Lecture 13 Pnictogens

Lecture 13
Descriptive Chemistry of the Elements

The Group VA Elements
© Ch111.20 / 211 2018-19

GROUP 15 ELEMENTS
GROUP 15 ELEMENTS
General trends:
Decrease in
electronegativity
Increase metallic
character
Stability of lower
oxidation state
Overview
• Nearly all the chemistry involves covalently bonded compounds

• Kinetically inert (to processes which involve making or breaking
covalent bonds)
• Substitution reactions
• Oxidation/Reduction reactions
• Chemistry of N and P is far more extensive than that of As, Sb and Bi
• Nitrogen forms a range of oxoacids and oxoanions and in aqueous
media can exist in all oxidation states from +5 to -3.
Occurrence
Occurrence
• Nitrogen (N2)
• Its availability in the atmosphere and its requirement by living
organisms makes nitrogen fixation in forms in which it may be
assimilated by plants of great importance
– No synthetic nitrogen-fixation process (mimicking the action
of bacteria living in root nodules of leguminous plants) has
been devised yet.
– N2 can be fixed by other processes (industrial conversion to
NH3)
• natural source of nitrogen suitably ‘fixed’ for uptake by plants is
crude NaNO3 (Chile saltpetre or sodanitre) which occurs in the
deserts of South America.
Occurrence
• Phosphorus
– essential constituent of plant and animal tissues
DNA
Calcium phosphate
ATP
Occurrence
• Phosphorus
– Occurs naturally in the form of apatites:
Ca5X(PO4)3, the important minerals being:
• fluorapatite (X=F)
• chlorapatite (X=Cl)
• hydroxyapatite (X=OH)
– Major deposits of the apatite-containing ore
phosphate rock occur in North Africa, North
America, Asia and the Middle East.
Occurrence
• Arsenic
• Occurs in the elemental form
• Commercial sources of the element are mispickel
(arsenopyrite, FeAsS), realgar (As4S4) and
orpiment (As2S3)
• Antimony
• Rare and the only commercial ore is stibnite (Sb2S3).
• Bismuth
• Occurs as the element, and as the ores bismuthinite
(Bi2S3) and bismite (Bi2O3).
Extraction
• Nitrogen (N2)
– Obtained industrially by fractional distillation of liquid air (product
contains some Ar and traces of O2)
• Dioxygen can be removed by addition of a small amount of H2 and
passage over a Pt catalyst or by bubbling the gas through an
aqueous solution of CrCl2
– Small amounts of N2 can be prepared by:
Potentially explosive!
Powerful oxidant & a component of
dynamite
Extraction
• Phosphorus
– Elemental phosphorus extracted from phosphate rock (which
approximates in composition to Ca3(PO4)2) by heating with sand
and coke in an electric furnace:
– Phosphorus vapor distils out and is condensed under water to yield

white phosphorus.
Extraction
• Arsenic
• Principal source is FeAsS, and the element is extracted by heating and
condensing the As sublimate:
• Additional method: air-oxidation of arsenic sulfide ores giving As 2O3

which is then reduced by C
• As2O3 is also recovered on a large scale from flue dusts in Cu and Pb
smelters
Extraction
• Antimony
– Obtained from stibnite by reduction using scrap iron or by conversion to
Sb2O3 followed by reduction with C
• Bismuth
– Extraction from its sulfide or oxide ores involves reduction with carbon
(via the oxide when the ore is Bi2S3)
– It can is also obtained as a byproduct of Pb, Cu, Sn, Ag and Au refining
processes.
Uses
• Nitrogen
– In the US, N2 ranks second in
industrial chemicals (large proportion
of N2 is converted to NH3)
– Gaseous N2 is widely used to provide
inert atmospheres, both industrially
(e.g. in the electronics industry during
the production of transistors etc.) and
in laboratories
– Liquid N2 (bp: 77 K) is an important
coolant with applications in some
freezing processes.
Uses
• Nitrogen
• Nitrogen-based chemicals are extremely

important: nitrogenous fertilizers, nitric acid and
nitrate salts, explosives such as nitroglycerine
and trinitrotoluene, nitrite salts (e.g. in the
curing of meat where they prevent discoloration
Nitroglycerine
by inhibiting oxidation of blood), cyanides and
azides (e.g. in motor vehicle airbags where
decomposition produces N2 to inflate the airbag)
TNT
Uses
• Phosphorus
• Important use is in phosphate fertilizers
• Bone ash (calcium phosphate) is used in the manufacture of bone china
• White phosphorus is converted to H3PO4 or to compounds such as P4O10,
P4S10, PCl3 and POCl3
• Phosphoric acid is industrially very important
– used on a large scale in the production of fertilizers, detergents and
food additives
– responsible for the sharp taste of many soft drinks
– used to remove oxide and scale from the surfaces of iron and steel
Uses
• Phosphorus
• Phosphorus trichloride is also manufactured on a large scale
– it is a precursor to many organophosphorus compounds including
nerve gases, flame retardants and insecticides
• Phosphorus is important in steel manufacture and phosphor bronzes
• Red phosphorus is used in safety matches and in the generation of
smoke (e.g. fireworks, smoke bombs)
Uses
• Arsenic
• Arsenic salts and arsines are extremely toxic: used
in weedkillers, sheep- and cattle-dips and poisons
against vermin
• Arsenic is a doping agent in semiconductors and
GaAs has widespread uses in solid state devices and
semiconductors
• Used in the semiconductor industry, in alloys (e.g. it
increases the strength of Pb) and in batteries
Uses
• Antimony
• Less toxic than arsenic but large doses result in liver damage
• Potassium antimony tartrate (tartar emetic) was used medicinally as
an emetic and expectorant but has now been replaced by less toxic
reagents
• Sb2O3 is used in paints, adhesives and plastics and as a flame
retardant
• Sb2S3 is used in photoelectric devices and electrophotographic
recording materials, and as a flame retardant
Uses
• Bismuth
• Major uses of bismuth: in alloys (e.g. with Sn) and as Bi-containing
compounds such as BiOCl in cosmetic products (e.g. creams, hair dyes
and tints)
• Other uses are as oxidation catalysts and in high-temperature
superconductors
• Bi2O3 has many uses in the glass and ceramics industry, and for catalysts
and magnets
• The move towards lead-free solders has resulted in increased use of Bi-
containing solders, e.g. Sn/Bi/Ag alloys
PHYSICAL PROPERTIES
PHYSICAL PROPERTIES
• Ionization energy:
– Increase sharply after removal of the “p electrons”
– Decrease only slightly between P and As (similar behavior to that
between Al and Ga, and between Si and Ge)
– For removal of the s electrons, there is an increase between Sb and Bi
(just as between In and Tl, and between Sn and Pb)
PHYSICAL PROPERTIES
• Bonding considerations:
PHYSICAL PROPERTIES
• N forms stronger bonds with H than does P, but weaker bonds with F, Cl or O:
• Existence of PF5, AsF5, SbF5 and BiF5 but not NF5
• N atom is simply too small to accommodate five atoms around it
• It is possible to account for the bonding in hypervalent molecules of the p-
block elements in terms of a valence set of ns and np orbitals (be cautious
about using sp3d and sp3d2 hybridization schemes to describe trigonal
bipyramidal and octahedral species of p-block elements)
PHYSICAL PROPERTIES
- a line between two atoms does not - more realistic

- shows the role that charge-
necessarily mean the presence of a
localized two-centre two electron separated species play when
bond considering electronic contributions
- representation of a double line of ions or molecules
- not a good representation of the
between two atoms does not
necessarily imply that the interaction molecule when focusing on its
comprises covalent σ- and π- structure – obscure the observed
contributions. geometry.
PHYSICAL PROPERTIES
• Group 14 vs Group 15
N ≡ N is thermodynamically C ≡ C is thermodynamically
stable with respect to unstable with respect to
oligomerization to species oligomerization to species
containing N−N containing C−C
N=N bond enthalpy more than twice N−N C=C bond enthalpy less than twice C−C
PHYSICAL PROPERTIES
• Why is N−N bond very weak?

