LE CYCLE DE VIE DE
L’ACIDE SULFURIQUE
Guy Desgagnés, représentant
technique, acide sulfurique
NORANDA INC.
GESTION RESPONSABLE
NORANDA INC.
FABRICATION
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Noranda DuPont LLC est le principal producteur distributeur d’acide sulfurique en Amérique du Nord.
Noranda, DuPont et Falconbridge avec ses onze usines
produisent plus de 3 millions de tonnes d’acide par année.
Noranda DuPont LLC fabrique l ’acide sulfurique selon
deux procédés distincts, soit en utilisant du soufre
élémentaire, soit de l ’anhydride sulfureux récupéré lors
de la fonte des sulfures métalliques.
NORANDA INC.
TRANSPORT
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Tous les moyens de transport sont mis à contribution pour
distribuer les 3 millions de tonnes d’acide sulfurique soit:
- Routier :
100-150 camions d’acide /jour
- Ferroviaire : Une flotte de 2 200 wagons
- Maritime : 1 navire citerne d’une capacité de 7 000
tonnes et une flotte de chalands d’une
capacité de 2 200 tonnes.
NORANDA INC.
UTILISATION
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Matériaux de construction
Produits pharmaceutiques et cosmétiques
Pneus, batteries, pièces des véhicules
Textiles synthétiques
Jouets, articles de sport
Fabrication du papier
Eau potable, nourriture
NORANDA INC.
ÉLIMINATION
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L’acide, à cause de son caractère corrosif, ne peut pas
être éliminé dans des eaux de ruissellement ou dans un
réseau de drainage des eaux usées.
Se conformer à la législation fédérale, provinciale et
locale.
Après avoir obtenu l’autorisation, neutraliser et transférer
dans le système de traitement des effluents.
NORANDA INC.
RÉGLEMENTATION
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Les usines d ’acide sulfurique sont tenues d’opérer avec
un certificat d’autorisation du ministère de
l ’Environnement et aussi se conformer aux règlements
des établissements industriels et commerciaux.
Pour le transport, l’acide sulfurique doit suivre les
réglementations canadienne et américaine sur le transport
des marchandises dangereuses.
De plus, l’acide sulfurique fait partie des marchandises
dangereuses qui nécessitent le dépôt d’un plan
d’intervention d’urgence auprès de Transports Canada.
NORANDA INC.
CARACTÉRISTIQUES
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Forme : Huileuse, liquide limpide à trouble
Odeur : Inodore
Couleur: Incolore
pH : <1
Point de congélation : -35 à 11 C
Densité: 1,835
Solubilité dans l ’eau: 100% poids
Pression de vapeur: < 0,3 mm de Hg @ 25 C
NORANDA INC.
CARACTÉRISTIQUES SUITE...
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Stabilité : Produit stable. Réaction violente au contact de
l ’eau et des matières organiques avec dégagement de
chaleur.
Incompatibilité: très réactif avec les solutions alcalines,
des métaux (production d ’hydrogène), poudres
métalliques, des chlorates, matières combustibles et
substances organiques.
Décomposition: Émissions d’anhydride sulfureux à très
hautes températures.
Polymérisation: Absence de polymérisation.
NORANDA INC.
CARACTÉRISTIQUES SUITE...
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Déversement mineur: Absorber les petits déversements
avec du sable sec, de l’argile ou de la terre diatomée.
Déversement important: Endiguer, diluer et neutraliser
avec précaution avec de la chaux ou du carbonate de
sodium et transférer vers un système de traitement des
eaux usées.
Déversement majeur: Endiguer, récupérer le plus d’acide
possible avec un camion-aspirateur et par la suite
neutralise.
NORANDA INC.
CARACTÉRISTIQUES
CARACTÉRISTIQUES DE
DE L’ACIDE
L’ACIDE
SULFURIQUE
SULFURIQUE ::
LES
LES RISQUES
RISQUES ET
ET LES
LES INTERVENTIONS
INTERVENTIONS
POUR
POUR PROTÉGER
PROTÉGER l’ENVIRONNEMENT
l’ENVIRONNEMENT
Pierre-André Côté, D.Sc., chimiste
Service de l'environnement
Plan
Plan de
de présentation
présentation
„
„
„
„
„
„
„
Quelques définitions utiles
Cas des dépôts acides
Risques d'expositions environnementales
Quelques propriétés
Production industrielle
Risques lors de déversements accidentels
Conclusion
Quelques
Quelques définitions
définitions utiles
utiles
Généralement, pour obtenir de l'acide sulfurique :
S º SO2 º SO3 º H2SO4
„
S
‹Soufre élémentaire
„
SO2
‹ Anhydride sulfureux
‹ Produit par la combustion du
soufre présent dans :
™ Charbon
™ Produits pétroliers
™ Volcans
™ Minerai de cuivre et zinc
Quelques
Quelques définitions
définitions utiles
utiles (suite)
(suite)
„
SO3
„
‹ Anhydride sulfurique
‹ Produit par l'oxydation de
SO2
‹ Processus très lent dans
l'environnement; requiert
haute température /
catalyse
‹ En présence d'humidité,
se transforme
rapidement en acide
sulfurique
H2SO4
‹ Acide sulfurique
‹ Liquide clair, sans couleur, très
corrosif
‹ Avec ajout d'eau, production
intense de chaleur, projections
possibles
™ Donc toujours ajouter l'acide dans
l'eau
‹ Si chauffé haute température,
peut émettre SO3
‹ Présent dans les batteries
d'automobiles
‹ Avec SO3 ajouté dans H2SO4,
acide sulfurique fumant
Quelques
Quelques définitions
définitions utiles
utiles (suite)
(suite)
„
H2S
‹Hydrogène sulfuré
‹Très toxique
‹Provient de la mise en solution de
sulfures (S2-) par des acides
S2-+2 H+
H2S (g)
CAS
CAS DES
DES DÉPÔTS
DÉPÔTS ACIDES
ACIDES
SO2 oxyd. SO3 + H2O
lent
rapide
H2SO4 (part. / aérosol)
pluie
S+O2
combustion /
oxydation
H2SO4 (ruissellement)
sol
H2SO4 (ruissellement)
sol
H+ + HS04-
H+ + SO42-
CAS
CAS DES
DES DÉPÔTS
DÉPÔTS ACIDES
ACIDES (suite)
(suite)
„
H2SO4 (ruissellement)
‹ Cause d'acidification
‹ Cause de relargage (métaux, par exemple)
„ H2SO4 (part. / aérosol)
‹ Cause de la pollution atmosphérique
‹ Impact sur la santé
‹ Impact sur les infrastructures
Risques
Risques d'expositions
d'expositions
environnementales
environnementales
„
Batterie / automobile
‹ Toucher / aérosol
„
Nettoyeur / toilette
‹ Aérosol / contact
„
Couper des oignons
‹ Propanethiol-s-oxyde
‹ aérosol / mains
Quelques
Quelques propriétés
propriétés
„
„
„
„
Poids moléculaire : 98
Liquide incolore
Masse volumique (96-98%) : 1,84 g/cm3
Très soluble dans l'eau
Production
Production industrielle
industrielle
„
Avant (Chamber)
2 NO + 02
„
2 NO2 + 2 SO2 + 2 H2O
2 H2SO4 + 2 NO
Aujourd'hui (contact)
S
O2
air sec
SO 2
T ≥ 400C
catalyseur
SO3
T ≤ 220C
H2O
H2 SO 4
Risques
Risques lors
lors de
de
déversements
déversements accidentels
accidentels
„
Production d'aérosols acides
‹Réaction exothermique, émission
d'aérosol d'acide sulfurique
‹S03 réagit avec l'humidité de l'air
‹Régénération de H2SO4 en aérosol
Risques
Risques lors
lors de
de déversements
déversements
accidentels
accidentels (suite)
(suite)
„
Production de gaz divers
‹ Production d'hydrogène (H2) avec métaux
™ Risque de feu ou explosion
„
„
Production de CO2 en présence de calcaire
(CaCO3)
‹ Risque d'asphyxie / espace clos
Production d'hydrogène sulfuré (H2S)
‹Risque toxique
‹Très probable dans infrastructure d'égouts
Risques
Risques lors
lors de
de déversements
déversements
accidentels
accidentels (suite)
(suite)
„
Écoulement vers le fond des plans d'eau
‹ En raison de sa densité
‹ Acidification locale
‹ Besoin de neutralisation
„
Destruction des infrastructures
‹ Corrosion
‹ Dissolution
Conclusion
Conclusion
„
Lors de déversement
‹
‹
‹
‹
Protection respiratoire et vestimentaire
Confinement local
Récupération ou neutralisation
Nettoyage
1
H2SO4
Les Risques à la Santé et
l’Intervention de Santé Publique
Jacques Normandeau, PhD
Jacques Normandeau, PhD
2
SYNOPSIS
1. Un Risque Majeur?
2. L’Oléum (acide sulfurique fumant)
3. Toxicité et séquelles (RADS)
4. Limites d’exposition
5. Groupes à Risque
6. L’exposition
7. L’intervention de Santé Publique
Jacques Normandeau, PhD
Jacques Normandeau, PhD
3
1. Un Risque Majeur?
1. Absent de la liste des matières dangereuses (CRAIM-MM)
(oléum présent) ;
2. Déraillement Hervey-Jonction (Qc), aucun décès ou blessé
21 janvier 1995; 256 500 L. (28 wagons)
(« dispersion in air is not a concern »);
EAU POTABLE (pH estomac: 1,4 – 2,0 (HCl));
3. Pelham ONT., 1er décembre 1972, 8 citernes ferroviaires,
80 évacués (800 m.), aucun décès ou blessé;
4. Sudbury, ONT., 2 octobre 1989, camion-citerne (30 T.),
2 morts 1 blessé dans la collision;
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
4
1. Un Risque Majeur? (suite)
5. INCIDENTS OLÉUM (1970-1998);
aucun décès dans la population)
1985, Nouvelle Delhi, Indes: Oléum (1 décès; évacués)
1987, Nantichoke, U.S.: Incendie (18 000 évacués)
1993, Richmond, U.S.: Oléum surchauffé (20-50 T.)
(6 250 incommodés; irritations, toux)
(OECD)
6. Allied Signal Corp., Hopewell VA (U.S.):
RMP (EPA, 1999): pas d’impact.
Non, sauf pour l’Oléum, et l’approvisionnement
en eau potable.
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
5
2. L’Oléum (acide sulfurique fumant)
1. Liste des matières dangereuses (CRAIM-MM)
2. Acide sulfurique concentré (plus de 51% + SO3)
(ad 80% S03 libre)
3. Fumées corrosives et très irritantes, TOXIQUE;
4. Dégagement de SOx en présence d’humidité
SO3 + H2O H2SO 4;
5. « Fume off » (C-E Zinc, Valleyfield) (?)
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
6
3. Toxicité et séquelles (RADS)
•
•
•
•
•
CORROSIF: Irritations et brûlures;
(Hygroscopique)
Toux, Larmoiement, Nausées, Brûlures, O.A.P. retardé
RADS
DL 100: 10 ml.
Traitement de support
Human data: In exposures of 5 to 15 minutes, some
volunteers found 5 mg/m3 to be very objectionable, while others
found it less so [Amdur et al. 1952b]. The lethal oral dose has
been reported to be 135 mg/kg [Arena 1970]. [Note: An oral
dose of 135 mg/kg is equivalent to a worker being exposed to
about 6,300 mg/m3 for 30 minutes, assuming a
breathing rate of 50 liters per minute and 100% absorption.]
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
7
4. Limites d’exposition
OSHA PEL:
ACGIH TLV:
1 mg/m3 TWA
1 mg/m3 TWA, 3 mg/m3 STEL
IDLH: 15 mg/m3
Basis for revised IDLH: The IDLH for sulfuric acid is
15 mg/m3 based on acute inhalation toxicity data in humans
[Amdur et al. 1952b] and animals [Amdur et al. 1952a; Treon et
al. 1950]. This may be a conservative value due to the lack of
relevant acute toxicity data for workers exposed to
concentrations above 5 mg/m3.
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
8
4. Limites d’exposition (suite)
ERPG-1: 2 mg/m3
ERPG-2: 10 mg/m3
ERPG-3 30 mg/m3
(CL100, 30 min.: 6 300 mg/m3)
(NOAEL:
0,1 – 0,45 mg/m3)
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
9
5. Groupes à Risque
1. Intervenants
(ne pas arroser L’OLÉUM)
2. Jeunes enfants
3. Maladies respiratoires chroniques
(asthme)
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
10
6. L’exposition
1. OLÉUM « Fume Off » en présence
d’humidité ou d’eau(brouillard irritant);
2. Contact Direct OU AVEC DES PERSONNES
OU DES OBJETS CONTAMINÉS;
ATTENTION:
Équipement d’approvisionnement en eau potable.
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
11
7. L’intervention de Santé Publique
SANTÉ
1. Identifier des situations
dangereuses;
2. Voir à la mise en place des
mesures de protection;
3. Informer la population.
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
12
7. L’intervention de Santé Publique (suite)
Identifier des situations dangereuses:
Soutien aux intervenants dans l’estimation du
risque:
DONNÉES ESSENTIELLES POUR NOTRE INTERVENTION
1.
2.
3.
4.
5.
Incident (description et localisation);
Substances en cause;
Quantités;
Conditions météorologiques;
Évolution de la situation
(interventions, déversement, étapes, prévisions, durée);
6. Évolution de la contamination (Air, Eau, Sol) ;
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
13
7. L’intervention de Santé Publique (suite)
Voir à la mise en place des mesures de protection:
1. Périmètre ;
2. Évacuation / Confinement ;
3. Décontamination ;
4. Traitement ;
5. Suivi des groupes (blessés, évacués) ;
6. Vulnérables (intervenants, enfants, malades)
(écoles, garderies…);
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
14
7. L’intervention de Santé Publique (suite)
Informer la population:
(Richmond, 3 000 consultations pour inconfort)
• Effets (irritations et inconfort; symptômes, m.d.);
• Conduite à suivre;
• Eau (aqueduc, puits);
• Aliments ;
• Eaux récréatives (pêche);
• Jardins;
• Consultation médicale (lignes directrices);
• Réintégration (décontamination);
• Productions animales et végétales;
• Animaux de compagnie;
• Activités extérieures (sites à risque);
• Bilan et recommandations.
Jacques N ormandeau, P hD
Jacques Normandeau, PhD
DOCUMENTATION ADDITIONNELLE
The following in formation was generated from the
Hazardous Substances Databank (HSDB ),
a database of the Natio nal Library of Medicine's TOXNET system
(http://toxnet.nlm.nih.gov) on May 25, 2001.
sulfuric acid Chemid Name: pyrosulphuric acid [8014-95-7]
( dithionic acid, disulp huric acid, oleum )
sulfuric acid ( sulphuric acid, mattling acid, battery acid, acido solforico,
acide sulfurique )
Registry Numbers:
8014-95-7 7664-93-9
1
NAME: SULFURIC ACID
HSN: 1811
RN: 7664-93-9
HUMAN HEALTH EFFECTS:
SYMPTOMATOLOGY (after ingestion or skin contact): 1) Corrosion of mucous
membranes of mouth, throat, and esophagus, with immediate pain and
dysphagia. The necrotic areas are at first grayish white but soon acquire
a blackish discoloration and sometimes a shrunken or wrinkled texture; the
process is described as a "coagulation necrosis." 2) Epigastric pain ,
which may be associated with nausea and the vomiting of mucoid and
"coffee-ground" material. At times, gastric hemorrhage may be in tense, and
the vomitus then contains fresh blood. Profound thrist. 3) Ulceration of
all membranes and tissues with which the acid comes in contact. ...
