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Nitrogen Group

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Nitrogen (N2)
Rutherford discovered it (75 %, by weight by 80 % by vol.) At no Configuration

N2 is the first element of GR- 15 in the 2nd period .

Differences
N2 is a gas, while all the other elements are solids N2 ism diatomic, others are tetra atomic, P 4 As4 N2 does not exhibit allotropy (solid N 2 exhibits allotropy), while others exhibit allotropy. N2 occurs in free state in nature, others do not. N2 exhibits a number of oxidation states e.g exhibit such a no. of oxidation states. Due to absence of d orbital N 2 cannot expand its octet hence its valency is 3, while others members expect Bi, from trid pent valent compounds.Bi is always trivalent because of inert pair effect. Hydride of N2 (NH3) is stable and not poisonous , while those of other elements become less stable and poisonous. Due to the small size and high electronegativity of N 2 , NH3 molecules get associated with each other due to the formation of H2 bond in between them for which b.p of NH 3 is very high. NCl3 is very unstable while other trichlorides are progressively stable. Pentachloride of N 2 does not exist but P,As, Sb form. N2 does not form sulphide compound , whereas all others form. All the elements in +3 state are good electron pair donor , valence shell act as electron pair acceptor. exhibits this property to the maximum extent,but due to the absence of d orbital in their , in others do not

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Nitrogen Group

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The catenation property is most pronounced in N . N choices of 8 atoms are known.For others catenation of only 2 members are known.4 P atoms are self linked in molecule.B.E shows that C-C bonds > N-N > P-P bonds in stability. most electronegative element, is an inert element. being very strong b.l = 109.4 .It requires a high energy In spite of being the The bond present in to split

molecule to form active N atom because of bond in other molecules,

they are reactive as they require lesser energy. N2 cannot form pentahalides as it does not have d orbitals. So it C.N is S & cannot be increased

Preparation of

From Ammonium Nitrite Ammonium nitrite is very unstable, its thermal decomposition may take place with explosion. So, a conc-solution of NaNo 2 and NH4Cl is gently hated to form NH 4NO2 which then decompose to give N2 and H2O. (unstable)

Purification Cl2 passing through a conc. Solution of NaOH. conc H2SO4 solution Red not tube containing Cu. Pure N2 over Hg. NH3 and H2O Oxide of N2 2NO+2Cu

From ammonium dichromate

red crystals used. By oxidation of NH3

violent reaction green residue. is

The reaction may be controlled if a conc solution containing

N2 is obtained when NH3 must be used to prevent the formation of highly explosive NCl3 or NBr 3.

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Nitrogen Group

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(excess) yellow oily explosive liquid. From Ammonia Reaction between ammonia and Cupric acid When NH3 is passed over red hot cupric oxide, -3 +2(black) dull red

From HNO 3 When HNO3 vapour is passed over red red hot Cu From oxides of N 2 N2O, NO etc. on being passed over heated Cu, are reduced to N 2. (heated) From zides By the thermal decomposition of Barium or sodium a zide. Thermal decomposition of NaN3 is used to inflate the air bags used as safety devices in some areas.

From urea: Urea on treatment with alkaline sodium hypobronite evolves N 2. is obtained from air is slightly heavier than obtained in the laboratory because it contains small amount of CO2, water vapour and inert gases like He, Ne, Ar, Kr, Xe which cannot be removed because of their chemical inertness ( the noble ones).

Properties of N 2
Physical Properties: N2 is a colourless, odourless and tasteless gas It is slightly heavier than air and almost insoluble in water.

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Nitrogen Group Non-poisonous but does not support respiration

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Can be liquefied to a colourless liquid which freezes to a white solid Chemical Properties The N2 triple bond (1

b.p

is a very strong and stable bond. Although N 2

molecule contains 2 lps they are firmly bound to the nucleus (sp hybrid character) and so they are not available for protonation. N2 is incombustible and a non-supporter of combustion. Action On Metals: N2 does not react with metals at ordinary temperature, but react with heated metals like Ca, Mg, Al to produce the respective metallic nitrides. These nitrides react with boiling water to produce NH 3 and metallic hydroxides.

NH3 Commercial preparation of N 2 By liquifaction of air and its subsequent fractional distillation.N 2 (b.p = 77 K) distils over first leaving behind O2 (b.p = 90 k). It contains some noble gases and little O 2 Action on non-metals With H : At above 550 , pressure of 200 atm. In presence of Fe and Mo promoter; With O2: At 3000 from NO [Endothermic Reaction] With B and Si : At red hot condition, B and Si combine with N 2 yield the corresponding nitrides Serpeck 2100 Action on calcium carbide Heated CaC2 reacts with N2 at 1100 to yield calcium cyananide and carbon.The commercial name is nitrolim. Used as a mixture of CaC2 and C is brown coloured under the influence of electric spark, N 2 combines with O2 to

chemical fertilizer. Calcium cyananide undergo hydrolysis with super heated system to EDUDIGM 1B Panditya Road, Kolkata 29
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Nitrogen Group

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yield NH3 and calcium carbonate.CaCN 2 is hydrolysed in the soil to urea and ammonium carbonate.

3 atm

Tests for N 2
N2 is a colourless and odourless gas in which a lighted taper is extinguished, but does not turn lime water milky like CO2. A burning Mg ribbon continues to burn in it producing white Mg 3N2. The white residue on treatment with boiling water gives NH 3 which is recognized by its characteristic pungent smell. Active N 2 : When N2 is subjected to the action of electric discharge at low pressure (less than 1 mm) a bright glow ( yellow pink) appears which persists for some time even when the discharge is stopped. This indicates the slow release of energy in the process. This nitrogen is more active than ordinary N 2, known as active N2. It has a short life. Nitrogen fixation: The conversion of free atmospheric nitrogen into useful nitrogenous compound is called fixation of N2. BARKLAND AND EYDE PROCESS 2 NO arc

HABER PROCESS

atm . pressure Fe catalyst Mo promoter EDUDIGM 1B Panditya Road, Kolkata 29

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Nitrogen Group OSTWALD PROCESS

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gauge , 700 SERPECK PROCESS

CYANAMIDE PROCESS

Brown color nitrogen Steam

Hydrides of N 2
Hydrazine 1st step 2nd step Fuming, colorless, poisonous covalent liquid. Decomposes by disproportionation to N 2 and NH3. - (Rashing Process)

Its a weak base and powerful reducing agent.

Hydrazoic acid: (N 3 H)

(Linear) Colorless, lightly poisonous and dangerously explosive liquid. It is a weak acid. It dissolves may metals with the formation of azides.N 3 is isoelectronic with CO2 (16 electrons).

Ammonia NH3

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Nitrogen Group

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Preparation

NH3 is not collected over water because it is highly soluble in it. Abo ut 1 volume of water at ordinary temperature and pressure dissolves 1200 volumes of NH 3 NH3 is alkaline in nature and so it reacts with acid or acidic oxide with the formation of salt. Thus, NH3 reacts with conc. H2SO4 to produce ammonium sulphate.

