6
SIMILARITY LAWS OF DEFLAGRATION 430 For a mixture of fixed composition, this reduces to P t F+ G(T~ -- To) - ks = A(7'~ - 7'0) + B'PI where the constants F, G and B' increase with in- crease of inert gas concentration. It follows that P~ increases with inert gas addition; but that the increase will be less the greater To, as found ex- perimentally. Treating equation 7 as in (a) and remember- hag that in the experimental work PN/P~ + 1)oo was constant, it can be shown that PE ~ and (Po:)0 should be increased by inert gas addition, as found experimentally. Remembering too that Ce ;>> C N and that, in the experimental work, Px/PE is ~1, it can be further shown that K should be little affected by inert gas addition. ACKNOWLEDGMENT We are grateful to Messrs. Ricardo and Co. for the design and gift of the fine wire resistance thermometer and for much other generous help. REFERENCES 1. TOWNEND AN D CH AMBERLAIN: Pr oc . Ro y. Soc ., A158, 415 (1937). 2. HSlEH AND TOWNEND: J. Chem. Soe., 332, 337, 341 (1939). 3. ~IACCO RMAC AN D TOWNEND: ibid., 143 (1940). 4. WHITE AND PRICE: ibid., 115, 1462 (1OlO); White: ibid., 498 (1927). 5. SPENCE A ND TOWNEND: Rev. Inst. Franqais du P6trole, 4, 389 (1949). 6. SPENCE AND TOWNEND: Third SymlJoshmr on Combustion, Flame and Explosion Phenomena, p. 404. Baltimore, The Williams & Wilkins Co. (194'9). 7. CHAMBERLAI N AND WALSII: ibid., (a) 368, (b) 375 (1949). 8. CHAMBER LAIN AND WALSI I: Rev. Inst. Fram;ais du P6trole, 4, 301 (1949). 9. DOWNS, WALSlI AND WIIEE[ ER: Phil. Trans. Roy. Sot., A243, 463 (1951). 10. WALSH: Unpublished work. 1 l . SeENCE: Thesis, Leeds (1945). 12. JosT: Explosion and Com bustion Processes in Gases, p. 113. New York, McG raw-Hill Book Co. (1946). 13. MALHERBE ANt) WALSH: Trans. Faraday Soe., 4 6, (a) 824; (b) 835 (1950). 14. DAINTON AND NORRISIt: Proc. Ro y. Soc., A177, 393 (1941); see also Dainton: Trans. Faraday Soc., 3 8 , 227 (1942). 15. WALSH: Discussions Faraday Soc., No. 10, 320 (1951). 16. SMALL AND UBBELOHDE: (a) Nature, 16(?, 20 1 (1951); (b) J. Chem. Soc., 723 (1950). 17. PRETTRE: Ann. Com b. L iq., 1 1 , 669 (1936); ibid., 1 2 , 411 (1937). 18. PEASE: J. Amer. Chem. Soc., 5 1, 1839 (1929). 19. P~ETT~E: Acta Physicochim., 9, 581 (1938); Sci. Petroleum, 4, 2954 (1938). 5 6 SIMILARITY LAWS OF DEFLAGRATION B y F. SCHULTZ-GRUNOW The early theories of deflagration led to the folio wing equation for the burning velocity w,, : ( i , = f (0) (1) where a is the therm al diffusivity ira cm~ r is a characteristic reaction time, and the quan- tity ~b is a temperature ratio based on the con- cept of an ignition temperature. Later the concept of ignition occurring at some fixed temperature was eliminated (1) and r was expressed by func- tions based on more detailed considerations of reaction kinetics (2). These developments modified the parameter q~, but the form of equation 1 for the dimensionless representation of burning velocity was riot affected. However, it was not possible to explain all 9 xperimental results in terms of equation (1). No explanation could be given for the fact that flame velocities in mixtures diluted with argon and helium do not (lifter greatly although the thermal diffusivity of helium is nine times greater than that of argon and thus there should be a great difference according to equation (1). This has rightly been called by Jost (3) the experimentum crucis of the deflagration theory.

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S I M I L A R I T Y L A W S O F D E F L A G R A T I O N 4 3 0

F o r a m i x t u r e o f f ix e d c o m p o s i t i o n , t h i s re d u c e s t o

P t

F + G ( T ~ - - T o ) - k s

= A ( 7 ' ~ - 7 ' 0) + B ' P I

w h e r e t h e c o n s t a n t s F , G a n d B ' i n c re a s e w i t h i n -

c r e a s e o f i n e r t g a s c o n c e n t r a t i o n . I t f o l l o w s t h a t

P ~ i n c r e a s e s w i t h i n e r t g a s a d d i t i o n ; b u t t h a t t h e

i n c r e a s e w i l l b e l e ss t h e g r e a t e r T o , a s f o u n d e x -

p e r i m e n t a l l y .

