| Identification | Back Directory | [Name]
HYDROGEN CYANIDE | [CAS]
74-90-8 | [Synonyms]
HCN
Blausure
formonitrile
prussic acid
Formic nitrile
methanenitrile
Hydrocyanic acid
HYDROGEN CYANIDE
LELOWRISYMNNSU-UHFFFAOYSA-N
hydrogen cyanide hydrocyanic acid
HYDROGEN CYANIDE, ANHYDROUS, STABILIZED
hydrogen cyanide, stabilized, absorbed in porous material | [EINECS(EC#)]
200-821-6 | [Molecular Formula]
CHN | [MDL Number]
MFCD00242847 | [MOL File]
74-90-8.mol | [Molecular Weight]
27.03 |
| Chemical Properties | Back Directory | [Appearance]
Water-white liquid at temperatures
below 26.5C; faint odor of bitter almonds. Usual
commercial material is 96–99% pure.Soluble in
water. The solution is weakly acidic, sensitive
to light. When not absolutely pure or stabilized, hydrogen cyanide polymerize | [Melting point ]
-13.4° | [Boiling point ]
bp 25.6° | [density ]
d(gas) 0.941 (air = 1); d(liq) 0.687 | [vapor pressure ]
750 mmHg at 25 °C | [refractive index ]
1.2594 | [solubility ]
very soluble in H2O, ethanol; soluble in ethyl ether | [form ]
colorless liquid | [pka]
9.2(at 25℃) | [color ]
colorless liquid or gas | [Odor]
Bitter almond odor detectable at 1 to 5 ppm; however, 20 to 60% of the population
are reported to be unable to detect the odor of HCN | [Water Solubility ]
miscible with H2O, alcohol; slightly soluble ether [MER06] | [Dielectric constant]
158.0（0℃） | [Exposure limits]
Ceiling 11 mg/m3 (10 ppm) (ACGIH), 5 mg CN/m3/10 min (NIOSH); TWA air 11 mg/m3 (10 ppm) skin (OSHA); IDLH 50 ppm. | [LogP]
-0.250 | [EPA Substance Registry System]
Hydrogen cyanide (74-90-8) |
| Hazard Information | Back Directory | [Chemical Properties]
HCN is a colorless to pale blue liquid or gas. It has a distinct odor resembling bitter
almonds. HCN reacts with amines, oxidizers, acids, sodium hydroxide, calcium hydroxide, sodium carbonate, caustic substances, and ammonia. HCN was fi rst isolated from a
blue dye, Prussian blue, in 1704. HCN is obtainable from fruits that have a pit, such as cherries, apricots, and bitter almonds, from which almond oil and fl avoring are made. HCN
is used in fumigating, electroplating, mining, and in producing synthetic fi bers, plastics,
dyes, and pesticides. It is also used as an intermediate in chemical syntheses. Exposures
to cyanide occur in workplaces such as the electroplating, metallurgical, fi refi ghting, steel
manufacturing, and metal cleaning industries. Human exposures to cyanide also occur
from wastewater discharges of industrial organic chemicals, iron and steel works, and
wastewater treatment facilities | [Chemical Properties]
Hydrocyanic acid (hydrogen cyanide) is a clear colorless liquid with a faint odor of bitter
almonds. It evaporates easily (or boils) at room temperature and the vapors are slightly
lighter than air. It is soluble in water. It is reactive and incompatible with amines, oxi-
dizers, acids, sodium hydroxide, calcium hydroxide, sodium carbonate, caustics, and
ammonia.
Hydrogen cyanide is manufactured by the oxidation of ammonia–methane mixtures
under controlled conditions and by the catalytic decomposition of formamide. It may
be generated by treating cyanide salts with acid, and it is a combustion by-product of
nitrogen-containing materials such as wool, silk, and plastics. It is also produced by enzy-
matic hydrolysis of nitriles and related chemicals. Hydrogen cyanide gas is a by-product
of coke-oven and blast furnace operations. Industrial applications of hydrogen cyanide are
many. For instance, in fumigation, electroplating, mining, metallurgical, fi refi ghting, steel
manufacturing, and metal cleaning industries, to producing synthetic fi bers, plastics, dyes,
pesticides, and also as an intermediate in chemical syntheses. | [Definition]
ChEBI: A one-carbon compound consisting of a methine group triple bonded to a nitrogen atom. Also known as formonitrile, hydrogencyanide and prussic acid,HCN is a highly toxic liquid that has the odor of bitter almonds and boils at 25.6 °C.