(addition compound ) Quick lime is a base. So, NH3 does not react with it and so it is conveniently dried by it (CaO) By heating ammonium salts with strong base or alkaline:

At room temperature liquor ammonia is reacted with solid NaOH to get NH 3 By hydrolysis of metallic nitrides: Ca3N3, Mg3N2, AlN on being treated with boiling water give NH 3. By the reduction of metallic nitrates or nitrites: Metallic nitrates or nitrites are reduced to NH 3 by heating with metallic Zn dust or Al powder and conc KOH or NaOH solution.

NH3 has high m.p, b.p, heats of vaporization, fusion because of hydrogen bonding with itself and with H2O. By the reduction of NO or NO2:

Pt. cat By the thermal decomposition of ammonium salts: EDUDIGM 1B Panditya Road, Kolkata 29
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Nitrogen Group

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( rev. of drying reaction)

Properties of Ammonia
Physical Properties: Colourless gas with a pungent smell. Lighter than air. Highly soluble in water Liquefies when cooled under pressure to a colourless liquid boiling at 33.4 Converted to ice like solid at Chemical Properties: Basic nature: Turns red litmus blue; forms salts with acids. It gives dense white fumes when it comes in contact with HCl. Formation of a solid product because of interaction of 2 gases. (g) (g) ions and

Its aq. Solution is known as ammonium hydroxide which ionizes as

Action on O2: (a) NH3 does not support combustion but burns in an atmosphere of O2 with a yellow flame. NH3 is oxidized by O2 to produce N2.

Osturlls process:

Gauge 700 Action on Cl2: (a) Excess of NH3 is oxidized by Cl2 to produce N2 and HCl. HCl further reacts to form NH4Cl

Action on Halogens:

(nitrogen trioxide ammonate) EDUDIGM 1B Panditya Road, Kolkata 29


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Nitrogen Group With excessive Cl2, NH3 is oxidized to NCl3, a yellow oily explosive liquid. Bleaching powder oxidizes NH 3 to N2. (Dry state)

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Action on metals when NH3 is passed over heated alkali metals like Na or K at about 360 amides are formed with the evolution of H 2. 2 (proves that NH3 has H2)

Amides on treatment with water are decomposed to give NH 3 and hydroxides.

(Potassamide) Reducing property: not at ordinary temperature, but at elevated temperatures. [Proves NH3 has N2] (red hot) Action on CO2: (a) Aq. Solution of NH 3 reacts with a CO2 yielding ammonium carbonate. gives the smell of NH3 At 200 , 150 atm. Pressure, NH 3 reacts with CO2 to give urea:

Atm pressure Ammonium carbonate Urea Action on metal salts: Aq. solution of NH3 (ammonium hydroxide) reacts with solutions of ferric salts, aluminium salts to produce the respective hydroxides.

(Reddish brown ppt.)

Formation of complex salts: NH 3 reacts with some metallic salts producing soluble complexes because it can coordinate with other atoms or cations which need electron pair for their stability ( N has a lone pair of electrons).

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Nitrogen Group

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With Cu salts : When NH4OH is gradually added to CuSO4 solution, a bluish white ppt. of basic CuSO4 is first obtained which dissolves on addition of excess of NH 4OH to form a deep blue solution of complex copper tetra amine sulphate.

(Bluish white ppt.) (Deep blue solution of complex copper tetra amine sulphate) With Ag salt: (i) on being treated with NH 4OH at first a white ppt. of AgOH is formed which is quickly converted to brown silver oxide. On addition of excess of NH4OH, the Ag2O dissolves to give a clear solution of complex argento ammonium hydroxide ( white ppt) (Brown) (Mercuriammine chloride) When excess of NH4OH is added to AgCl (in water) it dissolves to give a clear solution of complex argento ammonium chloride. Aq. Solution of Zn salts react with NH 4OH to produce a white ppt. of Zn(OH) 2 which dissolves in excess of NH 4OH to give a clear solution of zinc- amino hydroxide. (white) Formation of addition compounds Anhydrous CaCl2, ZnCl2 etc. absorb NH3 producing addition products.

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Nitrogen Group

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Action on Nesslers reagent: NH 3 when comes in contact with Nesslers reagent gives a brown ppt. (brown ppt) (Iodide of millions base) Aq. solution of NH3 on being treated with KMnO4 gives off N2

Tests For NH 3
It has a characteristic pungent smell. Dense white fumes of NH 4Cl when a drop of conc. HCl yellow orange is added to NH3 gas. NH3 on contact with Nesslers reagent gives a brown ppt. Turns moist turmeric paper brown. Reaction with CuSO4 Yellow ppt. with chloropatinic acid. Ammonium chloropitanate Nesslers Reagent (i) KI solution when added to an aqueous solution of mercuric chloride, a red ppt. of mercuric iodide is formed. On addition of excess KI solution, this red ppt. dissolves to produce a complex potassium mercuro iodide. When excess of KOH is added to this complex, Nesslers reagent is produced.

Nesslers reagent= Nesslers reagent is best obtained by adding excess KI so lution to an aqueous solution (suspension) of mercuric oxide. The resulting solution is alkaline.

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Nitrogen Group

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Some conversions
(1) N2 is passed over strongly heated Mg when Mg 3N2 is produced as white residue. Mg 3N2 is treated with boiling water (strongly heated) to give off NH3.

(2)

: is passed over strongly heated CuO (black) when CuO is reduced to dull red is oxidized to N2

coloured Cu and to Urea:

Liquid

is made to react under

with liquid CO2 at 200 of a trace of moisture in an autoclave to obtain urea. Two step reaction

150 atm. Pressure in presence

(4)Ammonia to NO.

when NH3 is oxidised

A mixture of NH3 and O2 is quickly passed over pt. gauge at 700

NO is further oxidized to yield brown ( reddish) of NO 2

(5) At first HNO3 is treated with NaOH to produce NaNO3. Then a mixture of NaNO3 and zn powder is treated with hot and conc. solution of NaOH when NaNO 3 undergoes redn to NH3.

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Nitrogen Group (6)

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When NH3 and CO2 are passed through finely powdered gyscum suspended in water, are formed. Insoluble is sep. by filtration, filtrate aq. Solution of (NH4)2 SO4 . by this process (NH4)2 SO4 is produced from NH3 without H2SO4 on being heated with strong alkali or base like NaOH, yields NH3.

Large Scale Preparation of NH 3 pressure ( 200 atm) and at 500

Habers Process

Principle: large scale prep. of NH3 is carried out by direct union of N2 and H2 at high in presence of a catalyst.

Physic Chemical Conditions Reqd. For Satisfactory Yield: The reaction is (a) reversible, (b) forward reaction is endothermic (c) formation of NH3 is accompanied by a decrease in volume. Effect of temp: forward exdothermic, Reverse endothermic According to L.C. Principle, if the reaction is carried out at high temp the reaction will proceed in a direction where the excess heat is absorbed. As the backward reaction is endothermic, the high temp will favour the backward reaction. So, yield of NH3 will be poor. If the reaction is carried out at low temp the reaction will proceed in s direction where the loss of heat is recovered .So, lowering of temperature will favour the forward reaction, but it decreases the rate of reaction to a great extent attain. The optimum temperature carried out at 550 takes longer period to ( good yield+ proper time)

Effect of pressure: As the forward reaction. is accompanied with a decrease in volume, high pressure will favour the forward reaction . So, a pressure of 200 atm is applied. Influence of catalyst: To increase the rate of reaction and reaction equilibrium quickly, reduced Fe powder is used at catalyst and Mo as promoter. At present as promoters. Concentration: By decreasing the conc. of NH 3, by removing the produced NH 3 quickly from the reaction chamber.