– In N2H4, N atoms carry lone pairs
– It is believed that N−N bond is
weakened by repulsion between
lone pairs on adjacent atoms
PHYSICAL PROPERTIES
• Lone pairs on larger atoms are further apart and experience less
mutual repulsion
• When N is singly bonded to an atom with no lone pairs (e.g. H), the
bond is strong
– In heteronuclear bond, extra energy contributions may be
attributed to partial ionic character
PHYSICAL PROPERTIES
• N can take part in strong hydrogen bonding

– much higher electronegativity of N compared with other group 15
elements
Group 15 elements Electronegativity
values (ᵡ)
N 3.0
P 2.2
As 2.2
Sb 2.1
Bi 2.0
THE ELEMENTS
• Nitrogen (N2)
– Generally unreactive
– Can also combine slowly with group 2 metals, Al, Si, Ge

Slowly and many
at ambient d-
temp.
block metals when heated
– Reacts to form nitrogenous fertilizer:
THE ELEMENTS
• Nitrogen (N2)
– Reduced to N2H4 by vanadium (II)
and magnesium hydroxide at
ambient temperature
– Large number of d-block metal
complexes contain coordinated N2
– N2 is isoelectronic with CO and the
bonding in complexes containing
the N2 ligand can be described in a
similar manner to that in metal [Sn(N3)6]2-
carbonyl complexes
trans- [Ru(en)2(N2)(N3)]+
THE ELEMENTS
• Phosphorus
– Exhibits complicated allotropy
– At least five forms are crystalline
Crystalline white phosphorus
- Contains tetrahedral P4 molecules in which the P−P distances
(221pm) are consistent with single bonds (rcov = 110 pm)
- Standard state of phosphorus but is actually “metastable”
Lower stability originates from strain

associated with 60° bond angle
THE ELEMENTS
• Phosphorus
• Crystalline white phosphorus
• Manufactured by:
• Heating this allotrope at inert atmosphere at ≈ 540K provides red

phosphorus
• Hittorf’s phosphorus (violet phosphorus)
- Well-characterized form of the red allotrope and its complicated
structure is best described in terms of interlocking chain
- All P-P bond distances are ≈ 222pm, indicating covalent single bonds
THE ELEMENTS
• Phosphorus
• Hittorf’s phosphorus (violet phosphorus)
[P16]2- [P21]3-
THE ELEMENTS
• Phosphorus
• Black phosphorus
– Most stable allotrope of phosphorus obtained by heating white
phosphorus under high pressure
– Appearance and electrical conductivity resemble those of graphite
and possesses a double-layer lattice of puckered 6-membered rings
P-P distances within a layer are

220pm and the shortest interlayer
P-P distance is 390 pm
THE ELEMENTS
• Phosphorus
• Most of the chemical differences between the allotropes of phosphorus are
due to differences in activation energies for reactions
• Black phosphorus - kinetically inert and does not ignite in air even at 670
K
• Red phosphorus – intermediate in reactivity between the white and black
allotropes
– Not poisonous, insoluble in organic solvents, does not react with
aqueous alkali, and ignites in air above 520 K
– Reacts with halogens, sulfur and metals, but less vigorously than does
white phosphorus
THE ELEMENTS
• Phosphorus
• White phosphorus
• Soft, waxy solid which becomes yellow on exposure to light
• Very poisonous, being readily absorbed into the blood and liver
• Soluble in benzene, PCl3 and CS2 but is virtually insoluble in water
(stored under water to prevent oxidation)
• In moist air, it undergoes chemiluminescent oxidation, emitting a green
glow and slowly forming P4O8 and some O3
THE ELEMENTS
• Phosphorus
– Above 323 K, white phosphorus inflames, yielding phosphorus (V) oxide
– In a limited supply of air, P4O6 may form

– Combines violently with all of the halogens giving PX3 (X=F, Cl, Br, I) or
PX5 (X=F, Cl, Br) depending on the relative amounts of P and X
THE ELEMENTS
• Phosphorus
– Concentrated HNO3 oxidizes P4 to H3PO4
– With hot aqueous NaOH, this reaction occurs:
– P4 can act as a ligand in d-block metal complexes:

THE ELEMENTS
• Arsenic, Antimony & Bismuth
• As, Sb and Bi are grey solids (at room T and P) with lattice structures
resembling that of black phosphorus:
• On descending the group, although intra-layer bond distances increase as

expected, similar increases in interlayer spacing do not occur, and the
coordination number of each atom effectively changes from 3 to 6
THE ELEMENTS
• Arsenic, Antimony & Bismuth
• Burn in air and combine with halogens:
• Not attacked by non-oxidizing acids but react with concentrated HNO3

giving H3AsO4 (hydrated As2O5), hydrated Sb2O5 and Bi(NO3)3
• Reacts with concentrated H2SO4 producing As4O6, Sb2 (SO4)3 and Bi2(SO4)3
• None of the elements reacts with aqueous alkali, but As is attacked by
fused NaOH:
THE ELEMENTS
• Arsenic
– Arsenic vapor contains As4 molecules and the unstable yellow form
of solid As probably also contains these units
• Antimony
– Antimony vapor contains molecular Sb4 at relatively low
temperatures
HYDRIDES
• Trihydrides, EH3 (E=N, P, As, Sb and Bi)

– Each group 15 element forms a trihydride:
Note: Lack of data for BiH3 stems from its instability

HYDRIDES
• Trihydride, NH3
– Obtained by :
– Industrial manufacture of NH3 involves the Haber process:
Classic application of physicochemical

principles to a system in equilibrium
HYDRIDES
• Trihydride, NH3
– Colorless gas with a pungent odor
– Oxidation products of NH3 depend on reaction conditions:
at ≈1200K in the presence of a

Pt/Rh catalyst and a contact
time of ≈1 ms, this less
exothermic reaction takes place
HYDRIDES
• Trihydride, NH3
– Solubility in water is greater than that of any other gas due to
hydrogen bond formation between NH3 and H2O
– Nearly all dissolved NH3 is non-ionized (consistent with the fact that
even dilute solutions retain the characteristic smell of NH3)
HYDRIDES
• Trihydride, NH3
– Ammonium salts are easily
prepared by neutralization
reactions:
– Industrial syntheses are carried

out using the Solvay process
HYDRIDES
• Trihydride, NH3
• Industrial syntheses of ammonium salts can also be carried out via:
• Ammonium salts often crystallize with lattices similar to those of the

corresponding K+, Rb+ or Cs+ salts
• The [NH4]+ ion can be approximated to a sphere with rion = 150 pm (a
value similar to that of Rb+)
HYDRIDES
• Trihydride, NH3
• In the solid state, when forming a hydrogen bond involving the [NH4]+
ions, ammonium salts adopt structures unlike those of their alkali metal
analogues
• NH4F possesses a wurtzite rather than an NaCl lattice.
• Majority of [NH4]+ salts are soluble in water, with hydrogen bonding
between [NH4]+ and H2O being a contributing factor
HYDRIDES
• Other trihydrides
– Can be obtained by:
HYDRIDES
• Trihydride, PH3 (Phosphine)

