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Prepared by Kosheila, Jordan, Sophia, Joshua and Ling Poh Ping.
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Nitrogen and Its Compounds
Chapter 4Jordan, Joshua, Kosheila, Poh Ping, Sophia
N N
1s2 2s2 2p3
Achieves stable octet electron formation –covalent triple bonding ◦ N2 molecule
N is for Nitrogen
N Nπ
πσ
Very stable and relatively inert◦ Very strong triple bond◦ Very short bond length◦ High bond length energy
N2 (g) → 2N (g) △H = +945kJmol-1
Bond must be broken with high energy before N can react with other substance ∴ inert
Inert nature of Nitrogen
Linear Non polar Distribution of electrons - symmetrical
∴ absence of polarity
Inert nature of Nitrogen
N●●●
●● N
XXx
Xx
δ + δ - X Xδ + δ - X X
Reactivity of N2
N N N N N NIncreasing reactivity
Very strong triple bond
Single polar bond
Weaker Single bond
δ + δ -
At high temperature & pressure :◦ N2 (g) + H2 (g) → 2NH3 (g)
◦ N2 (g) + O2 (g) → 2NO (g)
◦ N2 (g) + M (s) → MN (s)e.g.
N2 (g) + 2Al (s) → 2AlN (s)
N2(g) + 3Mg (s) → Mg3N2(s)
Reactivity of N2
fractional distillation of liquid air
Extraction of Nitrogen from Air
Ammonia: Its Formation, Properties
and UsesFormation and Properties of Ammonia
By heating a mixture of ammonium salt and a base
NH4+ + OH- NH3 + H20
Ammonia gas is dried by passing it through anhydrous calcium oxide.
Conc.H2SO4 & anhydrous CaCl2 can’t be used because they react with ammonia
Formation of Ammonia from Ammonium Salts
Industrial Preparation of
Ammonia The Haber Process
direct combination of N2 and H2 .
N2(g) + 3H2(g) Fe 2NH3(g)
-N2 from fractional distillation of liquefied air
-H2 from synthesis gas.
Mixture of N2 and H2 passed over ◦ finely divided Fe , or◦ Fe2O3 catalyst with K2O and Al2O3 as promoter ◦ (temp: 450-500o C, P: 200-500 atm).
NH3 condensed in the condenser and collected as liquid ammonia.
Haber Process
Physical Properties of Ammonia
Physical Properties of NH3
colourless pungent-smelling gas common alkaline gas. A covalent compound with a trigonal
pyramidal shape and with a lone pair of electrons.
Properties of Ammonia
a Lewis base (electron pair donor).
Form dative bond by donating electrons to any Lewis acid.
a Bronsted-Lowry base (accepts a proton)ammonium ion.
NH3 (g) + H2O (l) NH4+ (aq) + OH-
(aq) base acid conjugate acid conjugate base
Properties of Ammonia
b.p. - relatively high (presence of hydrogen bond)
soluble in water weak base solution with a low base dissociation constant.
NH3 (g) + H2O (l) H3N.H2O
liquid ammonia undergoes autoionisation NH4
+ and NH2- ions.
Liquid ammonia is a weak conductor of electricity.
2NH3 (l) NH4+ (l) + NH2
- (l)
Properties of Ammonia
Chemical Properties of Ammonia
A lone pair on N atom in the molecule act as proton acceptor
NH3 + H+ NH4+
Dissolved in water, aqueous ammonia undergoes partial dissociation NH4
+ and OH- ions:
H3N.H2O(aq) NH4+ (aq) + OH- (aq)
Aqueous ammonia reacts with acids to form salts NH3(aq) + HCl(aq) NH4Cl(aq)
2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
As a weak base
Precipitates insoluble metallic hydroxides from their salts (except Na+, K+ , and Ba2+ )
Cu2+(aq) + 2NH3(aq) + 2H2O(l) Cu(OH)2(s) + 2NH4
+(aq)
Some hydroxides dissolve in excess of NH3
formation of water soluble complexes. Cu(OH)2(s) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 2OH-
(aq)
As a weak base
Form a dative bond by donating the lone pair to the empty orbitals of metallic cations (esp. transition metal ions).
acts as Lewis base / ligand
Examples of complex formation:i. Tetraamminecopper(II), [Cu(NH3)4]2+
ii. Hexaamminenickel (II), [Ni(NH3)6]2+
As Ligands in complex formation
React with some substances◦addition compounds through the formation of
dative bonds.
Examples:i. NH3 + BF3 BF3 . NH3
ii. NH3 + AlCl3 AlCl3 . NH3
Formation of addition compounds
Acts a reducing agent oxidised to nitrogen. 2NH3 N2 + 6H+ + 6e-
Cl2 gas reacts with ammonia at room temp. N2 gas
8NH3(g) + 3Cl2(g) N2(g) + 6NH4Cl(s)
Excess of chlorine dangerously EXPLOSIVE OIL, NCl3 produced:
NH3(g) + 3Cl2(g) NCl3(l) + 3HCl(g)
Reduces aqueous sodium chlorate(I) at room temp. to the Cl- ion:
NH3 + 3ClO-(aq) N2(g) + 3Cl-(aq) + 3H2O(l)
As a reducing agent
- passing the dry gas over certain red hot metallic oxides.
