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Nitrogen oxoacids. Phosphorus oxides and oxoacids.
Salts of oxoacids. Properties, chemical reactions,
laboratory preparations, industrial productions,
practical applications.
Oxides, oxo-compounds and other derivatives of
nitrogen-group elements. Preparations, properties,
reactions, and uses.
Hyponitrous acid, H2N2O2

In the anhydrous state, it is a white solid, which can

explode. It cannot be prepared from the reaction of N2O
and H2O, thus N2O is not a real anhydride of hyponitrous
acid. However, N2O can be prepared by dehydration of
hyponitrous acid.
H2N2O2 → H2O + N2O
Hyponitrous acid is unstable in aqueous solution, it decomposes spontaneously
with a half life of 16 h.
It is a very weak, diprotic acid, pK1 = 7,21, pK2 = 11,54. Their salt are hyponitrites.

The bright yellow silver salt is prepared from sodium nitrite by a sodium
amalgam reduction, followed by the addition of silver nitrate.
2NaNO2 + 4Na(Hg) + 2H2O + 2AgNO3 → Ag2N2O2 + 2NaNO3 + 4NaOH +
(4Hg)
Anhydrous hyponitrous acid is prepared from its silver salt by dry hydrochloric
acid in a diethyl ether solution.
Ag2N2O2 + 2HCl → H2N2O2 + 2AgCl

Hyponitrous acid has no practical application, but the silver salt is used in the
organic chemistry to prepare hyponitrous acid esters.
Nitrous acid, HNO2
is an acid that exists only in aqueousm solution. It is
a weak acid. HNO2 ⇌ H+ + NO2ˉ pKa = 3,35

Nitrous acid disproportionates readily : 3HNO2 = NO3– + 2NO + H3O+

The aqueous solution is prepared in the laboratory from barium nitrite with a
dilute sulfuric acid. The precipitate barium sulfate is filtered off, and the
remaining filtrate is used.
Ba(NO2)2 + H2SO4 = BaSO4 + 2HNO2

Salts of nitrous acid are the nitrites Due to the intermittant oxidation state of
nitrogen it can react in both oxidation and reduction reactions.

Oxidized: 2KNO2 + 2KMnO4 + 3H2SO4 = 5KNO3 + 2MnSO4 + K2SO4 + 3H2O

Reduced: HNO2 + 3H2S + H+ = NH4+ + 3S + 2H2O

Nitrite ion is a good complexing ligand with two coordination modes: the fisrt
one is the nitro-type (or N-) coordination, and the second one is the nitrito-type
(or O-) coordination
O
Nitro- M N nitrito- M O N O
O
Nitric acid, HNO3

Nitric acid forms an azeotopic mixture with water at a concentration of 69

m/m%. Commercially, the concentrated nitric acid of 65 m/m%
concentration is available. For special applications, a 100 m/m% pure
nitric acid, the so called red fuming nitric acid is prepared. However, that
acid is labile and decomposes slowly to nitrogen dioxide NO2. It must be
stored at 0˚C.
2HNO3 ⇌ 2NO2 + H2O + ½O2
Oxidation power of nitric acid changes with the concentration. The higher the
concentration is, the higher the oxidation power is. Depending on the
concentration, the reaction products are different (NO2 or NO).
approx. 65% 2HNO3 ⇌ 2NO2 + O + H2O chng. of ox. no.: 1
below 30% 2HNO3 ⇌ 2NO + 3O + H2O chng. of ox. no.: 3

Concentrated nitric acid is a widely used nitration agent, in combination with cc.
sulfuric acid which acts as a proton source and dehydrating agent. The active
particle is the NO2+ nitryl cation:
HNO3 + H2SO4 ⇌ NO2+ + HSO4ˉ + H2O

Nitric acid is produced by the Ostwald process, reacting nitrogen dioxide with
water, in the presence of an excess of oxygen.
4NO2 + O2 + 2H2O = 4HNO3
Applications of HNO3 : production of nitrate fertilizers, nitration, production of
explosives, lacques, nitric acid esters, dissolving metals, etc.
„Kings water” (aqua regia): A mixture of cc. HCl and cc. HNO3 (3:1). It can
dissolve even the gold. The active agents are chlorine and nitrosyl chloride
formed in the reaction.
HNO3 + 3HCl ⇌ Cl2 + NOCl + 2H2O

demo video: dissolvation of gold in aqua regia

 Phosphorus oxides and oxoacids

Phosphorus has two major characteristic oxides: P4O6; and P4O10 Their
structure can be deduced from the structure of white phosphorus P4
molecules.