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Nitrogen Group

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The catalyst is very susceptible to poisoning, the gas mixture must be freed from impurities like P, S, As dust particles etc. NH3 is a weaker reducing agent than PH3: The size of the P-atom is larger than N-atom it is expected that P-H bond distance is >than N-H b.d and B.E. So, B.E of N.H>B.E of P-H. So, P-H bond requires lesser heat energy to break-up to give off nascent H than N-H bond. Thus, CuO is reduced by NH3 at 350 is reduced by PH3 at room temp. NH3 is alkaline in nature: Exp: to Lewis theory, a base is that which is capable of donating a lp of electrons to proton. In NH 3, the H-atoms are bonded to a N-atom which has an unshared pair of electrons with opp. Spin. As N is a strong electronegative element, the bonded pairs are attracted more towards the N-nucleus, thereby increasing the electron density around center N-atom. Thus the lp suffers a force of repulsion and is easily available for protonation. Thus NH3 exhibits alkaline property.

Ammonia as solvent: Just like water NH3 undergoes self ionization in liq. State and is used as solvent for dissolving many polar compounds and also for carrying out many reactions in non-aqueous medium.

Oxides of Nitrogen
N2 forms the largest number of oxides as it is capable of forming stable multiple bonds with O2. Nitrous Oxide or Laughing Gas: N2 O: Priestly 1772 Preparation: (a) N2O is prepared by heating NH 4NO3. The reaction is exothermic, NH4NO3 decomposes below 200 the reaction becomes so vigorous that explosion may take place. So, a mixture of (NH 4)SO2 and NaNO3 is heated.

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Nitrogen Group

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Purification: (i) NO2 (ii) NO

caustic soda ( NaoH) soln. FeSO4 solution. . Pure and dry N2O is collected over

(iii) NH3 & H2O Hg.

(b)By action of dil.HNO3 on Cu or Zn : cold and dilute. HNO3 on Cu or Zn (a) By the reduction of HNO3 : Stannous chloride acidified with HCl.

(b) By reduction of NO by SO2:

Properties: (a) Physical Properties: (i) N2O is a colourless gas having a faint sweet smell. (ii) times heavier than air (iii) Fairly soluble in cold water, more in alcohol (iv) Inhalation causes excitement accompanied by laughter (b) Chemical Properties: N2O is a neutral oxide, does not change the colour of litmus. Decomposition: Stable at ordinary temp. but at 500 into N2 and O2., complete at 900 Combustibility: N2O is not combustible, but a strong supporter of combustion. A glowing chip of wood burns brilliantly in this gas. Due to the thermal decomposition N2O splits to give off nascent oxygen which supports combustion. Pieces of Charcoal , S,P burn more vigorously in N 2O with the formation of N 2 and the oxides of the corresponding non-metals. begins to decompose laughing gas.

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Heated Fe, Cu burn in the gas to from their oxides and N 2.

Heated Na or K burn in this gas brightly producing N 2 and metallic perioxides.

With NH3: N2O reacts with NH3 with explosion producing N 2 and water .

Tests: (i) N2O rekindles a glowing chip of wood but does not produce brown fumes when comes in contact with O2. It is absorbed in alcohol but not in alkaline pyrogallate solution. Used as a mild anesthetic, propellent in whipped cream bombs. Structure: N2O is a linear molecule and a resonance hybrid of two structures.The N-N and N-O b.l are moment. It is iso electronic with CO2 has a small dipole

Nitrous Oxide ( N 2 O) (i) Colourless gas having a faint sweet smell, neutral oxide.

Oxygen (O 2 ) (i) (ii) Colourless and odourless gas. Supporter of combustion.

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Nitrogen Group (ii) (iii) Supporter of combustion. Does not produce brown fumes of NO2 in contact with NO. (iv) (v) It is absorbed in alcohol. Causes hysteric laughter and used as an ananthesia. (iv) (iii)

Page 17 Produce brown fumes of NO2 in contact with NO. 2NO+O2= 2NO2 Absorbed in alkaline pyrogallate solution and in ammonical cuprous chloride solution turning them brown and blue. (v) Supporter of combustion. when N2O is

A glowing chip of wood burns more brilliantly in N 2O than in O2 subjected to heat, it decomposes at lower temperature (500

to produce N2 and

nascent O2 . N2O = N2 + This nascent O2 is given off by N2O supports combustion. But molecular O2 splits up to give off nascent O2 at higher temp. An element is more active in nascent state than in molecular state. So.. In case of feebly burning and temperature is not high enough to decompose .N 2O and thus burning ans extinguishing in N 2O ( Different from O2, where it does not extinguish). Oxidising property : Reducing property : Nitric Oxide (NO)

Preparation : (1) NO is prepared by the action of moderately strong (1 : 1) HNO 3 an Cu turnings at ordinary temp.

Purification: NO contains N2 and oxides of N2. The gas is passed through a cold and freshly prepared FeSO4 solution when NO is absorbed yielding a dark brown solution of nitrosoferrous sulphate which on heating gives off pure NO. (2) By the reduction of KNO3 by acidified FeSO4 solution:

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(3) By catalytic oxidation of NH 3- NO is obtained by passing a mixture of NH 3 ( 1 vol) and air ( 8 vol) over pt.gauge at 700 Properties Physical Properties(1) NO is a colourless gas slightly heavier than air. (2) Almost insoluble in water. Chemical Properties1. NO is a neutral oxide. Cannot change colour of litmus. 2. Decomposition- It is one of the most stable oxide of NO2. It decomposes at about 1000 producing N2 and O2.

3. Supporter of combustion- Due its decomposition at high temp. vigorously burning P,S,Mg,C continue to burn in NO producing their corresponding oxides. The O2 liberated during the decomposition of NO at high temp, helps in combustion. 4P + 10 NO = 2 P2O5+ 5N2 2Mg+2NO=2MgO+N 2 , (But N2O does not, E-concept) 4. Oxidising Property: No acts as an oxidizing agent, itself being reduced to N 2, NH3 or N2O. (i) A mixture of NO and H2 on being passed over heated Pt-black, NO is reduced to NH3 and H2 is oxidized to H2O. 2NO+5H2= 2NH3+2H2O. (ii) When NO is passed over heated Na, K, Cu, Fe etc, the metals are oxidized to the corresponding oxides. 2Cu+2NO=2CuO+N2 , 4Na+2NO= 2Na 2O+N2 With N2O CO. 2CS2+10NO= 2 CO+4SO2+5N2. 5. Reducing Property: NO reduces acidified pink solution of KMNO4 to a colourless Manganous salt. Na2O2. (iii) A mixture of CS2 vapour and NO burns with a blue flame and CS 2 is oxidized to , C+2NO= CO2+N2 S+2NO = SO2+N2

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6. Formation of Addition Compounds- (i) NO is absorbed by cold and freshly prepared FeSO4 solution forming dark brown nitroferrous sulphate.