– Extremely toxic, colorless gas which is much less soluble in water than
is NH3
– P-H bond is not polar enough to form hydrogen bonds with H2O
– Aqueous solutions of PH3 are neutral, but in liquid NH3, PH3 acts as an
acid:
HYDRIDES
• Trihydride, PH3 (Phosphine)

• Phosphonium halides, PH4X, are formed by treating PH3 with HX but only
iodide is stable under ambient conditions
• [PH4]+ ion is decomposed by water:
• Acts as a Lewis base and a range of adducts (including those with low
oxidation state d-block metal centres) are known
• Combustion of PH3 yields H3PO4
HYDRIDES
• Trihydride, AsH3 and SbH3

– Resemble those of PH3 but are less stable with respect to
decomposition into their elements
– Extremely toxic gases - - SbH3 is liable to explode
– Less basic than PH3 but can be protonated with HF in the presence
of AsF5 or SbF5
HYDRIDES
• Hydrides E2H4 (E=N, P, As)

• Hydrazine, N2H4
• Colorless liquid (mp:275 K, bp: 386 K)
• Miscible with water and with a range of organic solvents
• Corrosive and toxic
• Vapor forms explosive mixtures with air (used in rocket fuels)
• Kinetically stable with respect to N2 and H2 at ambient temperature
HYDRIDES
• Hydrazine, N2H4
HYDRIDES
• Hydrazine, N2H4
• Has uses in the agricultural and plastics industries
• Obtained by the Raschig reaction (the basis for the industrial synthesis)
which involves the partial oxidation of NH3:
• Obtained from the Raschig process as the monohydrate and is used in

this form for many purposes (dehydration is difficult)
• Direct method to produce anhydrous N2H4:
HYDRIDES
• Hydrazine, N2H4
– In aqueous solution, N2H4 usually forms [N2H5]+ (hydrazinium) salts,
but some salts of [N2H6]2+ have been isolated
– pKb values for hydrazine:
Weaker base than NH3

HYDRIDES
• Hydrazine, N2H4
– Rocket fuels
– Stored energy in explosives and propellants (‘high energy density
materials’) usually arises either from oxidation of an organic
framework or from an inherent high positive enthalpy of formation
ΔfHo(s,298 K)=+858 kJ/mol

- High energy density material
HYDRIDES
• Diphosphane, P2H4
– Colorless liquid (mp:174 K, bp:329 K)
– Toxic and spontaneously inflammable
– Forms higher phosphanes when heated
– Formed as a minor product in several reactions in which PH3 is
prepared and may be separated from PH3 by condensation in a
freezing mixture.
– No basic properties
HYDRIDES
Chloramine and hydroxylamine

• Chloramine, NH2Cl
• Product of the reactions of NH3 and Cl2 (diluted with
N2) or aqueous NaOCl
• Compound responsible for the odor of water
containing nitrogenous matter that has been
sterilized with Cl2
• Unstable and violently explosive
• Reaction with Me2NH yields the rocket fuel 1,1-
dimethylhydrazine:
HYDRIDES
• Hydroxylamine, NH2OH
• One of several routes to hydroxylamine (usually handled as a salt
or in aqueous solution):
• Forms white, hygroscopic crystals which melt at 306K and

explode at higher temperatures
• Weaker base than NH3 or N2H4
• Many of its reactions arise from the great variety of redox
reactions in which it takes part in aqueous solution:
HYDRIDES
• Hydroxylamine, NH2OH
– Formation of N2O in most oxidations of NH2OH is an
interesting example of the triumph of kinetic over
thermodynamic factors
– On thermodynamic grounds, expected product from the
action of weak oxidizing agents on [NH3OH]+ (i.e. NH2OH
in acidic solution) would be N2, but it seems that the
reaction occurs by steps:
HYDRIDES
• Hydrogen azide and azide salts

• Sodium azide, NaN3
–Obtained from molten sodium amide by:
–Treatment of NaN3 with H2SO4 yields hydrogen

azide, HN3
HYDRIDES
• Hydrogen azide, HN3 (hydrazoic acid)

– Colorless liquid (mp:193 K, bp:309 K)
– Dangerously explosive and highly poisonous
– Aqueous solutions of HN3 are weakly acidic:
HYDRIDES
• Azide salts
– Ag(I), Cu(II) and Pb(II) azides are insoluble in water and are explosive
– Pb(N3)2 is used as an initiator for less sensitive explosives
– Group 1 metal azides decompose quietly when heated
– Azide group shows similarities to a halogen and is another example of a
pseudo-halogen
– Like halide ions, the azide ion acts as a ligand in a wide variety of metal
complexes:
[Au(N3)4]-, trans-[TiCl4(N3)2]2-, cis-[Co(en)2(N3)2]+, trans-[Ru(en)2(N2)
(N3)]+ and [Sn(N3)6]2-
HYDRIDES
• Azide salts
– Reaction of sodium azide with aryldiazonium salts yields arylpentazoles,
from which it has been possible to generate the cyclic anion [N5]-
through molecular fragmentation in an electrospray ionization mass
spectrometer
NITRIDES, PHOSPHIDES, ARSENIDES,
ANTIMONIDES and BISMUTHIDES
• Nitrides
– Nearly all nitrides fall into one of the following groups:
• Saline nitrides of the group 1 and 2 metals, and aluminium
• Covalently bonded nitrides of the p-block
• Interstitial nitrides of d-block metals
• Pernitrides of the group 2 metals
• Saline nitrides
• Li3N, Na3N, Be3N2, Mg3N2, Ca3N2, Ba3N2 and AlN.
• Hydrolysis of saline nitrides liberates NH3
• Sodium nitride is very hygroscopic, and samples are often
contaminated with NaOH
• Nitrides of p-block elements

• Sn3N4 and the γ-phase of Si3N4 represent the first examples of
spinel nitrides
NITRIDES, PHOSPHIDES, ARSENIDES, ANTIMONIDES
and BISMUTHIDES
• Nitrides of d-block elements

• Hard, inert solids which resemble metals in appearance, and have high
melting points and electrical conductivities
• Can be prepared from the metal or metal hydride with N2 or NH3 at high
temperatures
• Most possess structures in which the nitrogen atoms occupy octahedral
holes in a close-packed metal lattice
• Pernitrides
• Contain the [N2]2- ion and are known for barium and strontium
• Phosphides
• Most elements combine with phosphorus to give binary phosphides
(exceptions: Hg, Pb, Sb, Bi and Te)
• Types of solid state phosphides are very varied, and simple classification
is not possible
• Phosphides of the d-block metals are inert, metallic-looking compounds
with high melting points and electrical conductivities
• structures may contain isolated P centres, P2 groups, or rings, chains
or layers of P atoms
• Phosphides
– Group 1 and 2 metals form compounds M3P and M3P2 which are
hydrolysed by water and considered to be ionic
– Alkali metals also form phosphides which contain groups of P atoms
forming chains or cages (cages being either [P7]3- or [P11]3-
• Arsenides, antimonides and bismuthides