T r e a t i n g e q u a t i o n 7 a s in ( a ) a n d r e m e m b e r -

h ag t h a t i n t h e e x p e r i m e n t a l w o r k P N / P ~ + 1 ) o o

w a s c o n s t a n t , i t c a n b e s h o w n t h a t P E ~ a n d

( P o : ) 0 s h o u l d b e i n c r e a s e d b y i n e r t g a s a d d i t i o n ,

a s f o u n d e x p e r i m e n t a l l y . R e m e m b e r i n g t o o t h a t

C e ; > > C N a n d t h a t , i n t h e e x p e r i m e n t a l w o r k ,

P x / P E i s ~ 1 , i t c a n be f u r t h e r s h o w n t h a t K

s h o u l d b e l i t t l e a f f e c t e d b y i n e r t g a s a d d i t i o n .

ACKNOWLEDGMENT

W e a r e g r a te f u l t o M e s s r s . R i c a r d o a n d C o .

f o r t h e d e s i g n a n d g i f t of t h e f i n e w i r e r e s i s t a n c e

t h e r m o m e t e r a n d f o r m u c h o t h e r g e n e r o u s h e l p .

R E F E R E N C E S

1. TOWNEND AND CHAMBERLAIN: Proc. Roy. Soc.,

A 1 5 8 , 415 (1937).2. HSlEH AND TOWNEND: J. Che m . Soe., 332, 337,

341 (1939).

3. ~IACCORMAC AND TOWNEND: ibid. , 143 (1940).

4. WH ITE AND PRICE: ibid. , 115, 1 4 62 (1 OlO) ; W h i te :

ibid. , 498 (1927).

5. SPENCE AND TOWNEND: R ev . In s t . F r an q a is d u

P6trole, 4, 389 (1949).

6. SPENCE AND TOWNEND: Third SymlJoshmr on

C o m b u s t i o n , F l a m e a n d E x p l o s i o n P h e n o m e n a ,

p . 4 0 4 . B a l t imo re , Th e Wil l iams & W ilk in s C o .

(194'9).

7. CHAMBERLAIN AND W AL SII: ibid. , (a) 368, (b) 375

(1949).

8. CHAMBERLAIN AND WALSII: R e v . I n s t . F r a m ; a i s

du P6trole, 4, 301 (1949).

9. DOWNS, WALSlI AND WIIEE[ER: Ph i l . Tran s . R o y .

So t . , A 2 4 3 , 463 (1951).

10 . WA LSH: Unp ublishe d w ork .

1 l . SeENCE: Thesis, Leeds (1945).

1 2. Jo sT : Ex p lo s io n an d C o m b u s t io n P ro cesses in

Gases , p . 1 1 3 . New Y o rk , McG raw -Hi l l B o o kCo. (1946).

13. MALHERBEANt) WALSH: Tran s . Far ad a y So e ., 46,

(a) 824; (b) 835 (1950).

14. DAINTON AND NOR RISIt: Proc . Ro y. Soc., A 1 7 7 ,

393 (1941) ; see also Dain ton: Trans . Faraday

Soc., 38 , 227 (1942).

15 . WA LSH: Discussions Fa rad ay Soc., N o. 10 , 320

(1951).

16. SMALL AND UBBELO HDE: (a) N a t u r e , 16(?, 20 1

(1951); (b) J. Chem. Soc., 723 (1950).

17 . PRETTRE: Ann. Com b. L iq . , 11, 669 (1936); ibid. ,

12, 411 (1937).18 . PEASE: J . A me r . Chem . Soc. , 51, 183 9 (1929).

1 9. P~ETT ~E: Ac ta Physicochim., 9, 581 (1938); Sci.

Petro leum , 4 , 2954 (1938).

5 6

S I M I L A R I T Y L A W S O F DEFLAGRATION

B y F . S C H U L T Z - G R U N O W

T h e e a r l y t h e o r ie s o f d e f l a g r a t i o n l e d t o t h e

f o li o w i n g e q u a t i o n f o r t h e b u r n i n g v e l o c i t y w ,, :

( i, = f (0) (1)

w h e r e a i s t h e t h e r m a l d i f f u s i v i t y ira c m ~

r i s a c h a r a c t e r i s t i c r e a c t i o n t i m e , a n d t h e q u a n -

t i t y ~b i s a t e m p e r a t u r e r a t i o b a s e d o n t h e c o n -

c e p t o f a n i g n i t io n t e m p e r a t u r e . L a t e r t h e c o n c e p t

o f i g n i t i o n o c c u r r i n g a t s o m e f i x e d t e m p e r a t u r ew a s e l i m i n a t e d ( 1 ) a n d r w a s e x p r e s s e d b y f u n c -

t i o n s b a s e d o n m o r e d e t a i l e d c o n s i d e r a t i o n s o f

r e a c t i o n k i n e t i c s ( 2) . T h e s e d e v e l o p m e n t s m o d i f i e d

t h e p a r a m e t e r q~, b u t t h e f o r m o f e q u a t i o n 1 f o r

t h e d i m e n s i o n l e s s r e p r e s e n t a t i o n o f b u r n i n g

v e l o c i t y w a s r i o t a f f e c te d .