No combines with Cl2 in presence of charcoal catalyst to yield Nocl.

Tests for NO (i) No produces brown fumes of NO2 as soon as it comes in contact with O2. 2NO+O2= 2NO2 nitroso ferrous sulphate. FeSO4+NO= Fe(NO)SO4. Structure : NO molecular has 11 valence electrons, 5 due to N atom and 6 due to O atom. No contains and odd electron N- O b.d is the whole molecule. paragmetic. which lies between = and bond. As the gasoues No (brown fumes) (ii) It is absorbed in cold ferrous sulphate solution producing dark brown s olution of

donot exhibit tendency for dimerisation, it suggests that the odd electron is spread over

2HNO3 + NO This reaction explains why metals like Cu, Hg etc give nitric oxide with dil but NO2 with conc. HNO3. In case of dil HNO3 (i.e. when sufficient water is present), the reaction goes backwards giving NO2 while in case of conc. HNO3 the reaction proceeds in the forward direction giving NO 2. Hence at an intermediate conc. of HNO3 (5 N), both NO and NO2are produced with Cu. Conversion of NO N2O 2NO + H2O+2Fe N2O + Fe(OH) 2 N2O3 Nitrogen sesquioxide N + 3 state. NO+H2SO3 H2SO4 + N2O Dinitrogen trioxide (a) Preparation-

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N2O3 is prepared by distilling 60% HNO3 with equal amount of arsenous oxide or starch. HNO3is reduced by As 2O3 or starch to nitrogen sequionide. The red vapours of N 2O3 coming out of the flask are condensed to a deep blue liquid in a receiver kept in a freezing mixture. (1) (2)

(3) (b) Properties (i) N2O is very unstable at ordinary temp. 90% of it is decomposed to give NO and NO2. In the vapour state it is an equimotor mixture of NO and NO 2.

(ii) N2O3 is called the anhydride of nitrous acid because it dissolves in water forming HNO2.

(iii)When treated with alkali solution it produces alkali nitrates N2O3+KOH= 2KNO2+H2O. Thus , N2O3 is referred as anhydride of nitrous acid. Nitrogen Dioxide N Preparation (1) By heating Pb (NO3)2. Dinitrogen tetroxide [

This oxide is also called mixed acid anhydride as it gives both nitrous

acid and nitric acid when treated with water.

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NO2 comes out as brown fumes along with O2. The evolved gas mixture passes through the U-tube where NO2 condenses as a yellow liquid and O2 passes out. (2) From NO- At ordinary temp. NO combines with O2 to yield NO2. Large scale prep. Of NO2. (3) from HNO3- (a) Conc. HNO3 is thermally decomposed to give off NO2 when it is allowed to drop on red hot pumice stone. 4HNO3= 4NO2+2H2O+O2 (b) Conc. HNO3 is reduced by Cu or zn to produce NO2. Properties: (A) Physical Properties (i) At ordinary temp. it is a reddish brown gas having suffocating odour. (ii) it gradually fades at temp. falls.

(i)

NO2 is soluble in water, (iv)Poisonous, (v) Heavier than air.

(B) Chemical Properties(1) NO2 is an acidic oxide (a) When it is dissolved in cold water, a mixture of nitric and nitrous acid is obtained i.e. why NO2 is called a anhydride of nitrous and nitric acid.

(b) With hot water it produces HNO3 with NO. 3NO2+H2O= 2HNO3+NO (c) It is acidic towards litmus. With NaoH or KoH solution , it forms nitrite and nitrate salts. EDUDIGM 1B Panditya Road, Kolkata 29
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Nitrogen Group 2KoH+2NO2= KNO3+KNO2+H2O (2) NO2 is neither combustible nor a supporter of combustion.

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A burning chip of wood is extinguished in NO 2. But vig. Burning carbon, P,S,Mg etc continue to burn more vigorously in it and are oxidized to form their respective oxides, because at high temp.NO2 decomposes to give N 2 and O2. 2P4+No 2 = 4 P2O5, 2S+2NO2=2SO2+N2

4Mg+2NO2 = 4 MgO+N2, 2C+2NO2=2CO2+N2 Warmed Na or k inflames spontaneously in NO 2 to form nitrates. K+2NO2=KNO3+NO , Na+2NO2 = NaNO3+NO

Oxidizing property- NO2 has a remarkable oxidizing property. (i) (ii) It can oxidize Ki soln. into free I2 which turns starch soln. blue.

(iii)

(iv)

When NO2 is passed over strongly heated Cu, the latter is oxidized to black cupric oxide.

In liquid state N2O4 tends to ionize as , find, use as a non-aqueous solvent.

(Lewis acid base) and thus

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Nitrogen Group Tests for NO 2 : (i) (ii) (iii)

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NO2 is identified by its suffocating odour and brown colour. It gives a colourless soln. with water and the aq. Soln turns blue litmus red. Insoluble in CS2 or CCl4. Used as a rocked fuel and in HNO3 production.

Distinctions between NO2 and Br2- NO2 and Br2 vapours are both reddish brown in colour having suffocating smell. (i) (ii) NO2 dissolves in H2O forming a colourless solution containing HNO 2 and HNO3, while Br 2 vapour dissolve in water forming red coloured Br 2 water. NO2 does not dissolve in CCl4 or CS2 but Br2 readily dissolves in these solvents producing a red colored solution. Structure:- NO2 is a v-shaped molecule having O-N-O B.A = 132 and N-O b.d= 1.19.NO2 is an odd molecule. This structure shows that it has an unpaired electron and hence paramagnetic .Consequently, it has a tendency to dimerse to colourless N 2O4 molecule which is planar more stable than twisted one. N-N b.d = . N2O4 is diamagnetic. Longer than usual N-N bond length (1.47 cause repulsion. Solid N 2O5 is ionic. because of +3 charges on atoms which

Dintrogen pentaoxide : (N 2 O 5 ) N Preparatio n

oxidation state.

N2O5 is prep. By gently heating conc. HNO3 and P2O5 when HNO3 is dehydrated by P2O5 to form N2O5. The vapours of N2O5 are condensed in ice cold receiver as colourless shining crystals. 2HNO3+P2O5= N2O5+2HPO3

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Properties (1) In solid state it is a colourless shining crystal which melts at 30 (2)Unstable , tendency to decompose to N 2O4 and O2. (3)Acts vigorously with H2O It is called anhydride of from 2 HNO3 molecules. as this oxide is produced by extracting 1 H2O molecule

(4) It has oxidizing property. Oxidises I 2 to I2O5. I2+5N2O5=I2O5+10NO2 It is called nitronium nitrate pentroride consists of nitronium (NO 2+) and nitrate (NO3-) ion. Properties (1) Physical state (2) Odour N2O Colourless gas Faint pleasant to causes hysteric smell. (3) V D 22,1 times heavier than air. (4) Solubility Fairly soluble in (5) Nature cold water. Neutral oxide. Almost insoluble in water. Neutral oxide. Acidic oxide. (6) Action on alkali Does not react No reason. Reacts to form Highly soluble in water. NO Colourless gas Not possible to smell because it forms NO2 with O2. 15, heavier than air. 23,1.6 times heavier than air. Suffocating smell. NO 2 Reddish brown gas

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Nitrogen Group (7) Combustibility with alkali. Noncombustible but (8) Oxidizing a supporter of combustion. Noncombustible supports combustion of burning P,S Mg (9) Action on O 2. Has oxidation properties. (10)Reduction No action. O2 produces brown fumes in contact with it. (11)Absorbants Redn by hot metals like Cu, Mg to N2. (12)Physiological action. Absorbed by alcohol. Poisonous laughing gas By freshly prepared FeSO4 soln. Poisonous. Poisonous. Redn by hot metals like Cu, Mg to N2. Redn by hot No action. etc. Has oxidation properties. Noncumbustible supports nitrate and nitrite salts.