• Prepared by direct combination of the metal and group 15 element
• Classification is not simple, and structure types vary
• Arsenide
• Gallium arsenide
– Important semiconductor and crystallizes with a zinc blende lattice
– Slow hydrolysis occurs in moist air (protection of semiconductor devices
from the air is essential)
• Arsenide
– Nickel arsenide (NiAs)
• Gives its name to a well-known structure type, being adopted by a
number of d-block metal arsenides, antimonides, sulfides,
selenides and tellurides
• Lattice can be described as a hexagonal close-packed (hcp) array
of As atoms with Ni atoms occupying octahedral holes (but
bonding is not purely ionic)
and BISMUTHIDES
• Arsenide
– Nickel arsenide (NiAs)
• Unit cell of NiAs:
– Coordination environment of
the As centres is trigonal
prismatic
and BISMUTHIDES
• Arsenides and antimonides containing the [As7]3- and [Sb7]3- ions

can be prepared by:
• Zintl ions are structurally related to [P7]3-

• Heteroatomic Zintl ions incorporating group 15 elements are present in
the compounds [K(crypt-222)]2[Pb2Sb2], [K(crypt-222)]2[GaBi3], [K(crypt-
222)]2[InBi3] and [Na(crypt-222)]3[In4Bi5], all of which are prepared
(mostly as solvates with 1,2-ethanediamine) in a similar way to reaction
14.52..
HALIDES, OXOHALIDES and COMPLEX HALIDES
• Nitrogen halides
– Nitrogen is restricted to an octet of valence electrons and does not form
pentahalides
– This can also be attributed to the steric crowding of five halogen atoms
around the small N atom in case of pentahalides
• Nitrogen trifluoride
• Made by electrolysis of anhydrous NH4F/HF mixtures or through the
following reaction:
• Most stable of the trihalides of nitrogen, being the only one to have a
negative value of ΔfH°
• Colorless gas which is resistant to attack by acids and alkalis but is
decomposed by sparking with H2:
• Nitrogen trifluoride
– Trigonal pyramidal
– Molecular dipole moment is very small
– Shows no donor properties (in contrast to NH3 and PF3)
• Nitrogen trichloride
– Oily, yellow liquid at 289 K but is highly endothermic and dangerously
explosive
– Difference in stabilities of NF3 and NCl3 lies in the relative bond
strengths of NF over NCl, and of Cl2 over F2
– Can be prepared by:
• Nitrogen trichloride
– Diluted with air, NCl3 is used for bleaching flour since hydrolysis
by moisture forms HOCl
– Alkalis hydrolyse NCl3:
• Nitrogen tribromide
– More reactive than NCl3 and explodes at temperatures as low as 175 K
– It can be prepared by:
• Nitrogen triiodide
– Made by reacting IF with boron nitride in CFCl3
– Stable at 77K but highly explosive at higher temperatures
– Reaction between concentrated aqueous NH3 and [I3]- yields NH3∙NI3
black crystals of which are dangerously explosive (decomposes to
NH3, N2 and I2)
–
• Other nitrogen fluorides

–N2F4 and N2F2 can be obtained by:
–Both fluorides are explosives


• N2F4
– Resembles hydrazine, except
that both the gauche and trans
(staggered) conformers are
present in the liquid and gas
phases
– At 298K, reversibly dissociates
into blue NF2* radicals which
undergo many interesting
reactions:

• Dinitrogen difluoride (N2F2)
– Exists in both the trans- and cis-
forms with the cis-isomer being
thermodynamically more stable
but also the more reactive
– Isomerization by heating gives a
mixture of isomers from which
cis-N2F2 can be isolated by
treatment with AsF5
• Dinitrogen difluoride (N2F2)
– N2F2 (and also N2F4) can donate F- to strong acceptors such as AsF5
and SbF5
• Oxofluorides and Oxochlorides of nitrogen

• All are unstable gases or volatile liquids which
are rapidly hydrolysed
• Formed in reactions of NO with F2, Cl2 and Br2
• Short N-O bond lengths indicate triple rather
than double bond character
• [NO]+X- form becomes more dominant on going
from gaseous to solid XNO
• Oxofluorides and Oxochlorides of nitrogen

– Nitryl fluoride, FNO2 is prepared by:
– Nitryl chloride, ClNO2 is prepared by oxidation of ClNO

– Oxohalides FNO, ClNO, FNO+ and ClNO+ combine with suitable fluorides or
chlorides to give salts containing [NO]+ or [NO2]+
• Phosphorus halides
– PX3 (X=F, Cl, Br and I) and PX5 (X=F, Cl and Br)
– PI5 is unknown
– Made by direct combination of the elements with the product
determined by which element is in excess. PF3 must be made by:
– The halides are all hydrolysed by water:

• Trihalides has a trigonal pyramidal structure
• Phosphorus trifluoride
• Very poisonous, colorless and odorless gas
• Able to form complexes with metals and Lewis
acids such as BH3, and its toxicity arises from
complex formation with haemoglobin
• Phosphorus trifluoride
– Protonation of PF3:
– Reaction of PF3 with Me4NF in MeCN gives [Me4N][PF4]

– When treated with an equimolar amount of water, [PF4]- hydrolyses:
• Phosphorus trichloride
– Colorless liquid (mp:179.5 K, bp:349 K) which fumes in moist air
and is toxic
– Reactions:
Important reagent
for the preparation
of phosphate esters
• Phosphorus pentafluoride
– Electron diffraction data show that in the gas phase, PCl5 has a
molecular, trigonal bipyramidal structure
– In the solid state, tetrahedral [PCl4]+ and octahedral [PCl6]- ions are
present, and the compound crystallizes with a CsCl lattice
• Phosphorus pentafluoride
– Solid KPF6 decomposes on heating to give PF5 (useful means of
preparing PF5)
– Strong Lewis acid and forms stable complexes with amines and ethers
– The hexafluorophosphate ion, [PF6]- is made in aqueous solution by
reacting H3PO4 with concentrated HF
– [PF6]- is used to precipitate salts containing large organic or complex
cations
• Phosphorus pentachloride
– An important reagent made industrially
by the reaction of PCl3 and Cl2.
– Selected reactions of PCl5:
• Phosphorus pentabromide
– Crystallizes in the form of [PBr4]+Br-
• Phosphoryl trichloride, POCl3
– Phosphorus oxohalide prepared by reaction of PCl3 with O2
– Colorless, fuming liquid (mp:275 K, bp:378 K)
– Readily hydrolysed by water liberating HCl
– Used as a phosphorylating and chlorinating agent, and as a reagent
in the preparation of phosphate esters
• Arsenic halides
– AsX3 (X=F, Cl, Br, I) and AsX5 (X=F, Cl)
– Trihalides AsCl3, AsBr3 and AsI3 can be made by direct
combination of the elements
– Another route to AsCl3:
– To prepare AsF3 (though AsF3 is hydrolyzed by water):
Removed with excess H2SO4
– Glass containers are not practical for AsF3 as it reacts with

silica in the presence of moisture.
• Arsenic halides
– AsF3 and AsCl3 have molecular, trigonal pyramidal structures (in solid,
liquid and gas states)
– AsF3 may act as either an F- donor or acceptor:
– AsCl3 is used as a non-aqueous solvent:

• Arsenic halides
– Salts containing the [AsX4]+ (X=F, Cl, Br, I) ions include [AsF4][PtF6] and [AsCl4]
[AsF6] (stable compounds) and [AsBr4][AsF6] and [AsI4][AlCl4](unstable
compounds)
– AsF5 : the only stable pentahalide of arsenic prepared by:
• Colorless gas at 298 K

• Structure is the same as PF5
• Arsenic halides
– Arsenic pentafluoride, AsF5
• Strong fluoride acceptor:
• One interesting reaction is with metallic Bi to give [Bi5][AsF6]3 which

contains the trigonal bipyramidal cluster [Bi5] 3+
• Antimony halides
• Antimony trihalides
– Low melting solids
– Contain trigonal pyramidal molecules, but each Sb centre has
additional, longer range, intermolecular Sb-----X interactions
– Trifluoride and trichloride are prepared by reacting Sb2O3 with
concentrated HF and HCl, respectively
– SbF3 is a widely used fluorinating agent
• Converts B2Cl4 to B2F4, CHCl3 to CHF2Cl, COCl2 to COClF and COF2,
SiCl4 to SiF4 and SOCl2 to SOF2
• Antimony pentafluoride
– (mp:280 K, bp:422 K) is prepared from SbF3 and F2 or by reaction:
In In the solid state, SbF5 is tetrameric

and the presence of Sb-F-Sb bridges
accounts for the very high viscosity of the
liquid
• Antimony pentachloride
– (mp:276 K, bp:352 K) is prepared from the elements, or by
reaction of Cl2 with SbCl3
– Liquid SbCl5 contains discrete trigonal bipyramidal molecules (also
present in the solid between 219K and the melting point)
– Axial bonds longer than the equatorial bonds
– Below 219 K, the solid undergoes a reversible change involving
dimerization of the SbCl5 molecules
• Antimony pentachloride
– One of the strongest chloride acceptors known
– Reactions of SbF5 and SbCl6 with alkali metal fluorides and chlorides
yield compounds of the type M[SbF6] and M[SbCl6]
• Bismuth halides
– Trihalides BiF3, BiCl3, BiBr3 and BiI3 are all well
characterized, but BiF3 is the only Bi(V) halide known
– All are solids at 298 K
– In the vapor phase, the trihalides have molecular , trigonal
pyramidal structures
– In the solid state, β-BiF3 contains 9-coordinate Bi(III)
centres, BiCl3 and BiBr3 have molecular structures but with
an additional five long Bi-----X contacts, and in BiI 3, the Bi
atoms occupy octahedral sites in an hcp array of I atoms
• Bismuth halides
– Trihalides can be formed by combination of the elements at high
temperature
• Reaction of BiF3 with F2 (880 K) yields BiF5 which is a powerful
fluorinating agent
• Lewis acids and form donor–acceptor complexes with a number of
ethers
• fac-[BiCl3(THF)3], mer-[BiI3(py)3], cis-[BiI4(py)2-], [BiCl3(py)4] (14.43) and
the macrocyclic ligand complexes
• Bismuth halides
OXIDES OF NITROGEN
• Nitrogen
– Stands apart in forming oxides in which ( p–p) π-bonding is
important
OXIDES OF NITROGEN
• Dinitrogen monoxide, N2O
– Prepared by:
Purer product
is obtained!
– Has faint, sweet odor

– Dissolves in water to give a neutral solution, but does not react to
any significant extent:
OXIDES OF NITROGEN
• Dinitrogen monoxide, N2O

– Non-toxic gas- fairly unreactive at 298 K
– Molecule is linear, bonding can be represented as:
– Used as a general anaesthetic (‘laughing gas’)

– Used in the preparation of whipped cream
– Reactivity is higher at elevated temperatures
• it supports combustion, and reacts with NaNH2 at 460K (used
commercially to prepare NaN3)
OXIDES OF NITROGEN
• Nitrogen monoxide, NO
– Made industrially from NH3:
– On a laboratory scale it is prepared by reducing HNO3 in the

presence of H2SO4
Basis of the brown ring test for

[NO3]- : due to the formation of
[Fe(NO)(H2O)5]2+
OXIDES OF NITROGEN
– A radical
– Unlike NO2, does not dimerize unless cooled to low temperature under
high pressure
– Reaction with O2 is important in the manufacture of nitric acid , but
NO can also be oxidized directly to HNO3 by acidified [MnO4]-
– Reduction depends on the reducing agent
– Although NO is thermodynamically unstable with respect to its
elements, it does not decompose at an appreciable rate below 1270 K,
and so does not support combustion well
OXIDES OF NITROGEN
– Positive value of ΔfH° means that at high temperatures, its formation is

favored
• significant during combustion of motor and aircraft fuels where NO is
one of several oxides formed
– Oxides are collectively described by NOx and contribute to the formation
of smogs over large cities
OXIDES OF NITROGEN
• Dinitrogen trioxide, N2O3
– Obtained as a dark blue liquid in reaction at low temperatures
but even at 195 K, extensive dissociation back to NO and N2O4
occurs
– Water-soluble and is the acid anhydride of HNO2

OXIDES OF NITROGEN
• Dinitrogen tetraoxide, N2O4 and Nitrogen dioxide, NO2

– They exist in equilibrium and must be discussed together
OXIDES OF NITROGEN
– The solid is colorless and is diamagnetic (consistent with the presence
of only N2O4)
– Dissociation of this dimer gives the brown NO2 radical
– Solid N2O4 melts to give a yellow liquid (arising from the presence of a
little NO2)
– At 294K (bp): brown vapor contains 15% NO2
– Color of the vapor darkens as the temperature is raised, and at 413 K
dissociation of N2O4 almost complete
– Above 413 K, the color lightens again as NO2 dissociates to NO and O2
OXIDES OF NITROGEN
– Laboratory-scale preparations:
– If brown gaseous NO2 is cooled to 273 K, N2O4 condenses as

yellow liquid
– Dinitrogen tetraoxide is a powerful oxidizing agent which attacks
many metals, including Hg, at 298 K
– Reaction of NO2 or N2O4 with water gives a 1 :1 mixture of
nitrous and nitric acids
– Because of the formation of these acids, atmospheric NO2 is

corrosive and contributes to ‘acid rain’
OXIDES OF NITROGEN
• Dinitrogen pentaoxide, N2O5
• Acid anhydride of HNO3 and is prepared by reaction:
• Forms colorless deliquescent crystals but slowly decomposes above

273K to give N2O4 and O2
• In the solid state, N2O5 consists of [NO2]+ and [NO3]- ions, but the
vapor contains planar molecules
• Reacts violently with water, yielding HNO3, and is a powerful oxidizing
agent
OXOACIDS OF NITROGEN
• Hyponitrous acid, H2N2O2

– Aqueous solution of sodium hyponitrite can be made by reaction:
– Addition of Ag+ leads to the precipitation of Ag2N2O2

