All of these gases are dangerous due to toxicity.  Some are dangerous via other qualities as well (flammable, reactive....). 

REQUIRING WRITTEN APPROVAL ARE -- the white boldface on red background gases.  Use of any quantity of any of these pure gases require Department approval in writing before the work begins, in the Dept of Chemistry and possibly other Depts.  Mixtures containing these gases may also be included under the definition of highly toxic and require approval in writing.  Contact swihart@purdue.edu for information.

 

acetyl fluoride
ammonia
antimony hydride
arsenic pentafluoride
arsine
2-butene
boron trichloride
boron trifluoride
bromine chloride
carbon monoxide
carbonyl chlorofluoride
carbonyl fluoride
carbonyl sulfide
chlorine
chlorine dioxide
chlorine monoxide
chlorine pentafluoride
chlorine trifluoride
chlorosilane
chlorotrifluoroethylene
coal gas
cyanogen
cyanogen chloride
diborane
deuterium bromide
deuterium chloride
deuterium iodide
deuterium sulfide
diazomethane
dichloroacetylene
dichlorosilane
dinitrogen tetroxide
diphosgene
ethyl nitrite
ethylene oxide
fluorine
formaldehyde
germane
hexaethyl tetraphosphate
hexafluoroacetone
1,3-hexafluorobutadiene
hexafluoropropene
hydrogen bromide
hydrogen chloride
hydrogen cyanide
hydrogen fluoride
hydrogen iodide
hydrogen selenide
hydrogen sulfide
ketene
methyl bromide
methyl chloride
methylchlorosilane
methyl mercaptan
mustard gas
nickel carbonyl
nitric oxide
(nitrogen monoxide)
nitrogen dioxide
nitrous oxide
nitrogen trifluoride
nitrogen trifluoride oxide
nitrogen trioxide
nitrosyl chloride
oil gas
oxalyl bromide
oxygen difluoride
ozone
perchloryl fluoride
perfluoroisobutylene
phosgene
phosphine
phosphorus pentafluoride
selenium hexafluoride
silicon tetrafluoride
stibine
sulfur dioxide
sulfur pentafluoride
sulfur tetrafluoride
sulfuryl fluoride
tellurium hexafluoride
trifluoroacetyl fluoride
trifluorochloroethylene
bis(trifluoromethyl)peroxide
tungsten hexafluoride
vinyl chloride

 

background

 

Poison Gases

see list below

Indiana Fire Code (8004.2.3.7) 
    Special requirements for highly toxic and toxic compressed gases: 
Compressed gas cylinders shall be within gas cabinets, exhausted enclosures, or gas rooms.  Gas cabinets and gas enclosures shall be in accordance with 8003.3.1.3.2 and 8003.3.1.3.3, respectively.  Gas cabinets and gas enclosures shall be internally sprinklered.   
8003.3.1.3.2 Gas cabinets must
1 operate at negative pressure w/re to surrounding area
2 be provided with self-closing limited access pots or noncombustible windows to give access to equipment controls, average velocity at windows/port must be at least 200 fpm, min at any point 150 fpm
3 be connected to an exhaust system
4 be provided with self-closing doors
5 be constructed of not less than 0.097" (12 gauge) steel.
8003.3.1.3.3 Exhausted enclosures must
Basically same as 1 and 2 above.
Definitions:
Toxic: 
(1) 50 mg/kg < LD50 ≤ 500 mg/kg ( body weight) oral albino rat 200 - 300 g  
OR
(2) 200 mg/kg < LD50 ≤ 1000 mg/kg (body weight) continuous 24 h contact
      (or less if death occurs before 24 h) albino rabbits 2 - 3 kg 
OR
(3) 200 ppm <  LC50 ≤   2000 ppm  (by volume of gas or vapor), or 2 mg/L <  LC50 ≤  20 mg/L (dust, fume, mist) continuous inhalation for 1 h (or less if death occurs in less than 1 h) to albino rats 200 - 300 g.