P4O6 (a.k.a. P2O3) P4O10 (a.k.a. P2O5)

Tetraphosphorus hexaoxide (aka phosphorus trioxide) P4O6 : It is

produced by a low temperature burning of white phosphorus in a controlled air
atmosphere. It reacts with water and gives orthophosphorous acid H3PO3.

P4(s) + 3O2(g) → P4O6(s)

P4O6 + 6H2O = 4H3PO3

Tetraphosphorus decaoxide (aka phosphorus pentoxide) P4O10: It is

produced by burning white or red phosphorus in an excess of oxygen. The
oxide is a very strong dehydrating agent. It reacts with water and gives
orthophosphoric acid.
P4 + 5O2 = P4O10
P4O10 + 6H2O = 4H3PO4
Decoding the structure of phosphorus oxoacids from their chemical composition
1) O 2) 3)
O O

P P P
OH H OH

First step, always all other oxygens as OH remaining Hs to P

4)
O O O O
P O P or P P catenation
OH OH
OH OH
Old nomenclature of di- and polyphosphoric acids
Formed by stepwise loss of water molecules
O O O O
O O
-H2O -H2O 1
P + P P P n P P
OH O OH O O
HO OH HO HO
OH OH OH OH OH
OH n
Phosphoric acid Diphosphoric acid Polyphosphoric acid
Orthophosphoric acid Pyrophosphoric acid Metaphosphoric acids
H3PO4 H4P2O7 HPO3
Hypoposphorous acid, H2P(O)OH, H3PO2
Monoprotic weak acid (!) Its potassium sal is a strong reducer,
KH2PO2, used to make thin metal layers.
The potassium salt is prepared by dissolving white phosphorus
in potassium hydroxide:
P4 + 3KOH + 3H2O → PH3 + 3KH2PO2
(ortho)Phosphorous acid, HP(O)(OH)2, H3PO3
Diprotic weak acid (!) Can be prepared in the crystalline state. A
weak reducing agent. prepared by hydrolysis of P4O6
P4O6 + 6H2O → 4HPO(OH)2

Industrial production of phosphorous acid is carried out by the

hydrolysis of phosphorus trichloride:
PCl3 + 3H2O = H3PO3 + 3HCl
The esters are widely used in organic chemistry, and in the
production of insecticides: HP(O)(OR)2

Phosphorous acid decomposes above 200 °C in a disproportion

reaction:
4H3PO3 → 3H3PO4 + PH3

The P(OH)3 structure does not exist in the free acid.

However, its P(OR)3 esters can be prepared.
 (ortho)Phosphoric acid, P(O)(OH)3, H3PO4

Anhydrous phosphoric acid is a low-melting white solid. A 85%

solution is available commercially. In contrast to sulfuric or
nitric acid, phosphoric acid is a non-oxidizing and non-toxic
acid. It contains three dissocialble protons, thus it is a triprotic
acid. The first step is of medium strength, the others are weak.

H3PO4 + H2O ⇌ H3O+ + H2PO4− Ka1= 7,25·10−3

H2PO4− + H2O ⇌ H3O+ + HPO42− Ka2= 6,31·10−8
HPO42− + H2O ⇌ H3O+ + PO43− Ka3= 3,98·10−13

Phosphoric acid is a good complexing agent. Alkali metal salts of phosphoric

acid are water-soluble solids, but the alkali metal or transition metal salts are
water-insoluble materials (Mg, Ca, Fe, Al, Cu, etc.) and can be found in the
nature as phosphate rocks.