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combustion of burning P,S,Mg etc. Has oxidation properties.

metals like Cu, Mg to N2. By KOH or NaOH soln.

The oxides of N2 (except to N2O5) are endothermic as a large amount of energy is reqd. to dissociate the stable molecules.The small electronegativity diff. betn N and O makes it easily breakable to give O2 and hence oxides of N 2 are good oxidizing agents. Incept N2O5 , all others are gases at ordinary temp Oxyacids of N2-(i) Nitrous acid, (ii) Nitric acid (i) Nitric acid-HNO2- (H.W=47, Eq,wt=47) (a)Preparation (1) By the action of ice cold soln. of (1)Ba(NO 2)2 (nitrite),(2)NaNO2 , (3) KNO2 on dil H2SO4.

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Nitrogen Group

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(2) N2O3 on treatment with ice cold water yields HNO2. N2O3+H2O=2HNO2 NH3+3H2O2=HNO2+4H2O. Properties-(1) HNO3 is very unstable even at ordinary temp.It decomposes to HNO 3 and NO.

At high temp, it decomposes to NO2 and NO. 2HNO2=NO2+NO+H2O. (2) Acid Property-Its is a weak monobasic acid. Turns blue litmus red . Reacts with alkalis ti from nitrite salts. NaOH+HNO2=NaNO2+H2O. Metallic Cu or Ag slowly dissolves in HNO2 forming the corresponding nitrites. Cu+4HNO2=Cu(NO2)2+2NO+2H2O. Ag+2HNO2=AgNO2+NO+H2O. (3)Oxidizing property- (a) HNO2 oxidises acidified KI soln to fre I 2 , thus turns the clear solution brown. SNCl2+2HNO2+2HCl=SnCl4+2NO+2H2O. (c) SO2 is oxidized to H2SO4. 2HNO3+SO2=H2SO4+2NO Acidified features salts are oxidized to yellow coloured ferric salts. 2FeSO4+2HNO2+H2SO4=Fe(SO4)3+2NO+2H2O (4)Reducing Property:HNO2 possess reducing property also, as it is capable of being oxidized to HNO3 by accepting an O-atom from other substances. (a)It reduces red coloured Br 2 water to colourles HBr. (b)When Cl2 is passed through HNO2, it is reduced to HCl. EDUDIGM 1B Panditya Road, Kolkata 29
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(b) Acidified stannous salts are oxidized to stanmic salts.

Nitrogen Group Cl2+HNO2+H2O=2HCl+HNO3 2HNO2+H2SO4 (c)H2O2 is reduced to water.

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(d)HNO2 decolourises the violet colour of acidified KMnO 4 to colourless manganous salts. 2KMnO4+5HNO2+3H2SO4=K2SO4+2MnSO4+5HNO3+3H2O. (e)HNO2 reacts with NH3 or ammonium salts or organic compounds containing NH2 group with the evolution of N 2.

HNO2 possess both oxidizing and reducing properties-why-

So,it scope to either increase or decrease its oxidation no.

Tests for HNO2- (i) When HNO2 acidfied KI soln are reacted,clear siln of KI turns brown due to the liberation of free I 2. The liberated I2 may be identified by the formation of deep blue colour on its treatment with starch soln.

(II) HNO2 decolourises the pink colour of acidified soln of KMnO 4.

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Nitrogen Group 2KMnO4+5HNO2+3H2SO4=K2SO4+2MnSO4+5HNO3+3H2O. (iii)Brown fumes are evolved when HNO2 is heated. 2HNO2=H2O+NO2+NO Structure

Page 28

It has a slight bluish colour in soln. which is believed to be due to anhydride, N 2O5. (b) Nitric Acid- HNO3- Mol.wt= 63, Eq,wt= 63 Aqua fortis because it attacks nearly all metals. (a)Preparation (1)HNO3 is far more volatile than H 2SO4 .By heating KNO3 or NaNO3 with conc. H2SO4 , the reaction takes place in 2 steps. 1st step-KNO3+H2SO4 2nd step- KNO3+KHSO4 Purification HNO3 contains moisture and dissolved NO2. It is distilled with conc.H2SO4 at low pressure when H 2O removed. Air is then bubbled at 70 through the acid till it becomes colourles.The dissolved NO 2 is thus removed from the acid.The product thus obtained is 98% pure. Pure HNO 3 may be obtained as colourless crystals on cooling the 98% acid to -42 HNO3 obtained in the lab is slightly yellowish: Due to the presence of dissolved NO 2 in it which comes from the thermal decomposition of the produced HNO 3. 4HNO3=2H2O+4NO2+O2 HCl is not used in the prep. of HNO3 The b.p of H2SO4 (338 of HNO3 (86 easier to expel the more volatile HNO3 from a nitrate. HCl is more volatile than HNO3 .When HCl is heated with a nitrate, most of HCl distill along with some HNO3 vapour and are collected in the receiver. The produced HNO 3 reacts with HCl yielding nitrosyl chloride with Cl2. 3HCl+HNO3=NoCl+Cl2+2H2O The temp. is not allowed to exceed 200 because EDUDIGM 1B Panditya Road, Kolkata 29
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strong water,

KHSO4+HNO3

is much higher than that

.Thus, conc.H2SO4 is much less volatile than HNO3.Consequuently , it is

, the produce KHSO4 reacts with the

unreacted with KNO3 producing more HNO3, but temp is not allowed to exceed 200

Nitrogen Group The HNO3 produced thermally decomposes at this high temp. to NO 2 and O2. 4HNO3=2H2O+4NO2+O2 The KHSO4 produced remains in the molten state at 200 the retort and cannot be removed . At higher temp. HNO3 vapour attacks the material of the glass retort.

