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FACHBEREICH D
SICHERHEITSTECHNIK
ABWEHRENDEN BRANDSCHUTZ
PROF. DR. ROLAND GOERTZLtd. Branddirektor a. D.
Chemical and physical aspects of fire
smoke
Exploration/control
Dangersetting:
Kind and cause of damage
Damaged object and surroudings
Size of damagepeople, animalsenvironment and things
Thoughts of the highest-in-charge- The process of leadership
PlanningDecision/assessment
Decision:
Which dangers for people,animals, environment and things?
Which danger to combat first at which location?
Which possibilities exist withwhich advantages anddisadvantages?
What is the best possibility?
Thoughts of the highest-in-charge- The process of leadership
Voice of press – opinion of people
Flames destroy
galvanizing
companyNo toxic compounds released
With ash it rained dioxines
on housesAfter plastic-fire 900 inhabitants evacuated
Fear the day after:
„Everything is contaminated now“School and kindergarten closed/ beddings closed
Dioxin-alarm after fire
on verandaPolice: Possibly no Seveso-toxics
released
Cloud of poison gas threatens SchwelmConflagration in storage/ chloride-fumes released
Poison gas-alarm: no
harvesting of fruitFear in Schwelm: inhabitants leave cities/ closures
Conflagration: Poison gas-
Alarm derailed HagenFire in galvanizing company/ No school for kids
Voice of press – opinion of people
General composition of fire smoke
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
anorganische
Brandgase
organische Brand-
zersetzungsprodukte
Ruß
PC
DD
/F
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
Inorganic
fire gasses
organische Brand-
zersetzungsprodukte
Ruß
PC
DD
/FGeneral composition of fire smoke
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
Organic fire-
decompositionproducts
Ruß
PC
DD
/FGeneral composition of fire smoke
Inorganic
fire gasses
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
Soot
PC
DD
/FGeneral composition of fire smoke
Organic fire-
decompositionproducts
Inorganic
fire gasses
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
PC
DD
/FGeneral composition of fire smoke
Soot
Organic fire-
decompositionproducts
Inorganic
fire gasses
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
organische Brand-
zersetzungsprodukte
Ruß
PC
DD
/FAnorganic fire gasses
Inorganic
fire gasses
11-12 important inorganic fire gasses
C
COCO2
N
NOx
HCNNH3
Cl
Cl2COCl2
HCl
S
SO2
H2S
P
PH3
Carbonmonoxide:
8.000 ppm Sudden death
3.000 ppm Dead after 30 min inhalation
1.500 ppm Dead after 1 hr inhalation
1.000 ppm Walking problems, dead after 1-2 hr
500 ppm Hallucinations after 30-120 min
200 ppm Headache after 2-3 hr
50 ppm MAK-value
F
HF
Roland Goertz Abwehrender Brandschutz
Determination of danger
Which dangers exist
- for people
- animals
- environment
- things?
Measure-tactical (analytical) questions
Roland Goertz Abwehrender Brandschutz
Measure-tactics inorganic firegasses
1. Overview of source
2. Determination of
danger of emission
Roland Goertz Abwehrender Brandschutz
Organic fire-decompositionproducts
NOx
HCN
NH3
SO2
H2S
Cl2
HClCOCl2
PH3CO
CO2
anorganische
Brandgase
Soot
PC
DD
/F
Organic fire-
decomposionproducts
Roland Goertz Abwehrender Brandschutz
Reaction zone
„After-burning“
of gasses
Fuel
Air inflowAir inflow
Thermic load
Fire-decompositionproducts
Combustionzones
Roland Goertz Abwehrender Brandschutz
Formation of aromaticcompounds and soot
SootAromatic
compounds
PAK
CH2
Radicals
en small
molecules
•
C2H2
+O2 +O2 +O2
CO2 + H2O
Carbon-
containing
fuel
„After-burning“
Roland Goertz Abwehrender Brandschutz
C CH H C C
H
HH
Acetylen
Vinylradikal
+ H.
+ C2H2 - H2
C C
H
H
C
C
H
H
H
1,3-Butadienradikal
+ C2H2
C
H
C
C
H
C
C
H
C
H
H
Phenylradikal
+ C2H2
- H2
C CH
Phenylacetylen
CCH
.H +
- H2
H
CCH
C C
H
+ C2H2
.
Naphthylradikal
+ C2H2
- H2.
..