Dilute phosphoric acid can be found in soft drinks. Although phosphoric acid is
non-toxic, several questions emerged lately regarding its health effects. It
seems that overuse of water soluble phosphates may have non-wanted
consquences. The dispute is not closed, it is still continuing. Until that, a
moderate consumption of phosphoric acid may be a good choice.
In the industry, technical grade phosphoric acid is prepared by concentrated
sulfuric acid dissolvation of phosphate rocks (i.e. apaptites). In case of
fluorapatite, phosphoric acid will be contaminated with hydrofluoric acid.
Technical grade phosphoric acid must not be used in the food industry!
Ca5(PO4)8F + 5H2SO4 + 10H2O = 3H3PO4 + 5CaSO4·2H2O + HF

Food grade phosphoric acid is prepared by burning white phosphorus in air,

followed by dissolvating the product P4O10 in water.
P4O10 + 6H2O = 4H3PO4

Calcium dihydrogen phosphate is a moderately acidic food additive used in

baking powders. It helps developing carbon dioxide from sodium bycarbonate
(baking soda) in the oven, and increase the volume of dough. In addition, it
prevents the formation of sodium carbonate, which would give the food a bitter
taste. :
Ca(H2PO4)2·2H2O + 2NaHCO3 = 2CO2 + 3H2O + Na2Ca(HPO4)2

Applications: metal treatment, production of fertilizers, food industry, medical

uses, etc.
Superphosphate fertilizer: disoolvation of hydroxyapatite in sulfuric or
phosphoric acid thus making it water-soluble:
2Ca5(PO4)3OH + 7H2SO4 + 15H2O = 3Ca(H2PO4)2·H2O + 7CaSO4·2H2O
 Polyphosphates
High-temperature heating of phosphoric acid results in a glassy
material called polyphosphoric acid (metaphosphoric aicd). It has
a polymeric structure in which phosphorus atoms are connected
to each other through an oxygen atom, resulting in a long
polymeric chain. At lower temperature, shorter chains can be Polyphosphoric acid

made.
The P(O)-O-P(O) bonds-containing polyphosphates are acid
anhydrides. They hydrolyse reluctantly, developing energy in the
process. The hydrolysis is catalyzed in the cells by enzimes. A
Triphosphoric acid
triphosphate-containg organic molecule adenosine triphosphate
(ATP) is one of the most important energy strorage and transfer
materials in the living organisms.
ATP

Sodium triphosphate is an important complexing agent used in wash powders to

bind calcium and magnesium ions from water and to prevent calc formation. I is
prepared by heating a mixture of sodium mono- and dihydrogen phosphates at
200 °C temperature.
NaH2PO4+2NaHPO4=Na5P3O10+2H2O
 Arsenic, antimony and bismuth: oxides, oxo-compounds
Arsenic trioxide, As2O3 : White solid. Important starting material in the
production of arsenic-organic compounds and drugs. It is a very toxic water-
soluble materials. Produced by the roasting of auripigment (As2S3)
2As2S3 + 9O2 = 2As2O3 + 6SO2

It is an amphoteric oxide, dissolves in acids and bases.

The aqueous solution is moderately acidic.
As2O3 + H2O ⇌ H2AsO3– + H+
In cc. HCl the covalent halide AsCl3 is formed.
As2O3 + 6 cc.HCl = 2AsCl3 + 3H2O

Arsenic pentoxide, As2O5 : White solid, hygroscopic. It is prepared from As2O3

by cc. nitric acid oxidation, followed by careful dehydration of arsenic acid by
heating. It is a strong oxidation agent. When heated, it decomposes to arsenic
trioxide and oxygen. Acidic oxide, with water it gives arsenic acid.
As2O3 + cc.HNO3 = 2H3AsO4 + 2NO2
As2O5 ⇌ As2O3 + O2
2H3AsO4 ⇌ As2O5 + 3H2O
Antimony and bismuth does not form oxoacids with a distinct composition.
Instead of that, Sb(III) és Bi(III) salts hydrolyze in water producing several oxo-
species in equilibrium, and can be kept in solution under very acidic solution.
 Nitrogen/sulfur compounds – sulfur nitrides
Regarding the electronegativities, chemicla compounds of nitrogen and
sulfur should be considered as sulfur nitrides (and not nitrogen sulfides)

S4N4 Tetrasulfur tetranitride. It was first prepared in 1835 from disulfur

dichloride and ammonia:
6S2Cl2 + 16NH3 = S4N4 + S8 + 12NH4Cl

It is a golden colored and endothermic solid, which is stable at room

temperature, but explodes when is hit, producing nitrogen and sulfur.

