The Group 15 Elements:

The Pnictogens

“Read in the name your God who created “ )I( Inorganic Chemistry 3 )I( Miftahul Khair, M.Sc (miftah@fmipa.unp.ac.id1)

http://kimia.unp.ac.id

Pnictogen (IUPAC
2005)

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Intro
•Urine distillation gives a white, waxy,
flammable solid with a low m.p —white
phosphorus.

History of matches :
- white phosphorus bad, toxic
- red phosphorus good, by instant explosion with an oxidizing agent

very exothermic oxidation rx

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15.1 Group Trends

Nitrogen and phosphorus are both nonconductors of electricity, and both
form acidic oxides, nonmetals.

As : subliming and semi metal

recondensing

Sb and Bi have high

electrical resistivities
metals.
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 Like Alkali :
- m.p of main group metals tend to decrease down a group,
- m.p of nonmetals tend to increase down a group.

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15.2 Contrasts in the Chemistry of

Nitrogen and Phosphorus

In acidic solution.

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The Thermodynamic Stability of Dinitrogen

smaller difference between the single and triple

N2 is the stable form bond energies

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N≅Nbond energy >> N¬N bond strengths N2 molecule in a reaction

Ex:

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The Bonding Limitations of Nitrogen

N NF3 ; P PF5 and PF3

octet is exceeded for P

(hypervalent compounds.)

- N atom is too small to accommodate > 3 F

- Larger/lower members of the group can manage 5 or 6 nearest neighbors

P- O bond has some

double bond character.9
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The Electronegativity Difference of Nitrogen and Phosphorus

N electronegativity >> other members of the group

Polarity of the bonds in N compounds is often the reverse of that in P

and the other heavier members of the group.

N-H covalent bond is strongly polar NH3 is basic,

whereas the hydrides of the other Group 15 elements—
phosphine, PH3

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15.3 Overview of Nitrogen Chemistry

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Nitrogen
Inert diluent for the highly reactive gas, O2.

N2 is not very soluble in water, although its solubility increases

rapidly with increasing pressure problem for deep-sea divers.

To avoid this, O2-He gas mixtures are now used because He has a
much lower blood solubility
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N2 preparation industrially :

1. liquefying air and then slowly warming

the liquid mixture. (N2 b.p = -196 C, O2 b.p = -183 C)

2. using a zeolite to separate from other gases ,

N2 preparation in the lab :

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Uses :
• inert atmosphere when highly reactive compounds are
being handled or stored.
• in steel production as an inert atmosphere and in oil
refiNeries to purge the flammable hydrocarbons from the
pipes and reactor vessels when they need maintenance.
• Liquid nitrogen is used as a safe refrigerant where very
Rapid cooling is required.
• Manufacture of ammonia and other nitrogen-containing
compounds.

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 Few chemical reactions involving dinitrogen as a reactant :

dinitrogen and dioxygen is sparked in :

•Lightning flash

•high-
compression
gasoline engines
catalytic converter
accelerate the rx from pollutant
NO2 to the left.

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Nitrogen Hydrides

Ammonia hyd az ne
hydrazine Hydrogen azide

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 Nitrogen Hydrides
Ammonia
colorless, basic, poisonous gas with a very strong smell.

dissolves readily in water (S=50 g/ 100 g of water,

density 0.88 g/mL.

“aqueous ammonia” solution, but is misleadingly called

“ammonium hydroxide.” ; A small proportion reacts with the water to
give ammonium and hydroxide ions:

equilibrium lies to the left

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Ammonia preparation:

Ammonia reactions :

strong Lewis base :

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The Industrial Synthesis of Ammonia

N – compounds (NaNO3 firtilizer) are essential for plants.

NaNO3 firtilizer deposits would one day be exhausted.

Need to find method of forming nitrogen compounds from

the unlimited resource of unreactive nitrogen gas.

Fritz Haber, 1908

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The Industrial Synthesis of Ammonia

Fritz Haber, 1908

In fact, above reaction ∆H<0 , Vgas ↓, and ∆S<0

To “force” to the right, the Le Chatelier : T<, and P>.

However : at T<, the rate < , at which equilibrium is reached.

A catalyst ? but there are limits to the practical minimum T .

