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❖Hydrides, oxides & halides

❖ Hydride of nitrogen : ammonia, hydrazine, nitric acid
❖Oxides of nitrogen :
❖nitrous oxide, N2O, nitric oxide, NO, nitrogen dioxide, NO2
& dinitrogen tetroxide, N2O4 , dinitrogen pentoxide, N2O5
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GROUP 15 (PNICTOGENS) ELEMENTS : N, P, As, Sb, Bi

PROPERTIES (CHARACTERISTIC):
❖Nitrogen and phosphorus non-metal, arsenic and antimony are
metalloids, bismuth metal
❖elemental nitrogen is a diatomic gas(N2). Oxides are (NO, N2O, NO2, N2O4
and N2O5 (solid) others are gases)
❖Nitrogen has tendency to accept 3 electrons to form the nitride ion, N3-(thus
achieving the electron configuration 2s2 2p6, which is isoelectronic with neon)
❖Most metallic nitrides (Li3N and Mg3N2) are ionic compounds. Phosphorus
exists as P4 molecules. It forms two solid oxides with formula P4O6 and P4O10
❖Arsenic, antimony and bismuth have extensive 3D structures. Bismuth is a
far less reactive metal than those in the proceeding group
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Explain why the bond energy for the P-P bond (+200 kJ/mol)
is greater than both the N-N single bond (+160 kJ/mol) and
the As-As single bond (+175 kJ/mol)

-owing to the small atomic size – closer proximity in N2

compared to P2

-lone pairs of electrons on adjacent nitrogen atoms repel

each other (increase repulsion )

-weakening the N-N bond

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HYDRIDES

1) Ammonia, NH3 – pyramidal shape, ability to form hydrogen bond, to

dissolve in water

2) Phosphine, PH3 – pyramidal shape, does not have hydrogen bond or

dissolve in water, P-H bonds are nonpolar

3) Arsine (AsH3), stibine (SbH3) and bismuthine (BiH3) – much less stable
than others

OXIDES
Limited O2 : P4(s) + 3O2(g) P4O6(s)
Excess O2 : P4(s) + 5O2(g) P4O10(s)

P4O6(s) + 6H2O(l) 4H3PO3(aq)

P4O10(s) + 6H2O(l) 4H3PO4(aq)
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Phosphorous pentoxide
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White phosphorous

Phosphorous trioxide
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HALIDES
•Nitrogen – forms only pyramidal trihalides (no d orbitals available to
expand the octet)
•Phosphorous – forms pyramidal trihalides and trigonal bipyramidal
pentahalides
•Halides : reacts with all halogens to form P(III) or P(V) halides
Limited X2: P4 + 6X2 4PX3
Excess X2: P4 + 10X2 4PX5
•The halides react with water to form acids:
PCl3(l) + 3H2O(l) H3PO3(aq) + 3HCl(aq)
PCl5(l) + 4H2O(l) H3PO4(aq) + 5HCl(aq)
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PHOSPHORUS TRICHLORIDE
•PCl3 : toxic, corrosive liquid (at room temperature & pressure) – react
violently with water
•Has a lone pair electrons – Lewis base

P
Cl
Cl
Cl

PHOSPHORUS PENTACHLORIDE
•Lewis acid – chloride ion acceptor Cl

Cl
Cl P
Cl

Cl
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HYDRIDE NITROGEN (Ammonia):

❑ Laboratory preparation :

➢ NH4X (ammonium halide salt) + OH- NH3 + H2O + X-

➢ N3- (azide) + 3H2O 3OH- + NH3

➢ prepared by heating ammonium salt with any solid alkali and water :

NH4Cl(s) + Ca(OH)2 (s) CaCl2(s) + 2H2O(g) + 2NH3(g)

➢ generated by action of water on the nitrides of Ca, Mg and Al:

Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3

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❑ Industrial preparation :

•Nitrogen – from air

•Hydrogen – from water and natural
gas in steam reforming:

CH4(g) + H2O(l) Ni CO(g) + 3H2(g)

900ºC

-Haber Process : N2(g) + 3H2(g) 2NH3(g) H = -92 kJ/mol

-using Le Chatelier’s Principle
•pressure :high pressure 102-103 atm (usually 200 atm)
•temperature : high 400-500°C (usually used 400°C)
•catalyst : iron (Fe)
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• properties : colourless gas, has a characteristic pungent (b.p. 33.35°C),

choking smell
• extremely soluble in water (hydrogen bonding)
+
H H N
H H H
- + - + H
H N + H O H N H O H
-
H H

• solutions of the weak base NH4OH, called ammonium hydroxide

NH3 (aq) + H2O(l) NH4+(aq) + OH-(aq)