/Acids/ [Gosselin, R.E., R.P. Smith, H.C. Hodge. Clinical Toxicology of
Commercial Products. 5th ed. Baltimore: Williams and Wilkins, 1984.,p.
II-102]**PEER REVIEWED**
Jacques Normandeau, PhD
15
16
SYMPTOMATOLOGY (after ingestion or skin contact): 4) Circulatory collapse
with clammy skin, weak and rapid pulse, shallow respirations, and scanty
urine. Circulatory shock is often the immediate cause of death. 5)
Asphyxial death due to glottic edema. 6) Late esophageal, gastric and
pyloric strictures and stenoses, which may require majo r surgical repair,
should be anticipated. Signs of obstruction commonly appear within a few
weeks but may be delayed for months and even years. Permanent scars may
also appear in the cornea, skin and oropharynx. 7) Uncorrected circulatory
collapse of several hours' duration may lead to renal failure and ischemic
lesions in the liver and heart. /Acids/ [Gosselin, R.E., R.P. Smith, H.C.
Hodge. Clinical Toxicology of Commercial Products. 5th ed. Baltimore:
Williams and Wilkins, 1984.,p. II-102]**PEER REVIEWED**
INHALATION OF CONCN VAPOR MAY CAUSE SERIOUS LUNG DAMAGE. CONTACT WITH EYES
MAY RESULT IN TOTAL LOSS OF VISION; SKIN CONTACT MAY PRODUCE SEVERE
NECROSIS. [The Merck Index. 10th ed. Rahway, New Jersey: Merck Co., Inc.,
1983. 1289]**PEER REVIEWED**
The pulmonary sensitivity of normal and asthmatic subjects to ammonium
sulfate, ammonium bisulfate, and sulfuric acid were reviewed and compared.
Normal subjects performing moderate exercise in an environmental chamber
were exposed to 100 and 450 ug/cu m sulfuric acid for 4 hours. Carbachol
was administered by inhala tion following the 4 hour exposure and 24 hours
later. Mild throat irritation and enhanced carbachol induced
bronchoconstriction occurred at 24 hours post exposure at the 450 ug/cu m
level. The bronchial reactivity of normal subjects to oral inhalation of
1000 ug/cu m sulfuric acid, ammonium sulfate, and ammonium bisulfate was
minimal although carbachol bronchoconstriction was enhanced in relation to
the acidity of the sulfates. The acute exposure of asthmatic volunteers to
1000 ug/cu m sulfuric acid, and ammonium bisulfate significantly reduced
specific airway conductance and 1 second forced expiratory volume. Some
asthmatic subjects showed enhanced carbachol responses at 100 ug/cu m.
Jacques Normandeau, PhD
17
Asthmatics exposed to 100 and 450 ug/cu m sulfuric acid in an
environmental chamber with intermittent moderate exercise for 4 hours
showed decreases in flow rates and airway conductance after 1 to 2 hours
at the 450 u/cu m dose level. Results differed from a study of asthmatic
adolescents in which exposure with exercise at the 100 ug/cu m level
resulted in significant changes in 1 second forced expiratory volume,
Vmax50, and total respiratory resistance. ... asthmatics were more
sensitive to the effects of inhaled acid sulfates and that exercise
potentiated the adverse effects of the aerosol pollutants. ... Evidence
indicated that asthmatics bronchoconstricted upon inhalation of nitrogen
dioxide at near ambient levels. [Utell MJ; Environ Health Perspect 63:
39-44 (1985)]**PEER REVIEWED**
Concern about the health effects of acidic aerosols, and particularly
sulfuric acid and acid sulfates, was accentuated by the episodes of smog
in London in the 1950s and 1960s, during which thousands more deaths than
expected were recorded. People at particular risk were those with
pre-existing cardiovascular and pulmonary disease. Similar gas-aerosol
complexes have been responsible for acute and chronic lung disease,
including potentiation of respiratory tract infections and chronic
bronchitis in geographical areas where there is significant air pollution
from stationary sources of fossil fuel combustion. Although sulfuric acid
is only one component of these complexes, it has been suggested that
hydrogen ion concentration, presumably primarily reflecting sulfuric and
nitric acids, is correlated with bronchitic symptoms in children. Levels
of sulfate and fine particles may also be better predictors of mortality
than are concentrations of total suspended particles or inhalable
particles. [IARC. Monographs on the Evaluation of the Carcinogenic Risk of
Chemicals to Man. Geneva: World Health Organization, Internatio nal Agency
for Research on Cancer,1972-PRESENT. (Multivolume work).,p. V54 99
(1992)]**PEER REVIEWED**
Jacques Normandeau, PhD
18
Controlled human exposures to relatively high levels of sulfuric acid
resulted in acute symptoms and other findings suggestive of
bronchoconstriction. Effects have generally not been observed in healthy
adults exposed acutely to levels of less than 500 ug/cu m over a broad
range of particle sizes, although delayed symptomatology (mild throat
irritation and increased carbachol bronchorestrictor response) was noted
after exposure to 450 ug/cu m for 4 hours while exercising moderately.
Concentrations (0, 500, 1000 and 2000 ug/cu m)-related increased in upper
respiratory symptoms (cough) without change in pulmonary function have
also been noted. Exercising asthmatics were reported to be highly
responsive (in terms of decreased forced expiratory volume in 1 sec) to a
low level of sulfuric acid (100 ug/cu m) [IARC. Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Man. Geneva: World
Health Organization, International Agency for Research on
Cancer,1972-PRESENT. (Multivolume work).,p. V54 100 (1992)]**PEER
REVIEWED**
Acute exposure of human volunteers to 100 ug/cu m of sulfuric acid
resulted in increased mucociliary clearance of particles from the large
proximal airways; at higher levels 100 ug/cu m), the opposite occurred.
Clearance from the distal airways was reduced at both levels. [IARC.
Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man.
Geneva: World Health Organization, International Agency for Research on
Cancer,1972-PRESENT. (Multivolume work).,p. V54 101 (1992)]**PEER
REVIEWED**
HUMAN TOXICITY VALUES:
TCLO Human inhalation 5 mg/cu m/15 min. Toxic Effects: Pulmonary System
Effect (Sulfuric Acid Aerosol) [ITII. Toxic and Hazarous Industrial
Chemicals Safety Manual. Tokyo, Japan: The International Technical
Information Institute, 1982. 499]**PEER REVIEWED**
Jacques Normandeau, PhD
19
SKIN, EYE AND RESPIRATORY IRRITATIONS:
... SULFURIC ACID MIST ... STRONGLY IRRITANT & INHALATION OF CONCN OF
AROUND 3 MG/CU M CAUSES CHOKING SENSATION IN UNINITIATED. PERSONS
ACCUSTOMED TO EXPOSURE ARE UNABLE TO NOTICE CONCN OF THIS ORDER OF
MAGNITUDE. [Patty, F. (ed.). Industrial Hygiene and Toxicology: Volume II:
Toxicology. 2nd ed. New York: Interscience Publishers, 1963. 896]**PEER
REVIEWED**
EMERGENCY MEDICAL TREATMENT:
CLINICAL EFFECTS:
SUMMARY OF EXPOSURE
0.2.1.1 ACUTE EXPOSURE
o Sulfuric acid can be corrosive to the skin, eyes, nose,
mucous membranes, respiratory tract and
gastrointestinal tract, or any tissue with which it
comes in contact. Concentrated sulfuric acid chars the
tissue by removing water. Ingestion may cause
hemorrhaging, necrosis and perforation in the
gastrointestinal tract, typically more severe in the
stomach and intestinal tract than in the esophagus.
o Severe and fatal skin burns can occur with necrosis and
scarring. The eye is especially sensitive to the
corrosive effects and can be destroyed. Respiratory
effects of acute exposure include tickling in the nose
and throat, coughing, sneezing, reflex bronchospasm,
dyspnea, and pulmonary edema. Death may be from sudden
circulatory collapse, glottic or esophageal edema,
perforation of the stomach, gastric hemorrhage, or
delayed stricture.
o Milder exposures can cause irritation of the eyes,
skin, mucous membranes and respiratory and digestive
tracts.
Jacques Normandeau, PhD
20
0.2.1.2 CHRONIC EXPOSURE
o Chronic exposure may be associated with changes in
pulmonary function, chronic bronchitis, conjunctivitis,
emphysema, frequent respiratory infections, gastritis,
erosion of dental enamel, and possibly upper
respiratory cancer.
VITAL SIGNS
0.2.3.1 ACUTE EXPOSURE
o Inhalation of sulfuric acid mist causes a reflex
increase in respiratory rate and diminution of depth
with reflex bronchoconstriction, resulting in increased
pulmonary air flow resistance. Exposure to strong
mineral acids may produce circulatory collapse with
clammy skin, weak and rapid pulse, and shallow
respirations.
HEENT
0.2.4.1 ACUTE EXPOSURE
o The eyes are especially sensitive to the corrosive and
irritant effects of sulfuric acid. Sulfuric acid vapor
or mist is a strong irritant and can cause lacrimation
and conjunctivitis. Sulfuric acid is a strong irritant
of the mucous membranes and upper respiratory tract.
Ingestion of concentrated sulfuric acid can cause
corrosion and serious burns of mucous membranes of the
mouth, throat, and esophagus with necrosis and charring
of tissue. Laryngeal spasm or edema can occur.
0.2.4.2 CHRONIC EXPOSURE
o Discoloration or erosion of teeth, rhinorrhea and
frequent respiratory infections can occur from
prolonged or chronic exposure to sulfuric acid.
Jacques Normandeau, PhD
21
CARDIOVASCULAR
0.2.5.1 ACUTE EXPOSURE
o Sudden circulatory collapse can occur with shock if
large areas of the skin have been burned or with
gastric perforation and peritonitis. Ischemic lesions
in the heart may occur.
RESPIRATORY
0.2.6.1 ACUTE EXPOSURE
o Sulfuric acid mist is a severe irritant of the upper
respiratory tract in acute exposures. Inhalation of
sulfuric acid mist causes a reflex increase in
respiratory rate and diminution of depth with reflex
bronchoconstriction resulting in increased pulmonary
air flow resistance. Tracheobronchia l or pulmonary
edema can occur.
0.2.6.2 CHRONIC EXPOSURE
o Chronic exposure may be associated with chronic
bronchitis, frequent respiratory infections, and
emphysema.
GASTROINTESTINAL
0.2.8.1 ACUTE EXPOSURE
o Ingestion of sulfuric acid can cause epigastric pain,
nausea, and vomiting of mucoid and "coffee ground"
material. Occasionally vomiting of fresh blood has
been seen. Ingestion of concentrated sulfuric acid may
produce esophageal corrosion or stricture, or necrosis
and perforation of the esophagus or stomach especially
at the pylorus, and occasionally injury to the small
bowel.
0.2.8.2 CHRONIC EXPOSURE
o Chronic exposure has been associated with digestive
disturbances.
HEPATIC
0.2.9.1 ACUTE EXPOSURE
o Ischemic lesions may occur in the liver after several
hours of uncorrected circulatory collapse.
Jacques Normandeau, PhD
22
GENITOURINARY
0.2.10.1 ACUTE EXPOSURE
o Kidney failure and decreased urine output can occur.
ACID-BASE
0.2.11.1 ACUTE EXPOSURE
o Metabolic acidosis may be seen following ingestion.
HEMATOLOGIC
0.2.13.1 ACUTE EXPOSURE
o Leukocytosis is common after exposure to strong mineral
acids.
DERMATOLOGIC
0.2.14.1 ACUTE EXPOSURE
o Sulfuric acid is corrosive to the skin and in dilute
concentrations may cause dermatitis.
IMMUNOLOGIC
0.2.19.2 CHRONIC EXPOSURE
o Immunological alterations have been reported.
REPRODUCTIVE HAZARDS
o Sulfuric acid was teratogenic in one animal study.
Toxic effects have been observed in pregnancy.
CARCINOGENICITY
0.2.21.2 HUMAN OVERVIEW
o Several epidemiologic studies of workers chronically
exposed have suggested increased risk for respiratory
cancers.
LABORATORY:
o If respiratory tract irritation or respiratory depression
is evident, monitor arterial blood gases, chest x-ray, and
pulmonary function tests.
TREATMENT OVERVIEW:
Jacques Normandeau, PhD
23
SUMMARY EXPOSURE
o Move victims of inhala tion exposure from the toxic
environment and administer 100 percent humidified
supplemental oxygen with assisted ventilation as
required. Exposed skin and eyes should be copiously
flushed with water.
o Due to the potential for esophageal or gastrointestinal
tract burns following ingestion, emesis should not be
induced and gastric lavage done only with caution.
Immediate dilution with water or milk might be
beneficial. Do not give sodium bicarbonate in an
attempt to neutralize the acid.
ORAL EXPOSURE
o The possible benefit of early removal of some ingested
material by cautious gastric lavage must be weighed
against potential complications of perforation or
bleeding if significant esophageal or gastrointestinal
burns are present.
1. GASTRIC LAVAGE: Consider after ingestion of a
potentially life-threatening amount of poison if it can
be performed soon after ingestion (generally within 1
hour). Protect airway by placement in Trendelenburg
and left lateral decubitus position or by endotracheal
intubation. Control any seizures first.
a. CONTRAINDICATIONS: Loss of airway protective reflexes
or decreased level of consciousness in unintubated
patients; following ingestion of corrosives;
hydrocarbons (high aspiration potential); patients at
risk of hemorrhage or gastrointestinal perforation;
and trivial or non-toxic ingestion.
o DILUTION: Following ingestion and/or prior to gastric
evacuation, immediately dilute with 4 to 8 ounces (120
to 240 mL) of milk or water (not to exceed 15 mL/kg in a
child).
Jacques Normandeau, PhD
24
o Observe patients with ingestion carefully for the
possible development of esophageal or gastrointestinal
tract irritation or burns. If signs or symptoms of
esophageal irritation or burns are present, consider
endoscopy to determine the extent of injury.
o Steroid use is controversial. Surgical consultation
should be obtained if GI necrosis or perforation is
suspected.
INHALATION EXPOSURE
o DECONTAMINATION: Move patient to fresh air. Monitor
for respiratory distress. If cough or difficulty in
breathing develops, evaluate for respiratory tract
irritation, bronchitis, or pneumonitis. Administer 100
percent humidified supplemental oxygen with assisted
ventilation as required.
o PULMONARY EDEMA (NONCARDIOGENIC): Maintain ventilation
and oxygenation and evaluate with frequent arterial
blood gas or pulse oximetry monitoring. Early use of
PEEP and mechanical ventilation may be needed.
EYE EXPOSURE
o DECONTAMINATION: Exposed eyes should be irrigated with
copious amounts of tepid water for at least 15 minutes.
If irritation, pain, swelling, lacrimation, or
photophobia persist, the patient should be seen in a
health care facility.
o Prolonged initial flushing and early ophthalmologic
consultation are advisable.
DERMAL EXPOSURE
o DECONTAMINATION: Wash exposed area extremely thoroughly
with soap and water. A physician may need to examine
the area if irritation or pain persists.
o Treat dermal irritation or burns with standard topical
therapy. Patients developing dermal hypersensitivity
reactions may require treatment with systemic or topical
corticosteroids or antihistamines.