also known as hydrocyanic acid, prussic acid, and fonnonitrile, is a very poisonous colorless gas with a characteristic fragrance of bitter almonds. Small amounts of hydrogen cyanide derivatives in combination with glucose and benzaldehyde are found in nature in apricot,peach,cherry, and plum pits.It liquifies at 26°C (79 OF) and is soluble in water,alcohol,and ether. Hydrogen cyanide is usually sold commercially as an aqueous solution containing 2 to 10% hydrogen cyanide. HCN reacts with amines, oxidisers, acids, sodium hydroxide, calcium hydroxide, sodium carbonate, caustic substances, and ammonia. The aqueous solutions of hydrogen cyani dedecompose slowly to form anunonium formate. In some uses, it is preferable to generate hydrogen cyanide as needed, thus eliminating handling and storage problems.
| [Uses]
HCN was first isolated from a blue dye, Prussian blue, in 1704. HCN is obtainable from fruits that have a pit, such as cherries, apricots, and bitter almonds, from which almond oil and flavouring are made. HCN is used in fumigating, electroplating, mining, and producing synthetic fibres, plastics, dyes, and pesticides. It also is used as an intermediate in chemical syntheses.
Besides, hydrogen cyanide is used in manufacturing cyanide salts, aerylonitrile,and dyes.It is also used as a horticultural fumigant.
| [General Description]
Hydrocyanic acid solution is water containing up to 5% dissolved hydrocyanic acid with the faint odor of almonds. HYDROGEN CYANIDE is toxic by inhalation and skin absorption. Prolonged exposure to low concentrations or short term exposure to high concentrations may result in adverse health effects. Its vapors are just barely lighter than air. | [Reactivity Profile]
This particular record contains hydrogen cyanide dissolved in water. Hydrogen cyanide is a very volatile liquid or colorless gas smelling of bitter almonds, b.p. 26° C. A deadly human poison by all routes. The gas (hydrogen cyanide) forms explosive mixtures with air, HYDROGEN CYANIDE reacts violently with acetaldehyde. HYDROGEN CYANIDE is a severe explosion hazard when heated or exposed to oxidizers. HYDROGEN CYANIDE may polymerize explosively at elevated temperature (50-60° C) or in the presence of traces of alkali [Wohler, L. et al., Chem. Ztg., 1926, 50, p. 761, 781]. In the absence of a stabilizer (e.g., phosphoric acid) HYDROGEN CYANIDE may undergo explosively rapid spontaneous (autocatalytic) polymerization leading to a fire. The reaction is autocatalytic because of ammonia formation. The anhydrous acid should be stabilized by the addition of acid. [Bond, J., Loss Prev. Bull., 1991, 101, p.3]. During the preparation of imidoester hydrochlorides, hydrogen chloride was rapidly passed over alcoholic hydrogen cyanide. An explosion ensued, even with cooling of the process, [J. Org. Chem., 1955, 20, 1573]. | [Fire Hazard]
Hydrogen cyanide is a highly flammable liquid. Liquid HCN contains a stabilizer
(usually phosphoric acid), and old samples may explode if the acid stabilizer is not
maintained at a sufficient concentration.
| [Fire Hazard]
Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Some are oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. | [Hazard]
Flammable, dangerous fire risk, explosive
limits in air 6–41%. Toxic by ingestion, inhalation,
and skin absorption. TLV: ceiling 4.7 ppm. | [Health Hazard]
Exposures to hydrogen cyanide cause adverse health effects to animals and humans.