– Treatment with anhydrous HCl in dry diethyl ether leads to the
formation of hyponitrous acid
• Hyponitrous acid, H2N2O2

– Free H2N2O2 is a weak acid
– Potentially explosive, decomposing spontaneously into N2O and
H2 O
– Spectroscopic data for H2N2O2 indicate a trans-configuration:
• Nitrous acid, HNO2

– Known only in solution and in the vapor phase, and in the latter, it has
structure:
– A weak acid (pKa= 3.37) but is unstable with respect to

disproportionation in solution:
• Nitrous acid, HNO2

– It may be prepared in situ by:
– Can be oxidized to [NO3]- by powerful oxidants such as acidified

[MnO4]-
– Products of the reduction of HNO2 depend on the reducing agent
– It is a faster, rather than a more powerful, oxidizing agent than dilute
nitric acid
• Nitric acid, HNO3, and its derivatives

– An important industrial chemical and is manufactured on a large scale
in the Haber–Bosch process closely tied to NH3 production
– First step is the oxidation of NH3 to NO
– After cooling, NO is mixed with air and absorbed in a countercurrent of
water

• Pure nitric acid can be made in the laboratory by adding H2SO4 to
KNO3 and distilling the product in vacuo
• A colorless liquid but must be stored below 273K to prevent slight
decomposition which gives the acid a yellow color
• Fuming HNO3 is orange owing to the presence of an excess of NO2


– Acts as a strong acid (in aqueous solution) which attacks most
metals, often more rapidly if a trace of HNO2 is present
– Tin, arsenic and a few d-block metals are converted to their oxides
when treated with HNO3 (others form nitrates)
– Only Mg, Mn and Zn liberate H2 from very dilute nitric acid

– If the metal is a more powerful reducing agent than H2, reaction
with HNO3 reduces the acid to N2, NH3,NH2OH or N2O
– Other metals liberate NO or NO2

– Organic and inorganic compounds are oxidized by concentrated
HNO3, although nitrate ion in aqueous solution is usually a very
slow oxidizing agent
– Concentrated HNO3 oxidizes I2, P4 and S8 to HIO3, H3PO4 and
H2SO4, respectively

– Molecular structure:
– Trigonal planar (D3h)

– Differences in NO bond distances are readily understood in terms of
the resonance structures
OXIDES OF PHOSPHORUS, ARSENIC,
ANTIMONY AND BISMUTH
• Each of the group 15 elements from P to Bi forms two oxides: E2O3 (or
E4O6) and E2O5 (or E4O10), the latter becoming less stable as the group is
descended:
– E2O5 (E=P, As, Sb, Bi) are acidic
– P4O6 is acidic
– As4O6 and Sb4O6 are amphoteric
– Bi2O3 is basic
• Oxides of phosphorus
• Phosphorus(III) oxide, P4O6
– Obtained by burning white phosphorus in a
restricted supply of O2
– It is a colorless,volatile solid (mp:297 K, bp: 447
K) with molecular structure
– P-O bond distances (165 pm) are consistent
with single bonds, and the angles P-O-P and O-
P-O are 1288 and 998 respectively
– Dimerization of P4O6 has occurred through P-O
bond cleavage and reformation of P-O bonds
between monomeric units
• Phosphorus(III) oxide, P4O6
– Oxide is soluble in diethyl ether or
benzene, but reacts with cold water:
– Can act as a Lewis base due to the lone

pairs on each phosphorus atom
– Reaction with one equivalent of Me2S∙BH3
followed by slow crystallization from
toluene solution at 244K gives P8O12(BH3)2
• Phosphorus(V) oxide, P4O10 (phosphorus
pentoxide)
– Most important oxide of phosphorus
– Made directly from P4 or by oxidizing P4O6
– In the vapor phase, phosphorus(V) oxide
contains P4O10 molecules with structure:
• Phosphorus(V) oxide, P4O10 (phosphorus
pentoxide)
– When the vapor is condensed rapidly, a volatile
and extremely hygroscopic solid is obtained
which also contains P4O10 molecules
– Three polymorphic forms exist at ordinary
pressure and temperature, with the basic
building block being unit:
– Only three of the four O atoms are available for
interconnecting the PO4 units via P-O-P bridges
• Phosphorus(V) oxide, P4O10 (phosphorus pentoxide)
– Has a great affinity for water
– The anhydride of the wide range of oxoacids

– Used as a drying agent
• Other oxides of phosphorus
P4O7 P4O8 P4O9

– These oxides are mixed P(III)P(V) species, each centre bearing a
terminal oxo group being oxidized to P(V)
– P4O8 is made by heating P4O6 in a sealed tube at 710 K, the other
product being red phosphorus
• Oxides of arsenic, antimony and bismuth

– Normal combustion products of As and Sb are As(III) and Sb(III) oxides
– Vapor and high temperature solid polymorph of each oxide contains
E4O6 (E=As or Sb) molecules structurally related to:
– Lower temperature polymorphs have layer structures containing

trigonal pyramidal As or Sb atoms
• Oxides of Arsenic
– Condensation of As4O6 vapor above 520K leads to the formation of
As2O3 glass
– Arsenic(III) oxide is an important precursor in arsenic chemistry and
is made industrially from the sulfide
• Dissolution of As2O3 in water gives a very weakly acidic solution,
and it is probable that the species present is As(OH)3 (arsenous
acid)—never isolated
• Crystallization of aqueous solutions yields As2O3
• Oxides of Arsenic
– Arsenic(III) oxide dissolves in aqueous alkali to give salts containing
the [AsO2]- ion, and in aqueous HCl with the formation of AsCl3
– Arsenic(V) oxide is most readily made by (rather than by direct
oxidation of the elements):
• As2O5 is the acid anhydride of arsenic acid, H3AsO4

• In the solid state, it has a lattice structure consisting of As-O-As
linked octahedral AsO6 and tetrahedral AsO4- units
• Oxides of Antimony
– Antimony(III) oxide: properties of Sb2O3 in water and aqueous alkali
or HCl resemble those of As2O3
– Antimony(V) oxide may be made by reacting Sb2O3 with O2 at high
temperatures and pressures
• It crystallizes with a lattice structure in which the Sb atoms are
octahedrally sited with respect to six O atoms
• Oxides of Bismuth
– Bismuth(III) oxide occurs naturally as bismite, and is formed when
Bi combines with O2 on heating
• Molecular species are not observed for Bi2O3, and the structure
is more like that of a typical metal oxide (unlike the other
members of group 15)
– Bismuth(V) oxide is poorly characterized, and its formation requires
the action of strong oxidants (e.g. alkaline hypochlorite) on Bi2O3
OXOACIDS OF PHOSPHORUS
• Basicity of each acid corresponds to the number of OH-groups, and not

simply to the total number of hydrogen atoms
– H3PO3: dibasic
– H3PO2:monobasic
• P-attached hydrogens do not ionize in aqueous solution
• Phosphinic acid, H3PO2
– Reaction of white phosphorus with aqueous alkali produces the
phosphinate (or hypophosphite) ion,[H2PO2]-
– By using Ba(OH)2 as alkali, precipitating the Ba2+ ions as BaSO4, and
evaporating the aqueous solution, white deliquescent crystals of
H3PO2 can be obtained
– A fairly strong monobasic acid:
• Phosphinic acid, H3PO2
– Phosphinic acid and its salts are reducing agents, and
NaH2PO2∙H2O is used industrially in a non-electrochemical
reductive process which plates nickel onto steel
– When heated, H3PO2 disproportionates:
• Phosphonic acid, H3PO3
– Commonly called phosphorous acid
– May be crystallized from the solution obtained by adding ice-cold
water to P4O6 or PCl3
– Pure H3PO3 forms colorless, deliquescent crystals (mp:343 K) and in

the solid state, molecules of the acid are linked by hydrogen bonds
to form a three-dimensional network
• Phosphonic acid, H3PO3
– In aqueous solution, it is dibasic:
– Salts containing the [HPO3]2- ion are called phosphonates