S2N2 (cyclo)-Disulfur dinitride. It is formed from S4N4 on

heating in the presence of Ag powder. This is an explosive
nitride too. It polymerizes slowly to (SN)x poly(sulfur nitride),
which is a bronze-colored solid with a metallic luster. That was
the first inorganic conducting polymer and become
superconducting near zero Kelvin temperature. Based on the
structure and conductivity, it is called a one-dimensional metal.

Several resonance structures can be written.

Tetraphosphorus-decasulfide (phosphorus pentasulfide), P4S10
It has an analogous structure to the oxide. It is prepared from sulfur and
phosphorus.
4P4 + 5S8 = 4P4S10 (300 °C)

P4S10 is a covalent solid, which hydrolizes in water to phosphoric acid and

hydrogen sulfide.
P4S10 + 16H2O = 4H3PO4 + 10H2S

It is used to transform carbonyl compounds (i.e. carboxylic amides, esters,

ketones) to thiocarbonyl compounds.
O P4S10 S
H3C H3C
NH2 NH2

In the practice, P4S10 is used to produce phosphorus organic compounds,

insecticides, etc.

Tetraphosphorus trisulfide (phosphorus sesquisulfide), P4S3

This is a hydrolytically stable solid compound, the main component of
the heads of strike-on-all matches. It is produced from red phosphorus
and sulfur.
 Sulfides of arsenic, antimony and bismuth

Sulfide minerals can be found int the nature, and can be precipitated from their
aqueous solution with sulfide ions

As2S3 yellow As2S5 red solid, hydrolyze

Sb2S3 orange (turn gray) Sb2S5 red, hydrolyze in hot water

Bi2S3 fekete

They are used in the classical qualitative analytical chemistry to identify metal ions.

Sulfides of As és Sb are thioacid anhydrides, which react with the thiobase

ammonium sulfide to give i.e. ammonium thioantimonate.

Sb2S3 + 3(NH4)2S = 2(NH4)3SbS4

Arsenic pentasulfide dissolves in an ammonia solution and gives equimolar mixture

of thioarsenate and arsenate ions:

As2S5 + 6NH3 + 3H2O = (NH4)3AsS4 + (NH4)3AsO4

 Thio analogues of oxoacids and oxobases: thioacids and thiobases

The solvent with ordinary acids and bases is: H2 O

The solvent with the thio analogues is: H2 S

The oxides can be acid anhydrides, base anhydrides or amphoteric.

The sulfides can thioacid anhydrides, thiobase anhydrides or amphoteric.

Examples for the analogous reactions:

Acid: CO2 CS2

CO2 + H2O = H2CO3 CS2 + H2S = H2CS3

Base: Na2O Na2S

Na2O + H2O = 2NaOH Na2S + H2S = 2NaSH

Amphoteric: As2O3 Sb2O3 As2S3 Sb2S3

As2O3 + 6NaOH = 2Na3AsO3 As2S3 + 6NaSH = 2Na3AsS3
 Nitrides of phosphorus (compounds with P-N and P=N bonds)

Very many chemical compounds containing a P-N bond is known. Some of

them show exceptionally high stability

Phosphoric acid amides : a foszforsav részleges vagy teljes amidjai

Hexamethyl-phosphoramide (HMPA): colorless liquid with ,

high boiling point. It is an excellent solvent of polymers and
organometallic compounds. Extensively used in organic
chemistry..

Phosphazanes (aminophosphines): contain single P-N bonds.

CH3 Used in catalyst research mainly. Hexamethyl

H3C N CH3 phophatriazane P(NMe2)3 is prepared from PCl3 with
P N Me2NH. It is a reactive molecule, reacts with boranes,
H3C N CH3 alcohols, amines, acids, oxygen, halogens under mild
CH3 conditions..
Polyphosphazenes: hybrid inorganic-organic polymers with the backbone P=N-
P=N-P=N- backbone, substituted with organic moieties: (R = -OH, -NH2, -alkyl,
Cl, etc.)
R

N P
R
n
The amino or alkyl group-contaning derivatives are of high stability polymers, that
can withstand even 700 °C temperature. Other derivatives are biocompatible and
used in surgery or artificial tissue inplants.

NH2 O CH2CF 3
N P N P
NH2 n
O CH2CF 3
n

Thin, transparent film Fire and UV resistant textiles

for biomedical use. Hydrophobic surface repells water droplets