Hydrogen cyanide is readily absorbed from the lungs and the symptoms of poisoning
begin within seconds to minutes. The symptoms of toxicity and poisoning include, but
are not restricted to, asphyxia, lassitude or weakness, exhaustion, headache, confusion,
nausea, vomiting, increased rate and depth of respiration, or respiration slow and gasp-
ing, thyroid and blood changes. Inhalation of hydrogen cyanide causes headache, dizzi-
ness, confusion, nausea, shortness of breath, convulsions, vomiting, weakness, anxiety,
irregular heart beat, tightness in the chest, and unconsciousness, and these effects may be
delayed. The target organs of induced toxicity and poisoning include the CNS, cardiovas-
cular system, thyroid, and blood. | [Health Hazard]
HCN is particularly dangerous because of its toxic and asphyxiating effects on all life
requiring oxygen to survive. HCN combines with the enzymes in tissue associated with
cellular oxidation. The signs and symptoms of HCN poisoning are non-specifi c and very
rapid. The symptoms include excitement, dizziness, nausea, vomiting, headache, weakness, drowsiness, gasping, thyroid, blood changes, confusion, fainting, tetanic spasm,
lockjaw, convulsions, hallucinations, loss of consciousness, coma, and death. When oxygen becomes unavailable to the tissues, it leads to asphyxia and causes death. Children are
more vulnerable to HCN exposure. HCN is readily absorbed from the lungs; symptoms of
poisoning begin within seconds to minutes. Inhalation of HCN results in the rapid onset
of poisoning, producing almost immediate collapse, respiratory arrest, and death within
minutes (Table 1) | [Description]
Hydrocyanic acid, HCN, is corrosive in addition to toxic. It is also a dangerous fire and explosion risk. It has a wide flammable range of 6%–41% in air. The boiling point is 79°F (26°C), the flash point is 0°F, and the ignition temperature is 1004°F (540°C). It is toxic by inhalation and ingestion and through skin absorption. The TLV of hydrocyanic acid is 10 ppm in air. It is used in the manufacture of acrylonitrile, acrylates, cyanide salts, dyes, rodenticides, and other pesticides. | [Physical properties]
Colorless liquid or gas; odor of bitter almond; burns in air with a blue flame;refractive index 1.2675; autoignition temperature 538°C; vapor density at31°C 0.947 (air=1); liquid density 0.715 g/mL at 0°C and 0.688 g/mL at 20°C;boils at 25.7°C; melts at 13.24°C; vapor pressure 264 torr at 0°C; critical tem-perature 183.5°C; critical pressure 53.20 atm; critical volume 139 cm3/moldielectric constant 158.1 at 0°C and 114.9 at 20°C; conductivity 3.3 mhos/cmat 25°C; viscosity 0.201 centipoise at 20°C; surface tension 19.68 dyn/cm;readily mixes with water and alcohols; density of a 10% aqueous solution0.984 g/mL at 20°C; pKaat 25°C 9.21. | [Occurrence]
Peaches, apricots, bitter almonds, cherries, and plums contain some HCN derivatives in their kernels, frequently in combination with glucose and benzaldehyde as a glucoside (amygdalin). The bitter almond fragrance of HCN and its derivatives sometimes can be detected in such kernels. | [History]
Hydrogen cyanide in pure form was prepared first in 1815 by Gay-Lussac.Earlier, in 1782, Scheel prepared this compound in dilute solution. The mostimportant application of hydrogen cyanide is to produce methyl methacrylatefor methacrylate resins and plastics. Other products made from hydrogencyanide include potassium cyanide, sodium cyanide, adiponitrile, methionine,cyanuric chloride, cyanogen, nitrilotriacetic acid, and several triazine pesti-cides. The compound also is used in small amounts for extermination ofrodents. | [Preparation]
Hydrogen cyanide is generally produced in industrial quantities by hightemperature catalytic reaction between ammonia, methane, and air (theAndrussow process). The stoichiometry of the process is:
2CH4 + 2NH3 + 3O2 → HCN + 3H2O ΔHrxn = 230.4 kcal
The above reaction is endothermic requiring a temperature of 1,100°C and acatalyst such as platinum or rhodium. Other hydrocarbons may be usedinstead of methane.