Page 29

and 80 can be easily

removed, but at high temp.,KHSO4 remains in the solid state and sticks to the walls of

Fuming HNO3-It is produced by distilling conc. HNO3 with a little starch. Some of the acid id reduced by starch to NO2 and N2O3 which dissolve in the remainining HNO3 to form fuming HNO3. Due to the presence of dissolved oxides of N 2 (NO2 and N2O3) it colour becomes yellow.Fuming HNO3 is more powerful oxidizing and nitrating agent than conc. HNO3.Fuming HNO3 (98% HNO3,sp.gr=1.51) Properties (a)Physical- (i) Pure HNO3 is a colourless fuming liquid with a suffocating smell. It boils at 86 and freezes at -42 .It is highly soluble in water. . Dil.HNO3 (50-60%) is conc. distillation till it forms constant boiling mixture(121 (b)Chemical-This is conc.HNO3 (68% in strength and 1.414 sp.gr) (1)Action on heat-HNO3 is completely decomposed on heating yielding O 2, steam and NO2. 4HNO3=4NO2+2H2O+O2 HNO3 has a corrosion action on skin and produces painful blisters. Even in sunlight , HNO3 is decomposed to give NO2 which dissolve in the acid to give it a yellow colour. (2) Acid property-HNO3 is a strong monobasic acid.It ionizes completely to nitrate ions (NO3-) and hydrogen (hydroxonium) ion. (a)It reacts with basic oxides and hydroxides producing nitrate salts and water.

Reacts with metallic carbonates or bicarbonates nitrates and liberating CO 2. Na2+2HNO3=2NaNO3+CO2+H2O CuCO3+2HNO3=Cu(NO3)2+CO2+H2O NaHCO3+HNO3=NaNO3+CO2+H2O. EDUDIGM 1B Panditya Road, Kolkata 29

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(b) Very dilute HNO3 reacts with Mg and Mn in cold yielding nitrates and H 2. Mg+2HNO3=Mg(NO3)2+H2 The metals which are above H 2 in the electrochemical series (Zn,Fe etc) fail to liberate H2, because though HNO3 liberates H2 due to its acid property when reacted with metals, but the liberated H2 is oxidized to H2O due to the oxidizing property of HNO

(3) Oxidising property-Nitric acid is a strong oxidizing agent.It decomposes easily to give oxides of N2 liberating nascent, oxygen.This liberated nascent oxygen oxidizes metals, non-metals and various compounds. concept] (1) Oxidation of non-metals-Most of the non-metals when (NO2 mainly) heated with HNO3 are oxidized to oxides or oxyacids. (i) C+4HNO3=CO2+2NO2+2H2O Si+4HNO3=SiO2+2NO2+2H2O. (ii) P is oxidized by hot and conc. HNO3 to H3P3, NO and NO2. 4P+10HNO3+H2O=4H3PO4+5NO+5NO2 (iii) I2 is oxidized to iodic acid by hot and conc. HNO 3 I2+10HNO3=2H703+10NO2+4H2O. As (i) Hot and conc. HNO3 oxidises S to H2SO4 has no reducing power [oxidation. No

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Sb (2) Oxidation of inorganic compounds-Moderately conc. HNO3 or even hot and dilute HNO3 oxidises many inorganic compounds. (i) HBr and HI are oxidized to Br 2 and I2, HNO3

(ii) 6KBr+8HNO3=6KNO3+3Br 2+2NO+4H2O. 6KI+8HNO3=6KNO3+3I2+2NO+4H2O. (iii)SO2 is oxidized to H2SO4 by conc. HNO3 with the evolution of brown fumes of NO2. SO2+2HNO3= H2SO4+2NO2 (iv)H2S is oxidized to free S ( yellow ppt)

Further reactionH2S+ = H2SO4+8NO2+4H2O

(v) An acidified colourless soln. of ferrous sulphate is oxidized to give a yellow solution of ferric sulpahte.

(i)

Oxidation of metals-HNO3 in its reaction with metals plays a double role 1.an acid 2.an oxidizing agent.

The nature of products obtained by the action of metals with HNO 3 depends upon(i) Conc. of the solid
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Nitrogen Group (ii) (iii) (iv) Temp of the reaction Electrochemical nature of the metals Products of the reaction.

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Note- (i) Noble metals like Au,Pt do not react with HNO3. (ii) Metals like Fe,Cr,Ni do not react with conc. HNO 3 as they are rendered passive by it. (iii)Mg and Mn can liberate H 2 from very dil.HNO3 (cold) (iv)Al is scarcely attached by HNO3. (v)Sn and Sb are converted to their respective oxides by HNO 3. (a) Action on metals which are above H 2 in the E.C.S(1) Action on Zinc(a) Hot and conc. HNO3- Zn+4HNO3=Zn(NO3)2+2NO2+2H2O. (b) Cold and mod. Strong (1: 1)-3 Zn+8HNO3=3Zn(NO3)2+2NO2+4H2O (c)Cold and dilute HNO3- 4Zn+10HNO3=4Zn(NO3)2+ N2O+5H2O (d) Cold and very dilute HNO3- 4Zn+10HNO3=4Zn(NO3)2+NH4NO3+3H2O (2) Action on Magnesium(a) Cold and moderately strong (1:1)3Mg+8HNO3=3Mg(NO3)2+NO+4H2O (b) Cold and very Mg+2HNO3=Mg(NO3)2+H2 (3) Action on iron(a) Conc. HNO3 or fuming HNO3 does not dissolve Fe but renders it passive. Cr and Ni are also rendered passive similarly.Passive Fe looses its properties like displacing Cu from Cu+2 solution.

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The passivity is due to the formation of an invisible and impermeable thin film of oxide (Fe2O3,Cr2O3) on the surface of the metal which protects it from further reaction. 1. Hot and dilute HNO3Fe+4HNO3=Fe(NO3)2+NO+2H2O. 2. Cold and dilute HNO34Fe+10HNO3=4Fe(NO3)2+NH4NO3+3H2O. 3. Action on Sn4Sn+10HNO3=Sn(NO3)2+NH4NO3+3H2O (a) ( cold and dil) 4. Hot and concSn+4HNO3= H2SnO3+4NO2+H2O (meta stannic acid) (b) Action of metals which are less electropositive than H 2(1) Action on Cu(a) Hot and conc. HNO3Cu+4HNO3=Cu(NO3)2+2NO2+2H2O. (b) Cold and moderately strong HNO33Cu+8HNO3=3Cu(NO3)2+2NO2+2H2O (c)Cold and dilute HNO34Cu+10HNO3=4Cu(NO3)2+N2O +5H2O (c) HNO3 vapours over heated Cu5Cu+2HNO3=5Cu+ N2+ H2O. (4) Aqua Regia-Action on Conc. HCl- When conc. HNO3 is mixed with conc.HCl in 1:3 ratio by volume, HCl is oxidized producing nascent Cl 2, nitric acid being reduced to NoCl. 3HCl+HNO3=NoCl+2Cl+2H2O. EDUDIGM 1B Panditya Road, Kolkata 29
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This mixture of conc. HCl and conc. HNO3 is called aqua regia.It can dissolve noble metals like Au, Pt which are not affected by the acids alone.The liberated nascent Cl 2 attachs these noble metals to form their chloro compounds.(Cl - forms complexes with metal ions) 2Au+6Cl+2HCl=2HAuCl4 ( chloro auric acid) Pt+4Cl+2HCl=H2(P+Cl6) ( chloro platonic acid) Insoluble sulphides of Hg,Co and Ni etc. are dissolved in it. (5) Nitrating property-Organic compounds like alcohols, sugar, terpentine etc. are oxidized by conc. HNO3.These substances burst into flames when HNO 3 Toluene Phenol HNO3 has nitrating property substitution by NO2 groups.