Roet
Formation of aromatic compounds –
Reaction mechanisms
Ofen
Quarzwolle
Gasumlenkung
synth. Luft
Probeneinwurf
Probenhalter
Quarzrohr
Adsorptionsröhrchen
Quarzwolle
Quarzrohr
VCI-combustion-apparatus
Condensate (0), Quarzwolle (1) + int. Standard-Mix
+ 5ml Aceton
Collectionlayer (2), Control layer (3) + int. Standard (Hexadeuterobenzol) + 5ml Aceton
15 Minuten
Ultrasonic bath
Cleaning of extracts
"Clean-up"
Quarzwolle
Natriumsulfate
Quarzwolle
Cleaned
Extracts
(1) (2) (3) (0)
GC-MS-Analysis
Adsorptiontube
tube
Quarz-use for condensate
Sample preparation
Roland Goertz Abwehrender Brandschutz
CH3
CH2
Benzol Toluol Styrol Inden
CH3
Naphthalin Methylnaphthalin Biphenyl Acenaphthylen
Fluoren Phenanthren Anthracen Fluoranthen
Pyren Chrysen Benzpyren
Typical fire-smoke organic
fire-decompositionproducts
Roland Goertz Abwehrender Brandschutz
0
10
20
30
40
50
60
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29
Substanz-Nr.
A
n
z
a
h
l
0
100
200
300
400
500
1 2 3 4 6 7 8 9 10 13 16 17 20 21 23 27 28 35 38 39 40 43 44 48
Hauptklasse
A
n
z
a
h
l
Frequency of compounds - Evaluation
Roland Goertz Abwehrender Brandschutz
1 2 3 4 5 6 7 8 90
100000
200000
300000
400000
counts
/mg
BrandgutStyropor
PU-Schaum
Polycarbonat
Milchpulver
Zucker
Mehl
Kaffee
Trinkschokolade
Kakao
Part of medium-volatile compounds
(Benzol, Toluol, Styrol, Inden Naphthalin)
Roland Goertz Abwehrender Brandschutz
CNCH3
NH
CN
N
Benzonitril Methylindolin Naphthalincarbonitril Acridin
NNH
CN
Benz(A)acridin Carbazol Anthracencarbonitril
Typical organic fire-decomposition
products of PU-foam
Roland Goertz Abwehrender Brandschutz
O OCH3
CH3
Cl
Cl
2-Methoxyfuran 1-Chlorethylbenzol Chlornaphthalin
O
Dibenzofuran
Typical organic fire-decomposition
products of PVC
Roland Goertz Abwehrender Brandschutz
(81,0%)
(19,0%)
(81,0%)
(19,0%)
Share of nitrogen-containingdecompositionproducts whenburning polyurethane
Share of chloride-containingdecompositionproducts whenburning polyvinylchloride
Roland Goertz Abwehrender Brandschutz
Aldehyde
can cause damage
Oil/fat
- Low odor-theshhold
- Irritation of eyes and mucous membranes
- Large quantities detectable
Also: psychological damage of population
e.g.
Acrolene
Roland Goertz Abwehrender Brandschutz
Chloride-containing fuels
lead to hydrochloric acid
Cl
Cl2 COCl2
HClChloride-containing
organic compounds
Roland Goertz Abwehrender Brandschutz
PCDD/F
Low temperature
Large quantities of
chloride-containing fuel
Copper
Precursor substances
(e.g. PCB)
Favourable factors in forming
relevant quantities of PCDD/F
O
O ClxCly
O ClxCly
Relevant quantities
PCDD/F
Roland Goertz Abwehrender Brandschutz
inorganic gasses,
aromates and PAK
Dioxine/Furane
Chlooraromates
Emergency measures determined by:
- inorganic firegasses,
- aromatic compounds and
- PAKs
Roland Goertz Abwehrender Brandschutz
Summary:
Danger-determination fire smoke
2. Aromatic compounds (Benzol etc. and PAK) with
carcinogenic potential are always present
1. Inorganic firegasses determine instant toxicity!
3. Warm fires: from soot carcinogenic substances are
released in the air
breathingprotection
Inorganic firegasses
Organic fire-decompositionproducts
Roland Goertz Abwehrender Brandschutz
4. Soot contains low-volatile toxic compounds with
long-term effects
Avoid skincontact and adsorption
5. Chloride-containing organic compounds and PCDD/F
are only relevant under certain circumstances
Summary:
Danger-determination fire smoke