Jacques Normandeau, PhD
25
RANGE OF TOXICITY:
o The lowest toxic concentratio n by inhalatio n in humans was
3 mg/m(3) exposure over 24 weeks.
ANTIDOTE AND EMERGENCY TREATMENT:
For basic treatment: Establish a patent airway. Suction if necessary.
Watch for signs of respiratory insufficiency and assist respirations if
needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor
for pulmonary edema and treat if necessary. Monitor for shock and treat if
necessary. For eye contamination, flush eyes immediately with water.
Irrigate each eye continuously with normal saline during transport. Do not
use emetics. Activated charcoal is not effective. For ingestion, rinse
mouth and administer 5 ml/kg up to 200 ml of water for dilution if the
patient can swallow, has a strong gag reflex, and does not drool. Do not
attempt to neutralize because of exothermic reaction. Cover skin burns
with dry, sterile dressings after decontamination. For advanced treatment:
Consider orotracheal or nasotracheal intubation for airway control in the
patient who is unconscious, has severe pulmonary edema, or is in
respiratory arrest. Early intubation, at the first sign of upper airway
obstruction, may be necessary. Positive-pressure ventilatio n techniques
with a bag-valve-mask device may be beneficial. Monitor cardia c rhythm and
treat arrhythmias as necessary. Start an IV with D5W TKO. Use lactated
Ringer's if signs of hypovolemia are present. Watch for signs of fluid
overload. Consider drug therapy for pulmonary edema. For hypotension with
signs of hypovolemia, administer fluid cautiously. Consider vasopressors
if patient is hypotensive with a normal fluid volume. Watch for signs of
fluid overload. Use proparacaine hydrochloride to assist eye irrigatio n.
[Bronstein, A.C., P.L. Currance; Emergency Care for Hazardous Materials
Exposure. 2nd ed. St. Louis, MO. Mosby Lifeline. 1994. 149]**PEER
REVIEWED**
Jacques Normandeau, PhD
26
MECHANISM OF ACTION:
Particle (droplet) size seems to interplay along with temperature and
humidity to influence the toxic effects of sulfuric acid in the
respiratory tract. 2.5 um particles produced a marked increase in
pulmonary flow resistance at a concn of 40 mg/cu m. However, median
particle sizes of about 0.8 um were more effective at concn below 2.0
mg/cu m. It was concluded that large particles probably exerted their
effects on the middle respiratory tract (trachea and bronchi) whereas the
smaller particles produced simple reflex, bronchoconstriction. [Amdur MO;
Arch Ind Health 18: 407-14 (1958) as cited in NIOSH; Criteria Document:
Sulfuric acid p.47 (1974) DHEW Pub. NIOSH 74-128]**PEER REVIEWED**
Inhaled insoluble particles that deposit along normal healthy
tracheobronchia l airways of humans and other mammals are transported on
the proximally moving mucous lining to the larynx, where they are
swallowed. The transit time from the most distal ciliated airways varies
from 0.1 to 1 days, with each individual having a relatively constant,
characteristic time. The exact time course of clearance depends on the
distributions of both particle deposition and mucus velocitie s alo ng the
airways. There are too few data on intrabronchial deposition and
mucociliary transport rates for laboratory animals to permit a thorough
intercomparison among species. However, enough is known about the rela tive
lung sizes and anatomical differences among the various species to make
some preliminary, but important, distinctions. As compared to commonly
used experimental animals, humans have larger lungs and a more symmetric
upper bronchial airway branching pattern. In addition, humans do
considerable oral breathing, thus bypassing the effective air cleaning
capability of the nasal airways. These differences contributed to a
greater amount of upper bronchial airway particle deposition in humans, as
well as to greater concentrations of deposition on localized surfaces near
airway bifurcations. Airborne irritants that deposit in small ciliated
airways may produce marked changes in mucociliary transport. Such
materials include cigarette smoke, submicrometer sized sulfuric acid mist,
nitrogen dioxide, and ozone. ... [Lippmann M, Schesinger RB; J Toxicol
Environ Health 13 (2-3): 441-69 (1984)]**PEER REVIEWED**
Jacques Normandeau, PhD
27
The mucociliary clearance system is a first line of defense against
inhale d agents, and so its compromise can adversely affect health. The
purpose of this paper is to provide a review of data on the effect of in
vivo air pollutant exposures on the clearance of test particles from
airways. Data from both animals and humans are compared whenever possible ,
so that estimates of human health effects may be made. Mechanisms of
action are also discussed, presenting the view that for low level
exposures, changes in secretions are propably responsible for most
observed changes in clearance. The pollutants pertinent to this review are
those that are common in the environment and most likely to have impacts
on large numbers of people: sulfur oxides, sulfuric acid mist, ozone,
nitrogen dioxide, particulates, diesel exhaust, and cigarette smoke.
[Wolff RK; Environ Health Perspect 66: 223-37 (1986)]**PEER REVIEWED**
INTERACTIONS:
The effects of a combination of sulfuric acid mist at 8 mg/cu m and sulfur
dioxide at 89 ppm on growth, lung pathology, and respiratory response were
reported. In 8 pigs exposed for 8 hr, weight had decreased the day
following exposure and growth was slower to resume than was observed for
either agent administered separately. Two guinea pigs were exposed 72 hr
following the initial exposure to the same concn for another 8 hr. In
these reexposed animals, growth ceased entirely during the period of
observation following reexposure. Pathologic lung changes were also more
extensive than that observed for either agent alone, consistin g of large
areas of complete consolidation and hepatization involving entire lobes in
all cases. In the reexposed animals, extensive hemorrhage and
consolidation were present. It was commented that the general ill health
of the animals was very likely related to the presence of the extensive
lung damage. Labored breathing was very pronounced, continuing for 24 to
48 hr after exposure. In contrast, there were no noticeable respiratory
effects in guinea pigs exposed to 8 mg/cu m sulfuric acid mist alone.
Restlessness and annoyance initially appeared in animals exposed to 89 ppm sulfur dioxide alone, but
disappeared after approximately 5 to 10 min exposure. It was therefore concluded that effects on growth, lung
changes, and respiration were much more marked than would have been predicted from the use of either agent
alone. [Amdur MO; Public Health Rep 69: 503-6 (1954) as cited in NIOSH; Criteria Document: Sulfuric acid p.42
(1974) DHEW Pub. NIOSH 74-128]**PEER REVIEWED**
Jacques Normandeau, PhD
28
CHEMICAL/PHYSICAL PROPERTIES:
MOLECULAR FORMULA:
H2-O4-S **PEER REVIEWED**
MOLECULAR WEIGHT:
98.08 [Budavari, S. (ed.). The Merck Index - An Encyclopedia of Chemicals,
Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co., Inc., 1996.
1535]**PEER REVIEWED**
COLOR/FORM:
CLEAR, COLORLESS, OILY LIQ WHEN PURE BUT BROWNISH IN HUE WHEN IMPURE
[International Labour Office. Encyclopedia of Occupational Health and
Safety. Vols. I&II. Geneva, Switzerland: International Labour Office,
1983. 2125]**PEER REVIEWED**
Colorless to dark brown, oily liquid (Note: Pure compound is a solid below
51 degrees F. Often used in an aqueous solution). [NIOSH. NIOSH Pocket
Guide to Chemical Hazards. DHHS (NIOSH) Publication No. 94-116.
Washington, D.C.: U.S. Government Printing Office, June 1994. 290]**PEER
REVIEWED**
ODOR:
ODORLESS [Budavari, S. (ed.). The Merck Index - An Encyclopedia of
Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co.,
Inc., 1996. 1535]**PEER REVIEWED**
TASTE:
MARKED ACID TASTE [International Labour Office. Encyclopedia of
Occupational Health and Safety. Vols. I&II. Geneva, Switzerland:
International Labour Office, 1983. 2125]**PEER REVIEWED**
BOILING POINT:
ABOUT 290 DEG C [Budavari, S. (ed.). The Merck Index - An Encyclopedia of
Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co.,
Inc., 1996. 1535]**PEER REVIEWED**
Jacques Normandeau, PhD
29
MELTING POINT:
10.31 deg C [Lide, D.R. (ed.). CRC Handbook of Chemistry and Physics. 76th
ed. Boca Raton, FL: CRC Press Inc., 1995-1996.,p. 4-88]**PEER REVIEWED**
CORROSIVITY:
CONCENTRATED ACID IS NON-CORROSIVE TO LEAD & MILD STEEL BUT DIL ACID
ATTACKS MOST METALS. [Worthing, C. R. (ed.). Pesticide Manual. 6th ed.
Worcestershire, England: British Crop Protection Council, l979. 487]**PEER
REVIEWED**
Corrosion data for ASTM Grade 2 Titanium: Boiling sulfuric acid @ a
concentration of 1% by weight had a corrosion rate of 2.5 mm/yr.
[Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Volumes 1-26.
New York, NY: John Wiley and Sons, 1978-1984.,p. 23(83) 111]**PEER
REVIEWED**
Attacks and corrodes many metals releasing hydrogen. [ITII. Toxic and
Hazarous Industrial Chemicals Safety Manual. Tokyo, Japan: The
International Technical Information Institute, 1982. 499]**PEER REVIEWED**
DENSITY/SPECIFIC GRAVITY:
1.8 g/cu cm [Lide, D.R. (ed.). CRC Handbook of Chemistry and Physics. 76th
ed. Boca Raton, FL: CRC Press Inc., 1995-1996.,p. 4-88]**PEER REVIEWED**
DISSOCIATION CONSTANTS:
pKa = 1.98 at 25 deg C (2 step) [Lide, D.R. (ed.). CRC Handbook of
Chemistry and Physics. 76th ed. Boca Raton, FL: CRC Press Inc., 1995-1996.
4088]**PEER REVIEWED**
HEAT OF VAPORIZATION:
56 kJ/mole [Environment Canada; Tech Info for Problem Spills: Sulfuric
acid and Oleum (Draft) p.6 (1984)]**PEER REVIEWED**
PH:
1 N sol= 0.3, 0.1 N sol= 1.2, 0.01 N sol= 2.1 [Weast, R.C. (ed.) Handbook of Chemistry and Physics. 69th
ed. Boca Raton, FL: CRC Press Inc., 1988-1989.,p. D-146]**QC REVIEWED**
Jacques Normandeau, PhD
30
SOLUBILITIES:
SOL IN WATER & ETHYL ALCOHOL [International Labour Office.
Encyclopedia of Occupational Health and Safety. Vols. I&II. Geneva,
Switzerland: International Labour Office, 1983. 2124]**PEER REVIEWED**
SURFACE TENSION:
In contact with air or vapor @ 20 deg C= 55.1 dynes/cm /98.5% Sulfuric
acid/ [Weast, R.C. (ed.) Handbook of Chemistry and Physics. 69th ed. Boca
Raton, FL: CRC Press Inc., 1988-1989.,p. F-37]**QC REVIEWED**
VAPOR DENSITY:
3.4 (air= 1 at boiling point of sulfuric acid) [Mackison, F. W., R. S.
Stricoff, and L. J. Partridge, Jr. (eds.). NIOSH/OSHA - Occupational
Health Guidelines for Chemical Hazards. DHHS(NIOSH) PublicationNo. 81-123
(3 VOLS). Washington, DC: U.S. Government Printing Office, Jan. 1981.
2]**PEER REVIEWED**
VAPOR PRESSURE:
5.93X10-5 mm Hg at 25 deg C /from experimentally-derived coefficients/
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure
Chemicals Data Compilation. Washington, D.C.: Taylor and Francis,
1989.]**PEER REVIEWED**
VISCOSITY:
21 mPa.s (est 25 deg C) [Environment Canada; Tech Info for Problem Spills:
Sulphuric acid & Oleum (Draft) p.6 (1984)]**PEER REVIEWED**
OTHER CHEMICAL/PHYSICAL PROPERTIES:
VERY GREAT AFFINITY FOR WATER, ABSTRACTING IT FROM AIR & FROM MANY ORG
SUBSTANCES; HENCE IT CHARS SUGAR, WOOD, ETC; @ 340 DEG C IT DECOMP INTO
SULFUR TRIOXIDE & WATER; MISCIBLE WITH WATER & ALCOHOL WITH
GENERATION OF HEAT & WITH CONTRACTION IN VOL [Budavari, S. (ed.). The
Merck Index - An Encyclopedia of Chemicals, Drugs, and Biologicals.
Whitehouse Station, NJ: Merck and Co., Inc., 1996. 1535]**PEER REVIEWED**
Jacques Normandeau, PhD
31
DECOMP IN ALCOHOL [Weast, R.C. (ed.) Handbook of Chemistry and Physics.
69th ed. Boca Raton, FL: CRC Press Inc., 1988-1989.,p. B-136]**PEER
REVIEWED**
DECOMP SALTS OF OTHER ACIDS EXCEPT SILICIC ACID [Internatio nal Labour
Office. Encyclopedia of Occupational Health and Safety. Vols. I&II.
Geneva, Switzerland: International Labour Office, 1983. 2125]**PEER
REVIEWED**
Heat of solution: -418.0 BTU/lb= -232.2 cal/g= -9.715X10+5 J/kg [U.S.
Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical
Data. Volume II. Washington, D.C.: U.S. Government Printing Office,
1984-5.]**PEER REVIEWED**
Heat capacity constant pressure 138.9 J/mole x deg C (25 deg C)
[Environment Canada; Tech Info for Problem Spills: Sulp huric acid and
Oleum (Draft) p.6 (1984)]**PEER REVIEWED**
98% H2SO4 freezes at +3 deg C; 93% at -32 deg C; 78% at -38 deg C; 74% at
-44 deg C; and 65% at -64 deg C. [Budavari, S. (ed.). The Merck Index - An
Encyclopedia of Chemicals, Drugs, and Biologicals. Whitehouse Statio n, NJ:
Merck and Co., Inc., 1996. 1535]**PEER REVIEWED**
Spent sulfuric acid is a black oily liquid [Association of American
Railroads. Emergency Handling of Hazardous Materials in Surface
Transportation. Washington, D.C.: Assoc. of American Railroads,Hazardous
Materials Systems (BOE), 1987. 661]**PEER REVIEWED**
Jacques Normandeau, PhD
32
CHEMICAL SAFETY & HANDLING:
DOT EMERGENCY GUIDELINES:
Health: TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors,
dusts or substance may cause severe injury, burns, or death. Reactio n with
water or moist air will release toxic, corrosive or flammable gases.
Reaction with water may generate much heat which will increase the
concentration of fumes in the air. Fire will produce irritating, corrosive
and/or toxic gases. Runoff from fire control or dilution water may be
corrosive and/or toxic and cause pollution. /Sulfuric acid, with not more
than 51% acid/ [U.S. Department of Transportation. 1996 North American
Emergency Response Guidebook. A Guidebook for First Responders During the
Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S.
Department of Transportation (U.S. DOT) Research and Specia l Programs
Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Fire or explosion: Non-combustible, substance itself does not burn but may
decompose upon heating to produce corrosive and/or toxic fumes. Vapors may
accumulate in confined areas (basement, tanks, hopper/tank cars etc.).
