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Introduction
Today, many industrial processes are operated at
elevated pressures. It is known that the AIT of a
fuel/air-mixture drops with increasing pressure, a fact
explained theoretically by Semenoff /1/ as early as
1928. Since then, a lot of work has been done to determine AITs at elevated pressure (see, for example, the
work of Gdde /3/ and references cited therein). Nevertheless, the safety characteristics of many technically
important substances are still poorly known under these
conditions. The present work deals with the determination of autoignition temperatures (AITs) of several
single compounds under high pressures.
Even less knowledge exists about the Upper Explosion Limit (UEL) at high pressures. A second series of
experiments was set up therefore to determine the UEL
at elevated pressure and a temperature near their AIT
for some of the pure compounds investigated.
Experimental set-up
AIT
Under atmospheric conditions, the AIT of a liquid is
usually determined by dropping the liquid into a preheated Erlenmeyer flask, ignition being indicated by the
occurrence of a visible flame /2/. Measurements at
elevated pressures require a closed reaction vessel as
shown in Fig. 1. We use a 0.5 l autoclave (1). Ignition is
indicated either by a temperature rise (observed by two
thermocouples (6) within the vessel) or by the pressure
rise observed by the pressure transducer (10). For an
experiment, air is first introduced into the autoclave
from its supply (4), regulated to the desired pressure by
the pneumatic valves (7), (8), and (9), then the liquid is
fed into the vessel from its supply (2) by a HPLC pump
(3). The resulting pressure is taken as the starting
pressure. As with the standard apparatus, the fuel is
trations of 25% and higher. Therefore for several compounds the influence of pressure on the UEL was
explored. The results are presented in Tab. 1.
Tab. 1: UEL of some single compounds at elevated temperature
and pressures of 10 bar
22
12
21
P
15
14
11
20
P
17
18
19
temperature of
measurement in C
16
UEL in % by vol.
at 10 bar
1-Propanol
28.8
41.8
200
2-Propanol
14.5
39.3
200
Cyclohexane
10.5
39.6
200
n-Hexane
22.1
42.7
180
n-Heptane
26.4
40.5
180
Pentane
10.7
44.4
180
Acetone
Compound
13
UEL in % by vol.
(atmospheric)
16.2
22.5
180
Butanone
12.6*)
22.5
180
Methylpropionat
13.0*)
26.7
200
Ethylacetat
12.8*)
24.6
200
Ethanol
36.4
52.8
200
Methanol
*) at 100C
54.1
59.4
200
50
40
Range of autoignition
at 10 bar
30
20
10
50
100
150
200
250
300
16
pressure
temperature at the centre of autoclave
temperature at the top of autoclave
T / C
40
R a n g e o f a u toig n itio n
a t 1 0 ba r
14
260
13
240
12
11
220
10
E xp lo sio n ra ng e at 1 0 b a r
L E L a t 1 b a r a n d 1 0 b ar
m a x. c o n ce n tra tio n a t 1 b a r
m a x.co n ce n tra tio n at 1 0 b a r
UEL at 1 bar
UEL at 10 bar
A IT a t 1 0 b a r
15
30
20
10
Pressure in bar
50
280
200
9
180
0
500
1000
1500
Time (from start of injection) in s
8
2500
2000
E xp lo sio n ran g e a t 1 b a r
10000
0
0
50
100
150
benzene
butyl amine
cyclohexanone
propionic acid
200
T /C
E AZV
exp
RT
pn
1000
100
10
200
250
300
350
Temperature in C
400
450
500
550
Semenoff plots
According to Semenoff's theory of thermal explosion /1/, the relation between the pressure pZ of a
fuel/air-mixture and its autoignition temperature TZ is
described by the relation:
2
( +1)
E ASem
)
RTZ
where EASem is an apparent activation energy of the
reaction and n is the overall reaction order (usually
assumed to be 2).
pZ = k Tz n
exp(
pZ/T 2Z in bar/K
1E-4
1E-5
n-Heptane
Benzene
Ethanol
Propionic acid
Methyl propionate
Butyl acetate
1E-6
200
250
300
350
Temperature in C
400
450
500 550
1 bar
2 bar
5 bar
10 bar
n-Hexane
230
235
210
197
n-Heptane
220
201
197
190
n-Octane
215
Cyclohexane
246
245
225
215
Benzene
565
526
470
451
Toluene
535
457
261
Dioxan
375
212
197
189
Methanol
440
300
260
Ethanol
400
283
250
Propanol-1
385
300
265
240
Butanl-1
325
292
255
240
Pentanol-1
320
250
240
Hexanol-1
280
280
262
232
Acetone
525
350*
275
260
Butanone-2
475
290
235
210
Pentanone-2
445
260
210
Hexanone-2
420
196
187
Cyclohexanone
430
279
230
215
Propionic acid
470
358
299
266
i-Butyric aldehyde
165
143
122
Propionic aldehyde
190
108
98
93
Methyl propionate
465
400
284
253
Ethyl formiate
440
312*
280
225
Propyl propionate
445
315
251
Butyl propionate
425
320
240
i-Propyl acetate
425
296
241
245
Methyl acetate
505
470
415
338
Ethyl acetate
470
380
260
230
Propyl acetate
455
300
260
240
n-Butyl acetate
393
252
240
230
t-Butyl acetate
450
395
370
310
n-Pentyl acetate
350
226
i-Pentyl acetate
280
261*
240
224
Methyl butyrate
445
400
256
n-Butyl amine
310
280
258
210
216
Acknowledgements
We thank M. Gdde, W. Mller, G Riesner and J.
Scheffler for carrying out the experiments and operating
the autoclaves.
For financial support we thank the Hauptverband der
gewerblichen Berufsgenossenschaften
References
1. Semenoff, N.: Zur Theorie des Verbrennungsprozesses, Z.Phys. 48(1928), 571
2. IEC 60079-4: Electrical apparatus for explosive gas
atmospheres. Part 4: Method of test for ignition temperature
3. Gdde, M.: Zndtemperaturen organischer Verbindungen in Abhngigkeit von chemischer Struktur
und Druck, PTB-Bericht ThEx-8, Wirtschaftsverlag
NW Verlag fr Neue Wissenschaft, Bremerhaven
1998
4. Semenoff, N.N.: Some Problems in Chemical Kinetics and Reactivity, Princeton Univ. Press, v.2, 1959,
331 pp.
5. Gdde, M, Brandes, E. and Cammenga, H. K.:
Zndtemperaturen homologer Reihen Teil 2, PTBMitteilungen 108(1998), 437