Highly Toxic: 
(1) LD50 of ≤ 50 mg/kg body weight oral albino rat 200 - 300 g  
OR
(2) LD50 of ≤ 200 mg/kg body weight  continuous 24 h contact (or less if death occurs before 24 h)         albino rabbits 2 - 3 kg 
OR
(3) LC50 ≤ 200 ppm by volume of gas or vapor, or > 2 mg/L dust/fume/mist continuous
        inhalation for 1 h (or less if death occurs in less than 1 h) to albino rats 200 - 300 g.

Calculating for Gas Mixtures

Binary mixture = haz component + nonhaz rest, LC50m = 1/[Ci/LC50i] 

LC50m  =  the LC50 of the mixture 
Ci = concentration of component i in decimal percent
LC50i  = LC50 of component i

MUST NORMALIZE for 1 h exposures via the table given A-VI-A-1 NORMALIZATION FACTOR

TIME (hours) Multiply by
0.5 0.7
1 1
1.5 1.2
2 1.4
3 1.7
4 2
5 2.2
6 2.4
7 2.6
8 2.8

Others 

Chemistry Dept policy -- Any person(s) ordering or receiving liquefied or compressed gases on this list will comply with all State and Federal rules pertaining to their use and storage, and will prepare well written SOPs (written standard operating procedures) pertaining to each substance, addressing storage, handling, training, waste disposal, decontamination, and emergency procedures.  No one will receive or handle such materials until after all qppropriate hazard assessments and training have been completed, and all staff working with and near the item(s) have been apprised of the hazards, the means of detecting releases, and the symptoms of exposure.   (SOPs must address normal precautions pertaining to health and safety, as well as emergency procedures)

Note -- low concentration mixtures of poson gas in inert gas are often not subject to the requirement for a fire-protected ventilated cabinet.  Contact swihart@purdue.edu

URL is http://www.chem.purdue.edu/chemsafety/Chem/poisongases.htm  or for table standing alone go to http://www.chem.purdue.edu/chemsafety/Chem/PoisonGasTable.htm   White type on red background indicates materials fitting the IFC definition of toxic or highly toxic.   LC50 values are rat 1 h inhalation or equivalent as per chart above.  Designations I, II, III, and NR are from the Santa Clara Co. TGO data and are included as a point of interest only.

Table still in progress 12/10/09

122
material*

LC50
ppm
IDLH**

cut-off***
I
II
III
NR
  
acetyl fluoride
 
 
 
3251.5
65.03
  
ammonia
4000
 
 
 
4000
80
 Baker MSDS A5472 07/29/03 rat inh 4h 2000 ppm
antimony hydride
20
5
 1% (1000 ppm)
20
10
0.67
0.40
 see stibine below
arsenic pentafluoride
~1.5
5 mg As/m3
 0.075% (750 ppm)
20
10
0.67
0.40
  1.5 calculated from IDLH (just converted to ppm)
arsine
<0.9
3
 0.045% (45 ppm)
20
10
0.67
0.40
 link   0.9 ppm is calc value from 15 min rat inh LC50 0.3 mg/m3
 Air Liquide MSDS gives 20 ppm (1 h) LC50 with no other info.
BOC gas MSDS says 390 mg/m3/10M rat LC50
2-butene
 
 
1398.3
46.61
27.97
  
boron trichloride
2541
 
 
2541
84.70
50.82
 link  DOES NOT SAY 1 h
RTECS data clear 2541 ppm is 1 h rat inh LC50
boron trifluoride
875
25
 43.7%
 
806
26.87
16.12
 TOXNET LC50 Rat inhalation 1.21 mg/L/4 hr
RTECS data says 1180 mg/m3/4h   Those are very close.  The 875 is calculated based on the lewer of the two.
bromine chloride
 
 
290
9.67
5.80
 have searched RTECS, Toxnet (there is a Fact sheet from 1988, purchasable but probably not helpful).  The use of this seems to be focused entirely on wastewater treatment and poliovirus pesticide activity.
carbon monoxide
3614
1200
  
 
 
3760
75.2
 link  1807 ppm/4 hour(s) inhalation-rat LC50 RTECS gives same data
carbonyl chlorofluoride
45 ppm
 
class II

53.33
32.00
 TGO assigned, failing tox data availability
carbonyl fluoride
360
18%
 