Substance will react with water (some viole ntly), rele asing corrosive
and/or toxic gases. Reaction with water may generate much heat which will
increase the concentration of fumes in the air. Contact with metals may
evolve flammable hydrogen gas. Containers may explode when heated or
contaminated with water. /Sulfuric acid, with not more than 51% acid/
[U.S. Department of Transportation. 1996 North American Emergency Response
Guidebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of
Transportation (U.S. DOT) Research and Special Programs Administration,
Office of HazardousMaterials Initiatives and Training (DHM-50),
Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Jacques Normandeau, PhD
33
Public safety: CALL Emergency Response Tele phone Number. ... Isolate spill
or leak area immediately for at least 50 to 100 meters (160 to 330 feet)
in all directions. Keep unauthorized personnel away. Stay upwind. Keep out
of low areas. Ventilate enclosed areas. /Sulfuric acid, with not more than
51% acid/ [U.S. Department of Transportation. 1996 North American
Emergency Response Guidebook. A Guidebook for First Responders During the
Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S.
Department of Transportation (U.S. DOT) Research and Specia l Programs
Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Protective clothing: Wear positive pressure self-contained breathing
apparatus (SCBA). Wear chemical protective clothing which is specifically
recommended by the manufacturer. Structural firefighters' protective
clothing is recommended for fire situations ONLY; it is not effective in
spill situatio ns. /Sulfuric acid, with not more than 51% acid / [U.S.
Department of Transportation. 1996 North American Emergency Response
Guidebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of
Transportation (U.S. DOT) Research and Special Programs Administration,
Office of HazardousMaterials Initiatives and Training (DHM-50),
Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Evacuation: ... Fire: If tank, rail car or tank truck is involved in a
fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consid er
initial evacuation for 800 meters (1/2 mile) in all directions. /Sulfuric
acid, with not more than 51% acid/ [U.S. Department of Transportatio n.
1996 North American Emergency Response Guidebook. A Guidebook for First
Responders During the Initial Phase of aHazardous Materials/Dangerous
Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and
Special Programs Administration, Office of HazardousMaterials Initiatives
and Training (DHM-50), Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Jacques Normandeau, PhD
34
Fire: Note: Most foams will react with the material and release
corrosive/toxic gases. Small fires: CO2 ... , dry chemical, dry sand,
alcohol-resistant foam. Large fires: Water spray, fog or alcohol-resistant
foam. Move containers from fire area if you can do it without risk. Do not
use straight streams. Dike fire control water for later disposal; do not
scatter the material. Fire involving tanks or car/trailer loads: Fight
fire from maximum distance or use unmanned hose holders or monitor
nozzles. Do not get water inside containers. Cool containers with flooding
quantities of water until well after fire is out. Withdraw immediately in
case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from the ends of tanks. /Sulfuric acid, with not more
than 51% acid/ [U.S. Department of Transportation. 1996 North American
Emergency Response Guidebook. A Guidebook for First Responders During the
Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S.
Department of Transportation (U.S. DOT) Research and Specia l Programs
Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Spill or leak: ELIMINATE all ignitio n sources (no smokin g, flares, sparks
or flames in immediate area). All equip ment used when handling the product
must be grounded. Do not touch damaged containers or spilled material
unless wearing appropriate protective clothing. Stop leak if you can do it
without risk. A vapor suppressing foam may be used to reduce vapors. DO
NOT GET WATER INSIDE CONTAINERS. Use water spray to reduce vapors or
divert vapor clo ud drift. Prevent entry into waterways, sewers, basements
or confined areas. Small spills: Cover with DRY earth, DRY sand, or other
non-combustible material followed with plastic sheet to minimize spreading
or contact with rain. Use clean non-sparking tools to collect material and
place it into loosely covered plastic containers for later disposal.
/Sulfuric acid, with not more than 51% acid/ [U.S. Department of
Transportation. 1996 North American Emergency Response Guidebook. A
Guidebook for First Responders During the Initial Phase of aHazardous
Materials/Dangerous Goods Incident. U.S. Department of Transportation
(U.S. DOT) Research and Special Programs Administration, Office of
HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C.
(1996).,p. G-157]**PEER REVIEWED**
Jacques Normandeau, PhD
35
First aid: Move victim to fresh air. Call emergency medical care. Apply
artificial respiration if victim is not breathing. Do not use
mouth-to-mouth method if victim ingested or inhaled the substance; induce
artificial respiration with the aid of a pocket mask equipped with a
one-way valve or other proper respiratory medical device. Administer
oxygen if breathing is difficult. Remove and isolate contaminated clo thing
and shoes. In case of contact with substance, immediately flush skin or
eyes with running water for at least 20 minutes. For minor skin contact,
avoid spreading material on unaffected skin. Keep victim warm and quiet.
Effects of exposure (inhalation, ingestion or skin contact) to substance
may be delayed. Ensure that medical personnel are aware of the material(s)
involved, and take precautions to protect themselves. /Sulfuric acid , with
not more than 51% acid/ [U.S. Department of Transportation. 1996 North
American Emergency Response Guidebook. A Guid ebook for First Responders
During the Initial Phase of aHazardous Materials/Dangerous Goods Incident.
U.S. Department of Transportation (U.S. DOT) Research and Special Programs
Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. G-157]**PEER REVIEWED**
Health: TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors,
dusts or substance may cause severe injury, burns, or death. Fire will
produce irritating, corrosive and/or toxic gases. Reaction with water may
generate much heat which will increase the concentration of fumes in the
air. Contact with molten substance may cause severe burns to skin and
eyes. Runoff from fire control or dilution water may cause pollution.
/Sulfuric acid; Sulfuric acid, fuming; Sulfuric acid, fuming, with less
than 30% free sulfur trioxide; Sulfuric acid, fuming, with not le ss than
30% free sulfur trioxide; Sulfuric acid, spent; Sulfuric acid, with more
than 51% acid; Sulfuric acid, with not more than 51% acid/ [U.S.
Department of Transportation. 1996 North American Emergency Response
Guidebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of
Transportation (U.S. DOT) Research and Special Programs Administration,
Office of HazardousMaterials Initiatives and Training (DHM-50),
Washington, D.C. (1996).,p. G-137]**PEER REVIEWED**
Jacques Normandeau, PhD
36
Fire or explosion: Some of these materials may burn, but none ig nite
readily. May ignite combustibles (wood, paper, oil, clothing, etc.).
Substance will react with water (some viole ntly), rele asing corrosive
and/or toxic gases. Flammable/toxic gases may accumulate in confined areas
(basement, tanks, hopper/tank cars etc.). Contact with metals may evolve
flammable hydrogen gas. Containers may explode when heated or if
contaminated with water. Substance may be transported in a molten form.
/Sulfuric acid; Sulfuric acid, fuming; Sulfuric acid, fuming, with less
than 30% free sulfur trioxide; Sulfuric acid, fuming, with not le ss than
30% free sulfur trioxide; Sulfuric acid, spent; Sulfuric acid, with more
than 51% acid; Sulfuric acid, with not more than 51% acid/ [U.S.
Department of Transportation. 1996 North American Emergency Response
Guidebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of
Transportation (U.S. DOT) Research and Special Programs Administration,
Office of HazardousMaterials Initiatives and Training (DHM-50),
Washington, D.C. (1996).,p. G-137]**PEER REVIEWED**
Public safety: CALL Emergency Response Tele phone Number. ... Isolate spill
or leak area immediately for at least 50 to 100 meters (160 to 330 feet)
in all directions. Keep unauthorized personnel away. Stay upwind. Keep out
of low areas. Ventilate enclosed areas. /Sulfuric acid; Sulfuric acid ,
fuming; Sulfuric acid, fuming, with less than 30% free sulfur trioxide;
Sulfuric acid, fuming, with not less than 30% free sulfur trioxide;
Sulfuric acid, spent; Sulfuric acid, with more than 51% acid; Sulfuric
acid, with not more than 51% acid/ [U.S. Department of Transportatio n.
1996 North American Emergency Response Guidebook. A Guidebook for First
Responders During the Initial Phase of aHazardous Materials/Dangerous
Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and
Special Programs Administration, Office of HazardousMaterials Initiatives
and Training (DHM-50), Washington, D.C. (1996).,p. G-137]**PEER REVIEWED**
Jacques Normandeau, PhD
37
Protective clothing: Wear positive pressure self-contained breathing
apparatus (SCBA). Wear chemical protective clothing which is specifically
recommended by the manufacturer. Structural firefighters' protective
clothing is recommended for fire situations ONLY; it is not effective in
spill situatio ns. /Sulfuric acid; Sulfuric acid, fuming; Sulfuric acid,
fuming, with less than 30% free sulfur trioxide; Sulfuric acid, fuming,
with not less than 30% free sulfur trioxide; Sulfuric acid, spent;
Sulfuric acid, with more than 51% acid; Sulfuric acid, with not more than
51% acid/ [U.S. Department of Transportation. 1996 North American
Emergency Response Guidebook. A Guidebook for First Responders During the
Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S.
Department of Transportation (U.S. DOT) Research and Specia l Programs
Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. G-137]**PEER REVIEWED**
Evacuation: ... Fire: If tank, rail car or tank truck is involved in a
fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consid er
initial evacuation for 800 meters (1/2 mile) in all directions. /Sulfuric
acid; Sulfuric acid, fuming; Sulfuric acid, fuming, with less than 30%
free sulfur trioxide; Sulfuric acid, fuming, with not less than 30% free
sulfur trioxide; Sulfuric acid, spent; Sulfuric acid, with more than 51%
acid; Sulfuric acid, with not more than 51% acid/ [U.S. Department of
Transportation. 1996 North American Emergency Response Guidebook. A
Guidebook for First Responders During the Initial Phase of aHazardous
Materials/Dangerous Goods Incident. U.S. Department of Transportation
(U.S. DOT) Research and Special Programs Administration, Office of
HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C.
(1996).,p. G-137]**PEER REVIEWED**
Fire: When material is not involved in fire: do not use water on material
itself. Small fires: Dry chemical or C02. Move containers from fire area
if you can do it without risk. Large Fires: Flood fire area with large
quantities of water, while knocking down vapors with water fog. If
insufficient water supply: knock down vapors only. Fire in volving tanks or
car/trailer loads: Cool containers with flooding quantities of water until
well after fire is out. Do not get water inside containers. Withdraw
Jacques Normandeau, PhD
38
immediately in case of rising sound from venting safety devices or
discoloration of tank. ALWAYS stay away from the ends of tanks. /Sulfuric
acid; Sulfuric acid, fuming; Sulfuric acid, fuming, with less than 30%
free sulfur trioxide; Sulfuric acid, fuming, with not less than 30% free
sulfur trioxide; Sulfuric acid, spent; Sulfuric acid, with more than 51%
acid; Sulfuric acid, with not more than 51% acid/ [U.S. Department of
Transportation. 1996 North American Emergency Response Guidebook. A
Guidebook for First Responders During the Initial Phase of aHazardous
Materials/Dangerous Goods Incident. U.S. Department of Transportation
(U.S. DOT) Research and Special Programs Administration, Office of
HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C.
(1996).,p. G-137]**PEER REVIEWED**
Spill or leak: Fully encapsula ting, vapor protective clothing should be
worn for spills and leaks with no fire. Do not touch damaged containers or
spilled material unless wearing appropriate protective clothing. Stop le ak
if you can do it without risk. Use water spray to reduce vapors; do not
put water directly on leak, spill area or inside contain er. Keep
combustibles (wood, paper, oil, etc.) away from spilled material. Small
spills: Cover with DRY earth, DRY sand, or other non-combustible material
followed with plastic sheet to minimize spreading or contact with rain.
Use clean non-sparking tools to collect material and place it into loosely
covered plastic containers for later disposal. Prevent entry into
waterways, sewers, basements or confined areas. /Sulfuric acid; Sulfuric
acid, fuming; Sulfuric acid, fuming, with less than 30% free sulfur
trioxide; Sulfuric acid, fuming, with not less than 30% free sulfur
trioxide; Sulfuric acid, spent; Sulfuric acid, with more than 51% acid;
Sulfuric acid, with not more than 51% acid/ [U.S. Department of
Transportation. 1996 North American Emergency Response Guidebook. A
Guidebook for First Responders During the Initial Phase of aHazardous
Materials/Dangerous Goods Incident. U.S. Department of Transportation
(U.S. DOT) Research and Special Programs Administration, Office of
HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C.
(1996).,p. G-137]**PEER REVIEWED**
Jacques Normandeau, PhD
39
First aid: Move victim to fresh air. Call emergency medical care. Apply
artificial respiration if victim is not breathing. Do not use
mouth-to-mouth method if victim ingested or inhaled the substance; induce
artificial respiration with the aid of a pocket mask equipped with a
one-way valve or other proper respiratory medical device. Administer
oxygen if breathing is difficult. Remove and isolate contaminated clo thing
and shoes. In case of contact with substance, immediately flush skin or
eyes with running water for at least 20 minutes. For minor skin contact,
avoid spreading material on unaffected skin. Removal of solidified molten
material from skin requires medical assistance. Keep victim warm and
quiet. Effects of exposure (inhala tion, ingestio n or skin contact) to
substance may be delayed. Ensure that medical personnel are aware of the
material(s) involved, and take precautions to protect themselves.
/Sulfuric acid; Sulfuric acid, fuming; Sulfuric acid, fuming, with less
than 30% free sulfur trioxide; Sulfuric acid, fuming, with not le ss than
30% free sulfur trioxide; Sulfuric acid, spent; Sulfuric acid, with more
than 51% acid; Sulfuric acid, with not more than 51% acid/ [U.S.
Department of Transportation. 1996 North American Emergency Response
Guidebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of
Transportation (U.S. DOT) Research and Special Programs Administration,
Office of HazardousMaterials Initiatives and Training (DHM-50),
Washington, D.C. (1996).,p. G-137]**PEER REVIEWED**
Initial Isolation and Protective Action Distances: Small Spills (from a small package or small leak from a large
package): First, ISOLATE in all Directions 60 meters (200 feet); then, PROTECT persons Downwind during DAY
0.2 kilometers (0.1 miles) and NIGHT 0.8 kilometers (0.5 miles). LARGE SPILLS (from a large package or from
many small packages): First, ISOLATE in all Directions 185 meters (600 feet); then, PROTECT persons
Downwind during DAY 0.6 kilometers (0.4 miles) and NIGHT 2.9 kilometers (1.8 miles). /Sulfuric acid, fuming;
Sulfuric acid, fuming, with not less than 30% free sulfur trioxide/ [U.S. Department of Transportation. 1996 North
American Emergency Response Guid ebook. A Guidebook for First Responders During the Initial Phase of
aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and
Special Programs Administration, Office of HazardousMaterials Initiatives and Training
(DHM-50), Washington, D.C. (1996).,p. TABLE]**PEER REVIEWED**
ODOR THRESHOLD:
Jacques Normandeau, PhD
40
GREATER THAN 1 MG/CU M. [U.S. Coast Guard, Department of Transportatio n.
CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S.