– Phosphonic acid is a reducing agent, but disproportionates
when heated:
• Hypophosphoric acid, H4P2O6
– Reaction between red phosphorus and NaOCl
or NaClO2 yields Na2H2P2O6, which can be
converted in aqueous solution into the
dihydrate of the free acid which is best
formulated as [H3O]2[H2P2O6]
– Dehydration using P4O10 gives H4P2O6
– Structural feature: P-P bonded dimer, All four
terminal P-O bonds are of equal length (157
pm)
– This description is more appropriate than a
pair of resonance structures, each involving
one P=O and one P-O- bond
• Hypophosphoric acid, H4P2O6
– Thermodynamically unstable with respect to disproportionation

and the following reaction occurs slowly in aqueous solution:
– So, H4P2O6 cannot be made by reduction of H3PO4 or by oxidation of

H3PO3 in aqueous media
• Phosphoric acid, H3PO4, and its derivatives
– Phosphoric acid is made from phosphate rock or by hydration of P4O10
– Pure acid forms deliquescent, colorless crystals (mp: 315 K)

– It has a molecular structure with P-OH and P-O bond distances of 157
and 152 pm (significantly less than in P4O10 due to extensive hydrogen
bonding in the crystalline state which links H3PO4 molecules into a
layered network)

– On standing, crystalline H3PO4 rapidly forms a viscous liquid (due to
extensive hydrogen bonding)
– In dilute aqueous solutions, acid molecules are hydrogen-bonded to
water molecules rather than to each other
– Very stable and has no oxidizing properties (except at very high T)
– Aqueous H3PO4 is a tribasic acid and salts containing [H2PO4]-, [HPO4]2-
and [PO4]3- can be isolated.
• Extensively used for buffering aqueous solutions
– When heated at 510 K:
• Water is eliminated with concomitant P-O-P bridge formation:
– Further heating yields triphosphoric acid:
• Such species containing P-O-P bridges are commonly called condensed

phosphates and the following shows the general condensation process:
– Number of OH groups in a particular unit determines the extent of the
condensation processes
– In condensed phosphate anion formation:
• chain-terminating end groups (14.64) are formed from [HPO4]2-
• chain members (14.65) from [H2PO4]-
• and cross-linking groups (14.66) from H3PO4
– H4P2O7 is the simplest condensed phosphoric acid
• Stronger acid than phosphoric acid
• Solid at 298K and can be obtained from reaction:
– Different salts can be obtained from the oxoacids of phosphorus

• Changes in the conditions of heating Na2HPO4 or NaH2PO4 cause salt
product variation
OXOACIDS OF ARSENIC, ANTIMONY
and BISMUTH
• Oxoacid of Arsenic
• ‘Arsenous acid’ (As(OH)3 or H3AsO3) has not been isolated
– Aqueous solutions of As2O3 probably contain H3AsO3
– There is little evidence for the existence of an acid of formula
As(O)OH
and BISMUTH
– Several arsenite and metaarsenite salts containing [AsO3]3- and
[AsO2]- respectively have been isolated
• Sodium meta-arsenite, NaAsO2 (commercially available),
contains Na+ ions and infinite chains with trigonal pyramidal
As(III) centres
and BISMUTH
• Arsenic acid, H3AsO4 is obtained by dissolving As2O5 in
water or by oxidation of As2O3 using nitric acid:
– pKa (1) = 2.25, pKa (2) = 6.77 and pKa (3)= 11.60
– In acidic solution, it acts as an oxidizing agent
and BISMUTH
– Condensed polyarsenate ions are kinetically much less stable with

respect to hydrolysis than condensed polyphosphate ions
• only monomeric [AsO4]3- exists in aqueous solution
– All condensed Arsenates (i.e (NaAsO3)n) revert to [AsO4]3- on adding
water
and BISMUTH
• Oxoacids of Antimony
• Oxoacids of Sb(III) are not stable and few antimonite salts are well
characterized
– Meta-antimonites include NaSbO2 which can be prepared as the trihydrate
from Sb2O3 and aqueous NaOH
• No oxoacids of Sb(V) are known, and neither is the tetrahedral anion ‘[SbO4]3-’
• well-defined antimonates can be obtained, for example, by dissolving
antimony(V) oxide in aqueous alkali and crystallizing the product
• Some antimonates contain the octahedral [Sb(OH)6]- ion
• Remaining antimonates should be considered as mixed metal oxides
and BISMUTH
• Oxoacids of Bismuth
– No oxoacids of Bi are known, although some bismuthate salts are well
characterized
– Sodium bismuthate is an insoluble, orange solid, obtained by fusing Bi2O3
with NaOH in air or with Na2O2
– Very powerful oxidizing agent, e.g. in the presence of acid, it oxidizes
Mn(II) to [MnO4]- and liberates Cl2 from hydrochloric acid
– Like antimonates, some of the bismuthates are better considered as
mixed metal oxides
PHOSPHAZENES
• Group of P(V)/N(III) compounds featuring chain or cyclic

structures and are oligomers of the hypothetical N≡PR2
• Reaction of PCl5 with NH4Cl in a chlorinated solvent (e.g. C6H5Cl)
gives a mixture of colorless solids of formula (NPCl2)n :
predominant species have n = 3 or 4
• Compounds (NPCl2)3 and (NPCl2)4 are readily separated by
distillation under reduced pressure
PHOSPHAZENES
• Overall reaction:
– Traditional method of preparing (NPCl2)3, but yields are typically

≈50%
– To improve yield:
Competes with
• Both reactions pathways are complicated

PHOSPHAZENES
• Yields of (NPCl2)3 can be optimized by ensuring a slow rate of addition of

PCl5 to N(SiMe3)3 in CH2Cl2
• (NPBr2)n or (NPMe2)n by using PBr5 or Me2PCl3 (in place of PCl5)
respectively
• Fluoro derivatives (NPF2)n (n = 3 or 4) are not made directly but are
prepared by treating (NPCl2)n with NaF suspended in MeCN or C6H5NO2
PHOSPHAZENES
• Structures of (NPCl2)3, (NPCl2 )4, (NPF2 )3 and (NPF2)4

