40

IGNITION OF EXPLOSIVE GAS MIXTURES BY ELECTRIC SPARKS III. M i n i m u m Ignition Energies and Q u e n c h i n g Distances of Mixtures of Hydrocarbons and Ether with Oxygen and Inert Gases
By M. V. BLANC,~P. G. GUESTfl GUENTHER VON ELBEfl ANDBERNARD LEWIS4
In a previous paper, 5 minimum energies for igniting mixtures of methane, oxygen, and inert gases were reported, using capacitor discharge sparks. The study has been continued for a number of other hydrocarbon gases, with various oxygen-nitrogen atmospheres; and for diethyl ether, with oxygen-nitrogen and oxygen-helium atmospheres. isolated from the charging source, electricity is delivered to the high-voltage terminal of the bomb through a bakelite ro& placed between points (a) and (b) as shown. When conditions for a test are satisfactory, no perceptible movement of the voltmeter pointer is observed until a spark occurs; then a slight pulse is noted. When working with very small capacitances of a few micro-micro farads a miniature electroscope is mounted on the terminal to assist in observing the occurrence of a spark. In ignition tests requiring, large capacitance, (a) and (b) are connected by a copper con-

APPARATUS AND TECHNIQUE

The apparatus and technique employed in carrying out the experiments are essentially the same as described previously,s,6 except that some improvements have been made in the construction of spark terminals and low-capacity high-voltage condensers. For the mo~t part, the rotary charger employed in former tests has been replaced by a resistor of the order of 10" ohms, as it has been found that the transfer of charge from the power unit to the spark circuit can be accomplished very satisfactorily by this means. When working with small capacitances up to about I00 micro-micro farads, the large capacitors, totaling about 4500 micro-micro farads, and the static voltmeter are connected in parallel and used as a reservoir (fig. l). From this reservoir, charged to a constant known potential and then

~!10 volts a.c.

Input Output I power unit I Static 'voltmeter

'k]--i i +0-~ 30 kilovolt T d.c./ T.~ esistor Large air capacitors arid voltmeter used as reservoir

Protective+
Electroscope

rod and extension capacitors

Srnall ~

ball f

"-"~e

"-~" ~

o,,.gecoo

t Scientific Aide, Physical Chemistry and Physics Section, Explosives Branch, Bureau of Mines, Pittsburgh, Pa. FIG. 1. Apparatus arranged for spark circuits of very Electrical Engineer, Physical Chemistry and Physics Section, Explosives Branch, Bureau of Mines, low capacitance. Pittsburgh, Pa. SSupervising Chemist, Physical Chemistry and ductor and the bakelite rod is placed in the circuit Physics Section, Explosives Branch, Bureau of Mines, at location (cd). When this high-resistance Pittsburgh, Pa. Physical Chemist, Chief, Explosives Branch, method of charging is used, fine adjustment of Bureau of Mines, Pittsburgh, Pa. the voltage at (b) is accomplished at the power This research is part of the work being done at the U. S. Bureau of Mines on Project No. NA onr 25-47, unit by" means of an auxiliary voltage control supported by the Office of Naval Research and Army conveniently placed. Air Forces. The energy required for igniting mixtures rich M. V. Blanc, P. G. Guest, Guenther yon Elbe, and in oxygen is very small. To obtain sparks of the Bernard Lewis: J. Chem. Phys., 15, 798 (1947). 6p. G. Guest, U. S. Bureau of Mines, R. I. 3753 7Laminated paper rod impregnated with bakelite. 0944). 363

,oa' .dao @ G

i i i

- "

'

:-~

t.

.01

i ~ ,~ .......
.001

~
'1 I .

'

. . . . .

0 5 At

" )

0.33 At m

:'."