Government Printing Office, 1984-5.]**PEER REVIEWED**
Threshold for odor= 1.0 mg/cu m, Irritating concn= 1.1 mg/cu m [Ruth JH;
Am Ind Hyg Assoc J 47: A-142-51 (1986)]**PEER REVIEWED**
SKIN, EYE AND RESPIRATORY IRRITATIONS:
... SULFURIC ACID MIST ... STRONGLY IRRITANT & INHALATION OF CONCN OF
AROUND 3 MG/CU M CAUSES CHOKING SENSATION IN UNINITIATED. PERSONS
ACCUSTOMED TO EXPOSURE ARE UNABLE TO NOTICE CONCN OF THIS ORDER OF
MAGNITUDE. [Patty, F. (ed.). Industrial Hygiene and Toxicology: Volume II:
Toxicology. 2nd ed. New York: Interscience Publishers, 1963. 896]**PEER
REVIEWED**
FIRE POTENTIAL:
NOT COMBUSTIBLE. [National Fire Protection Guide. Fire Protection Guide on
Hazardous Materials. 10 th ed. Quincy, MA: National Fire Protection
Association, 1991.,p. 49-105]**PEER REVIEWED**
NFPA HAZARD CLASSIFICATION:
Health: 3. 3= Materials that, on short exposure, could cause serious
temporary or residual injury, including those requiring protection from
all bodily contact. Fire fighters may enter the area only if they are
protected from all contact with the material. Full protective clothing,
incl self-contained breathing apparatus, coat, pants, gloves, boots and
bands around legs, arms and waist should be provided. No skin surface
should be exposed. [National Fire Protection Guide. Fire Protection Guid e
on Hazardous Materials. 10 th ed. Quincy, MA: National Fire Protection
Association, 1991.,p. 49-165]**PEER REVIEWED**
Flammability: 0. 0= Any material that will not burn. [National Fire
Protection Guide. Fire Protection Guide on Hazardous Materials. 10 th ed.
Quincy, MA: National Fire Protection Association, 1991.,p. 49-165]**PEER
REVIEWED**
Reactivity: 2. 2= Includs materials that, are normally unstable and
Jacques Normandeau, PhD
41
readily undergo violent chemical change, but are not capable of
detonation. This includes materials that can undergo chemical change with
rapid releases of energy at normal temperatures and pressures and
materials that can undergo viole nt chemical change at elevated
temperatures and pressures. This also includes materials that may react
violently with water or which may form potentially explosive mixtures with
water. In advanced or massive fires, fire fighting should be done from a
safe distance or a protected location. [National Fire Protection Guide.
Fire Protection Guide on Hazardous Materials. 10 th ed. Quincy, MA:
National Fire Protection Association, 1991.,p. 49-165]**PEER REVIEWED**
FIRE FIGHTING PROCEDURES:
Extinguish fire using agents suitable for nearly fires. Use water spray
only to keep fire-exposed containers cool. [National Fire Protection
Guide. Fire Protection Guide on Hazardous Materials. 10 th ed. Quincy, MA:
National Fire Protection Association, 1991.,p. 49-165]**PEER REVIEWED**
TOXIC COMBUSTION PRODUCTS:
WHEN HEATED, IT EMITS HIGHLY TOXIC FUMES. [Lewis, R.J. Sax's Dangerous
Properties of Industrial Materials. 9th ed. Volumes 1-3. New York, NY: Van
Nostrand Reinhold, 1996. 3047]**PEER REVIEWED**
HAZARDOUS REACTIVITIES & INCOMPATIBILITIES:
Concn-acid oxidizes, dehydrates, or sulfonates most organic compounds.
[ITII. Toxic and Hazarous Industrial Chemicals Safety Manual. Tokyo,
Japan: The International Technical Information Institute, 1982. 499]**PEER
REVIEWED**
p-Chloronitrobenzene, sulfur trioxide and sulfuric acid: The reactio n
mixture from sulfonation of the nitro-compound in 20% oleum, containing
35% wt of 2-chloro-5-nitrobenzene-sulfonic acid, shows two exothermic
stages at 100 deg C, respectively, the latter being violently rapid. The
adiabatic reaction mixture, initially at 89 deg C, attained 285 deg C with
boiling after 17 hr. At 180 deg C the induction period was about 20 min.
Sulfonation of p-chloronitrobenzene with 65% oleum at 46 deg C led to a
runaway decomposition reaction in a 2000 l vessel. The original process
Jacques Normandeau, PhD
42
using 20% oleum was less sensitive to heating rate and temperature.
Knowledge that the reaction could be dangerous above 50 deg C had not been
applied. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed.
Boston, MA: Butterworth-Heinemann Ltd., 1990 1216]**PEER REVIEWED**
Addition of sulfuric acid to the cyano-alcohol caused a vigorous reaction
which pressure-ruptured. This seems likely to have been due to
insufficient cooling to prevent dehydration of the alcohol to
methylacrylonitrile and lack of inhibitors to prevent exothermic
polymerization of the nitrile. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
1217]**PEER REVIEWED**
Cyclopentanone oxime and sulfuric acid: Heating the oxime with 85%
sulfuric acid to effect the Beckmann rearrangement caused eruption of the
stirred flask contents. Benzenesulfonyl chloride in alkali was a less
vigorous reagent. [Bretherick, L. Handbook of Reactive Chemical Hazards.
4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 536]**PEER REVIEWED**
Metal acetylides or carbides and sulfuric acid: Monocesium and
monorubidium acetylides ignite with concn sulfuric acid. Other carbides
are hazardous in contact. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 1219]**PEER
REVIEWED**
Nitroaryl bases and derivatives and sulfuric acid: A series of o- and
p-nitroaniline derivatives and analogs when heated with sulfuric acid to
above 200 deg C undergo, after an induction period, a vigorous reaction.
This is accompanied by gas evolution which produces up to a 150-fold
increase in volume of a solid foam, and is rapid enough to be potentially
hazardous if confined. o-Nitroaniline reacts almost explosively and
p-nitroaniline, p-nitroacetanilide, aminonitrodiphenyls, /o and p/
naphthalenes and various derivatives, as well as some
nitro-N-heterocycles, also react vigorously. p-Nitroanilinium sulfate and
4-nitroaniline-2-sulfonic acid and its salts also generate foams when
heated without sulfuric acid. [Bretherick, L. Handbook of Reactive
Jacques Normandeau, PhD
43
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
1219]**PEER REVIEWED**
Permanganates and sulfuric acid: Interaction produces the powerful
oxidant, permanganic acid. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 1220]**PEER
REVIEWED**
Phosphorous and sulfuric acid: White phosphorous ignites in contact with
boiling sufuric acid or its vapor. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
1220]**PEER REVIEWED**
Tetramethylbenzenes and sulfuric acid: Sulfonation of the mixed isomers of
1,2,3,5- and 1,2,4,5-tetramethylbenzenes was too vio lent for shaking in a
closed glass vessel. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 1221]**PEER
REVIEWED**
Zinc iodide and sulfuric acid: Interaction with the concn acid is violent.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1221]**PEER REVIEWED**
Water and sulfuric acid: Dilution of sulfuric acid with water is
vigorously exothermic, and must be effected by adding acid to water to
avoid local boiling. Mixtures of sulfuric acid and excess snow form
powerful freezing mixtures. Fuming sulfuric acid (containing sulfur
trioxides) reacts violently with water. [Bretherick, L. Handbook of
Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd.,
1990 1221]**PEER REVIEWED**
Acetaldehyde and sulfuric acid: Acetaldehyde is polymerized violently by
the concn acid. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th
ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 272]**PEER REVIEWED**
Nitric acid, acetone and sulfuric acid: Acetone is oxidized violently by
Jacques Normandeau, PhD
44
mixed nitric-sulfuric acids, and if the mixture is confined in a
narrow-mouthed vessel, it may be ejected or explode. [Bretherick, L.
Handbook of Reactive Chemical Hazards. 2nd ed. Boston MA: Butterworths,
1979. 925]**PEER REVIEWED**
Acetonitrile, sulfur trioxide, and sulfuric acid: A mixture of
acetonitrile and sulfuric acid on heating (or self heating) to 53 deg C
underwent an uncontrollable exotherm to 160 deg C in a few seconds. The
presence of 28 mol % of sulfur trioxide reduces the in itiation temperature
to about 15 deg C. Polymerization of acetonitrile is suspected.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 2nd ed. Boston MA:
Butterworths, 1979. 363]**PEER REVIEWED**
Acrylonitrile and acids: Contact of strong acids (sulfuric or nitric) with
acrylonitrile may lead to vigorous reactions. Even small amounts of acid
are potentially dangerous, as these may neutralize the aqueous ammonia
present as polymerization inhibitor and leave the nitrile unstabilized. It
is essential to use well-chilled in gredients (acrylonitrile, diluted
sulfuric acid, hydroquinone, copper powder) to avoid eruption and
carbonization. A really wide bore condenser is necessary to cope with
vigorous boiling of unhydrolysed acrylonitrile. [Bretherick, L. Handbook
of Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann
Ltd., 1990 350]**PEER REVIEWED**
Bromine pentafluoride and strong sulfuric acid: Contact at ambient or
slightly elevated temperatures is violent, ignition often occurring.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 93]**PEER REVIEWED**
1-chloro-2,3-epoxypropane and sulfuric acid: Interaction is viole nt.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 364]**PEER REVIEWED**
Jacques Normandeau, PhD
45
2-Cyano-4-nitrobenzenediazonium hydrogen sulfate and sulfuric acid: ...
35% solution of the diazonium salt in sulfuric acid showed three
exotherms, corresponding to hydrolysis of the nitrile group (peak at 95
deg C), decomposition of the diazonium salt (peak at 160 deg C) and lo ss
of the nitro group (large peak at 240 deg C). Adiabatic decomposition of
the solution from 50 deg C also showed three steps, with in duction periods
of a 30, 340 and 380 min, respectively. [Bretherick, L. Handbook of
Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd.,
1990 686]**PEER REVIEWED**
1,3-Diazidobenzene and sulfuric acid: The azide ignites and explodes
mildly with concn acid. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 591]**PEER
REVIEWED**
Mixo-dimethoxydinitroanthraquinone and sulfuric acid: During hydrolysis of
crude dimethoxydinitroanthraquinone by heating in sulfuric acid , a runaway
exothermic decomposition occurred causing vessel failure. Experiment
showed a threshold decomposition temperature of 150-155 deg C, and
oxidizing effect of nitro groups, yieldin g carbon monoxide and carbon
dioxide above 162 deg C. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 881]**PEER
REVIEWED**
1,5-Dinitronaphthalene, sulfur, and sulfuric acid: For industrial
conversion to 5-aminonaphthoquinone derivatives, dinitronaphthalene was
mixed cold with sulfuric acid and sulfur. The unheated mixture exploded
violently. Investigation in the safety colorimeter showed that an
exothermic reaction begins at only 30 deg C, and that the onset and
intensity of the exotherm markedly depends upon quality of the
dinitronaphthalene. [Bretherick, L. Handbook of Reactive Chemical Hazards.
4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 798]**PEER REVIEWED**
Nitromethane and acids: Addition of acids to nitromethane renders it susceptible to in itiation by a detonator.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
162]**PEER REVIEWED**
Jacques Normandeau, PhD
46
Phosphorus (III) oxide and sulfuric acid: Addition of sulfuric acid to the
oxide causes violent oxidation, and ignition if more than 1-2 g is used.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1432]**PEER REVIEWED**
Sodium carbonate and sulfuric acid: Lack of any mixing arrangements caused
stratification of strong sulfuric acid and ... sodium carbonate solutions
in the same tank. When gas evolution caused intermixture of the layers, a
violent eruption of the tank contents occurred. [Bretherick, L. Handbook
of Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann
Ltd., 1990 192]**PEER REVIEWED**
Sodium tetrahydroborate (sodium borohydride): Ignition may occur if the
mixture is not cooled. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 65]**PEER
REVIEWED**
1,2,4,5-Tetrazine and sulfuric acid: The solid base decomposes violently
in contact with the concn acid. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
241]**PEER REVIEWED**
Cesium acetylene carbide burns with sulfuric acid. [National Fire
Protection Guide. Fire Protection Guide on Hazardous Materials. 10 th ed.
Quincy, MA: National Fire Protection Association, 1991.,p. 491M-50]**PEER
REVIEWED**
Sulfuric acid reacts violently with the following: bromine pentafluoride,
chlorine trifluoride, cuprous nitride, ethylene cyanohydrin,
epichlorhydrin, phosphorus isocyanate. [National Fire Protection Guide.
Fire Protection Guide on Hazardous Materials. 10 th ed. Quincy, MA:
National Fire Protection Association, 1991.,p. 491M-205]**PEER REVIEWED**
Jacques Normandeau, PhD
47
Mixing any of the following with 96% sulfuric acid in a clo sed contain er
caused the temp and pressure to increase: hydrochloric acid, hydrofluoric
acid, vinyl acetate, acetic anhydride, acetonitrile, acrolein,
2-aminoethanol, ammonium hydroxide, aniline, n-butyraldehyde,
chlorosulfonic acid, diisobutylene, ethylenediamine, ethylene glycol,
isoprene, mesityl oxide, propiolactone, propylene oxide, pyridine, sodium
hydroxide, styrene monomer. [National Fire Protection Guide. Fire
Protection Guide on Hazardous Materials. 10 th ed. Quincy, MA: Natio nal
Fire Protection Association, 1991.,p. 491M-205]**PEER REVIEWED**
Mixtures of sulfuric acid and any of the following can explode:
p-nitrotoluene, pentasilver trihydroxydiaminophosphate, perchlorates,
alcohols with strong hydrogen peroxide, ammonium tetraperoxychromate,
mercuric nitrite, potassium chlorate, potassium permanganate with
potassium chloride. [National Fire Protection Guide. Fire Protection Guide
on Hazardous Materials. 10 th ed. Quincy, MA: National Fire Protection
Association, 1991.,p. 491M-205]**PEER REVIEWED**
Sulfuric acid, nitric acid and fat were placed in a tightly clo sed
container. Within 10 minutes, the container exploded. [National Fire
Protection Guide. Fire Protection Guide on Hazardous Materials. 10 th ed.
Quincy, MA: National Fire Protection Association, 1991.,p. 491M-138]**PEER
REVIEWED**
It is fairly easy to produce the dangerous anhydrous perchloric acid from
either its salts or its aqueous solutions by heating with high-boiling
acids and dehydrating agents such as sulfuric acid and phosphorus
pentoxide. [National Fire Protection Guide. Fire Protection Guide on
Hazardous Materials. 10 th ed. Quincy, MA: National Fire Protection
Association, 1991.,p. 491M-154]**PEER REVIEWED**
Ammonium iron (III) sulfate dodecahydrate and sulfuric acid: A few dense
crystals heated with sulfuric acid exploded, owing to the exotherm in
contact with water liberated as the crystals disintegrated. [Bretherick,
L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1216]**PEER REVIEWED**
Jacques Normandeau, PhD
48
Benzyl alcohol and sulfuric acid: A mixture of the alcohol with 58%
sulfuric acid decomposes explosively at about 180 deg C. [Bretherick, L.
Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1216]**PEER REVIEWED**
Cyclopentadiene and sulfuric acid: It reacts violently with charring, or
explodes in contact with concn sulfuric acid. [Bretherick, L. Handbook of
Reactive Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd.,
1990 1217]**PEER REVIEWED**
p-Dimethylaminobenzaldehyde and sulfuric acid: During preparation of a
solution of the aldehyde in dilute sulfuric acid, the latter should be
prepared before addition of the aldehyde. An attempt to prepare the
solution in concn acid from a slurry of the aldehyde in a little water
caused the stoppered flask to explode. This was attributed to the exotherm
caused by addition of a little water and the basic aldehyde to the concn
acid. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed.