PHOSPHAZENES
• Each of the 6-membered rings is planar while the 8-

membered rings are puckered
• P-N bond lengths in a given ring are equal
• P-N bond distances are significantly shorter than expected
for a P-N single bond indicating a degree of multiple bond
character
PHOSPHAZENES
• For bonding in the planar 6-membered rings:
• Suggests the involvement of N(2p)–P(3d ) overlap,
both in and perpendicular to the plane of the
P3N3-ring
• But phosphorus makes little or no use of its 3d
orbitals
• Another resonance form for a 6-membered
cyclophosphazene and is consistent with the
observed P-N bond equivalence, as well as the
observation that the N and P atoms are subject to
attack by electrophiles and nucleophiles:
SULFIDES AND SELENIDES
• Sulfides and selenides of phosphorus

• Sulfides of phosphorus
– Although the structures of the sulfides appear to be closely related
to those of the oxides, there are some notable differences:
• P4O6 and P4S6 are not isostructural
• Terminal P-S bonds are shorter than those in the cage (e.g. 191
versus 208pm in P4S10)

– Above 570 K, white phosphorus combines with sulfur to give P4S10 : most
useful of the phosphorus sulfides
– It is a thiating agent (i.e. one that introduces sulfur into a system) in
organic reactions and is a precursor to organothiophosphorus
compounds
– Red phosphorus reacts with sulfur above 450K yielding P4S3 and P4S7 can
also be made by direct combination under appropriate conditions

– Other sulfides are made by one of the general routes:
• Abstraction of sulfur using PPh3
• Treatment of a phosphorus sulfide with sulfur
• Treatment of a phosphorus sulfide with phosphorus
• Reaction of α- (14.73) or β-P4S3I2 (14.74) with (Me3Sn)2S

– Phosphorus sulfides ignite easily (P4S3 is used in ‘strike anywhere’
matches)
– P4S3 is stable to water but other phosphorus sulfides are slowly
hydrolysed:
• Selenides of phosphorus
– P2Se5 and P4Se10 are distinct species
– Both can be made by direct combination of P and Se under
appropriate conditions
– P2Se5 is also formed by the decomposition of P3Se4I, and P4Se10 from
the reaction of P4Se3 and selenium at 620 K
P2Se5 P4Se10 is isostructural with P4S10 and P4O10

• Sulfides of Arsenic, Antimony and Bismuth

– Arsenic and antimony sulfide ores are major sources of the group 15
elements
• Sulfides of Arsenic
– As2S3 and As2S5 are usually precipitated from aqueous solutions of
arsenite or arsenate
– If the temperature is lowered to 273K and the rate of flow of H2S is

increased, the product is As2S5
– Solid As2S3 has the same layer structure as the low-temperature
polymorph of As2O3 but vaporizes to give As4S6 molecules
– As2S5 exists in crystalline and vitreous forms (structural details not
known)
– Both As2S3 and As2S5 are readily soluble in alkali metal sulfide
solutions with the formation of thioarsenites and thioarsenates
– Sulfides As4S3 (dimorphite), As4S4 (realgar --red) and As2S3
(orpiment -- golden yellow) occur naturally
– The last two were used as pigments in early times
dimorphite realgar orpiment

• Sulfides of Antimony
• Sb2S3(stibnite)
– Only well-characterized binary sulfide of Sb
– Has a double-chain structure in which each Sb(III) is
pyramidally sited with respect to three S atoms
– The sulfide can be made by direct combination of the
elements
– A metastable red form can be precipitated from aqueous
solution, but reverts to the stable black form on heating
– Like As2S3, Sb2S3 dissolves in alkali metal sulfide solutions
• Sulfides of Bismuth
• Bismuth(III) sulfide, Bi2S3, is isostructural with Sb2S3, but in
contrast to its As and Sb analogues, Bi2S3 does not dissolve in
alkali metal sulfide solutions
AQUEOUS SOLUTION CHEMISTRY
• Aqueous solution species by Sb(III):
– Solutions of Sb(III) contain either hydrolysis products or
complex ions
– Complexes are formed with ligands such as oxalate,
tartrate or trifluoroacetate ions
– It is usual to observe an arrangement of donor atoms
about the Sb atom that reflects the presence of a
stereochemically active lone pair of electrons
AQUEOUS SOLUTION CHEMISTRY
• Aqueous solution species by Bi(III):

– Cation [Bi6(OH)12]6+ is the dominant species in highly acidic
aqueous media
– Six Bi(III) centres are arranged in an octahedron but at non-
bonded separations and each of the twelve Bi–Bi edges is
supported by a bridging hydroxo ligand
– In more alkaline solutions: [Bi6O6(OH)3]3+ is formed, and
ultimately, Bi(OH)3 is precipitated
----END OF PRESENTATION---

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Lecture 13

Descriptive Chemistry of the Elements

© Ch111.20 / 211 2018-19

• Nearly all the chemistry involves covalently bonded compounds

– Phosphorus vapor distils out and is condensed under water to yield

• Additional method: air-oxidation of arsenic sulfide ores giving As 2O3

• Nitrogen-based chemicals are extremely

- a line between two atoms does not - more realistic

• Why is N−N bond very weak?

• N can take part in strong hydrogen bonding

– Can also combine slowly with group 2 metals, Al, Si, Ge

Lower stability originates from strain

• Heating this allotrope at inert atmosphere at ≈ 540K provides red

P-P distances within a layer are

– In a limited supply of air, P4O6 may form

– P4 can act as a ligand in d-block metal complexes:

• On descending the group, although intra-layer bond distances increase as

• Not attacked by non-oxidizing acids but react with concentrated HNO3

• Trihydrides, EH3 (E=N, P, As, Sb and Bi)

Note: Lack of data for BiH3 stems from its instability

– Industrial manufacture of NH3 involves the Haber process:

Classic application of physicochemical

at ≈1200K in the presence of a

– Industrial syntheses are carried

• Ammonium salts often crystallize with lattices similar to those of the

• Trihydride, PH3 (Phosphine)

• Trihydride, PH3 (Phosphine)

• Trihydride, AsH3 and SbH3

• Hydrides E2H4 (E=N, P, As)

• Obtained from the Raschig process as the monohydrate and is used in

Weaker base than NH3

ΔfHo(s,298 K)=+858 kJ/mol

Chloramine and hydroxylamine

• Forms white, hygroscopic crystals which melt at 306K and

• Hydrogen azide and azide salts

–Treatment of NaN3 with H2SO4 yields hydrogen

• Hydrogen azide, HN3 (hydrazoic acid)

• Nitrides of p-block elements

• Nitrides of d-block elements

• Arsenides, antimonides and bismuthides

• Arsenides and antimonides containing the [As7]3- and [Sb7]3- ions

• Zintl ions are structurally related to [P7]3-

• Other nitrogen fluorides

–Both fluorides are explosives

• Other nitrogen fluorides

• Other nitrogen fluorides

• Oxofluorides and Oxochlorides of nitrogen

• Oxofluorides and Oxochlorides of nitrogen

– Nitryl chloride, ClNO2 is prepared by oxidation of ClNO

– The halides are all hydrolysed by water:

– Reaction of PF3 with Me4NF in MeCN gives [Me4N][PF4]

– To prepare AsF3 (though AsF3 is hydrolyzed by water):

Removed with excess H2SO4

– Glass containers are not practical for AsF3 as it reacts with

– AsCl3 is used as a non-aqueous solvent:

• Colorless gas at 298 K

• One interesting reaction is with metallic Bi to give [Bi5][AsF6]3 which

In In the solid state, SbF5 is tetrameric