H o w e v e r , i t w a s n o t p o s s i b l e t o e x p l a i n a l l

9 x p e r i m e n t a l r e s u l t s i n t e r m s o f e q u a t i o n ( 1) . N o

e x p l a n a t i o n c o u l d b e g i v e n f o r th e f a c t t h a t f l a m e

v e l o c i t i e s i n m i x t u r e s d i l u t e d w i t h a r g o n a n d

h e l i u m d o n o t (l if te r g r e a t l y a l t h o u g h t h e t h e r m a l

d i f f u s i v i t y o f h e l i u m i s n i n e t i m e s g r e a t e r t h a n

t h a t o f a r g o n a n d t h u s t h e r e s h o u l d b e a g r e a t

d i f fe r e n c e a c c o r d i n g t o e q u a t i o n ( 1) . T h i s h a s

r i g h t l y b e e n c a l l e d b y J o s t ( 3) t h e e x p e r i m e n t u m

cruc is o f t h e d e f l a g r a t i o n t h e o r y .

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4 4 0 L A M I N A R C O M B U S T I O N A N D D E T O N A T I O N W A V E S

I t c a n b e sh o w n t h a t e q u a t i o n ( i ) i s n o t c o m -

p l e t e a n d t h e r e f o r e c a n n o t b e a p p l ie d g e n e r a l l y t o

t h e d e t e r m i n a t i o n o f b u r n i n g v e l o c i ti e s , b e c a u s e

t h e d i m e n s i o n l e s s v e l o c i t y ~o = w , , V / ~ / / a i s no t a

f u n c t i o n o f a s i n g l e d i m e n s i o n l e s s g r o u p 4 , , b u t o fs e v e r a l . T h e s e g r o u p s c a n b e d e t e r m i n e d w i t h o u t

t h e u s u a l a s s u m p t i o n o f e q u a l i t y o f h e a t a n d

m a s s t r a n s fe r . T h e i g n i t i o n l i m i t s c a n a l s o b e

e x p r e s s e d i n t e r m s o f t h e s e g r o u p s .

W e w i l l n o t i n t r o d u c e h e r e t h e d i f f e r e n t ia l e q u a -

t i o n s g o v e r n i n g d e f l a g r a t i o n , a l t h o u g h t h i s l e a d s

t o t h e s a m e r e s u l t s. I n s t e a d , w e w i ll m a k e u s e of

t h e m e t h o d o f d i m e n s i o n a l a n a l y s i s. T h e u s u a l

r e s t r i c t i o n t h a t d i f f u s i o n a u d h e a t c o n d u c t i o n a r e

s i m i l a r w i l l n o t b e m a d e .

F o r s i m p l i c i t y , t h e p h y s i c a l a n d c h e m i c a l c o n -s t a n t s a r e a t p r e s e n t a s s u m e d t o b e i n d e p e n d e n t

o f te m p e r a t u r e . M o r e o v e r , a s i m p l e b i m o l e c u l a r

r e a c t i o n i s a s s u m e d .

A s d e f l a g r a ti o n is a n e f f ec t of h e a t c o n d u c t i v i t y ,

d i f f u s i o n a n d c h e m i c a l r e a c t i o n , t h e f o l l o w i n g

v a r i a b l e s o c c u r :

w ,, t h e b u r n i n g v e l o c i t y ( c m / s e c ) , w h i c h i s t o b e

d e t e r m i n e d

c~ t h e i n i t ia l c o n c e n t r g t i o n o f t h e f i r s t r e a c t a n t

( m o l / c m a)

c~ t h e i n i t ia l c o n c e n t r a t i o n o f t h e s e c o n d r e a c t a n t

( m o l / c m a)

X t h e t h e r m a l c o n d u c t i v i t y ( c a l / c m s e c ~

c p t h e s p e c i f ic h e a t ( c a l / g ~

-g t h e s p e c i f ic w e i g h t ( g / c m a)

D the d i f fu s ion coe f f i c i en t ( cm"- / sec)

q t h e h e a t l i b e r a t io n b y t h e c h e m i c a l r e a c t i o n

p e r m o l e ( c a l / m o l e )

k t h e v e l o c i t y c o e f fi c ie n t o f t h e r e a c t i o n a c c o r d -

ing t o dc l /d t = ] , ' c l c2

T h e f o l lo w i n g u n i ts w i l l b e u s e d :

~ f o r t e m p e r a t u r e T

s e c f o r t i m e !c m f o r l e n g t h l

c a l . f o r q u a n t i t y o f h e a t q

g f o r m a s s

S i n c e th e r e a c t i o n i s p o s t u l a t e d t o b e b i m o l e c u -

l a r , n o s t o i c h i o m e t r i c n u m b e r v o c c u rs . T h e r e a r e

n i n e v a r i a b l e s a n d f i v e u n i t s . I f t h e r e s u l t i s t o b e

i n d e p e n d e n t o f u n i t s, a l l t h e v a r i a b l e s m u s t o c c u r

a s p r o d u c t s i n th e f la m e p r o p a g a t i o n e q u a t i o n , a s

m u l t i p l i c a t i o n a n d d i v i s i o n a r e t h e o n l y p r o c e s s e s

b y w h i c h d i m e n s i o n l e s s g r o u p s a r e o b t a i n e d . T h e r e

e x i s t s a c e r t a i n n u m b e r o f d i m e n s i o n l e s s g r o u p s o f

v a r i a b l e s . T h i s n u m b e r i s t h e d i f f e r e n c e b e t w e e n

t h e n u m b e r o f v a r i a b l e s a n d t h e n u m b e r o f u n i t s .