The compound may be made by several other methods, which include:1. Heating methanol and ammonia in the absence of air at elevated temperatures (600 to 950°C) using a catalyst:
CH3OH + NH3 → HCN + H2O + H2
2. Thermal decomposition of formamide at elevated temperatures and reduced pressure:
HCONH2 → HCN + H2O
3. Heating acetonitrile and ammonia at 1,100 to 1,300°C:
CH3CN + NH3 → 2HCN +2H2
4. Reaction of sodium cyanide or potassium cyanide or potassium ferrocyanide with a mineral acid:
NaCN + HCl → HCN + NaCl
K4Fe(CN)6 + 6HCl → 6HCN + 4KCl + FeCl2
| [Production Methods]
Hydrogen cyanide can be prepared from a mixture of NH3, methane, and air by partial combustion in the presence of a platinum catalyst: HN3 + CH4 + 1.5 O2 +6 N2 → HCN +3 H2O + 6N2 The process is carried out at about 900–1,000 °C; yield ranges from 55–60%. In another process, methane (contained in natural gas) is reacted with NH3 over a platinum catalyst at from 1,200–1,300 °C, the reaction requiring considerable heat input. In still another process, a mixture of methane and propane is reacted with NH3 : C3H8 + 3NH3 → 3HCN + 7H2; or CH4 + NH3 → HCN + 3H2. An electrically heated fluidized bed reactor is used. Reaction temperature is approximately 1,510 °C. | [Production Methods]
Hydrogen cyanide has been manufactured from sodium
cyanide and mineral acid and from formamide by catalytic
dehydration. Two synthesis processes account for most of the
hydrogen cyanide produced. The dominant commercial process
for direct production of hydrogen cyanide is based on
classic technology involving the reaction of ammonia,
methane (natural gas), and air over a platinum catalyst; it
is called the Andrussow process. The second process, which involves the reaction of ammonia and methane, is called the
Blaus€aure–Methan–Ammoniak (BMA) process;
it was developed by Degussa in Germany. Hydrogen cyanide
is also obtained as a by-product in the manufacture of
acrylonitrile by the ammoxidation of propylene (Sohio
process). | [Reactions]
Hydrogen cyanide reacts with hydrogen at 140 °C in the presence of a catalyst, e.g., platinum black, to form methyl amine CH3NH2. When burned in air, it produces a pale violet flame; when heated with dilute sulfuric acid, it forms formamide HCONH2 and ammonium formate HCOONH4; when exposed to sunlight with chlorine it forms cyanogen chloride CNCl, plus hydrogen chloride. An important reaction of hydrogen cyanide is that with aldehydes or ketones, whereby cyanhydrins are formed, e.g., acetaldehyde cyanhydrin CH3CHOH·CH, and the resulting cyanhydrins are readily converted into alpha-hydroxy acids, e.g., alphahydroxypropionic acid CH3·CHOH·COOH. | [Purification Methods]
HCN is prepared from NaCN and H2SO4, and dried by passage through H2SO4 and over CaCl2, then distilled in a vacuum system and degassed at 77oK before use [Arnold & Smith J Chem Soc, Faraday Trans 2 77 861 1981]. Cylinder HCN may contain stabilisers against explosive polymerisation, together with small amounts of H3PO4, H2SO4, SO2, and water. It can be purified by distillaton over P2O5, then frozen in Pyrex bottles at Dry-ice temperature for storage. [Zeigler Org Synth Coll Vol I 314 1941, Glemser in Handbook of Preparative Inorganic Chemistry (Ed. Brauer) Academic Press Vol I pp 658-660 1963.] Liquid HCN, like liquid ammonia, evaporates very slowly since the latent heat of evaporation is high and keeps it in the liquid state because the temperature of the liquid is lowered to below its boiling point. EXTREMELY POISONOUS; all due precautions should be taken. | [Flammability and Explosibility]
Hydrogen cyanide is a highly flammable liquid. Liquid HCN contains a stabilizer
(usually phosphoric acid), and old samples may explode if the acid stabilizer is not
maintained at a sufficient concentration. | [Potential Exposure]
