Group 15 : Nitrogen & Its Compounds

4.1 Nitrogen : Its Inert Nature & its Extraction from Air

The Inert Nature of Nitrogen

atom :1s2 2s2 2p3 - achieves stable octet electron arrangement through formation of covalent bonds in the nitrogen molecule.  Consists of simple diatomic molecules covalent triple bond.
N

N molecule is very stable & relatively inert. Reasons : a) The two N atoms held by a very strong triple bond very short bond length & very high bond energy. N2 (g) 2N(g) H = + 945 kJmol-1

Since a large amount of energy is needed to dissociate the molecule, nitrogen is relatively chemically inert. b) Nitrogen molecule is linear & non-polar. N molecule nonhas symmetrical distribution of electrons. N molecule is not reactive due to absence of polarity.
* At high temperature & pressure, nitrogen can react with hydrogen to form ammonia, oxygen to form nitric oxides & metals to form metal nitrides.

Extraction of Nitrogen from Air

 


Air main source of nitrogen. Reason : air consists of up to 78% nitrogen by volume. Nitrogen is extracted from air by fractional distillation of liquid air. Consists of 2 stages : *refer ace ahead vol.2 (chap.4) pg. 57/ Longman
chap.5 pg. 83

 

a) Liquefaction of air Clean air (after removal of dust particles and carbon dioxide) is fed into a compressor compressed under high pressure about 250 atm and low temperature until liquefied - Left only Nitrogen and Oxygen gas in the liquid air.

b) Fractional distillation Nitrogen gas collected before oxygen because nitrogen has lower boiling point than oxygen : - nitrogen (-196 C) (- oxygen (-183 C) (-

Questions: Questions:


Nitrogen dioxide and dinitrogen tetroxide exists in equilibrium in the gas phase. Which of the following statements is true? A. N2O4 molecule has two dative bond. B. NO2 molecule has one sigma and one pi bonds. C. The bond angle in NO2 molecule is 1200. D. The hybridisation of nitrogen atom in N2O4 molecule is sp3.

Solution: N2O4 has two dative bonds and undergoes sp2 hybridisation. hybridisation. NO2 has two sigma bonds and one pi bond and the bond angle is less than 1200 because of the repulsion from the odd electron. Answer : A

A catalytic converter reduces air pollution by 1 oxidising lead to lead (II) oxide 2 reduces oxides of nitrogen to nitrogen and oxygen 3 oxidising carbon monoxide and hydrocarbons to carbon dioxide and water. Solution : A catalytic converter reduces NO and NO2 to N2 and O2 in one chamber and oxidises CO and unburnt hydrocarbons to CO2 in the other. Answer : C (2 & 3)

The photochemical smog is a type of air pollution. The gas which causes the pollution is A. O3 B. NO C. NO2 D. SO2

Solution : NO2 combines with the hydrocarbon from automobile exhausts to produce photochemical smog. First, ultraviolet light causes the formation of oxygen radicals from NO2. The oxygen radical subsequently reacts with O2 to form O3. The ozone combines with unsaturated hydrocarbon to form organic radical which then combines with NO to form the component of smog. Answer : C

Which of the following reactions occur(s) in a catalytic converter? 1 2CO(g) + O2 2CO2(g) 2 2NO(g) + 2CO(g) N2(g) + 2CO2(g) 3 2C8H18(g) + 25O2(g) 16CO2(g) + 18HO2(g)

Solution : In a catalytic converter, CO is oxidised to CO2 whereas NO is reduced to N2. Hydrocarbons are oxidised to CO2. Answer : D (1,2 & 3)

4.2 AMMONIA: ITS FORMATION, PROPERTIES AND ITS

WHAT IS AMMONIA???

FORMATION OF AMMONIA FROM AMMONIUM SALTS

 Ammonia

gas is prepared by heating a mixture of ammonium salt and a base (Examples: NaOH, KOH, CaO) salt + base Ammonia gas NH3 +H2O

 Ammonium  NH4 +

+ OH

 Ammonia

gas is dried by passing through anhydrous Calcium Oxide and it is collected by upward delivery  Concentrated H2SO4 and anhydrous CaCl2 are common dehydrating agents that cannot be used

PROPERTIES
Ammonia is: - Colourless, Pungent-smelling gas Pungent- Only common in alkaline gas - The molecule is pyramidal in shape due to its lone pair

1.

