BUXI JAGABANDHU BIDYAHAR AUTONOMOUS

COLLEGE

A PROJECT REPORT ON
“PHOSPHINE GAS”
NASHRIN FARHAD
ROLL NO-72023069
UNDER THE GUIDANCE OF DR. RAJESH KUMAR SAHOO
DEPARTMENT OF CHEMISTRY, BUXI JAGABANDHU BIDYAHAR
COLLEGE, ODISHA
CERTIFICATE
I do here by certify that, this project titled
“CHEMISRTY OF PHOSPHINE GAS” is completed by
NASHRIN FARHAD of +3 final year degree
(Chemistry Honours) bearing Examination roll no-
72023069 of BUXI JAGABANDHU BIDYADHAR
COLLEGE, Bhubaneswar. It is an original project
work have been submitted under my supervision
and guided by Dr. Rajesh Kumar Sahoo during the
academic session 2020-23.

Signature of head of Signature of the

The department guide
DECLARATION
I do here by declare that the dissertation
entitled “CHEMISTRY OF PHOSPHINE” in the
partial fulfillment of the requirement for the
Bachelor degree in science submitted by me
to the Department Of Chemistry, BJB
Autonomous College, Bhubaneswar is an
authentic record and has not been submitted
elsewhere for the award any other degree in
full.

Name: Nashrin Farhad

Roll No:72023069
Department of chemistry
ACKNOWLEDGEMENT
I express my deep sence of gratitude and sincere
obligation to my adorable HOD Dr. Renuka Sahu BJB
Autonomous College for her prolific guidance and
meticulous effort at every stage of my project without
which I would not be able to complete my research
work. I would like to convey my deep sence of
profound gratitude to my esteemed teacher and
guide Dr.Rajesh Kumar Sahoo.
BJB Autonomous College for his timely guidance, deep
interest, precious suggestion and advice. Then I would
like to convey my regards to my parents for their co-
operation and financial help to complete this project,
also thanks to my friends who have helped me for the
completion of the project in various phase.

Nashrin Farhad
Roll no.-72023069
preface
Phosphine is a colorless, flammable, highly toxic
compound with the chemical formula PH3,
classed as a pnictogen hydride. Pure phosphine is
odorless, but technical grade samples have a
highly unpleasant odor like rotting fish, due to
the presence of substituted phosphine and
diphosphane (P2H4). With traces of P2H4 present
PH3 is spontaneously flammable in air, burning
with a luminous flame. Phosphine is a highly toxix
respiratory poison, and is immediately dangerous
to life or hralth at 50ppm. Phosphine has a
trigonal pyramidal structure.
contents
 Introduction
 Structure and formula of
phosphine
 Preparation methods of phosphine
 History
 Purification of phosphine
 Physical properties of phosphine
 Chemical properties of phosphine
 Uses of phosphine
 Phosphine-Toxilogical overview
 Conclusion
 Bibiliography
introduction
Phosphine (PH3), commonly known as
hydrogen phosphide, is a colourless,
flammable, highly poisonous gas with a
garlic-like odour. Although phosphine is
structurally identical to ammonia . It is a
considerably worse solvent and is much less
water soluble. When a strong base or hot
water reacts with white phosphorus, or
when water reacts with calcium phosphide
phosphine is generated. Phosphine has
boiling point of -126℉ and a freezing point
of -209℉. In extremely low quantities it is
extremely poisonous when inhaled.
Additionally, long term heating could cause
containers to explode violently, resulting in
possible injuries and fatalities. Workers
exposed to phosphine on a long term basis
has nasal and throat irritation, weakness,
dizziness, nausea, gastro-intestinal, cardio-
respiratory, central nervous system
symptoms, jaundice, lever effects and
enhanced bone density.
Structure and formula of
phosphine
Phosphine has a trigonal pyramidal
structure. The lone pair of electrons
present on phosphorous causes the
molecule symmetry to alter. sp3
hybridisation occurs in phosphorous.
Three bond pairs and one lone pairs of
electrons are present. The angel of the
H−P−H bond is 93.5°, while the length
of the P−H bond is 1.42pm.