• act as Lewis base : electronic structure (lone-pair of electron)

• for domestic purposes; in laundering of woolens. It is a constituent of silver
polishes and smelling salts
• used industrially in the manufacture of urea, of nitric acid and ammonium
sulphate
• used in refrigeration because of its volatility and its high heat of vaporation
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Hydrazine :
❑derived from ammonia by replacement of hydrogen atom by the NH2
group. It is a bifunctional base and two series of hydrazinium salts are
obtainable
N2H4 (aq) + H2O N2H5+ + OH-
N2H5+ (aq) + H2O N2H62+ + OH-

❑N2H5+ are stable in water, while those of N2H62+ are extensively

hydrolyzed
❑Salts of N2H62+ can be obtained by crystallization of aqueous solution
containing a large excess of the acid, since they are usually less soluble
than the monoacid salts
❑Anhydrous N2H4 is fuming colorless liquid (b.p. 114°C)
❑reducing properties: hydrazine and its sulphate are very vigorous
reducing agents
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Nitric acid :
❑Preparation in laboratory, nitric acid is usually prepared by distilling a
mixture of potassium nitrate and concentrated sulphuric acid:
KNO3 + H2SO4 KHSO4 + HNO3
❑Manufacture of nitric acid : Ostwald process
1) NH3 gas (10%) and air (90% by volume) are passed through a platinum
gauze catalyst, kept at red heat (850°C). The ammonia is oxidized to nitric
oxide:
4NH3 + 5O2 4NO + 6H2O
2) After cooling, the nitric oxide is allowed to pass slowly with excess of air
through an oxidizing chamber where it is converted to nitrogen dioxide
2NO + O2 2NO2
3) If heated, NO2 dissociates into nitric oxide and oxygen (beginning at
150°C under atm. pressure) so, that maximum yield of NO2 can only be
obtained at low temperature. The NO2 in the presence of excess air, is then
absorbed in water at about 80°C. This avoids formation of nitrous acid
(unstable to heat) and enforces the final reaction:
4NO2 + O2 + 2H2O 4HNO3
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OXIDE NITROGEN
▪There are four stable oxides of nitrogen as below:
-nitrous oxide, N2O (dinitrogen monoxide): colourless gas with slight,
sweetish smell. It has anesthetic action and is used in dentistry. It is fairly
soluble in water to give neutral solution. It can assist combustion once
reaction has started
- nitrous oxide release extra oxygen during combustion

2N2O 2N2 + O2

Nitrous oxide is an oxidizing agent used to increase an engine's power output by
allowing more fuel (usually gasoline or alcohol) to be burned
▪nitric oxide, NO (nitrogen monoxide): colourless gas, slightly soluble in
water and much more stable than nitrous oxide. Paramagnetic, slightly toxic
gas. It forms brown fumes of nitrogen dioxide on contact with air
N2(g) + O2(g) 2NO(g)
2NO + O2 2NO2
Nitrous oxide (N2O) is used in internal combustion engines as a way
of delivering more oxygen into the cylinder.

It isn't flammable itself, but when it is heated sufficiently, it separates

into nitrogen and oxygen, and the oxygen is free to assist in the
combustion of a fuel such as gasoline.

It performs a task similar to that of a turbocharger (increasing the rate

of oxygen delivery), but it uses a consumable tank of liquid, while the
turbo uses a mechanical device to increase pressure, driving more
oxygen into the engine.

the development of nitrous oxide injection systems for automotive

performance use
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▪nitrogen dioxide, NO2 and (dimer : dinitrogen tetroxide, N2O4)

At above 22°C (low temperature), it is mainly N2O4. At 150°C (high
temperature), it is NO2. NO2 very toxic gas. N2O4 is a colourless gas.
2 NO2 N2O4
brown colourless
paramagnetic diamagnetic
O O
O N O N N

O O

▪dinitrogen pentoxide, N2O5 is colourless solid (unstable colourless

crystal), which melts at 29.5C. It is very hygroscopic and decomposes
slowly at ordinary temperature and explosively if heated suddenly:
2N2O4 + O2 2N2O5
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Combustion of fossil fuels and air pollution

•Compounds of nitrogen – impurities in fossil fuels
(burn to form nitric oxide, NO)

•Most nitrogen in NO from : furnaces, automobiles, airplanes,

N2(g) + O2(g) 2NO(g)

•NO can further oxidized to nitrogen dioxide, NO2

(reaction enhanced in the presence of UV light from the sun)
UV
2NO(g) + O2(g) 2NO2(g) (reddish-brown gas)
light
•NO2 reacts with water in the air to form nitric acid
(major contributor to acid rain)

3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)