Boston, MA: Butterworth-Heinemann Ltd., 1990 1218]**PEER REVIEWED**
1,3-Diazidobenzene and sulfuric acid: The azide ignites and explodes
mildly with concn acid. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 591]**PEER
REVIEWED**
Hexalithium disilicide and acids: The silicide incandesces in concn
hydrochloric acid, and with dilute acid evolves silicon hydrides which
ignite. It explodes with nitric acid and incandesces when floated on
sulfuric acid. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th
ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 1320]**PEER REVIEWED**
Hydrogen peroxide and sulfuric acid: Evaporation of mixtures of excess 50%
hydrogen peroxide solution with sulfuric acid (10:1) leads to loud but
non-shattering explosions of the peroxomonsulfuric acid formed.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1214]**PEER REVIEWED**
Jacques Normandeau, PhD
49
Nitric amide and sulfuric acid: Nitramide decomposes explosively on
contact with concn sulfuric acid. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
1196]**PEER REVIEWED**
Nitric acid and sulfuric acid: The gland of a centrifugal pump bein g used
to pump nitrating acid (nitric-sulfuric acids, 1:3) exploded after 10 min
use. This was attributed to nitration of the gland packing, followed by
frictional detonation. Insert shaft sealing material is advocated.
[Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1176]**PEER REVIEWED**
Nitric acid, organic matter, and sulfuric acid: Use of the mixed concn
acids to dissolve an organic residue caused a violent explosion. Nitric
acid is a very powerful and rapid oxidant and may form unstable fulminic
acid or polynitro compounds under these conditions. [Bretherick, L.
Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1173]**PEER REVIEWED**
Nitrobenzene was washed with dilute (5%) sulfuric acid to remove amines,
and became contaminated with some acid emulsion which had formed. After
distillation, the hot, acid, tarry residue attacked the iron vessel,
evolving hydrogen, and eventually exploded. It was later found that
addition of the nitrobenzene to the diluted acid did not give emulsions,
while the reversed addition did. A final wash with sodium carbonate
solution was added to the process. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
605]**PEER REVIEWED**
m-Nitrobenzenesulfonic acid and sulfuric acid: A 270 l batch of a solu tion in sulfuric acid explo ded viole ntly
after storage at about 150 deg C for several hr. An exotherm develops at 145 deg C, and the acid is known to
decompose at about 200 deg C. The earlier case history describes a similar incident when water, leakin g from a
cooling coil into the fuming sulphuric acid medium, caused an exotherm to over 150 deg C, and subsequent
violent decomposition. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 608]**PEER REVIEWED**
Jacques Normandeau, PhD
50
N-Nitromethylamine and sulfuric acid: The nitroamine is decomposed
explosively by concn sulfuric acid. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990
172]**PEER REVIEWED**
p-Nitrotoluene and sulfuric acid: Solutions of p-nitrotoluene in 93%
sulfuric acid decompose very violently if heated to 160 deg C. This
happened on plant-scale when automatic temperature control failed. The
explosion temperature of 160 deg C for the mixture (presumably containing
a high proportion of 4-nitrotoluene-2-sulfonic acid) is 22 deg C lower
than that observed for onset of decomposition when p-nitrotoluene and 93%
sulfuric acid are heated at a rate of 100 deg C/hr. Mixtures of
p-nitrotoluene with 98% acid or 20% oleum begin to decompose at 180 deg C
and 190 deg C, respectively. Thereafter, decomposition accelerates
(190-224 deg C in 14 min, 224-270 deg C in 1.5 min) until eruption occurs
with evolution of much gas. [Bretherick, L. Handbook of Reactive Chemical
Hazards. 4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 708]**PEER
REVIEWED**
Potassium and sulfuric acid: Interaction is explosive. [Bretherick, L.
Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1292]**PEER REVIEWED**
Silver peroxochromate and sulfuric acid: In attempts to prepare
"perchromic acid," a mixture of silver (or barium) peroxochromate and 50%
sulfuric acid prepared at -80 deg C reacted explosively on slo w warming to
about -30 deg C. [Bretherick, L. Handbook of Reactive Chemical Hazards.
4th ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 15]**PEER REVIEWED**
Sulfuric acids react slowly with sodium, while the aqueous solutions react
explosively. [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th
ed. Boston, MA: Butterworth-Heinemann Ltd., 1990 1371]**PEER REVIEWED**
Thallium (I) azidodithiocarbonate and sulfuric acid: The highly unstable explosive salt is initiated by contact
with sulfuric acid . [Bretherick, L. Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 188]**PEER REVIEWED**
Jacques Normandeau, PhD
51
Mercury nitride and sulfuric acid: Explodes on contact. [Bretherick, L.
Handbook of Reactive Chemical Hazards. 4th ed. Boston, MA:
Butterworth-Heinemann Ltd., 1990 1277]**PEER REVIEWED**
1,3,5-Trinitrosohexahydro-1,3,5-triazine and sulfuric acid: Concn sulfuric
acid causes explosive decomposition. [Bretherick, L. Handbook of Reactive
Chemical Hazards. 2nd ed. Boston MA: Butterworths, 1979. 438]**PEER
REVIEWED**
Organic materials, chlorinates, carbides, fulminates, water, powdered
metals. [Note: Reacts violently with water with evolution of heat.
Corrosive to metals.] [NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS
(NIOSH) Publication No. 97-140. Washington, D.C. U.S. Government Printing
Office, 1997. 290]**QC REVIEWED**
OTHER HAZARDOUS REACTION:
Oxides of sulfur may be produced in fire. [National Fire Protection Guide.
Fire Protection Guide on Hazardous Materials. 10 th ed. Quincy, MA:
National Fire Protection Association, 1991.,p. 49-165]**PEER REVIEWED**
IMMEDIATELY DANGEROUS TO LIFE OR HEALTH:
15 mg/cu m [NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS (NIOSH)
Publication No. 97-140. Washington, D.C. U.S. Government Printing Office,
1997. 290]**QC REVIEWED**
PROTECTIVE EQUIPMENT & CLOTHING:
... CHEM GOGGLES, FACE SCREENS, GLOVES, NEOPRENE OR PVC BOOTS &
ACID-RESISTANT TROUSERS, THE LEGS OF WHICH SHOULD FALL OVER THE BOOTS AND
NOT BE TUCKED INTO THEM. [International Labour Office. Encyclopedia of
Occupational Health and Safety. Vols. I&II. Geneva, Switzerland:
International Labour Office, 1983. 2126]**PEER REVIEWED**
Breakthrough times of sulfuric acid through neoprene or polyvinyl chloride
are greater than one hour reported by (normally) two or more testers.
[ACGIH; Guidelines Select of Chem Protect Clothing Volume #1 Field Guide
p.66 (1983)]**PEER REVIEWED**
Jacques Normandeau, PhD
52
There is some data suggesting that the breakthrough times of sulfuric acid
( < 30%, 30-70%, and > 70%) through polyethylene, Saranex, chlorinated
polyethylene, neoprene, nitrile, polyvinyl chloride, viton, or
styrene-butadiene are approximately an hour or more. [ACGIH; Guidelines
Select of Chem Protect Clothing Volume #1 Field Guide p.66 (1983)]**PEER
REVIEWED**
Wear appropriate personal protective clothing to prevent skin contact.
[NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS (NIOSH) Publication
No. 97-140. Washington, D.C. U.S. Government Printing Office, 1997.
291]**QC REVIEWED**
Wear appropriate eye protection to prevent eye contact. [NIOSH. NIOSH
Pocket Guide to Chemical Hazards. DHHS (NIOSH) Publicatio n No. 97-140.
Washington, D.C. U.S. Government Printing Office, 1997. 291]**QC
REVIEWED**
Eyewash fountains should be provided in areas where there is any
possbility that workers could be exposed to the substance; this is
irrespective of the recommendation involving the wearing of eye
protection. / > 1%/ [NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS
(NIOSH) Publication No. 97-140. Washington, D.C. U.S. Government Printing
Office, 1997. 291]**QC REVIEWED**
Facilities for quickly drenchin g the body should be provid ed within the
immediate work area for emergency use where there is a possibility of
exposure. (Note: It is intended that these facilities provide a sufficient
quantity or flow of water to quickly remove the substance from any body
areas likely to be exposed. The actual determination of what constitutes
an adequate quick drench facility depends on the specific circumstances.
In certain instances, a deluge shower should be readily available , whereas
in others, the availability of water from a sin k or hose could be
considered adequate.) / > 1%/ [NIOSH. NIOSH Pocket Guide to Chemical
Hazards. DHHS (NIOSH) Publication No. 97-140. Washington, D.C. U.S.
Government Printing Office, 1997. 291]**QC REVIEWED**
Jacques Normandeau, PhD
53
Recommendations for respirator selection. Max concn for use: 15 mg/cu m.
Respirator Class(es): Any supplied-air respirator operated in a
continuous-flow mode. Eye protection needed. Any powered, air-purifying
respirator with acid gas cartridge(s) in combination with a
high-efficiency particulate filter. Eye protection needed. Any chemical
cartridge respirator with a full facepiece and acid gas cartridge(s) in
combination with a high-efficiency particulate filter. Any air-purifying,
full-facepiece respirator (gas mask) with a chin-style, front- or
back-mounted acid gas canister having a high-efficiency particulate
filter. Any self-contained breathing apparatus with a full facepiece. Any
supplied-air respirator with a full facepiece. [NIOSH. NIOSH Pocket Guide
to Chemical Hazards. DHHS (NIOSH) Publication No. 97-140. Washin gton, D.C.
U.S. Government Printing Office, 1997. 291]**QC REVIEWED**
Recommendations for respirator selection. Condition: Emergency or pla nned
entry into unknown concn or IDLH conditions: Respirator Class(es): Any
self-contained breathing apparatus that has a full facepiece and is
operated in a pressure-demand or other positive-pressure mode. Any
supplied-air respirator that has a full facepiece and is operated in a
pressure-demand or other positive-pressure mode in combination with an
auxiliary self-contained breathin g apparatus operated in pressure-demand
or other positive-pressure mode. [NIOSH. NIOSH Pocket Guide to Chemical
Hazards. DHHS (NIOSH) Publication No. 97-140. Washington, D.C. U.S.
Government Printing Office, 1997. 291]**QC REVIEWED**
Recommendations for respirator selection. Condition: Escape from suddenly
occurring respiratory hazards: Respirator Class(es): Any air-purifying,
full-facepiece respirator (gas mask) with a chin-style, front- or
back-mounted acid gas canister having a high-efficiency particulate
filter. Any appropriate escape-type, self-contained breathing apparatus.
[NIOSH. NIOSH Pocket Guide to Chemical Hazards. DHHS (NIOSH) Publication
No. 97-140. Washington, D.C. U.S. Government Printing Office, 1997.
291]**QC REVIEWED**
Jacques Normandeau, PhD
54
CLEANUP METHODS:
On Land: For small spills, cover the contaminated area with sodium
bicarbonate or a mixture of soda ash/slaked lime (50/50) and mix. Shovel
the neutralized residues into containers for disposal. If neutralizing
agent is not available, cover the area with sand or earth to absorb the
liquid and shovel into containers for disposal. [Environment Canada; Tech
Info for Problem Spills: Sulphuric acid & Oleum (Draft) p.111
(1984)]**PEER REVIEWED**
In Water: Sodium bicarbonate is recommended as an in situ neutralizing
agent to avoid overdosing, resulting in too great a pH increase as well as
the lower heat of reaction. Other treating agents that may be considered
for neutralization are: calcined dolomite (where overrun of alkali; can be
tolerated), calcium oxide (where overrun of alkali can be tolerated), and
calcium hydroxide (where gypsum forms and slows neutralization), and
sodium carbonate (where Ca and Mg content are to be kept low).
[Environment Canada; Tech Info for Problem Spills: Sulp huric acid &
Oleum (Draft) p.111 (1984)]**PEER REVIEWED**
Spills of hazardous chemicals (such as inorganic sulfur acids, oleums of
strength 35 to 65%, liquid sulfur trioxide, or chlorosulfonic acid) can be
treated with high molecular weight polyacrylamide, polymethyl methacrylate
or a blend of polyacrylamides. Each forms a polymer skin over the liquid
surface, suppressing the fume & allowing access to the spill so that
cleanup can be done in a controlled manner. Polyacrylamide variant DP 1916
is best treatment for chlorosulfonic acid & oleum 20. Polycarbonate
granules used in a layer approx 80 mm thick topped off with Sorboil (an
absorbent clay) is best treatment for diked spills of oleums of all
strengths & liq sulfur trioxide. The acid beneath the skin is best
recovered by pumping. Unconfined spills of sulfur trioxide & oleums of
all strengths can be treated with excess anhydrous sodium sulfate which
forms a concrete-like residue that can be sprayed with water within 1
hour, dissolving it slowly. Expanded perlite, if contained in degradable bags, will effectively absorb & contain
sulfur acids. Fumes of oleum 65% arising from spillage of 80 to 750 kg can be killed within 4 to 13 min. Asphalt
or concrete is slightly affected. [Brale y GK; Haz Mat Spills Conf Proc: 139-44 (1982)]**PEER REVIEWED**
Keep water away from release. Stop or control the leak, if this can be
Jacques Normandeau, PhD
55
done without undue risk. Control runoff and isolate discharged material
for proper disposal. [National Fire Protection Guide. Fire Protection
Guide on Hazardous Materials. 10 th ed. Quincy, MA: National Fire
Protection Association, 1991.,p. 49-165]**PEER REVIEWED**
DISPOSAL METHODS:
SRP: At the time of review, criteria for land treatment or burial
(sanitary landfill) disposal practices are subject to significant
revision. Prior to implementing land disposal of waste residue (including
waste sludge), consult with environmental regula tory agencies for guidance
on acceptable disposal practices. **PEER REVIEWED**
SULFURIC ACID MAY BE PLACED IN SEALED CONTAINERS OR ABSORBED IN
VERMICULITE, DRY SAND, EARTH, OR A SIMILAR MATERIAL ... IT MAY ALSO BE
DILUTED AND NEUTRALIZED. [Mackison, F. W., R. S. Stricoff, and L. J.
Partridge, Jr. (eds.). NIOSH/OSHA - Occupational Health Guid elines for
Chemical Hazards. DHHS(NIOSH) PublicationNo. 81-123 (3 VOLS). Washington,
DC: U.S. Government Printing Office, Jan. 1981. 3]**PEER REVIEWED**
Add slowly to soln of soda ash and slaked lime with stirring. ...
(Peer-review conclusions of an IRPTC expert consultation (May 1985))
[United Nations. Treatment and Disposal Methods for Waste Chemicals (IRPTC
File). Data Profile Series No. 5. Geneva, Switzerland: United Nations
Environmental Programme, Dec. 1985. 286]**PEER REVIEWED**
FORMULATIONS/PREPARATIONS:
SULFURIC ACID OF COMMERCE CONTAINS 93-98% SULFURIC ACID; REMAINDER IS
WATER. [Budavari, S. (ed.). The Merck Index - An Encyclopedia of
Chemicals, Drugs, and Biologicals. Whitehouse Station, NJ: Merck and Co.,
Inc., 1996. 1535]**PEER REVIEWED**
GRADES: CP, USP, TECHNICAL, AT 33%-98% (50 DEG BE TO 66 DEG BE). [U.S.
Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical
Data. Volume II. Washington, D.C.: U.S. Government Printing Office,
1984-5.]**PEER REVIEWED**
Jacques Normandeau, PhD
56
Grades: Commercial 60 degrees Be: (density 1.71, 77.7% sulfuric acid ); 66
degrees Be (density 1.84, 93.2% sulfuric acid ); 98% (density 1.84); 99%
(density 1.84); 100% (density 1.84), depending on supplier; reagent ACS,
CP. [Lewis, R.J., Sr (Ed.). Hawley's Condensed Chemical Dictionary. 12th
ed. New York, NY: Van Nostrand Rheinhold Co., 1993 1104]**PEER REVIEWED**
IMPURITIES:
Non-volatiles, 0.02-0.03 ppm; SO2, 40-80 ppm; iron, 50-100 ppm; nitrate,
5-20 ppm /technical grade, industry type, 66 deg Baume'/ [Kirk-Othmer
Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John
Wiley and Sons, 1991-Present.,p. V23 400]**PEER REVIEWED**
Iron, arsenic, sulfur dioxide, nitrogen compounds, chloride, and fluoride.
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry.
5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p.
VA25 697]**PEER REVIEWED**
SPECIAL REFERENCES:
SPECIAL REPORTS:
Environment Canada; Tech Info for Problem Spills: Sulphuric acid & Oleum (Draft) (1984).
NIOSH; Criteria Document: Sulfuric acid (1974) DHEW Pub. NIOSH 74-128.
Toxicology Review: Environmental Health Perspectives 10: 35 (1975)
Toxicology Review: Archives of Toxicology 39: 299 (1978).
Institut National de Rech erche et de Securite; Cah Notes Doc 130: 167-71
1988. Toxicological Data Sheet No 30 : Sulfuric acid.
Dang Prop Ind Mater Rep 5 (3): 70-74 (1985). Review of safety, health
hazards, and toxicology of sulfuric acid.
Lahmann E; VDI-Ber 530: 23-48 1985. Review of sulfur pollution.
SYNONYMS AND IDENTIFIERS:
RELATED HSDB RECORDS:
1236 [OLEUM]
Jacques Normandeau, PhD
57
INCIDENTS
CNN.com
Chemical spill prompts
Pennsylvania evacuation
October
6,
Web posted at: 6:53 p.m. EDT (2253 GMT)
1998
Firemen
PORTLAND MILLS,
Pennsylvania (CNN) -- About
200 people in this small,
northeastern Pennsylvania
community remained away from
home on Tuesday. They were
Firemen clean up the chemical spill
evacuated Monday after a train carrying hazardous chemicals
derailed at the edge of the Allegheny National Forest.
Toxic sulfuric acid and caustic sodium hydroxide leaked from
two of four tankers of a Buffalo & Pittsburgh train that
overturned about 6:30 p.m. on Monday, authorities said.
No injuries were reported but a pungent haze lingered Tuesday
morning over the Clarion River and Portland Mills, a town about
60 miles southeast of Erie.
Emergency crews brought in huge quantities of lime to
neutralize the acid but it was not immediately clear when
evacuees would be allowed to return home.
Jacques Normandeau, PhD
58
A spokesman for the Ridgway Fire Department said he not
know what caused the derailment.
The railroad runs between state Route 949 and the Clarion
River, and cities downstream were notified about potential river
contamination.
If inhaled, sulfuric acid can cause respiratory problems or skin,
eye and ear irritation. In greater concentrations, exposure could
be deadly.
The Associated Press contributed to this report.
Jacques Normandeau, PhD
59
CHEMICAL REPORT ( ARIP DATA )
search used- Chemical Name: OLEUM
This search was taken from RTK NET's (the Right-To-Know Network)'s copy
of EPA's ARIP database. RTK NET is run by OMB Watch and Unison Institute
at 1742 Connecticut Ave. NW, Washington DC 20009 Phone: 202-234-8494
This copy of the database was last updated on 09/01/1997.
Reporting Year: 1989
--------------------------------------------------------------------------Facility: DUPONT
Reporting Year: 1989
Address: 3460 HIGHWAY 44
City: DARROW
State: LA Zip: 70725
County:
Dun & Bradstreet #: 05-104-7223
Phone:
SIC(s): 2819
Owner:
Number of employees: 23
Primary Product: SULFURIC ACID MANUFACTURING
Release start date: 08/17/1989 Time: 16:00
Release end date : 08/18/1989 Time: 07:00
Chemical Name: OLEUM
CAS Number: 8014957
Concentration (%): 100%
Physical State: LIQUID
Air:
700.00
Land:
3,200.00 Treatment Facility:
Total:
Surface Water:
0.00 (lbs)
0.00 (lbs)
3,900.00 (lbs)
No injuries, deaths, or evacuations were reported.
No cost for property damage was reported.
--------------------------------------------------------------------------Authorities notifiedName
Federal: NRC
LA DEQ
Date
Time Contact Name
08/18/1989 11:30
08/18/1989 11:30 MS. BOBBI PURPERA
Jacques Normandeau, PhD
60
MiscellaneousERNS ID:
NRC ID:
18614 ARIP ID: 1510
Latitude: 30-07 Longitude: 90-54
Release caused by: B (A=Equipment Failure, B=Operator Error)
Location of loss of containment: PIPING: JOINT
EPA Region: 06 ERNS Report Date: / /
Time:
When release occuredDURING ROUTINE OPERATION
Status of process lineNO INTERRUPTION; CONTINUED OPERATIONS
How release was discoveredOBSERVATION BY EMPLOYEE(S)
Immediate activities in response to releaseDILUTE AND/OR NEUTRALIZE
PLANT/PROCESS SHUTDOWN
Causes(s) of releaseOTHER (PLEASE DESCRIBE)
End effect(s) of releaseSPILL
VAPOR RELEASE
Environmental effect(s)SOIL CONTAMINATION
OTHER (PLEASE DESCRIBE)
Methods of communication with publicOTHER (PLEASE DESCRIBE)
Training, procedures, and management used before this rele aseEMPLOYEE SAFETY TRAINING
EMERGENCY RESPONSE TRAINING
OTHER (PLEASE DESCRIBE)
INVENTORY/CAPACITY REDUCTIONS
STANDARD OPERATING PROCEDURES
New training, procedures, and management used after this releaseNONE
INVENTORY/CAPACITY REDUCTIONS
Engineering systems or controls used before this release-
Jacques Normandeau, PhD
61
BACKUP/REDUNDANT SYSTEMS
BYPASS/SURGE SYSTEMS
NONE
New engineering systems or controls used after this releaseEQUIPMENT: UPGRADE/REFINE/REPAIR/REPLACEMENT/INSTALL
EVALUATE/REFINE/IMPROVE PROCESS
Reporting Year: 1991
--------------------------------------------------------------------------Facility: RHONE-POULENC
Reporting Year: 1991
Address: 100 MOCOCO RD.
City: MARTINEZ
State: CA Zip: 94553
County: CONTRA COSTA
Dun & Bradstreet #: 05-304-9490
Phone: (510) 228-5530 SIC(s): 2819
Owner: J.M. ODRZYWOLSKI/PLANT MANAGER Number of employees: 70
Primary Product: SULFURIC ACID, OLEUM PRODUCTION
Release : 100 MOCOCO RD.
City: MARTINEZ
State: CA Zip: 94553
County: CONTRA COSTA
Phone: (510) 228-5530
Release start date: 05/20/1991 Time: 14:00
Release end date : 05/20/1991 Time: 14:18
Chemical Name: OLEUM
Concentration (%):
Air:
Land:
Total:
400.00
CAS Number: 8014957
Physical State: LIQUID
Surface Water:
0.00 Treatment Facility:
0.00 (lbs)
1,900.00 (lbs)
2,300.00 (lbs)
No injuries, deaths, or evacuations were reported.
No cost for property damage was reported.
---------------------------------------------------------------------------
Jacques Normandeau, PhD
62
Authorities notifiedName
Date
CA OES
Time Contact Name
05/20/1991 14:50 SUE PLANTZ
CONTRA COSTA CO. DHS
05/20/1991 14:25 LORI
MiscellaneousERNS ID: 914149 NRC ID:
72705 ARIP ID: 3642
Latitude: 38:02 Longitude: 122:06
Release caused by: A (A=Equipment Failure, B=Operator Error)
Location of lo ss of containment: STORAGE VESSEL: WALL
EPA Region: 09 ERNS Report Date: 05/20/1991 Time: 17:30
When release occuredDURING ROUTINE OPERATION
Status of process lineNO INTERRUPTION; CONTINUED OPERATIONS
How release was discoveredOBSERVATION BY EMPLOYEE(S)
Immediate activities in response to releaseREDUCE SYSTEM PRESSURE/TEMPERATURE
APPLY SPRAY SCRUBBER/CURTAIN
TRANSFER CONTENTS FROM FAILED EQUIPMENT
DILUTE AND/OR NEUTRALIZE
CONTAINMENT
DIVERT RELEASE TO TREATMENT
Causes(s) of releaseOTHER (PLEASE DESCRIBE)
End effect(s) of releaseSPILL
VAPOR RELEASE
Environmental effect(s)NONE
Training, procedures, and management used before this rele asePREVENTIVE MAINTENANCE/INSPECTIONS
ACCIDENT INVESTIGATIONS
AUDITS
EMPLOYEE SAFETY TRAINING
STANDARD OPERATING PROCEDURES
Jacques Normandeau, PhD
63
EMERGENCY RESPONSE TRAINING
New training, procedures, and management used after this releaseEMPLOYEE SAFETY TRAINING
Engineering systems or controls used before this releaseBACKUP/REDUNDANT SYSTEMS
AUTOMATIC SHUT-OFFS
CONTROLS FOR OPERATIONS MONITORING AND WARNING
New engineering systems or controls used after this releaseMONITORING EQUIPMENT: INSPECTION/REPAIR/REPLACEMENT/INSTALL
Jacques Normandeau, PhD
64
The following information was generated from the
Hazardous Substances Databank (HSDB),
a database of the National Library of Medicine's TOXNET system
(http://toxnet.nlm.nih.gov) on June 6, 2001.
NAME: OLEUM
PRIOR HISTORY OF ACCIDENTS:
Twenty to fifty tons of oleum ... spilled ... after a safety relief valve
failed on a railroad tank car at the General Chemical Corporation plant in
Richmond, CA. ... The resulting cloud of sulfuric acid drifted northeast
with prevailing winds over a number of populated areas, causing more than
3,000 people to seek medical attention on the day of the spill for burning
eyes, coughing, headaches, and nausea. The spill caused the closure of
five freeways in the region, as well as of a number of Bay Area Rapid
Transit system stations. ...
[Chemical &amp; Engineering News 71 (31): 7
(8/2/93)]**QC REVIEWED**
Part of a small town in Sweden was covered by an oleum gas cloud as a
result of an industrial accident. Although no serious damage was caused at
the time, unclear threat, resulted in partial evacuation as well as the
shut down of transport, schools, businesses etc. The perception of this
threat by those exposed to the gas as well as by a control group was
mapped by means of a special instrument, the Wheel, as well as by
intensive interviews. The report describes and analyzes the relationship
between the perception of the threat and the reported coping style with
it. Results show that the quality of perception assessed along three
dimensions: structure, involvement, and sense of control, can predict the
type and effectiveness of coping with the perceived stress. [Shalit B;
Perception of Threat by a Noxious Gas Accident and the Reported Coping
Style. Govt Reports Announcements &amp; Index (GRA &amp; I) Issue 11
NTIS/PB86-162260 (1986)]**PEER REVIEWED**
Jacques Normandeau, PhD
65
BASE DE DONNÉES DES DÉSASTRES PCC
Déversement de produits chimiques dangereux : Pelham (Ont.), le 1er décembre 1972. Un train de
marchandises de la ligne Toronto, Hamilton et Buffalo (TH&B) déraille. Environ 24 ou 25 wagons chargés
d'acide sulfurique se renversent dans les champs. Au moins huit d'e ntre eux éclatent et répandent leur contenu.
Une vingtaine de ménages (sur la base d'une famille de quatre personnes) sont évacués dans un rayon d'un
demi-mille de l'accident. Du carbonate de sodium et de la soude caustique sont répandus pour neutraliser
l'acide.
Produits toxiques; Sudbury (Ontario); une collision entraîne l’écrasement dans un fossé d’un camion-citerne
contenant 42 tonnes d'acide sulfurique; un rocher perce le réservoir; 30 tonnes d’acide sont déversées; des
mesures de neutralisation de l’a cide et de nettoyage sont prises; l'accident fait deux morts parmi les occupants
du véhicule, et le chauffeur du camion est blessé.
Produits chimiques; Hervey Junction (Québec); 28 des 44 wagons d’un train contenant de l’a cide sulfurique
déraillent et répandent une grande partie de leur contenu; 234 m³ d'a cide sont déversés dans le lac Masketi et la
rivière Towachiche; le pH du lac descend à 2,7, mais remonte à 5,3 après l’ajout de 170 tonnes de calcaire et de
soude; toute la faune et la flore est détruite; les activités récréatives sont interdites pendant huit ans sur le lac et
pendant cinq ans sur la rivière.
Jacques Normandeau, PhD
66
Awareness and Preparedness for Emergencies at Local LevelList of selected
accidents
List of Selected Accidents Invol ving Hazardous S ubstances
A List for the years 1970-1989 was originally compiled by the OECD and
appeared in its 1991 publication "The State of the Environment".
With OECD's permission, UNEP IE has now extended the List to cover the years
1990-1997. We thank the OECD and the individuals and organisations which
provided the information, particularly the Bureau d'Analyses des Risques et des
Pollutions Industrielles (BARPI) of the French Ministry of the Environment. We
also thank Andrea Krenz of the University of Lüneburg, Germany, who did the
work in March-April 1998 as part of an internship with UNEP IE. UNEP IE now
intends to add further information from time to time, as it becomes available.
Please note the criteria for inclusion at the foot of the List. UNEP IE has followed
the original criteria in its updating.
During June - July 1998 a number of individuals and organisations reviewed the
draft revised "List" and supplied comments and corrections. We are particularly
grateful to staff of the UK AEA's MHIDAS database for their extensive input at
this stage. The information for 1990-1998 has been amended accordingly; in
particular, some cases for which we have only disputed data have been removed
altogether. It should also be noted in general that there are minor discrepancies
for the whole 1970- 1998 period between different major accident databases
around the world. It is UNEP's view that this does not reduce the overall impact
of the List as background information for decision-makers.
Jacques Normandeau, PhD
67
Although we have done our best to check and use the information supplied to us,
it is of course possible that the updated List still contains errors and that
accidents meeting the criteria are not reported here. If you spot errors or
omissions, please inform UNEP IE so that we can make corrections.
Please regard this as "Work in Progress".
Selected Accidents Involving Hazardous Substances, 1970 - 1998
Coun
try
and
locati
on
Origin of
accident
India, New Delhi
Release
Sulphuric
acid
1
340
>10
Fire
Sulphuric
acid
-
-
18 000
Date
1985
4.12
1987
24.03 USA, Nantichoke
1993 26.07 USA, Richmond
1991
Products
inv olved
Release
21.08 *Australia,
Melbourne
Fire at a
chemical
store
Sulphuric
acid
Deaths
Number of
Inj ured Ev acuated
>6250
Phenol,
Acrylonitrile
>1 000
Note: Inclusion criteria
-25 death or more; or
-125 injured or more;
-10000 evacuated or more; or 10 thousand people or more deprived of water;
-10 million US$ or more damages to third parties referred to by*.