AgriculturalChemical; Human Data. Hydrogen cyanide is used in chem-ical synthesis of sequestrants, polymers, weed killers, andpharmaceuticals; as a fumagant; in electroplating, mining,chemical synthesis, and the production of synthetic fibers,plastics, dyes, and pesticides; in chemical synthesis of acry-lates and nitriles, particularly acrylonitrile. It may be gener-ated in blast furnaces, gas works, and coke ovens. Cyanidesalts have a wide variety of uses, including steel hardening,gold and silver extraction from ores. AC is used as a chemi-cal warfare agent (blood agent); systemic agent. It formscyanide in the body. | [First aid]
If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seek med-ical attention immediately. If this chemical contacts theskin, remove contaminated clothing and wash immediatelywith soap and water. Seek medical attention immediately. Ifthis chemical has been inhaled, remove from exposure,begin rescue breathing (using universal precautions, includ-ing resuscitation mask) if breathing has stopped and CPR ifheart action has stopped. Transfer promptly to a medicalfacility. When this chemical has been swallowed, get medi-cal attention. Give large quantities of water and inducevomiting. Do not make an unconscious person vomit. Useamyl nitratecapsules if symptoms develop. Allareaemployees should be trained regularly in emergency mea-sures for cyanide poisoning and in CPR. A cyanide antidotekit should be kept in the immediate work area and must berapidly available. Kit ingredients should be replaced every1-2 years to ensure freshness. Persons trained in the use ofthis kit, oxygen use, and CPR must be quickly available. | [Shipping]
Hydrocyanicacid,aqueoussolutionsorHydrogen cyanide, solutions with not > 20% hydrogen cya-nide requires a shipping label of“POISONOUS/TOXIC .MATERIALS." It falls in Hazard Class 6.1 and PackingGroup I.Hydrogen cyanide, stabilized, with <3% water requires ashipping label of“POISONOUS/TOXIC MATERIALS,FLAMMABLE LIQUID.”" It falls in Hazard Class 6.1 andPacking Group I.Hydrogen cyanide,stabilized, with <3%water andabsorbed in a porous inert material requires a shipping labelof“POISONOUS/TOXIC MATERIALS." It falls in HazardClass 6.1 and Packing Group I. | [Incompatibilities]
HCN can polymerize explosively if heated above 50 °C or in the presence of trace
amounts of alkali. | [Waste Disposal]
In the event of a spill, remove all ignition sources. Cleanup should be conducted
wearing appropriate chemical-resistant clothing and respiratory protection
Disposal Excess hydrogen cyanide and waste material containing this substance should be
placed in an appropriate container, clearly labeled, and handled according to your
institution's waste disposal guidelines. For more information on disposal procedures,
see Chapter 7 of this volume. |
| Safety Data | Back Directory | [Hazard Codes ]
F+,T+,N | [Risk Statements ]
12-26-50/53-26/27/28 | [Safety Statements ]
7/9-16-36/37-38-45-60-61 | [RIDADR ]
1051 | [Autoignition Temperature]
538 °C | [HazardClass ]
6.1(a) | [PackingGroup ]
I | [storage]
Hydrogen cyanide should be stored in a cool, dry, well-ventilated area in tightly sealed
containers and with the correct label. Containers of hydrogen cyanide should be protected
from physical damage and should be stored separately from amines and oxidizers, such
as perchlorates, peroxides, permanganates, chlorates, and nitrates. It should be kept sepa-
rated from strong acids, such as hydrochloric, sulfuric, and nitric acids, away from sodium
hydroxide, calcium hydroxide, sodium carbonate, water, ammonia, acetaldehyde, and
caustics. | [Precautions]
Occupational workers should be very careful in the management of HCN since the gas in
air is explosive at concentrations over 5.6%, equivalent to 56,000 ppm and it does not provide adequate warning of hazardous concentrations. HCN at a concentration of 300 mg/m3
in air becomes fatal within about 10 min and HCN at a concentration of 3500 ppm (about
3200 mg/m3
) kills a human in about 1 min.
| [Hazardous Substances Data]
74-90-8(Hazardous Substances Data) | [Toxicity]
LC50 in rats, mice, dogs: 544 ppm (5 min), 169 ppm (30 min), 300 ppm (3 min) by inhalation, K. C. Back et al., Reclassification of Materials Listed as Transportation Health Hazards (TSA-20-72-3; PB214-270, 1972) | [IDLA]
50 ppm |
|