A c c o r d i n g l y , i n s t e a d o f t h e t w o d i m e n s i o n l e s s

g r o u p s i n e q u a t i o n ( 1 ) , t h e r e a r e f o u r , a n d t h e

m o s t g e n e r a l e x p r e s s i o n f o r f l a m e p r o p a g a t i o n

m u s t h a v e t h e f o r m

~0 = f ( 4 , , , 4 , " - , 4 , 3 ) . ( 2 )

T h e t e r m o ) s h o u l d b e s o d e f in e d t h a t i t c o n t a i n s

t h e b u r n i n g v e l o c i t y w , l i n e a r l y s i n c e w , i s t h e

q u a n t i t y t o b e d e t e r m i n e d . S u c h e x p r e s s i o n f o r r

i s a l r e a d y g i v e n i n e q u a t i o n ( 1 ) , if r i s r e p l a c e d b y

t h e q u a n t i t y 1 / k C l o r 1//,'c,. w h i c h h a s t h e s a m e

d i m e n s i o n . F u r t h e r m o r e , f o r t h e t h e r m a l d i f f u -

s i v i t y , a = k / c ~ , , o n e m a y s u b s t i t u t e t h e d i ff u s io n

c o e f f i c ie n t D , s o t h a t s e v e r a l s u i t a b l e d e f i n i t i o n s

o f t h e d i m e n s i o n l e s s b u r n i n g v e l o c i t y a r e p o s s i b l e .

W e c h o os e

~// )n

( ) n e o f t h e d i m e n s i o n l e s s g r o u p s m u s t c o n t a i n

t h e h e a t o f r e a c t i o n q . T h e m o s t c o n v e n i e n t t h e

e x p r e s s i o n i s

q c l4,1 --

T c v ' g '

w h e r e T c a n b e t h e t c m p e r a t u r e o f t h e u n b u r n e d

g a s .

A n o t h e r i m p o r t a n t e x p r e s s i o n f o r 4,1 c a n b eg i v e n b y i n t r o d u c i n g t h e e q u a t i o n o f s t a t e :

q R c ~4,l =

p c p

w h i c h g i v e s t h e i n f l u e n c e o f p r e s s u r e o n f l a m e

p r o p a g a t i o n .

T h e s e c o n d d i m e n s i o n l e s s g r o u p 4,"- i s t h e

S c h m i d t n u m b e r :

D c p ' l D4 , 2 - -

X a "

T h e t h i r d g r o u p 4 ,3 m a y r e p r e s e n t t h e r e l a t i v e

c o n c e n t r a t i o n o f t h e r e a c t a n t s :

C 1

C 2q

F o r o t h e r o r d e r s o f r e a c t i o n , t h e s t o i c h i o m e t r i c

n u m b e r v b e i n g i t s e l f d i m e n s i o n l e s s o c c u r s a s t h e

f o u r t h d i m e n s i o n l e s s g r o u p :

4 , 4 ~ / 2 .

T h e f u n c t i o n f ( ~ l , 4 ,2 , 4 , a, " - - ) i ts e l f w o u l dh a v e t o be d e t e r m i n e d e i t h e r t h e o r e ti c a l l y o r

e x p e r i m e n t a l l y . I t m a y b e n o t e d , h o w e v e r , t h a t

d i m e n s i o n a l a n a l y s i s p r o v i d e s a n a d v a n t a g e i n a s -

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S I M I L A R I T Y L A W S O F D E F L A G R A T I O N 4 - t l

n m c h a s t h e r e ar e n o w o n l y t h re e i n d e p e n d e n t

p a r a m e t e r s , n a m e l y r r q53. M o r e o v e r , a

g e n e r a l d i s c u s s i o n of e x p e r i m e n t a l d a t a i s n o w

p o s s i b l e s i n c e fo r d i f fe r e n t c a s e s t h e d i m e n s i o n l e s s

b u r n i n g v e l o c i t y 60 is t h e s a m e if t h e g r o u p s h a v e

t h e s a m e v a l u es , e v en t h o u g h t h e i n d i v id u a l

v a r i a b l e s a r e d i ff e r en t . F o r e x a m p l e , t h e e x p r e s -

t h o s e i n c a s e tw o . ( ) t h e r w i s e n o d i m e n s i o n l e s s

r e l a ti o n c o u l d ho M . T h e s a m e r e s u h c a n b e d e-

r i v e d f ro m t h e d i ff e r e n t i a l e q u a t i o n s f or hu'at

c o n d u c t i o n a n d d i f f u s io n . T h i s s h o w s t h a i ( ' q U a -

t i o n ( 2 ) is t h e s i m i l a r i t y h t w f o r l l a m e p r o t )a ~ a t i, ~ n .