Exclusion of:
-Oil spills at sea from ships;
-Mining accidents;
-Voluntary destruction of ships or aeroplanes;
-Damage caused by defective products.
Source: OECD, MHIDAS, TNO, SEI, UBA-Handbuch Stoerfaelle, SIGMA, Press
Reports, UNEP, BARPI.
Jacques Normandeau, PhD
LE TRANSPORT ET
L’ENTREPOSAGE DE
L’ACIDE SULFURIQUE –
MESURES PRÉVENTIVES
Guy Desgagnés
NORANDA INC.
GESTION RESPONSABLE
NORANDA INC.
MÉTHODE DE TRANSPORT
z
z
Dépendant des demandes du client et de leur capacité
d ’entreposage, on peut livrer notre acide sulfurique par 4
moyens différents: - camions ( jusqu’à 40 T.M.)
- wagons ( 85 T.M.)
- chalands ( jusqu’à 2200 T.M.)
- navire citerne ( 7,000 à 25,000T.M.)
Noranda ne livre pas d’acide sulfurique en baril ou en
contenant d’une tonne métrique (tote tank)
NORANDA INC.
MESURES PRÉVENTIVES
z
z
z
z
z
Sélection des transporteurs routiers et maritimes
Évaluation de chaque terminal du transporteur routier et
de chaque compagnie ferroviaire et maritime
Formation Noranda de tous les chauffeurs à chaque
terminal avec carte de certification
Rencontre annuelle avec tous les transporteurs
Évaluation des risques routiers, ferroviaires et maritimes
NORANDA INC.
MESURES PRÉVENTIVES
(SUITE...)
z
Numéro 24 heures 877-377-2243
z
Système informatisé pour les prises d’appel d’urgence
z
Conseillers techniques en lien direct avec l’appelant
z
Transfert automatique de l’appel à Canutec en cas de
panne de notre système
NORANDA INC.
MANIPULATION
z
z
z
z
Protection personnelle: chapeau de sécurité, lunettes à
coques ou à écrans latéraux avec visière complète,
manteau, pantalon, gants et bottes antiacides
Protection collective: douche déluge et douche oculaire
partout où l’on manipule de l’acide
Procédures écrites pour le chargement et le déchargement
de tous les moyens de transport
Équipements de chargement, de déchargement et moyens
de transport tous compatibles avec le produit.
NORANDA INC.
NORME D ’ENTREPOSAGE
z
z
z
z
z
Réservoir construit selon les normes API 650 ou NACE
Sélection d’un contracteur qualifié
Aire de confinement autour des réservoirs
Noranda a développé ses propres standards de
construction et d’inspection
Inspection visuelle externe à tous les ans et inspection
interne à tous les 5 ans (3 ans acide chaud)
NORANDA INC.
INSPECTIONS ET ENTRETIENS DES
ÉQUIPEMENTS
z
z
z
Équipements de production : maintenance préventive
plus arrêt annuel planifié.
Équipements de transport: d ’après les normes établies par
Transport Canada et le « Department of Transportation ».
De plus, une inspection visuelle des conteneurs est faite
avant, pendant et après le chargement.
Tous les wagons d’acide sont pressurisés pour vérifier
les fuites, puis on baisse la pression avant l’expédition. De
plus, on appose des sceaux afin d’assurer l’intégrité du
produit pendant le transport vers le client.
NORANDA INC.
DÉVERSEMENTS
z
z
z
Déversement mineur: Absorber les petits déversements
avec du sable sec, de l’argile ou de la terre diatomée.
Déversement important: Endiguer, diluer et neutraliser
avec précaution avec de la chaux ou du carbonate de
sodium et transférer vers un système de traitement des
eaux usées.
Déversement majeur: Endiguer, récupérer le plus d’acide
possible avec un camion-aspirateur et par la suite
neutraliser.
NORANDA INC.
INCENDIE
z
z
z
z
L’acide sulfurique est ininflammable.
Réagit avec la plupart des métaux, produit un gaz
inflammable et potentiellement explosif, l ’hydrogène.
Utiliser un jet d ’eau pour refroidir les contenants exposés
à l ’incendie; ne pas laisser entrer d ’eau dans les
contenants.
Contenir les eaux de ruissellement pour les neutraliser
par la suite.
NORANDA INC.
INTERVENTION
z
z
z
NORANDA:
-Valleyfield : 9 Certifiés pour Canada et U.S.
-Rouyn-Noranda: 7 Certifiés pour Canada et U.S.
-Murdochville : 7 Certifiés pour Canada
-Belledune : 5 Certifiés pour Canada
FALCONBRIDGE:
-Timmins : 4 Certifiés pour Canada et U.S.
-Sudbury : 9 Certifiés pour Canada et U.S.
DuPONT
- 6 Équipes aux États-Unis
NORANDA INC.
ÉQUIPEMENTS
z
z
z
z
z
z
5 VÉHICULES D ’URGENCE AVEC POSTE DE
COMMANDEMENT INTÉGRÉ
6 POMPES PORTATIVES CENTRIFUGES
3 DOUCHES D’URGENCE AVEC CHAUFFE-EAU AU
PROPANE
6 GÉNÉRATRICES PORTATIVES
24 APPAREILS RESPIRATOIRES AUTONOMES
CHAQUE MEMBRE A SON PROPRE ÉQUIPEMENT
D ’INTERVENTION
NORANDA INC.
NUMÉRO D ’URGENCE
z
NORANDA/FALCONBRIDGE
1-877-ERP-ACID
1-877-377-2243
SYSTÈME INFORMATISÉ, VALLEYFIELD
COORDONNATEUR EN DEVOIR 24 /24 HRS AVEC
PAGETTE ET CELLULAIRE.
NORANDA INC.
FORMATION
z
z
z
z
Employés de production et d ’entretien
Employés manipulant des marchandises
dangereuses
Transporteurs
Clients et terminaux
NORANDA INC.
21 JANVIER 1995
DÉRAILLEMENT AU PETIT LAC MASKETSI
NORANDA INC
TRAIN BLOC D’ACIDE SULFURIQUE
COMMUNICATION
PAR SATELLITE
DÉRAILLEMENT
WAGONS À LA DÉCHARGE DU LAC
DÉRAILLEMENT
WAGON SOUS LA GLACE
COLMATAGE INITIAL
NEUTRALISATION DE LA RIVIÈRE
AVEC DU CARBONATE DE CALCIUM
INSTALLATION DES
PUITS D’OBSERVATION
INSTALLATION TYPIQUE
INSTALLATION TYPIQUE
INSTALLATION TYPIQUE
DÉCONTAMINATION
DÉCONTAMINATION
DES FOSSÉS
NEUTRALISATION DU LAC
AVEC LE CARBONATE
DE CALCIUM
RÉSUMÉ
•
28 WAGONS-CITERNES SE SONT RENVERSÉS ET UN VOLUME
D’ENVIRON 255 000 LITRES D’ACIDE SULFURIQUE
CONCENTRÉE A ÉTÉ DÉVERSÉ.
•
DE CES 255 000 LITRES , 160 000 LITRES ON ATTEINT LA RIVIÈRE
TAWACHICHE, 40 000 LITRES ONT PÉNÉTRÉ LE SOL EN
BORDURE DE LA VOIE FERRÉE ET 55 000 LITRES SE SONT
DÉVERSÉS DANS LE PETIT LAC MASKETSI.
•
503 TONNES DE CARBONATE DE CALCIUM EN FINE POUDRE
ONT ÉTÉ INJECTÉES DANS LA RIVIÈRE ENTRE LE 21 ET 29
JANVIER.
RÉSUMÉ SUITE...
•
11 PUITS D’OBSERVATION ONT ÉTÉ INSTALLÉS POUR
SURVEILLER LA MIGRATION DE L’ACIDE DANS LE SOL.
•
DU 3 AU 13 FÉVRIER UN TOTAL DE 155 TONNES DE CARBONATE
DE SODIUM A ÉTÉ UTILISÉ AFIN DE TRAITER LE SOL.
•
LE 26 JANVIER 45 TROUS ONT ÉTÉ FORÉS DANS LA GLACE
POUR PERMETTRE L’INJECTION DE 20 TONNES DE
CARBONATE DE CALCIUM À MOUTURE FINE.
•
DU 27 AU 31 JANVIER ET LE 4 FÉVRIER , 249 TONNES DE
CARBONATE DE CALCIUM DE MOUTURE PLUS GROSSE ONT
ÉTÉ INJECTÉES DANS LE LAC À TRAVERS CES TROUS.
RÉSUMÉ SUITE...
•
LE pH MOYEN DE LA PARTIE INFÉRIEUR DU LAC LE 27
JANVIER ÉTAIT DE 2,55 ET LE VOLUME D’EAU CONTAMINÉE A
ÉTÉ ESTIMÉ À 710 MILLIONS DE MÈTRES CUBES.
•
DU 13 FÉVRIER AU 13 MARS 7 STATIONS DE POMPAGE ONT
INJECTÉ DANS LE LAC UNE SOLUTION D’HYDROXYDE DE
CALCIUM.
UN TOTAL DE 82 TONNES MÉTRIQUES DE CHAUX A ÉTÉ
UTILISÉES POUR AUGMENTER LE pH DU LAC DE 2,55 À 4, 95
DURANT CETTE PÉRIODE.
DIFFÉRENTS NEUTRALISANTS UTILISÉS POUR L’ACIDE SULFURIQUE
ACIDE
NEUTRALISANT
NOM
MASSE
MOLAIRE
H 2SO 4
Na2CO3
Carbonate de
sodium
106 g/mole
H 2SO 4
NaHCO 3
Bicarbonate de
sodium
H 2SO 4
NaOH
H 2SO 4
H 2SO 4
*
RÉSULTAT
COMMENTAIRES
1 mole par deux
moles d’ions H+
Na2SO 4 + CO2 +
H2O
Le CO 2 dégagé produit
beaucoup de
bouillonnement
84 g/mole
1 mole par mole
d’ions H+
Na2SO 4 + CO2 +
H2O
Le CO 2 dégagé produit
beaucoup de
bouillonnement
Hydroxyde de
sodium
40 g/mole
1 mole par mole
d’ions H+
Na2SO4 +H 2O
Réaction violente
CaO
Chaux
56 g/mole
1 mole par deux
moles d’ions H+
CaSO4 + H2O
La réaction produit un
produit stable qui est le
gypse
Ca(OH) 2
Chaux
hydratée
74 g/mole
1 mole par deux
moles d’ions H+
CaSO 4 + 2H2 O
La réaction produit un
produit stable qui est le
gypse
* = Quantité molaire de neutralisant nécessaire pour neutraliser une mole d’ions H +
RECETTE
LES DÉVERSEMENTS
D’ACIDE SULFURIQUE:
CAS CONCRETS AU QUÉBEC
Robert Reiss, B.Sc(chimie)
Responsable aux opérations d’urgence
Direction de la protection de
l’environnement
Section des urgences environnementales
STATISTIQUES
Acide sulfurique
• Au Canada de 1991 à 2000
– 329 cas rapportés
• Les plus importants :
– Cominco, B.C. : 5 tonnes
– Territoires Nord-ouest: 8 tonnes
– Montréal, (1992): 14 tonnes
– Masketsi, (1995): 500 tonnes
– St-Jean-Chrysostome, (1997): 90 tonnes
PRINCIPALES RAISONS DES
DÉVERSEMENTS
• défectuosité de
• 30%
l’équipement
• erreur humaine
• 20%
• corrosion
• 6%
PRINCIPAUX RISQUES
• délétère pour les espèces aquatiques
• contamination:
– des nappes phréatiques et des eaux de
surface
– du sol
• pas de risque de bioaccumulation
PRINCIPAUX RISQUES
• risques pour les intervenants
– inhalation:
• corrosif par les brouillards et vapeurs
– contact:
• graves brûlures pour la peau et les yeux
SAINT-JEAN-CHRYSOSTOME
24 novembre 1997
DÉV. ACIDE SULFURIQUE
•
•
•
•
•
•
•
Cause: défectuosité de
l’équipement: bris du wagon
Faire un chemin dans champs
(hiver)
Digue pour contenir l’H2SO4
dans les fossés
Neutraliser le produit avec
Hydroxyde de calcium
Analyse des puits d’eau potable
des résidences (santé)
Forages pour analyser nappe
phréatique
MENV, EC, CN, TC, Santé,
DGSC, Municipalité, pompiers,
Noranda, Golder (50 personnes)
2001-06-22
8
INTERVENTION
• Objectifs:
– arrêter la progression du produit
– pomper le plus de produit possible
– neutraliser le produit, les eaux contaminées
et le sol
INTERVENTION
(voir CSA-Z731-95)
• Évaluation de la situation (connaître le
problème)
• Connaître la quantité de produit
• Connaître le taux de fuite
• Situation de l’incident:
– stable
– instable
• Prévoir le devenir du produit
INTERVENTION
• Prévoir le devenir du produit:
– Connaître le lieu:
• la population?
• type de terrain?
• topographie et hydrogéologie?
– Conditions météorologiques
– Mesures d’intervention:
• ressources
• délais
INTERVENTION
• Identifier les enjeux:
– mesures préventives:
• protéger contre les expositions (évacuer/confiner)
• contenir, et neutraliser
– mesures correctives:
• nettoyer
• restaurer / éliminer
S CÉ NARIO(S ) : D É VE RS EM EN T M A JE UR D ’ A CID E
E N JE U X
S TR ATÉ G IES
RE S P O N S AB LE
r iviè re
ba rr iè re s d an s le s fo s sé s
CN
p uits d ’ea u p ota ble
po m pe r le p rod uit da ns le s fos s é s
vé r ific ation e n c ontinu du pH de s
pu its
inter dic tion d e b oir e l’e a u
vé r ifie r la na pp e p hr éa tiqu e
fo ra ge e t v é rifica tion d u p H
po m pe r le p rod uit
ne utra lis ation à l’a ide de p elle s
m é c an iqu es e t u tilis ation de
hyd ro x yde de c alc ium et
bic a rbo na te d e s o dium
CN
EC , ME N V e t Sa n té Q ué be c
Mu nic ipa lité
n ap pe ph ré a tiq ue
s ol (les fos s és de
c ha q ue cô té de la vo ie)
ÉC H É AN C E
CN
Go lde r e t EC
ME N V
C N e t EC
13
INTERVENTION
• installation de barrières quelques heures
après le déversement
• pompage des liquides (9240 kg ou 10%)
• tests de Ph dans 14 puits résidentiels et
forages
• 200 t NaHCO3 sur les rails sur 600 m
• d’autres barrières installées
INTERVENTION
• 48 h après, neutralisation avec Ca(OH)2
pour 5 jours
• 140 tonnes de sol excavées à profondeur
de .15 à .6 m
• 68 tonnes de Ca(OH)2
• le 15 décembre les barrières ont été
retirées (ph de 7.4 à 9.7)
INTERVENTION
• Rôle d’Environnement Canada:
– superviser les travaux
– expertise scientifique, laboratoire mobile
– assurer la protection de la santé et de
l’environnement
– s’assurer d’un suivi
– cartographier la zone
– Loi sur les pêches (infraction)
CONCLUSION
• Les accidents, ça arrive !
• Il faut être prêt (exercices)
– minimise les dégâts
• St-Jean-Chrysostome
– la réponse rapide a limité les dégâts
– pas d’impact sur la santé
• Leçon apprise :
– choisir la bonne technique de neutralisation et le
bon produit
– laisser la réaction se produire