'

'

' -~F~

k-A--q

11/)

,a_~

~'~,d= + g - ~-~ # + ~ A : : ~ : L ~ - _

E T H A N E P ,E R C E N T Fi6. 2. Minimumsparkignitionenergiesin millijoulesof mixturesof ethane,oxygenandnitrogenat oneatmosphere and lower pressure. C u r v e s c o r r e s p o n d to c o n s t a I l t r a t i o s of o x y g e n a n d n i t r o g e n . Also, a p p r o x i m a t e
q u e n c h i n g d i s t a n c e s in c e n t i m e t e r s b e t w e e n p a r a l l e l p l a t e s for the s a m e m i x t u r e s . 10
-:~ _ ~ -

-01[ i i I I J t, ~ t 0 10 20 30 40 50

! 1At

10

20

30

40

50

10

20

30

40

SO

10

20

30

40

50

1111t II,t-_t_-I

1.0

~ii

~ ~ ~ ~. ~ i-t:~ ~ / ~ . l / ~ / ~

>. ~

~,

--i .I
9 o _ _

.01

.OOI~ !

),-o~

_z~
"~z

t7!
.01 0

~
10 20 30 40 50 ~ 0

I
10 20

o.s^t

o,aa~t

o.a

30

40

50

10

20

30

40- SO " 0

10

20

30

40

SO Also,

Fro. 3. M i n i m u m s p a r k i g n i t i o n energies in millijoules of m i x t u r e s of p r o p a n e , o x y g e n a n d n i t r o g e n . a p p r o x i m a t e q u e n c h i n g d i s t a n c e s in c e n t i m e t e r s b e t w e e n parallel p l a t e s for the s a m e m i x t u r e s . 364

I G N I T I O N OF GAS M I X T U R E S

365

required low energy, terminal system (e) was constructed. The smallest capacitance member used is that of the spark electrode itself and the stud into which it is threaded. This stud is cemented to the q~tartz tube to form a gastight seal. It is nonadjustable, and the gap distance can be

Gas mixtures are made by the partial-pressure method after the bomb has been thoroughly evacuated and dried of previous combustion prodtlcts. Often in tests with rich mixtures of the heavier hydrocarbons it is necessary to clean the electrodes and insulation of sooty deposits after each

-J 0 "~ >: 4 tw ,,~ 3

Z

0.2

0.4

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 FRACTION OF STOICHIOMETRIC PERCENTAGEOF COMBUSTIBLE IN AIR

3.2 3.4

=E
1 .8 .6 .5 .4 .3 .2

.1 0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0 2.5 FRACTION OF STOICHIOMETRIC PERCENTAGEOF COMBUSTIBLE IN AIR

i 3.0 3.5

%;-

FIG. 4. Minimum ignition energies of combustible-air mixtures in relation to the stoichiometric percentage n air. i measured only at the other terminal which carries a long conducting rod and packing gland, as depicted at (f). The cemented stud is threaded also at the other end, and small threaded metal sections of one or more micro-micro farad capacitance can be added. The largest section terminates in a 89 ball at (b). lTrom here the capacitance can be built up by adding vertical sections, each of about 1 micro-micro farad, until these can be replaced by the long inner rod of a vertical cylindrical condenser, ignition, and the bomb itself has to be cleaned frequently. RESULTS Figure 2 shows families of curves of minimum ignition energies and quenching distances for ~ ethane mixtures. These curves are very similar to those previously obtained for methane, although they exhibit the narrower inflammability limits found with the higher hydrocarbons. As before, the energy required for ignition decreases with