" Fo p r . v e t h e s e c o n s i d e r a t i o n s , J a h n ' s ( 4 ) c x l) c ri

m e r i t s o n h y d r o g e n a n(1 - x y g c n , m i x e d x vi lh

N , i C O. . O~! _

per p e r [ p e rc e n t : c e ~ t i c e n t

75 _ i 25

50 --50

8 2 . 5 - - 1 7 . 5

85 15

8 2 . 5 1 7 . 5

85 15

75 25

5 0 5 0

8 7 . 5 1 2 . 5

6 0 4 0

6 5 3 5

- - ~ i 1 00

1 . 5 9 8 . 5

H 2

p e rc e n t

5 0 0 . 3 4 5 0 . 8 3 3 0 . 1 8 9 0 . 6 5 6 1 4 . o 7 . 7

6 0 0 . 3 5 4 0 . 8 1 0 0 . 2 0 5 0 . 7 2 5 1 6 .7 1 3 . o

4 0 0 . 3 2 9 0 . 8 7 5 0 . 1 7 0 0 . 5 9 0 1 2 . 8 5 . 5

3 5 0 . 3 1 7 0 . 9 2 2 0 . 1 6 1 0 . 5 5 0 1 1 . 6 5 . 6

2 6 0 . 2 9 8 0 . 9 6 5 0 . 1 4 1 0 . 4 8 9 9 . 2 6 . 2

2 3 . 1 0 . 2 9 4 0 . 9 8 2 0 . 1 3 3 0 . 5 4 5 8 . 4 5 . 4

3 3 . 3 0 . 3 1 2 0 . 9 2 8 0 . 1 5 7 0 . 5 4 4 1 1 .2 8 . 4

5 0 0 . 3 3 4 0 . 8 6 1 0 . 1 89 0 . 6 5 7 1 4 , 9 1 4 . 9

0 . 3 1 2 0 . 9 2 6 0 . 1 5 2 0 . 5 2 6 1 0 .6 4 . 3

4 0 0 . 3 1 9 0 . 9 0 3 0 . 1 7 l 0 . 5 94 1 2 ,8 1 2 . 8

3 5 0 . 3 1 0 0 . 9 2 8 0 . 1 6 1 0 . 5 6 0 1 1 . 6 1 1 . 6

2 0 0 . 2 5 7 1 . 12 2 0 . 1 2 6 0 . 4 3 6 7 . 4 4 3 7 . 2

1 3 0 . 2 4 4 1 . 1 8 7 0 . 1 0 6 0 . 3 6 7 5 . 1 4 3 9 . 0

T A B L E 1

D i m e n s i o n l e s s q u a n t i l i e s o J, q h , q~.,- , t a k e n f r o m J a h n ' s e x p e r i m e n t s

ep 3 ' ~ - a e l l 2 103 CO. 103 ~ t 'n r

* N o t p l o t t e d .

t O O ~ l ~ 2 ~ :~

3 . 2 4 4 . 9 5 . 1 5

5 . 9 5 9 . 2 5. 9 1

2 . 0 3 4 . 8 1 4 . 4 3

1 . 6 2 8 . 1 : 3 . 9 7

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T A B L E 2

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0 . 2 0 3 0 . 6 6 9 1 7 . 3 1 3 , 6

0 . 1 7 1 0 . 5 2 5 1 4 . 3 . 6 , 4

0 . 1 8 2 0 . 5 8 6 1 4 . 8 1 4 . 8

0 . 1 8 0 0 , 5 7 1 4 , 9 1 1 .90 . 1 6 1 0 . 5 1 1 2 . 7 1 2 , 7

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s i o n s o f 4~t s h o w t h a t t h e i n f l u e n ce o f t e m p e r a t u r e

o n p r e s s u r e c a n b e c o m p e n s a t e d b y c o n c e n t r a t i o n

a n d t h a t i t is p o s s ib l e t o in d i c a t e t h e i n f l u e n c e o f

p r e s s u r e w i t h o u t f u r t h e r e x p e r i m e n t s i f t h e i n f lu -

e n c e o f t e m p e r a t u r e is d e t e r m i n e d .

I f in t w o d i f fe r e n t c a s e s t h e c o r r e s p o n d i n gd i m e n s i o n l e s s g r o u p s h a v e t h e s a m e v a l u e s , t h e

d i s t r i b u t i o n s o f t e m p e r a t u r e a n d o f c o n c e n t r a t i o n

i n t h e f l a m e f r o n t i n c as e o n e m u s t b e s i m i l a r t o

n i t r o g e n o r w i t h c a r b o n d i o x i d e a s in e r t g a s e s ,

w e r e p l o t t e d i n t h e d i m e n s i o n l e s s fo r r n c o r r e s p o n d -

i n g t o e q u a t i o n ( 2 ) , i . e . t h e d i m e n s i o n l e s s v e l o c i ty

r w a s p l o t t e d a g a i n s t th e d i m e n s i o n l e s s q u a n t i t y

q~l f o r s e l e c t e d e x p e r i m e n t s i n w h i c h ~b2 a n d (#~

w e r e m o r e o r le s s c o n s t a n t . I f o u r t h e o r y i s c o r -r e c t , a ll t h e s e e x p e r i m e n t s w i l l l ie a l o n g a s i n g l e

c u r v e , i r r e sp e c t i v e o f t h e i n e r t g a s u s e d .

T h e r e a c t i on o f o x y g e n a n d h y d r o g e n w a s

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4 4 2 L A M I N A R C O M B U S T I O N A N D D E T O N A T I O N W A V F S

c h o s e n a s it s m e c h a n i s m i s t h e b e s t k n o w n ( 5 ).