2NH3(g) + 3CuO(s) 3Cu(s) + N2(g) + 3H2O(l)
2NH3(g) + 3PbO(s) 3Pb(s) + N2(g) + 3H2O(l)
Magnesium burns in dry ammonia magnesium nitride &H2 gas
3Mg(s) + 2NH3(g) Mg3N2(s) + 3H2(g)
Oxidation to nitrogen and steam
Dry ammonia burns in oxygen to produce nitrogen and steam.
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g)
When dry ammonia and oxygen is passed over heated platinum, nitrogen monoxide is formed.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
- Involved in the Ostwald process .
Combustion of ammonia
Decompose when heated. Non-oxidising acids decompose to NH3 and the
corresponding acids. NH4Cl (s) NH3(g) + HCl(g)
(NH4)2CO3(s) 2NH3(g) + CO2(g) + H2O(l)
Oxidising acids decompose to either N2 or oxides of nitrogen.
NH4NO2(s) N2(g) + 2H2O(l)
(NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(l)
p/s : All these reactions can be EXPLOSIVE!!!
Action of heat on ammonium compounds
A reagent to identify cations in qualitative analysis.
All cations metal hydroxides (precipitates) except Na+, K+, and NH4
+.
Reactions of aqueous ammonia on certain cations
Cation Observations Solubility in excess NH3
Ag+ White ppt → light brown √
Zn2+ White ppt √
Mn2+ White ppt →brown X
Pb2+ White ppt X
Mg2+ White ppt X
Al3+ White ppt X
Cu2+ Blue ppt √(dark blue)
Cr3+ Great blue ppt X
Fe2+ Dirty green ppt X
Fe3+ Reddish brown ppt X
Ni2+ Green ppt √(light blue)
USES OF AMMONIA Nitrogenous fertilisers.
Manufacture of nitric acid in Ostwald process. catalytic oxidation of ammonia oxidation of nitrogen monoxide to nitrogen dioxide formation of nitric acid from nitrogen dioxide
Cooling agent / refrigerant
Cleaning agent
Formation of Oxides of Nitrogen
Nitrogen Monoxide colourless neutral gas, insoluble in water,
reducing agent
heptet electron configuration ( unpaired electron delocalised), paramagnetic
unstable, easily oxidised 2NO(g) + O2(g) 2NO2 (g)
brown acidic gas, pungent smell
V-shaped, heptet configuration (unpaired electron at nitrogen atom)
double and dative bond delocalised actually resonance hybrid structure
Nitrogen Dioxide
in the environment
Nitrogen, N2(g) Oxygen, O2(g)
2 NO(g)
(disassociated by lightning)
(Nitrogen monoxide)
2 NO(g)
Oxygen, O2(g)
2 NO2(g)
(Nitrogen dioxide)
IN THE INTERNAL COMBUSTION ENGINE
Volvo
2800˚C
N2(g) + O2(g) => 2 NO(g)
2 NO2(g) NxOy
ATMOSPHERIC POLLUTANTS FROM COMBUSTION OF FOSSIL
FUELS
Nitrogen oxides
Sulphur dioxides
Carbon monoxide
Unburnt hydrocarbon
Lead bromide(lead
petrol)
EFFECTS OF OXIDES OF NITROGEN ON AIR POLLUTION
Acid Rain Photochemical Smog
ACID RAIN
2 NO2(g) + H20 -> HNO2 + HNO3
4 NO2(g) + 2 H20 + O2-> 4 HNO3
Oxides of nitrogen dissolve in rain water to produce nitrous acid and nitric acid.
(one of the causes of acid rain)
Sulphur oxides and oxides of nitrogen are the primary pollutants of the atmosphere.
pH less than 5
ACID RAIN
Nitrogen dioxide also catalyses the oxidation of sulphur dioxide to produce sulphur trioxide.
NO2 + SO2 -> NO + SO3
NO + ½ O2 -> NO2
SO2 + ½ O2 -> SO3
(also one of the causes of acid rain)
ACID RAINThe oxides of sulphur dissolve in rain water to produce acid rain.
SO2 + H20 -> H2SO3 SO3 + H20 -> H2SO4
Sulphurous acid
Sulphuric acid
ACID RAIN
PHOTOCHEMICAL SMOG
PHOTOCHEMICAL SMOG
Nitrogen dioxide
Hydrocarbons
Smoke & Fog
Smog
NO2(g)
2 Stages:
NO(g) + O (g)
Stage1
Stage2
O (g) + O2(g)
O3(g)
uv light
Ozone molecule
PHOTOCHEMICAL SMOG
Ozone molecule
Unsaturated hydrocarbon (from incomplete
combustion)
combines
Organic radicles that form smog when combined with nitrogen monoxide
oxidize
Less volatile organic products that condenses on air particles to form smog
View of Beijing 2005
After rain Before rain
Tetranitrogen N4
Hydrogen Cyanide
HCN
Laughing Gas
N2O
Coolant agent Aircraft fuel
Further Uses of Nitrogen