The low dipole moments and almost

orthogonal bond angle lead to the
conclusion that in PH3 the P−H bonds
are almost entirely pσ(P) – sσ(H) and
phosphorus 3s orbital contributes little
to the bonding between phosphorus
and hydrogen in this molecule. For this
reason, the lone pair on phosphorus
may be regarded as predominantly
formed by the 3s orbital of phosphorus.
The upfield chemical shift of the
phosphorus atom in the 31P NMR
spectrum accords with the conclusion
that the lone pair electrons occupy the
3s orbital (Fluck, 1973). This electronic
structure leads to a lack of
nucleophilicity in general and lack of
basicity in particular (pKaH = –14), as well
as an ability to form only weak hydrogen
bonds.
PREPARATION OF PHOSPHINE
 Hydrolysis of metal phosphides
with calcium phosphides- Metal
phosphides react with water or HCl
to produce phosphine.
Ca3P2+6H2O→2PH3+3Ca(OH)2
Ca3P2+6HCl→2PH3+3CaCl2
 From phosphorous acid- Pure
phosphine is prepared via the
breakdown of phosphorous acid.
4H3PO3→3H3PO4+PH3
 Preparation from phosphorus-
Heating with phosphorus in
concentrated sodium hydroxide
solution in a inert carbon dioxide
environment produces phosphine.
P4+3NaOH+3H2O→PH3+3NaH2PO2
Laboratory routes:

It is prepared in the laboratory by

disproportionation of phosphorous acid:[16]
4 H3PO3 → PH3 + 3 H3PO4
Phosphine evolution occurs at around 200 °C.
Alternative methods are the hydrolysis of
tris(trimethylsilyl)phosphine, or of metal
phosphides such as aluminium phosphide, or
calcium phosphide:
Ca3P2 + 6 H2O → 3 Ca(OH)2 + 2 PH3
Pure samples of phosphine, free from P2H4, may
be prepared using the action of potassium
hydroxide on phosphonium iodide :
[PH4]I + KOH → PH3 + KI + H2O
Occurrence:

Phosphine is a worldwide constituent of the

Earth's atmosphere at very low and highly
variable concentrations. It may contribute
significantly to the global phosphorus
biochemical cycle. The most likely source is
reduction of phosphate in decaying organic
matter, possibly via partial reductions and
disproportionations, since environmental systems
do not have known reducing agents of sufficient
strength to directly convert phosphate to
phosphine.
It is also found in Jupiter's atmosphere.

In 2020 a spectroscopic analysis was reported to

show signs of phosphine in the atmosphere of
Venus in quantities that could not be explained
by known abiotic processes. Later re-analysis of
this work showed interpolation errors had been
made, re-analysis of data with the fixed
algorithm either do not result in the detection of
phosphine. The authors of the original study
then claimed to detect it with a much lower
concentration of 1 ppb.
HISTORY:
Philippe Gengembre (1764–1838), a student of Lavoisier,
first obtained phosphine in 1783 by heating white
phosphorus in an aqueous solution of potash (potassium
carbonate).[6][NB 1]
Perhaps because of its strong association with elemental
phosphorus, phosphine was once regarded as a gaseous
form of the element, but Lavoisier (1789) recognised it as a
combination of phosphorus with hydrogen and described it
as phosphure d'hydrogène (phosphide of hydrogen).[NB 2]
In 1844, Paul Thénard, son of the French chemist Louis
Jacques Thénard, used a cold trap to separate diphosphine
from phosphine that had been generated from calcium
phosphide, thereby demonstrating that P2H4 is responsible
for spontaneous flammability associated with PH3, and also
for the characteristic orange/brown color that can form on
surfaces, which is a polymerisation product.[7] He
considered diphosphine's formula to be PH2, and thus an
intermediate between elemental phosphorus, the higher
polymers, and phosphine. Calcium phosphide (nominally
Ca3P2) produces more P2H4 than other phosphides because
of the preponderance of P-P bonds in the starting material.
The name "phosphine" was first used for
organophosphorus compounds in 1857, being analogous to
organic amines (NR3).[NB 3][8] The gas PH3 was named
"phosphine" by 1865 (or earlier).[9]
Purification of phosphine
Pure phosphine is the non-flammable
substance. Due to the presence P2H4 or
P4 vapours, it becomes combustible.
Phosphine is refined by absorbing it in
HI and converting it to PH4I. When you
combine this with Potassium hydroxide
you get phosphine.
PH4I+KOH→PH3+KI+H2O
Physical properties of phosphine