A l t h o u g h i t is n o t a s i m p l e s e c o n d - o r d e r r e a c t i o n ,

i t m a y b e e x p r e s s e d a s

, ~ ( n _ ~ ) = t , . ( H . , ) ( O 2 ) , ( 3 )d t

w h e r e ( H e ) , ( O ~ ) s t a n d s f o r e l , o .,. T a b l e s 1 a n d 2

g i v e th e e x p e r i m e n t a l d a t a a n d t h e c a l c u l a t e d

d i m e n s i o n l e s s q u a n t i t i e s oa, ~ b ~, ~ b2 , O a . W i d e l y

d e v i a t i n g v a l u e s o f ~ b2 , ~ b a , w e r e n o t p l o t t e d .

H o w e v e r , e v e n t h e v a l u e s re t a i n e d s h o w d e v i a t i o n s

i n ~ b 2, q ~ a , s o t h a t a n e x a c t e x p e r i m e n t a l c u r v e i s

n o t t o b e e x p e c t e d ( f i g . I ) . N e v e r t h e l e s s , t a k i n g

i 5 o

zo

,o

o

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~j, g

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l e s s g r o u p ~ b. L e t u s c o n s i d e r a m i x t u r e o f a g i v e n

c o m b u s ti b le g a s I f o r e x a m p le , m e t h a n e - - a t c o n -

s t a n t c o n c e n t r a t i o n w i t h a n i n e r t g a s , sp e c i f ic a l l y

h e l i u m o r a r g o n. H e l i u m a n d a r g o n h a v e t h e s a m e

h e a t c a p a c i t i e s c p s, , b u t t h e d i f f u s i o n c o e f f i c i e n t o fm e t h a n e i s t h r e e t i m e s g r e a t e r in h e l i u m t h a n i n

a r g o n a n d t h e t h e r m a l d i f f u s i v i t y o f h e l i u m i s n i n e

t i m e s g r e a t e r t h a n t h a t o f a r g o n. C o n s e q u e n t l y ,

w h e n a r g o n i s re p l a c e d b y h e l i u m , i f2 b e c o m e s

t h r e e t i m e s s m a l le r . E x p e r i m e n t a l l y w e k n o w t h a t

t h e a b s o l u t e b u r n i n g v e l o c i t y w ,, i s v i r t u a l l y t h e

s a m e i n b o t h c a s e s , a n d h e n c e t h e d i m e n s i o n l e s s

b u r n i n g v e l o c i t y w v a r i e s p r o p o r t i o n a t e l y t o ~b2.

C o n c e r n i n g t h e e f f e c t o f t e m p e r a t u r e i t i s n o t e d

t h a t a s l o n g a s t h e s p e c if i c h e a t c ,, m a y b e c o n -

s i de r e d c o n s t a n t t h e t e m p e r a t u r e d e p e n d e n c e o f

t h e v a r i o u s p h y s i c a l c o n s t a n t s d o e s n o t e n t e r i n t o

t h e s i m i l a r i t y l a w e x c e p t f o r t h e r e a c t i o n v e l o c i t y

c o e f fi c i e nt k . A s r e g a r d s t h e i n f l u e n c e of t e m p e r a -

t u r e o n t h e l a t t e r c o e f f i c i e n t , d e f i n e d a s

] : = ] e 0 e A / n T

t h e c o n s t a n t k i n w b e c o m e s k o a n d a f i f t h d i m e n -

s i o n l e s s q u a n t i t y r e s u l t s :

~ 5 = e - A / R T .

T A B L E 3

D i m e n s i o n l e s s u p p e r l i m i t ~ l i g n i ti o n ~ o f s ~ 'e r a l b u r n i n g g a s es i n a i r a n d d i m e n s i o n l e s s p a r a m e l e r s ~ ., , ~ a

. . . . . ' - ~ I ! I

A b s . l i m i t v o l . i i i i X D f I ~ ~ ai n a i r * c ~ . . . ii c ~ = [ 0 2 ] " ~ o2 , c ~ , q T a [ _

. . . . . . . . i . . . . . i

p e r c e n t ] l

6 9 H2 0 .0 1 8 0 3 0 .0 0 5 5 8 0 .7 5 2 0 .3 8 2 5 7 70 0 1 2 9 3 ] 0 .2 1 7 5 0 .7 6 0 0 .7 5 4 1 2 .2 8 1 1 .0 1 3 .2 3 5

71 CO 0 .0185 .. 0 .00547 1 189 0 .2 4Y 67600 293 ! 0 .0585 0 .211 0 .201 14 .65 ~ 1.05 3 .375

15 CH , 0 .0 05 83 1 0 .0081 5 1 .136 1 0 .2511 191700 . 293[ 0 .063,5 12 .92 0 .691

28 .6 C. ,,H~ 0 .01 0 .007 28 1 .2 ] 0 .26 4 321000 2931 0 .05 75i( 0 .14 5 i(0 .182)! 34 . ,50 (0 .794 ) 1 .373

~2 .4 C eH ~, 0 .0 0 4 9 5 1 0 .0 0 8 3 3 1 .2 1 2 0 .2 5 7 3 '4 4 00 0 2 9 3 0 .0 5 9 6 ' i 1 8 .0 8 0 .5 9 4.: J . . . . . . . ~ ~ . . . . .