360
12.00
7.20
 link  360 ppm/1 hour(s) inhalation-rat LC50
carbonyl sulfide
2140
 
 
2220
740
44.4
 link  1070 ppm/4 hour(s) inhalation-rat LC50m  RTECS agrees
chlorine
293
10
 14.6%
 
 
9.77
5.86
link  293 ppm/1 hour(s) inhalation-rat LC50
chlorine dioxide
5
 200 ppm
 
250
8.33
5.00
 link (toxnet) gives much animal data but mostly aquatic.
chlorine monoxide
50 ppm
class I
50.00
3.33
2.00
 TGO assigned, failing tox data availability
chlorine pentafluoride
122
6.1%
 
 
 
not in TGO
link (toxnet, might have to re-search, the links seem to "expire")
chlorine trifluoride
299
20
 14.95%
 
299
9.97
5.98
 link  299 ppm/1 hour(s) inhalation-rat LC50
chlorosilane
2080
 
 
class II
53.33
32.00
 link
chlorotrifluoroethylene
 
 
2000
66.67
40
  
coal gas
 
 
 
 
not in TGO
RTECS, not much tox data, appears to be quite bad.
cyanogen
350
17.5%
 
350
11.67
7.00
 link  350 ppm/1 hour(s) inhalation-rat LC50
cyanogen chloride
1.26
 
80
40
2.67
1.60
 RTECS 3150 μg/kg rabbit LD50
link 6 mg/kg oral-cat LD50
diborane
80
15
  
 
 
 
 
 link  40 ppm/4 hour(s) inhalation-rat LC50
deuterium bromide
 
 
300
10.00
6.00
  
deuterium chloride
 
 
 
3120
62.40
  
deuterium iodide
 
 
class II
53.33
32.00
  
deuterium sulfide
 
 
710
23.67
14.20
  
diazomethane
2
  
20
10.00
0.67
0.40
 from TGO, IDLH
dichloroacetylene
438
 
153.1
76.56
5.10
3.06
 link gives 4h rat LC50 for mixtures
dichlorosilane
215
 
 
314
10.47
6.28
 RTECS (time not stated)
dinitrogen tetroxide
 
115
57.50
3.83
2.30
 see nitrogen dioxide.  They are in equilibrium.
diphosgene
 
2
1.00
0.07
0.04
  
ethyl nitrite
 
 
320
10.67
6.40
  
ethylene oxide
2924
800
  
 
 
4350
87.00
 RTECS 800 ppm 4H rat inh LC50
toxnet says 1462 4H rat inh LC50
fluorine
185
25
  
185
92.50
6.17
3.70
 link  185 ppm/1 hour(s) inhalation-rat LC50
formaldehyde
784
20
  
165.7
82.84
5.52
3.31
 toxnet says 0.48 mg/l (4 hr) rat which is 784 ppm 1h rat
germane
441
 
 
622
20.73
12.44
 link  1380 mg/m3 inh-rat LC50;     1250 mg/kg oral-mouse LD50
hexaethyl tetraphosphate
 
 
 
 
 

RTECS gives oral rat LD50 = 7 mg/kg
(not a gas?) (not in TGO)

hexafluoroacetone
468
 
 
470
15.67
9.4
 RTECS has 275 ppm as 3h rat inh LC50
1,3-hexafluorobutadiene
667
 
184.2
92.08
6.14
3.68
 link
hexafluoropropene
 
 
 
3659.7
73.19
  
hydrogen bromide
2858
30
  
 
2860
95.33
57.20
 link  2858 ppm/1 hour(s) inhalation-rat LC50
hydrogen chloride
3124
50
  
 
2810
93.67
56.20
 link  3124 ppm/1 hour inh-rat LC50;         900 mg/kg oral-rabbit LD50
hydrogen cyanide
112
50
  
40
20.00
1.33
0.80
 link   160 ppm/30 min inh-rat LC50;    3700 ug/kg oral-mouse LD50
hydrogen fluoride
1347
30
  
 
1300
43.33
26.00
 link  1100 mg/m3/60 minute(s) inhalation-rat LC50
hydrogen iodide
 