2.

In terms of Lewis theory, - Ammonia is a Lewis base because it acts an electronelectron-pair donor - It can form dative bond by donating its lone pair on the nitrogen atom to any Lewis acid

3. In terms of Bronsted-Lowry theory, Bronsted- Ammonia is a base because it is a proton acceptor. - It accepts a proton to form an ammonium ion

NH3 (g) + H20 (l) OH (aq) (Base) (Acid) (Conjugate (Conjugate Base {P.Acceptor} {P.Donor}

NH4 (aq) +

Acid)

4.

Ammonia is highly soluble in water producing a weak base solution with a low base dissociation constant (Kb = 1.81 10 ^-5 mol ^dm^dm^-3). - Its high solubility is due to hydrogen bonding between ammonia molecules and water molecules NH3 (g) + H2O (l) H3N.H20

5. It can react with aqueous acid to form ammonium salts. The unpaired electrons on the nitrogen atom can bond with a proton to form

6. Gaseous ammonia can react as a base towards acidic gases. - when it is reacted with gaseous HCl, white fumes of ammonium chloride are formed. - This is also used a test for the presence of ammonia gas. NH3 (g) + HCl (g) NH4Cl (g)

-A dative bond is formed between nitrogen in ammonia with hydrogen in hydrogen chloride

7.

Ammonia is used as a reagant to identify cations in qualitative analysis. All cations produce metal hydroxides as precipitates except Na+, K+ and NH4+.

8. Some metal hydroxides dissolve in excess ammonia to produce complexes that are soluble in water. Ammonia acta as ligands in the formation of complexes by donating the lone pair of electrons to the empty orbitals of metal ions. 9. Ammonia can act as a reducing agent in redox reactions. In the process, ammonia will be oxidised to nitrogen.

USES OF AMMONIA
1. Manufacture of nitrogen fertilizers (Example: Ammonium Sulphate, Ammonium Nitrate, Urea) NH3 + HNO3 nitrate) 2NH3 + H2SO4 ammonium sulphate) 2NH3 + C02 NH4NO3 (ammonium (NH4)2SO4 ( (NH2)2CO (Urea) + H2O

2. Manufacture nitric acid in the Ostwald process

Ostwald Process * Is the process for producing nitric acid Stage 1: Catalytic oxidation of ammonia Ammonia is oxidised by air to nitrogen monoxide at 850-900C in the presence of 850platinum as a catalyst. 4NH3 (g) + 5O2 (g) 6H2O (g) 4NO (g) +

Stage 2: Oxidation of nitrogen monoxide to nitrogen dioxide Nitrogen monoxide, NO is further oxidised by air to nitrogen dioxide, NO2.

Stage 3: Formation of nitric acid from nitrogen dioxide 1. Nitrogen dioxide gas dissolves in water to form nitric acid ( 50-60%) and nitrous acid. 502NO2 (g) + H2O (l) + HNO2 (l) HNO3 (l)

2. Nitrous acid, HNO2 is converted to HNO3 and NO on heating. 3HNO2 (l) 2NO (g) HNO (l) + H2O (l) +

Overall equation: 4NO2 + 2H2O + O2 4HNO3 3. Liquid ammonia is used as a cooling agent or refrigerant because of its low boiling point and high latent heat of vaporisation. 4. Liquid ammonia is used as a domestic cleaning agent. It is volatile and does not leave any residue after cleaning. Ammonia is used in agriculture industries for essential plant growth.

5.

QUESTIONS
 Ammonia

gas can be prepared in a laboratory by heating an ammonium salt with  A. Devardas alloy  B. Hydrochloric acid  C. Calcium hydroxide solution  D. Acidified solution of potassium manganate (VII)
 Answer:  C.

Calcium hydroxide solution.  When an NH4 + compound is heated with a base,NH3 gas will be liberated.