* W. Jo s t , Ex p lo s io n s u n d V erb ren n u n g sv n rg g n g e in Gasen , p p . 1 2 9 , 1 3 0 . B er l in (1 93 9 ).

Th e p aren th es ized v a lu es p ro b ab ly 2 5 p er cen t to o h ig h .

i n t o a c c o u n t a l l u n c e r t a i n t i e s i l l t h e m e t h o d o f

m e a s u r e m e n t a n d i n t h e v a l u e s o f t h e p h y s i c a l

c o n s t a n t s , i t w i l l b e s e e n t h a t t h e e x p e r i m e n t a l

d a t a l i e f a i r l y c l o s e t o a s i n g l e c u r v e .

T h e d i s c u s s i o n o f t h e e x p e r i m e n t u m c r u c i s m e n -

t i o n e d a b o v e c a l l n o w b e g i v e n i l l t h e f o l l o w i n g

w a y . S i n c e o n l y t h e t h e r m a l d i f f u s i v i t y is c h a n g e d ,

f ( d p ) i n e q u a t i o n 1 r e m a i n s c o n s t a n t a n d h e n c e

e q u a t i o n 1 p r e d i c t s t h a t t h e d i m e n s i o n l e s s b u r n i n g

v e l o c i t y c0 s h o u l d r e m a i n c o n s t a n t . N o w t h e e x -

p e r i m e n t s h o w s t h a t t h i s is n o t t h e c a s e , a n d

m o r e o v e r o u r d is c u s s i o n h a s s h o w n t h a t t h e r e

e x i s t s a d e p e n d e n c e o n m o r e t h a n o n e d i m e n s i o n -

A l l t h e s e l e c t e d e x p e r i m e n t s i n t a b l e s 1 a n d 2

l ie b e n e a t h t h e m a x i m u m b u r n i n g v e l o c i t y a s i t i s

o n l y i n t h i s r e g i o n t h a t t h e c o n c e n t r a t i o n o f

h y d r o g e n m a y b e c o n s i d e r e d s m a l l e n o u g h f o r

e q u a t i o n (3 ) t o a p p l y . A c c o r d i n g l y , i n fi g u r e 1 t h e

i n t e r s e c t i o n w i t h t h e a b s c i s s a g i v e s t h e l o w e r

i n f l a m m a b i l i t y l i m i t . I t w i l l b e s e e n t h a t t h i s l i m i t

a n d c o r r e s p o n d i n g l y a l so t h e u p p e r i n f l a m m a b i l i t y

l i m i t a re r e p r e s e n t e d b y t h e f u n c t i o n

~, = f ( ~ , . , , ~ 3 ) .

I t i s u s u a l t o e x p r e s s t h e i n f l a m m a b i l i t y l i m i t s

i n v o l u m e p e r c e n t. T h e r e f o r e t h e d i m e n s i o n l e ss

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A E R O D Y N A M I C F I E L D O F S T A B I L IZ E D F L A M E S 4 4 3

q u a n t i t y 4 ~ c a n t i e d e f i n e d d i r e c t l y f o r t h e c a s e

w h e r e ~o = 0 a s t he d i me ns i on l e s s e xp r e s s i on o f

t h e i g n i t i o n l i m i t

T h e r e e x i s t t w o v a l u e s , ~ ,, a n d ~ t , i n d i c a t i n g t h e

u p p e r a n d l o w e r l im i t . T h e g e n e r a l la w o f e a c h o f

t h e s e l i m i t s h a s t h e f o r m

= f ( , ~ , ~ ) (4 )

T a b l e 3 g i v e s l h e c o n v e r s i o n o f s e v e r a l e x p e r i -

m e n t a l v a l u e s ( 6 ) f o r u p p e r l i m i t s t o d i m e n s i o n l e s s

g r o u p s . T h e t a b l e s h o w s t h e i n t e r e s t i n g f a c t t h a t

t h e d i m e n s i o n l e s s l i m i t s o f m o s t g a s e s d o n o t

d i ff e r m u c h . A s t h i s h o l d s a l s o fo r t h e h e a t c a p a c i t y

c p3 ' t h i s r e s u l t a g r e e s w i t h a n e a r l ie r s t a t e m e n t b y

B u r g e s s a n d W h e e l e r ( 6) t h a t i n m a n y c a se s t h e

l o w e r i n f l a m m a b i l i t y l i m i t ( v o l u m e p e r c e n t )

m u l t i p l i e d w i t h t h e h e a t o f r e a c t i o n is a p p r o x i -

m a t e l y a c o n s t a n t . T h i s p r o d u c t i s th e n u m e r a -

t o r i n t he e x p r e s s i on f o r ~ b, , a n d c pyT i s the

d e n o m i n a t o r , T h a v i n g t h e s a m e v a l u e i n a l l

cases .

A n o t h e r i n t e r e s ti n g o b s e r v a t i o n i s th a t , a c c o rd -

i n g t o e q u a t i o n ( 4 ), t h e i n f l a m m a b i l i t y l i m i t s d o

n o t d e p e n d o n t h e r e a c t i o n m e c h a n i s n l . M or e ove r -

t h e c o n v e r s i o n f r o m t e m p e r a t u r e t o p r e s su r e h o l d s

a ls o i n t h e c a se o f i n f l a m m a b i l i t y li m i t s .