Tests (i) Cu turnings on being heated with conc.HNO 3, brown fumes of NO2 are evolved. (ii) Conc. solution of a nitrate on being heated with powdered Al or Zn and conc. NaOH soln.Liberates NH3 which can be identified by its formation of white fumes in contact with conc.HCl. 4Zn+7NaOH+NaNO3=4Na2ZnO2+NH3+2H2O. 8Al+5NaOH+3NaNO3+2H2O=8NaAlO2+3NH3.

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(iii)Ring test-Equal volumes of HNO3 or an aqueous soln of a nitrate and freshly prepared FeSO4 soln are taken in a test tube and mixed together.After cooling, conc.H2SO4 is poured down slowly from the side of the test tube.As H 2SO4 is heavier, it settles at the bottom of the test-tube with the layer of the mixture above it.A brown ring is formed at the junction of the 2 liquids. I.R studies confirm that No is present as NO+ state not as neutral No . of 3.89 B.M

confirms 3 unpaired electrons as that Fe is in +1 oxidation state.Correct formula Pb(NO3)2 is soluble in water , but while ring test is performed with it, on addition of FeSO4 and H2SO4 to an aq.soln of Pb(NO3)2 a curdy white ppt. of PbSO4 appears ring test not possible.The difficulty may be overcome by adding excess of H 2SO4 to the aq.soln of Pb(NO3)2 for comp. pption of PbSO4 and the ppt. filtered off. Now , the ring test is performed. (iv) Brucine test-When HNO3 or a nitrate is added to a solution of a brucine taken in a porcelain basin and pure H 2SO4 is added to it, a beautiful red colour if formed. Structure of HNO3-

Chemical tests for distinguishing HNO3 from HNO2(i) Nitrous acid comp. decolourises a pink soln of KNnO 4 with the formation of manganous salt. 2KMnO4+5HNO2+3H2SO4=5HNO3+K2SO4+2MnSO4+3H2O. Dilute HNO3 possess no reducing property.

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Nitrogen Group (ii) HNO3 gives brucine test, HNO2 does not. Nitrates Salts of HNO3 are known as nitrates.

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Preparation-Nitrates are prepared by the action of HNO3 on metals, metallic hydroxides or carbonates. Excepting the basic nitrates of Pb and Bi, all other metallic nitrates are soluble in water.Metallic nitrates decompose an heating. (1)Action of heat-(i)Nitrates of alkali metals e.g Na,K on being strongly heated decompose to give metallic nitrates with the evolution of O 2. 2NaNO3=2NaNO2+O2 , 2KNO3=2KNO2+O2. (ii)Nitrates of heavy metals (Pb,Cu,Al,Mg,Fe,Ca) on heating decompose to give metallic oxides , O2 and brown fumes of NO2.

(iii)AgNO3 on being heated to 450

decomposes at first to produce silver nitrite and

O2.On strong heating AgNO2 is further decomposed to metallic Ag,NO and O 2. Nitrites-Salts of HNO 2 . HNO2+NaOH+H2O. As HNO2 is a weak acid, it forms stable nitrite salts with strong bases. HNO2 +Strong bases=Stable nitrite salts water. So, nitrites of alkali metals, alkaline earth metals and Ag are available. Nitrites of tetravalent metals are known. Nitrites are soluble in water. Nitrites are decomposed easily. Alkali nitrites decompose at higher temperature. 3NaNO2=NaNO3+Na2O+2NO

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Nitrogen Group NH4NO2=N2+2H2O.

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Distinction between nitrates and nitrites

Expt

NO 2

NO 3 Brown evolved. fumes are not

1.Dil.HCl or H2SO4 is added. Brown fumes are evolved.

2.Soln. of KI acidified with The soln. turns blue. acetic acid is mixed with starch soln and the mixture is added.

Does not.

3.Brucine and conc. H2SO4 Red colour is not produced. Beautiful are added to the sample. produced.

red

colour

is

4.Soln of KMnO4 acidified Pink colour of KMnO4 is Not discharged. with H2SO4 is added. discharged.

5.The sample is heated with Colourless and odourless Not evolved. urea and dil H2SO4. 6.Ring test. N2 gas is evolved. -ve. +ve

Uses In manufacture of explosives (T.N.T, pioric acid, nitrogly cerine)

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Phosphorous
P, 15,Is2.2s2,2p6,3s2,3p3 , 31, -3,+1,3,+5. Occurrence P is a very active element and so it is not found in free state in nature. Chief minerals(a)Phosphorite[Ca 3(Po 4)2] , (b)Chloroptite(3Ca 3(PO4)2 . CaCl2) (c)Flouraptite[3Ca 3(PO4)2.CaF2] (d)Vivanite[Fe3(PO4)2. 8H2O] Bone ash is the chief source of P (contains about 80% P)

Preparation of White Phosphorus


(a) From bone ash-old retort process(i) Powdered bone ash is mixed with 60% H 2SO4 and the mixture is heated, when insoluble CaSO4 and H3PO4 are produced. Ca3(PO4)2+3H2SO4=3CaSO4 2H3PO4 CaSO4 is removed by filtration and H 3PO4 is obtained as filtrate. (ii)H3PO4 is conc. by heating to a syrupy liquid. (iii)Powdered C is then mixed with this syrup and the mixture is carefully heated to dryness in cast Fe vessels when,

(iv)HPO3 is then reduced by the coke to produce white P. 4HPO3+12C=P4+12CO+2H2O condense as a dark brown mass. (b)Modern electro -thermal process-Parker-Robinson-Readmann Process.

P2O5 is more acidic than SiO2 , but at high temp, silica replaces the more acidic P 2O5 from Ca3(PO4)2:The reaction is more reversible and by the forward reaction is produced. is

an acidic oxide and is volatile at high temp.The b.p of SiO is much high.At high temp. of

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Nitrogen Group the furnace the SiO2 displaces the more acidic and volatile high temp.the produced decreased.So, to make up for the loss of the conc. of also favours this conversion.

Page 39 forming CaSiO3.Thus, at the equb. of the reversible

is continuously eliminated from the system and its conc. is

reaction is shifted in the forward direction.The high lattice energy of the product CaSiO 3 White P is kept under water-As white P is highly reactive and readily inflames in air at ordinary temp.it is preserved under water as that it may not come in contact with air. When exposed to light W.P is covered with a thin coating of R.P giving it a yellow appearance (also known as yellow P)

Allotropy of Phosphorus
(i)White or yellow P (imp)-Conducts electricity (ii)Red P (imp)-Most thermodynamically stable allotrope (inactive form) (iii)Black P-Has metallic lusture. (iv)Violet P-B.P has a layer like structure in which each layer consists of P-atoms. Preparation of Red Phosphorus Red P from white P-Red P is prepared by heating white P at 240 in an inert atmosphere of N2 or CO2 in presence of a trace of I2 which acts as catalyst.The reaction is exothermic.If the rate of reaction increases,explosion may take place due to evolution of much heat.So, the reaction is conducted at 1 atm.pressure and temp. is mover allowed to rise above 250

Purification-R.P contains some unchanged W.P.It is ground to powder under water and then boiled with strong NaOH soln, when any unchanged W.P is removed in the form of PH3 and sodium hypophosphite. The r.p is left undissolved in NaOH , washed with water and dried in air.As R.P does not readily inflame in air,it is not kept under water. W.P from Red P-R.P on being heated to 550 in an inert atmosphere of N 2 or CO2 is vapourised.The vapours of R.P on rapid cooling yield white P.