 
2860
95.33
57.20
 not much tox reports, It seems to be of little interest for its toxicity.
hydrogen selenide
2.2
1
  
60
30.00
2.00
1.20
 link  300 ppb/8 hour(s) inhalation-guinea pig LC50, RTECS confirms
hydrogen sulfide
444
100
  
 
712
23.73
14.24
 link  444 ppm inhalation-rat LC50  (doesn't say 1 h)   another link
ketene
5
  
 
535.1
17.84
10.70
  
methyl bromide
846
250
  
 
1007
33.57
20.14
 link oral rat LD50 214 mg/kg
RTECS gives 302 ppm/8h rat LC50 and rat oral LD50 = 214 mg/kg
methyl chloride
5143
2300
  
 
 
 
 
 link IHL-RAT LC50 5300 mg/m3/4h
RTECS confirms and gives oral rat LD50 = 1800 mg/kg
methylchlorosilane
 
 
600
20.00
12.00
 not a lot of Tox data, RTECS gives some, no LC50 or LD50.  It is apparetnly not an acute toxin of the same league.
methyl mercaptan
675
150
  
 
1350
45.00
27.00
 link Ihl-rat 675 ppm (one h?)  another link
mustard gas
 
4
2.00
0.13
0.08
 not actually a gas at standard conditions
nickel carbonyl
24.5
2
  
 
 
 
 
 link  35 ppm/30 min inhalation-rat LC50.  not in TGO
nitric oxide
(nitrogen monoxide)
1739
100
  
115
57.50
3.83
2.30
 link IHL-RAT LC50 1068 mg/m3/4h, also reported in RTECS
link 160 mg/m3 inhalation-rat LC50, value also reported in RTECS
nitrogen dioxide
176
20
  
115
57.50
3.83
2.30
 link rat 4h inh 88 ppm
nitrogen oxide
(nitrous oxide)
 
 
 
 
 
 THIS is not a poison gas.  It is "laughing gas," still used as a dental anesthetic, and it has been added to this table simply to make a point about how similar the names can look.
nitrogen trifluoride
6700
1000
  
 
 
 
 
 link 6700 ppm/1 hour(s) inhalation-rat LC50, also in RTECS
nitrogen trifluoride oxide
48
 
 
 
 
 
 RTECS gives 24 ppm 4 h rat inh LC50
nitrogen trioxide
 
 
 
3350
67.00
 nothing in RTECS, little elsewhere, not finding tox data.  "Delayed effects."
nitrosyl chloride
35
 
 
class II
53.33
32.00
 link Air Liquide MSDS gives 35 ppm (1 h) LC50 with no other info.
oil gas
 
 
 
 
 
 We will assume it's very bad and research it more thoroughly it it ever comes up.
oxalyl bromide
 
class II
53.33
32.00
  
oxygen difluoride
2.6
0.5
  
3
1.50
0.10
0.06
 NIOSH RTECS
ozone
9.6
5
  
9
4.5

0.30
0.18
 BOC 1997 msds says 4800 ppb 4 H rat inh which is pretty low
perchloryl fluoride
770
100
  
 
770
25.67
15.40
 NIOSH RTECS gives 385 ppm/4 hour rat inh LC50
perfluoroisobutylene
1.47
 
1.2
0.61
0.04
0.02
 BOC msds of mixture gives LC50 for this component as 1.05 ppm rat ihn 2 h
phosgene note
4
2
  
5
2.50
0.17
0.10
 link
phosphine
22
200
  
20
10.00
0.67
0.40
 link 11 ppm/4 hour(s) inhalation-rat LC50
phosphorus pentafluoride
190
 
 
260
8.67
5.20
 Air Liquide MSDS gives 190 ppm (1 h) LC50 with no other info.
selenium hexafluoride
50
2
  
50
25.00
1.67
1.00
 Air Liquide MSDS gives 50 ppm (1 h) LC50 with no other info.
RTECS gives only LCLOs, but it looks unpleasant.
silicon tetrafluoride
450
 
 
2272
75.73
45.44
 Air Liquide MSDS gives 450 ppm (1 h) LC50 with no other info.
RTECS gives 2250 ppm, no time.
stibine
20
5
  