A d i f fe r e n t ig n i t i o n p r o b l e m , n a m e l y , t h a t o f

s p a r k i g n i t i o n , w a s t r e a t e d r e c e n t l y b y J o s t ( 7 ).H e r e t h e s p a r k i s t h e i n i t i a l h e a t s o u r c e . S u l >

s e q u e n t l y t h e s p a r k d i s a p p e a r s a n d t h e o n l y re -

m a i n i n g h e a t s o u r c e i s t h e c h e m i c a l r e a c t io n , s o

t h a t t h e a b o v e c o n s i d e r a t i o n s w i l l h o l d .

T h i s s h o w s t h e a d v a n t a g e s t o b e e x p e c t e d f r o m

t h e f u t u r e u s e o f t h e a b o v e d i m e n s i o n l e s s t r e a t -

m e n t i n t h e s t u d y o f d e f la g r a t io n p h e n o m e n a .

R E F E R E N C E S

1. LE w~ s, B., AND VON ELBE, G.: J ' . Chem. Phys . ,

2, 537 (1934).

2. Z E L D O W I T C H , J . , A N D F R A N K - K A M E N E T Z K I , D . :

Acta P hys . C hem. U .R .S .S . , 9, 341 (1938).

3 . j 'OST, W . : Explos ions un d Verb rennu ngsvo rg/ inge n

Gasen, p. 108. Berl in (1939).

4. J A H N , G.: Die Theor ie der Zt indgeschwindigke i t .

Dis s . Kar l s ruhe (1934) .

5. YON ELBE, G. AND LEW IS, B.: J . Chem . Ph ys . , 10 ,366 (1942).

6 . J 'OST, W . : Explos ions un d V erbrennungsvorg~inge n

Gasen, pp. 129-130. Berl in (1939).

7 . JosT, W. : Ze i tschr . f . Phy. Chem . , 196, 4, 298 (1950).

57

O N T H E A E R O D Y N A M I C F I E L D O F S T A B I L I Z E D F L A M E S

B y J . F A B R I , 1 R . S I E S T R U N C K 2 AND C. FOURF,a

1 . I N T R O D U C T I O N

T h e t w o - d i m e n s i o n a l f lo w o f a h o m o g e n e o u s

c o m b u s t i b l e ga s i n a c o n s t a n t s e c t io n d u c t is

c o n s i d e r e d . A f la m e , m a i n t a i n e d i n t h e w a k e o f a

s t a b i l i z e r , e x t e n d s d o w n s t r e a m o f t h i s s t a b i l i z e r a

f r o n t, w h i c h i s s y m m e t r ic a l , s t a ti o n a r y a n d n e a r l y

pa r a l l e l t o t he a x i s o f t he duc t ( f i g . 1 ) . T he s ha pe

a n d d i m e n s i o n s o f th e s t a b i l i z e r d o n o t a f f e c t

a p p r e c i a b l y t h e a e r o t h e r m o d y n a m i c a l f i e ld , p r o -

v i d e d t h a t f l a m e s t a b i l i t y i s a s s u r e d . A c c o r d i n g l y ,

s t a b i l i z a t i o n p a r a m e t e r s w i l l b e n e g l e c t e d i n s u c h

a w a y a s t o r e t a i n o n l y t h o s e c o n c e r n i n g fl a m e

l I ng6n i e u r C i v i l des M i ne s , G r oupe d ' A 6r ody-n a m i q u e I n t e r n e .

D r . S c. , C he f du G r oupe d ' A ~ r odyna m i que I n t e r ne .a I ng6n i e u r C i v i l de s M i ne s , G r oupe de C oml m s t ion .

p r o p a g a t i o n , i.e. m a i n l y t h e v e l o c i t y o f th e u n i f o r m

u p s t r e a m f lo w , th e c o m p o s i t io n o f t h e c o m b u s t i b l em i x t u r e a n d t h e c o m b u s t i o n f r o n t v e lo c i ty . T h e

f l a m e s t a b il i z e r i s a s s u m e d t o b e a l i n e a r b o d y a n d

i t s t r a c e o n t h e p l a n e o f f l o w i s t a k e n a s o r i g i n o f

t h e c o o r d i n a t e s .

I t w i l l b e a s s u m e d , a l s o , a s i s u s u a l i n e l e m e n t a r y

s t u d ie s o f c o m b u s t i o n c h a m b e r s , t h a t t h e s a m e

e q u a t i o n o f s t a t e a p p li e s t o l m r n e d a n d u n b u r n e d

ga s e s , w hos e s pe c i fi c he a t s a r e a s s um e d t o be i n -

d e p e n d e n t of t e m p e r a t u r e a n d m i x t u r e c o m p o s i-

t i o n . T h e s t a t i o n a r y f l a m e f r o n t i s a l s o c o n s i d e r e d

a s a l in e of d i s c o n t i n u i t y f o r t h e t h e r m o d y n a m i c a l

a n d a e r o d y n a m i c a l d a t a o f t h e f lo w , c o m b u s t i o n

i ts e lf b e i n g r e p l a c e d b y a s i m p l e d i s c o n t i n u i t y of

t h e t o t a l e n t h a l p y o f t h e f l o w . T h e r m a l c o n d u c -