366

TttIRD

SYMPOSIUM

ON COI~IBUSTION~ F L A M E

AND EXPLOSION

PHENOMENA

increasing oxygen content in the atmosphere and and cyclopropane have been cited in the literature with increasing initial pressure. It is noted that, and the use of helium is being considered in a at the minima of the curves, about 1/I00 as much growing number of hospitals. As mentioned, the energy is required to ignite oxyge n mixtures as air lowest energies for ether-air and cyclopropane-air mixtures. Experimental points are shown on mixtures are virtually identical, and they are these curves to illustrate the consistency of data located at nearly the same position with respect obtained. Each energy point represents the to the stoichiometric mixture (figure4). lowest value obtained in any series of tests for a Figure 5 is a comparison of ether in air and in given mixture. The quenching distance curves helium atmospheres containing a similar amount are similar also to the methane curves. of oxygen. The effect of helium is to raise the Figure 3 shows families of curves obtained for required energy for ignition very Considerably and propane. The curves follow the same pattern as to narrow the inflammation limits in the vicinmethane and ethane. For convenience the actual ity of easiest ignitability. experimental points are not included. 2o] L Consistent data are increasingly difficult to I obtain as hydrocarbons of larger molecular size are employed. Not only is contamination of elec10 L I 020 o .0791.el, t , trodes, insulation and bomb more troublesome, 8 t I but the quenching distances are less clearly deI fined in that the curves of minimum ignition energy ] versus electrode distance do not turn up as abruptly as for methane mixtures. At present it seems S o3 unprofitable to make such detailed studies of paraffin hydrocarbons higher than propane. i 2 f ~j/ It is noted from the curves in the upper l~art of 5 figure 4 that, in the homologous series of paraffins, the minimum energies shift toward the rich side 1 with increasing number of carbon atoms. The i ; (0.209 02 0.~91 N21~-9 3.8 abscissa of the curves is the ratio of the percentage .~.6 E T of combustible in the mixture to the stoichio.5 I : .4 metric percentage; the positions of the minima are indicated. The results in the lower part of i l figure 4 show that there is little differences bei i tween paraffins and other compounds of equal I i ; number of carbon atoms. For example, the energy values for hexane, cyclohexane and benzene .1 are virtually the same. Even the differences be2 0 4 6 8 10 DIETHyL ETHER, PERCENT tween butane and diethyl-ether and propane and p~,. ~4o ~o cyclopropane are small. It is also of interest to FIG. 5. Minimum ignition energies at one atmosphere note that in the paraffin series the minima of the for diethyl ether-air mixtures and for mixtures in which curves are practically identical, the spread being helium is substituted for nitrogen. from 0.23 to 0.28 e millijoules. Similarly, the effect Some work has been started on a family of curves of molecular structure is small. There is considerable current interest in the for ether-oxygen-nitrogen and ether-oxygen-helium hazards of explosions of anesthetic gas in hospital mixtures. The violence of explosions in the richer oxygen mixtures requires modification in the operating rooms. Experiments have been started to determine minimum ignition energies for several equipment for continuation of the studies. For 1 of the gases employed, particularly diethyl-ether atmosphere initial pressure and up to 67 percent and cyclopropane in the usual anesthetic mixture oxygen in the oxygen-nitrogen atmosphere, the range. The advantages of the use of helium in- lowest minimum energies for ether are closely the stead of nitrogen in the administration of ether same as for paraffin hydrocarbons. A tentative lowest minimum value for a 50-50 oxygen-nitrogen s More refined methods of measurement have shifted atmosphere is 0.01-millijoule; for a 50-50 oxygenthe methane-air curve to somewhat lower values than were previously reported (footnote 5). helium atmosphere it is 0.05-millijoule. On the

'

.i

!/

IGNITION OF GAS MIXTURES basis of families of curves obtained for hydrocarbons and the general similarity of the ether family for 1 atmosphere, the lowest ignition energy for 100 percent oxygen atmosphere is expected to be as small as 0.002-millijoule. Data of the type contained in this paper are of value in further theoretical developments of ignition. For this purpose, burning-velocity data must be determined. The data also furnish absolute limits in the evaluation of ignition hazards
SUMMARY

367

Minimum ignition energies have been determined for various mixtures of paraffin hydro-

carbons from ethane to heptane (excluding pentane) with oxygen-nitrogen atmospheres from air to 100 percent oxygen and for cyclopropane, diethyl-ether, cyclohexane and benzene in oxygennitrogen atmospheres. Values in oxygen-helium atmosphere have been determined for diethylether. In the homologous series of paraffins the minimum energies shift toward the rich side with increasing number of carbon atoms. In this respect the effect of molecular structure for the same number of carbon atoms is small. The smallest minimum energy for ignition (minima of the curves) is practically identical for all the compounds studied.