ity {I9k2)

4. B u rto n , T. M., P riv a,te Communication to H ass, H. B. (1 9 4 7 ).

5 . F o rs y th e , ¥• E ., and G ia rq u e , ¥ . F . , The E n tro p ie s o f N i t r i c A cid ,

J . Am. Chem. Soc. 48-61 (1 9 4 2 ).

6 . H ass, H. B ., S h e c h te r, H ., A le x a n d er, L. G ., and H a tc h er, D, B .,

E f f e c t o f P re s s u re on th e N i t r a t io n o f M ethane, In d . Eng. Chem. 3 9 ,

919 ( 1947) .

7 . H ass, H. B ., Hodge, E. B ., and V a n d e r b ilt, V. M. , N i t r a t i n g P a r a f f in

H ydrocarbons, U. S . P a te n t 1 ,9 6 7 ,6 6 7 (1 9 3 4 ).

8 . H a tc h e r. D. B ., Ph.D. T h e s is , Purdue U n iv e rs ity ( l 9 4 l ) .

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t h i v e r s i t y (1 9 4 0 ).

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Ph.D . T h e s is , Purdue U n iv e rs ity (1 9 3 6 ).

12. Kom blum, N ., snd O il v e to , S . P . . The Mechanism o f th e Thermal

D ecom position of A lk y l N i t r i t e s in th e L iq u id P h ase, J . Am. Chem.

Soc. 71; 226-8 ( 1949) .

1 3 . Landon, G. K . , N i t r a t io n of M ethane, U. S. P a te n t 2 ,1 6 4 ,7 7 4 (1 9 3 9 ).

14. Lew is, B ., and von E lb e , G ., ’’Combustion Flames and E x p lo sio n s o f

Gases" Cambridge U n iv e rs ity P r e s s , Cambridge (1 9 3 8 ).

1 5 . M cCleary, E . F . , R e a c tio n Mechanism f o r N i t r a t io n P a r a f f in Hydro­

c a rb o n s , Ph.D. T h e s is . Purdue U n iv e rs ity (1935)•

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6 2 3 , 1335 ( 1929) ; 64, 2702 ( 1931) .

1 7 . P e a se , E . N ., C h a r a c t e r i s ti c s o f N on-E xplosive O xid atio n o f P ropane,

J . Am. Chem. Soc. I 838 ( I 929) .

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Chem. Soc. 56 , 2034 (1 9 3 4 ).

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B a.ltim ore (1935) *

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Ph.D . T h e s is , Purdue U n iv e rs ity (1 9 4 6 ).

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 YTSA

L e s l i e M andeville A ddison was born May 12, 1922, in

Los A n g e le s, C a lif o r n ia , g ra d u a te d from C e n tra l High S c h o o l, J a c k so n ,

M is s i s s i p p i, in 1938, re c e iv e d th e B .S. d eg ree from M illsa p s C o lleg e

in 1941, and th e M.A. deg ree from th e U n iv e rs ity of N orth C a ro lin a in

194 3 . He became an en^loyee o f th e E sso S tan d ard O il Company in 1943,

s p e n t 1944-45 on a m i l i t a r y le a v e and 1947-48 on an e d u c a tio n a l le a v e

t o a tte n d . Purdue U n iv e rs ity . He m a rrie d P a t r i c i a MacLean in 1946,

has one d a u g h te r, C a th e rin e M argot, born Septem ber 18, 1948, and now

( 1949) r e s i d e s in Baton Rouge, L o u is ia n a .