20
10
0.67
0.40
 Air Liquide MSDS gives 20 ppm (1 h) LC50 with no other info.
RTECS -- all refs are LCLO, but they are pretty low. 
sulfur dioxide
2520
100
  
 
2520
84.00
50.40
 Air Liquide MSDS gives 2520 ppm (1 h) LC50 with no other info.
sulfur pentafluoride
1
  
10
5.00
0.33
0.20
 No rat inh data found.  10 is the IDLH according to TGO
sulfur tetrafluoride
40
 
40
20.00
1.33
0.80
 Air Liquide MSDS gives 40 ppm (1 h) LC50 with no other info.
sulfuryl fluoride
3020
200
  
 
 
3020
60.40
 Air Liquide MSDS gives 3020 ppm (1 h) LC50 with no other info.
tellurium hexafluoride

25

1
  
25
12.5
0.83
0.50
 Source of 25 ppm not known came from.  RTECS only gives LCLO values, very low.  OSHA tech bulletin also gives no LC50.  NIOSH RTECS too
trifluoroacetyl fluoride
 
 
1000
33.33
20.00
 tox info is elusive so far
trifluorochloroethylene
2000
 
 
 
 
 
 NIOSH RTECS reports rat 4 h inh LC50 is 1000 ppm
bis(trifluoromethyl)peroxide
 
10
5
0.33
0.20
  
tungsten hexafluoride
150
 
 
217
7.23
4.34
 217 link   Air Liquide MSDS gives 160 ppm (1 h) LC50 with no other info.
vinyl chloride
 
 
 
 
NR
 Oxford msds says rat LD50 is 500 mg/kg, which is the upper limit of toxic.  RTECS gives rat 15 min LC50 of 18 pph.

*Reference is to material which is a compressed or liquefied gas or gas mixture obtained in cryo-freezers, cylinders, lecture bottles, or other gas containers.  Does not apply liquid mixtures, e.g. BF3 etherate, nor aqueous NH3, HCl, HBr....
** IDLH is given as ppm unless otherwise indicated.
*** Cut-off concentration:  If concentration of toxic gas in any two-component mixture compressed gas cylinder is LESS THAN this amount, the requirement for sprinklered, continuously ventilated cabinet does not apply.

*reference is to compressed and liquefied gases obtained in cryo-freezers, cylinders, lecture bottles, or other gas containers, not to purchased liquid mixtures, e.g. BF3 etherate, nor aqueous NH3, HCl, HBr....

** IDLH is given as ppm unless otherwise indicated.

See copy of DOT hazmat table for more info on hazard classes of materials.  (The DOT hazmat table is the source of the designation of certain materials as Poison Gases.)

conc in ppm   = (24.45)(conc in mg/m3)/(gram molecular weight of substance)

 

CALCULATIONS and notes
AsH3 calculation:  (24.5) (0.3)/82.9 =  0.9 ppm (15 min)
BF3 calculation (24.5)(1210)/67.8 = 437.2 ppm (4h) normalize to 1 h ---> 875 ppm
HF calculation: (24.5)(1100)/20 = 1347 ppm
GeH4 calculation (24.5)(1380)/76.6 = 441 except it doesn't say 1 h in the original data....but even if it were 4 h it would still be toxic.....
COCl2 calculation (24.5)(16)/98.9 = 4 ppm for 75 min inh rat
cyanogen chloride calc (24.5)(3.15)/61.47 = 1.26 ppm
WF6 calculation (24.5)(1430)/298 = 217
CH3Cl calculation (24.5)(5300)/50.5 = 2571 ppm for 4 h rat inh
NO calculation (24.5) (160)/30.1 = 130 ppm but they do not give the time.
                      (24.5)(1068)/30.1 = 869 ppm for 4 h ---- 1739 ppm calc for 1 h LC50
formaldehyde calculations: (24.5)(480)/30 = 392 (4 h) and multiply by 2 for 1 h ---> 784 ppm
alternate from 1/2 hr LC50 (24.5)(820)/30 = 468 ppm. Well they don't agree but it's not important, they're close enough.

  

  

  

  

≥  Alt 242
≤ Alt 243