Toxicology

-:Cyanides:-
The King of Poisons
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 Moika Palace on bank of Neva river,
Petrograd (St. Petersburg)
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Hydrogen cyanide
⚫ Also called Hydrocyanic Acid, Prussic acid & HCN
⚫ Hydrogen cyanide is a clear to pale blue liquid or gas with the
odor of bitter almonds.(Smell appreciation is genetic)
⚫ HCN is obtainable from fruits that have a pit, such as cherries,
apricots, apples, and bitter almonds. “Bitter" roots of the cassava
plant may contain up to 1 gram of HCN per kilogram
⚫ It melts at -14 C and boils at 25.6 C.
⚫ Important poisonous salts are potassium cyanide (KCN) and
Sodium cyanide (NaCN) . They are identical
⚫ Its solution in water is called hydrocyanic acid, which is a weak
acid.
⚫ By reacting Potassium ferrocyanide or Pot. Cyanide with dilute
sulphuric acid HCN can be produced
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 Discovery
⚫ In 1752 the French chemist Pierre Macquer showed that Prussian blue
a dye could be converted to iron oxide plus a volatile component.
⚫ The volatile component was first isolated from Prussian blue in pure
form and characterized about 1783 by the Swedish chemist Carl
Wilhelm Scheele,
⚫ Because of its acidic nature in water and it was derived from Prussian
blue it was called Prussic acid in English.
⚫ In 1787 the French chemist Claude Louis Berthollet showed that Prussic
acid did not contain oxygen, an important contribution to acid theory.
⚫ In 1815 Joseph Louis Gay-Lussac deduced Prussic acid's chemical
formula. The radical cyanide in hydrogen cyanide was given its name
from the Greek word for blue, again due to its derivation from Prussian
blue.

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Properties
⚫ KCN reacts with acids & weak alkaline solutions to liberate toxic
and flammable hydrogen cyanide gas.
⚫ KCN can react with carbon dioxide of air in the presence of
moisture to produce hydrogen cyanide gas
⚫ Reacts slowly with moisture to form hydrogen cyanide gas or
with water to form hydrocyanic acid
⚫ Emits toxic fumes of cyanide when heated
⚫ Hydrogen cyanide concentration of 300 mg/m3 in air will kill a
human within about 10 minutes.
⚫ A concentration of 3500 ppm (about 3200 mg/m3) will kill a
human in about 1 minute. The toxicity is caused by the cyanide
ion.
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Mechanism of Action
⚫ Cyanides are potent inhibitor of cellular respiration, acting
on mitochondrial cytochrome c oxidase and hence blocking
oxidative phosphorylation.
⚫ Acute cyanide poisoning causes a red or ruddy complexion
in the victim because the tissues are not able to use the
oxygen in the blood
⚫ Lactic acidosis occurs as a consequence of anaerobic
metabolism.
⚫ The effects of potassium and sodium cyanide are identical.
⚫ There may be convulsions before death
⚫ Death is due to cardiac arrest
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USE of Hydrogen cyanide (HCN))
⚫The principal use of hydrogen cyanide is in the
manufacturing of acrylates, synthetic fibers (as a
starting material for nylon 66), plastics and cyanide
salts, especially sodium cyanide to extract gold & silver
from ore. It is used in the manufacturing of organic
chemicals; acrylonitrile, metal polishes, dyes,
rodenticides, pesticides, synthetic fibers, plastics, and
electroplating solutions
⚫Used to fumigate houses, ships, railway carriages and
warehouses.

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Poisoning
⚫On Inhalation:
Corrosive to the respiratory tract. The substance
inhibits cellular respiration and may cause blood,
central nervous system, and thyroid changes. May
cause headache, weakness, dizziness, laboured
breathing ,nausea, and vomiting,
⚫Followed by weak and irregular heart beat,
unconsciousness, convulsions, coma and death.

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Poisoning (Cont.)
⚫On Ingestion of KCN:
Highly Toxic! Corrosive to the gastro-intestinal tract
with burning in the mouth and oesophagus, and
abdominal pain. Larger doses may produce sudden loss
of consciousness and prompt death from respiratory
arrest. Smaller but still lethal doses may prolong the
illness for one or more hours. Bitter almonds odour may
be noted on the breath or vomitus. Other symptoms
may be similar to those noted for inhalation exposure.

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Poisoning (Cont.)
⚫On Skin Contact:
Corrosive. May cause severe pain and skin burns.
Solutions are corrosive to the skin and eyes, and may
cause deep ulcers which heal slowly. May be absorbed
through the skin, with symptoms similar to those
noted for inhalation.