 Which

of the following is true about ammonia?  A. Ammonia dissolves in water to form NH4OH  B. Ammonia gas is liberated when ammonium nitrate is heated with calcium oxide  C. Ammonia forms nitrogen dioxide when it reacts with oxygen  D. Ammonia reacts as a Lewis acid in the reaction with copper(II) ion to form a dark blue complex ion.
 Answer: B

 Gases

given off from vehicle exhausts affect the environment and living things. Which is not the effect of the gases?  A. Acid rain  B. Chemical corrosion  C. Toxicity of the blood  D. Thinning of the ozone layer
 Answer: D

4.3 OXIDES OF NITROGEN

NO NO2

N2O4

NITROGEN MONOXIDE


Is prepared by the action of copper on hot,50% nitric (v) acid. 3Cu(NO3)2(aq) + 4H2O(l) + 2NO(g)

3Cu(s) + 8HNO3(aq)

Is a colourless gas, but forms brown fumes of nitrogen oxides if contacted with air. 2NO(g) + O2(g) 2NO2(g)

Is only very slightly soluble in water.

The structure of nitrogen monoxide is a resonance structure of two forms.



Is purified by absorption into aqueous iron(ll) sulphate where a brown solid is formed. FeSO4(aq) + NO(g) FeSO4NO(s)

Heating the solid in the absence of air regenerates the nitrogen monoxide.

FeSO4NO(s)

FeSO4(s) + NO(g)

NITROGEN DIOXIDE
Is produced by the action of heat on the nitrate(v) of heavy metals.


eg.

2Pb(NO3)2(s)

2PbO(s) + 4NO2(g) + O2(g)

Can also be produced by the reaction of copper on hot concentrated nitric(v) acid. Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

Cu(s) + 4HNO3(aq)

Nitrogen dioxide is a brown gas that reacts rapidly with water at room temperature to form a mixture of nitric(v) acid and nitric(lll) acid. HNO3(aq) + HNO2(aq)

2NO2(g) + H2O(l)

With alkalis, 2NaOH(aq) + 2NO2(g) NaNO3(aq) + NaNO2(aq) + H2O(l)

DINITROGEN TETRAOXIDE
It is formed when a sample of nitrogen dioxide is cooled.It dimerises to form a colourless dimer,N2O4


2NO2(g)


cooling

N2O4(g)

Exists as a colourless solid at temperature below 11C . The solid melts to a pale yellow liquid when heated. When the temperature increases, the colour of the solution gets deeper and turns into a reddish-brown vapour.


POLLUTION CAUSED BY NITRIC OXIDE

Considered as a primary air pollutant. The environmental sources of nitric oxide are:
Burning of fossil fuels containing nitrogen compounds.  Reaction between nitrogen and oxygen in internal combustion engines at high temperatures.  Lightning which combines the atmospheric nitrogen and oxygen.





Causes pollution:

It dissolves in rainwater to form nitrous acid and nitric acid where these are considered as a secondary pollutant.  It will tend to combine with gaseous hydrocarbons in the atmosphere to form smog.

QUESTIONS....
1.Nitrogen

oxides have high positive standard enthalpies of formation . Which of the following is the major for the high positive value of ?
A. The tendency of oxygen to form oxides. B. The high electron affinity of the oxygen atom. C. The nitrogen and oxygen atoms have similar electronegativities. D. The high bond energy of the N2 molecule.

Ans : D
A lot of energy must be supplied to break the N bonds to form N atoms. Energy is liberated when N-O bonds are formed. Energy absorbed on bond breaking > energy liberated on bond formation. Hence, of nitrogen oxides are highly endothermic.

2.Nitrogen is an unreactive element because i.its enthalpy of atomisation is high ii.its bond energy is high iii.it is a non-polar molecule

Ans: all correct.

3.Oxides of nitrogen are produced by the reaction between i.nitrogen and oxygen in internal combustion engines. ii.nitrogen and oxygen during lightning. iii.ammonia and oxygen in the presence of heated platinum metal

Ans: all correct

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