Haber : good yeild !: P = 20 MPa (200 atm) and T= 500 C

Coincide with World war !

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Hydrazine

- fuming, colorless liquid.

- weak base : forming two series of salts:

- strong reducing agent :

- used as the reducing component of a rocket

fuel

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Hydrogen Azide

colorless liquid, acidic ( = pKa acetic acid )

Irritataing odor, poisonous.

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Nitrogen Ions

The Azide Anion : N3-

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Nitrogen Ions
The Azide Anion : N3-
- isoelectronic with CO2

- Used as automobile air bag.

in 40 ms.

- Lead(II) azide as detonator:

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The Ammonium Ion
• The most common nonmetallic cation
• pseudo-alkali-metal ion, K+.
• BUT, it can be hydrolyzed, dissociated, or oxidized.

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Nitrogen Oxides
Nitrogen forms a plethora of common oxides:
dinitrogen oxide, N2O;
nitrogen monoxide, NO;
dinitrogen trioxide, N2O3;
nitrogen dioxide, NO2;
dinitrogen tetroxide, N2O4;
dinitrogen pentoxide, N2O5.
nitrogen trioxide, NO3

Thermodynamically unstable with respect to decomposition to its elements,

but
kinetically stabilized.

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 Dinitrogen Oxide, N2O

• sweet-smelling, gaseous
• the only common gas other than oxygen to support
combustion

the central atom

usually possess the
lower electronegativity.

- Preparation :

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Nitrogen Monoxide

•colorless, neutral, paramagnetic gas.

•readily loses its electron from the

antibonding orbital to form the nitrosyl ion,
NO+,

•atmospheric pollutant, in high-compression

internal combustion engines :

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Nitrogen Dioxide and Dinitrogen Tetroxide

• the highly reactive free nitrate radical, NO3.

•play a major role in nighttime atmospheric chemistry.

the day, it is decomposed by light

at night, the nitrate radical is the oxidizing species on

the Earth’s surface,
HNO3 (g) reacts with water to give nitric acid.
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Nitrous Acid and Nitrites

•weak acid that is unstable except in

solution.

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Nitric Acid and Nitrates

•A colorless, oily liquid when pure, nitric
acid is extremely hazardous
Nitric Acid

•very strong oxidizing agent,

•yellow : light-induced decomposition

reaction:

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 Nitrates
•Nitrates of almost every metal ion in its common oxidation states
are known, and of particular note, all are water-soluble. used
whenever a solution of a cation is required.

•ammonium nitrate: source of nitrogen fertilizer,

explosive decomposition

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Overview of Phosphorus Chemistry

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Phosphorus
Allotropes of P ; white phosphorus, red phosphorus, black phosphorus.

White Phosphorus
formed when liquid phosphorus solidifies;
very poisonous,reactive

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Red Phosphorus

•stable in air,

•reacting with O2 in air only above about 400°C.

•a covalently bonded polymer insoluble in all

solvents.

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 Phosphorus element is reactive extreme methods have to be
used to extract it from its compounds.
Raw material : calcium phosphate, Using electric energy for electrlysis

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Phosphine

PH3
analog of ammonia,
a colorless, highly poisonous

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 Phosphorus Oxides
forms two oxides: P4O6, and P4O10.

dehydrating agent

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Phosphorus Chlorides

Phosphorus pentachloride in different phases :

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 Phosphorus Oxo-Acids and Phosphates
three oxyacids of phosphorus :
Phosphoric acid, H3PO4;
phosphonic acid, H3PO3 (phosphorous acid); and
phosphinic acid, H3PO2 (hypophosphorous acid).

•In an oxyacid:
for the hydrogen to be
significantly acidic, it must
be atached to an oxygen
atom

Other oxyacid : Nitric, nitrous acid

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Phosphoric Acid
colorless solid, melting at 42°C.
essentially nonoxidizing, (see frost diagram! )
weak acid

Preparation:

Most of the phosphoric acid is used for fertilizer

production 44
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 Phosphates
There are three series of phosphate salts:
1. phosphates, containing the PO4 3-;
2. hydrogen phosphates, containing the HPO4 2- and
3. dihydrogen phosphates, containing the H2PO4 2- ion.

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