1. It’s a colourless gas that is extremely

dangerous
2. As previously stated, Phosphorous in its
pure form is non-flammable. It is
nevertheless, combustible due to the
presence of P4 vapours. When
phosphorous comes into touch with
oxidizing substances like HNO3 chlorine or
bromine vapours it can catch fire. It can
catch fire even if just a little amount or
traces of this oxidizing chemicals are
present.
3. It has distinct rotten fish odour to it.
4. It’s just slightly soluble in water
5. It has boiling point -87.7 ℃.
Chemical properties of phosphine
1. Phosphine, like ammonia, is a lewis
base. When it reacts with HI, HBr, and
HCl, it produces phosphonium
compounds.
PH3+HI→PH4I
PH3+ HBr→PH4Br
PH3+HCl→PH4Cl

2. Combustibility- when
phosphorous is burned, produces
phosphorous pentaoxide and water.
2PH3+4O2→P2O5+ 3H2O
3. Reaction with chlorine-
PH3+4Cl2→PCl5+3HCl
 Under normal circumstances, it will
not ignite. It explodes with flame
when heated, releasing phosphoric
acid.
 When exposed to oxidizing
substances such as HNO3, Cl2, and
Br2, it explodes dramatically.
 PH3 in water decomposes in the
presence of light to produce red P
and H2O. (PH3(H2O)→P(Red) + H2O)
 Copper phosphide and mercuric
phosphide are generated when
phosphine is absorbed in copper
sulphate or mercuric chloride.
3CuSO4+2PH3→Cu3P2+3H2SO4
3HgCl2+2PH3→Hg3P2+6HCl
Uses of phosphine
Phosphine is a chemical that is used to make
metallic phosphides.
Holme’s signal and smokescreens contain
phosphorous.
 Holme’s signal: The fact that phosphine
spontaneously combusts makes it a
likely candidate for use in Holme’s
signal. When ships require assistance,
calcium carbide and calcium phosphide-
filled containers are pierced and tossed
into the water. Acetylene and
phosphine gases are produced as a
result of the interaction with water.
These gases emit a signal when they
burn in the air.
 Smoke Screen: when calcium
phosphide is soaked in wwster, it
creates a considerable amount of
phosphine, resulting in a smoke
screen. During the conflict, this was
employed to hide the troops from
the enemy. In rodent and insect
control formuklations, phosphine
fumigants and utilized.
PHOSPHINE-TOXILOGICAL OVERVIEW
Phosphine is rapidly absorbed and distributed
throughout the body and is acutely toxic. The
onset of symptoms is rapid following phosphine
inhalation or the ingestion/inhalation of metal
phosphides, which releases phosphine on contact
with moisture or stomach acuid. Dermal
absorption of phosphine or phosphides is not
considered a significant route of exposure.
Exposure to low doses of phosphine causes non-
specific symptoms such as headache, dizziness,
numbness, general fatigue, breathing difficulties
(tightness around the chest, pain in the region
diaphragm and cough) and gastro-intestinal
disturbance. At higher doses, subjects may
experience lung irritation, persistent coughing,
tremors and convulsions, leading to pulmonary
edema, myo-cardial injury, kidney damage and
coma, and sometimes death due to cardio-
vascular failure, usually within the first few hours
or after a delay of upto two weeks in the case of
liver failure.
Chronic exposure to phosphine is unlikely to
occur in the general population but many occur in
an occupational setting. Symptoms of chronic
exposure may include anaemia, bronchitis,
gastro-intestinal disorders, speech and motor
disturbances, weakness, weight loss, toothache,
swelling of the jaws, mandibular necrosis, and
spontaneous fractures. Some chronic effects can
be confused with symptoms of acute poisoning.
Children exposed to phosphine have the same
symptoms of toxicity as adults.
Conclusion:
Phosphine is a precursor to many organo-
phosphorus compounds. It reacts with
formaldehyde in the presence of hydrogen
chloride to give tetrakis (hydroxyl methyle)
phosphonium chloride, which is used in textiles.
Phosphine is used as a dopant in the semi-
conductor industry, and a precursor for the
deposition of compound semi-conductors.
Commercially significant products include gallium
phosphide and Indium phosphide.
For farm use, pallets of aluminium phosphide,
calcium phosphide or zinc phosphide release
phosphine upon contact with atmospheric water
or rodents stomach acid. These pallets also
contain agents to reduce the potentials for
ignition or explosion of the released phosphine.
bibliography
 https://en.wikipedia.org/wiki/Phosphine
 https://www.geeksforgeeks.org/phosphin
e-structure-preparation-properties-uses/