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Poisoning (Cont.)
⚫ Eye Contact:
Corrosive. Symptoms may include redness, pain, blurred
vision, and eye damage.
⚫ Chronic Exposure:
Prolonged or repeated skin exposure may cause a
"cyanide" rash and nasal sores.
⚫ Aggravation of Pre-existing Conditions:
Workers using cyanides should have a pre-placement and
periodic medical exam. Those with history of central
nervous system, thyroid, skin, heart or lung diseases may
be more susceptible to the effects of this substance.
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Vital Parameters
⚫ Fatal Dose
⚫ Probable oral lethal dose in humans is less than 5 mg/kg or
less than a taste (7 drops) for a 68Kg. person
⚫ HCN Liquid- 50 mg
⚫ Prussic or Scheele’s acid ( a 4% Soln.) 1-2 mL
⚫ KCN or NaCN- 200 mg
⚫ Fastest acting poison
⚫ Fatal Period
⚫ Depending on the dose- 1 minute to 1 hour. Those who
survive for an hour are likely to survive.
⚫ Usually within ½ hour majority dying within 5-10 minutes

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Management
⚫ A cyanide antidote kit (amyl nitrite, sodium nitrite and sodium
thiosulfate) should be available in Emergency of all hospitals
⚫ Give amyl nitrite by breaking the ample in a handkerchief asking
to inhale for 15-30 seconds per minute. A new amyl nitrite
ampoule should be used every 3 minutes.
⚫ Give Oxygen.
⚫ Do not give mouth to mouth resuscitation. Use respirator
⚫ 10mL of a 3% solution of sodium nitrite I.V. at a rate of not more
than 2.5 to 5 mL per minute, followed by 50 mL of 25% solution
of sodium thiosulfate 2.5-5 ml/mt I.V.
⚫ Methylene blue i.v. ; Cobalt EDTA. ; Para amino prophenone
(PAPP) which acts by forming meth.Hb. Are also said to be useful
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Management
⚫ Where taken orally give activated charcoal slurry
⚫ Gastric lavage with a mixture of 6% NaCO3; 15.3% ferrous
sulphate; and 3% citric acid in water
⚫ Administration of cytochrome oxidase
⚫ In case of skin contact, remove contaminated clothing and
shoes. Wash skin with plenty of water for at least 15
minutes. Administer antidote kit and oxygen, if symptoms
occur.
⚫ In case of contact with eyes, flush eyes with plenty of water
for at least 15 minutes.

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Management
⚫Watch for 24-48 hours.
⚫If signs of cyanide poisoning reappear, repeat nitrite
and thiosulfate injections 1 hour later in 1/2 the
original doses.
⚫Hydroxycobalamin (B12), 1 mg intramuscularly, may
speed recovery.
⚫Keep patient warm and at rest
⚫Treat mild cyanide exposures by supportive measures
such as bed rest and oxygen.

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 Post- mortem Appearance
⚫Autopsy surgeon to be careful in known cases.
⚫Post-mortem staining is bright red or pink
⚫Face, eyes and skin generally are congested
⚫Rigor mortis sets in early and lasts longer
⚫Smell of bitter almond may be appreciated on opening
the body cavities.
⚫Rt side of heart is full. Blood fluid and bright red
⚫In cases of ingestion stomach congested, inflamed and
mucosa may be ulcerated. There may be patches of
ecchymoses.
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Prevention
⚫ In the event of a fire, wear full protective clothing and
NIOSH-approved self-contained breathing apparatus with
full facepiece operated in the pressure demand or other
positive pressure mode.
⚫ In case of spills in storage area, Ventilate area of leak or
spill. Allow only qualified personnel to handle spill. Clean-
up personnel require protective clothing and respiratory
protection from vapours. Collect material and place in a
closed container for recovery or disposal. Do not flush to
sewer! Decontaminate liquid or solid residues in spill area
with sodium or calcium hypochlorite solution
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Prevention
⚫ Keep in a tightly closed container, stored in a cool, dry, ventilated area.
Protect against physical damage
⚫ Containers of this material may be hazardous when empty since they
retain product residues
⚫ Do not store near combustibles or flammables because subsequent fire
fighting with water could lead to cyanide solution runoff
⚫ Exhaust is recommended to prevent dispersion into the general work area
⚫ Wear impervious protective clothing, including boots, gloves, lab coat,
apron or coveralls, as appropriate, to prevent skin contact.
⚫ Eye Protection:
⚫ Use chemical safety goggles and/or full face shield where dusting or splashing
of solutions is possible. Maintain eye wash fountain and quick-drench facilities
in work area.

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ML Aspect
⚫A number of prominent persons were killed or
committed suicide using potassium cyanide, including
members of the Black Hand Gang (unsuccessfully) and
members of the Nazi Party, such as Hermann Gö ring
and Heinrich Himmler, WWII era British agents (using
purpose-made suicide pills), LTTE agents and various
other religious cults such as in Jonestown

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Medico-Legal Aspects
⚫ KCN carried in capsule by extremist groups to commit suicide by
ingestion if in danger of being caught
⚫ It is said to be ineffective if the person suffers from achlorhydria.
⚫ Poisoning may be fatal if swallowed, inhaled or absorbed
through the skin.
⚫ In nonfatal dose may cause burns to skin, eyes, and
respiratory tract, affects the blood, cardiovascular system,
central nervous system, and thyroid
⚫ It is alleged that Nazis killed people by using HCN in gas chambers
⚫ Used as a method of capital punishment in some states of the USA

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