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Nitrogen Group (C)Black P from W.P-B.P is prep. by heating W.P at about 200 1200 atmosphere in inert atmosphere.

Page 40 under high pressure of

Properties of White Phosphorus


(A) Physical Properties: (i)White (yellow) P is a translucent , waxy, white or light yellow crystalline solid.It is soft enough to cut with knife easily. (ii) b.p-288 (iii)Insoluble in water, dissolves in CS2, fairly soluble in CCl4, C6H6 , CHCl3 and other organic solvents. (iv) Non-conductor of heat and electricity.Has an odour reminiscent of garlic. (v) Very poisonous 0.1 gm taken internally causes death. (vi)Continued breathing of small amount of white P, causes decay of bones and nose.(Phossy jaw) (B) Chemical Properties: (i)Atomicity-Below 1000 monoatomic. (ii)Phosphorus-In moist air white P undergoes slow oxidation below its ignition temp.producing phosphorus trioxide along with some O 3 and emitting a greenish glow which is visible in dark.This phenomenon is known as phosphorescence.Under reduced pressure the glowing of P increases.The presence of traces of moisture and O 3 is essential for the production of phosphorescence R.P does not exhibit this property. (iii)Action on air or O2-White P ignites in air or O2 even at 35 giving off P2O3 and white fumes of P2O5.Ignition temp=above 30 P4+3O2=2P2O3, P4+502=2P2O5 (iv)Action on halogens-White P ignites spontaneously when it comes in contact with halogens,producing halides of phosphorus with the evolution of heat and light. (exothermic) P4+6Cl2=4PCl3 . P4+6I2=4PI3 . P4+6Br2=4PBr3 P4+10Cl2=4PCl5. and burns vigorously white P is tetraatomic.At about 1600 At above 1600 P4 partially P becomes dissociates to form diatomic molecule P 2.

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(v)Action on Sulphur-P combines with burning S producing phosphorus pentasulphide, P2S8P4S3 etc.P4S3 is used in strike anywhere matches. (Tetraphorus trisulphide): (vi)Action on strong alkalis-White P reacts with hot and conc. soln of NaOH or KOH forming PH3 and hypophosphites.Traces of H 2 and phosphorus dihydride are also formed. . Similar reaction. with Ca(OH) 2 in an inert atmosphere. 2P4+3Ca(OH) 2+6H2O=2PH3+3Ca(H2PO2)2. (vii)Action on metals-W.P combines with metals like Cu,Na,Mg,Al,Ca etc producing their corresponding phosphides. 6Cu+P4=2Cu3P2 6Ca+P4=2Ca3P2 , 6Mg+P4=2Mg3P2 , 12Na+P4=4Na3P

Metallic phosphides on treatment with boiling water or dilute acids evolve phosphine.

Reducing Property-W.P by acting as a reducing agent is converted to phosphoric acid. Redn of HNO3-W.P reduces hot and conc. HNO3 to NO2 and is itself oxidized to H 3PO4.

W.P reduces moderately strong HNO3 to NO2 and NO. 4P+10HNO3=4H3PO4+5NO+5NO2 (b)Reduction of metallic salts-W.P reduces the salts of Cu,Sg,Au in aq. Soln into the corresponding metals which are ppted from the soln.

Hands should be washed with CuSO4 soln. while working with white P-W.P is very corrosive and causes painful burns besides being highly poisonous.So, it should not be

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touched with hands.If accidently it id touched by hand,it should be immediately washed with CuSO4 aoln, as it reacts with it form H 3PO4 and hence destroys its harmful action. P4+10CuSO4+15H2O=4H3PO4+10Cu +10H2SO4. (c)Sulphuric Acid-W.P reduces conc. H2SO4 to SO2. 5H2SO4+2P=2H3PO4+5SO2+2H2O (d)Potassium iodates-P reduces potassium iodate to free I2. When it is treated with acidified KIO3 soln. 2P+2KIO3+H2SO4+2H2O=2H3PO4+I2+K2SO4 Properties of Red Phosphorus-(a)Physical-(i)R.P is a dark red solid with s.g and 1.6 ,(ii)Has no fixed m.p but becomes soft above 596 .At higher temp.it is converted to W.P. (iii)Insoluble in water, inorganic solvents like CS 2, CCl4,CHCl3,C6H6, other etc. (iv) Non-poisonous (v)Does not glow in air (phosphorescence not exhibited) and it is the stable isotope of P at ordinary temp. (b)Chemical-(i)R.P is much less active than W.P.It is not easily oxidized by air or O 2 and does not exhibit phosphorescence .On being heated in air or O 2 above 260 , forms P2O5.

(ii)It reacts with halogens forming halides.On being heated in Cl 2 it burns producing PCl3 and PCl5. P4+6Cl2=4PCl3 , P4+HOCl2=4PCl5. With Br2 and I2 also, on strong heating it produces similar compounds. (iii)R.P does not react with hot and conc. soln of strong alkali like NaOH or KOH. (iv)On boiling with conc.HNO3 , R.P is oxidized to H3PO4 and HNO3 is reduced to oxides of N2. 4P+10HNO3=4H3PO4+5NO2+5NO

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Comparison Between White and Red Phosphorus


Properties 1.Colur and Smell White P Yellow exposure of a garlic. 2.M.P 44 Red P on Dark to having smell. No definite soft red solid no

air,smell like that characteristic

m.p.Becomes at above 596 3.Ignition temp. 4.S.g 5.Solubility Ignites at 35 At 20 8 Ignites at 260 At 20

Insoluble in water Insoluble in water but e.g etc.This and W.P soluble in as well as other organic solvents organic solvents. CS2.CCl4 prop.is

used to sep. R.P 6.Chemical activity Highly ordinary temperature. 7.Phosphorescence Readily oxidized in Not oxidized by air air at ordinary at and exhibit greenish phosphorescence. in visible ordinary not temp.producing oxides emitting glow dark. 8.Action with Cl 2 Readily ignites in On being heated it temp.Does reactive Less reactive,

and less stable at stable at ordinary temperature.

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Nitrogen Group Cl2 producing PCl3 ignites and PCl5. 9.Action on strong alkalis PH3 is evolved Does forming not react

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PCl3 and PCl5.

with the formation with NaOH or KOH. of hypophosphites. slowly H3PO4

10.Action on hot Vigorously reacts Reacts and conc.HNO 3 with conc.HNO3 producing producing 11.Physiological action

H3PO4 and oxides of N 2. Non-poisonous.

and oxides of N 2. Very poisonous.

Uses of P
(i)Match industry (except W.P because it is poisonous). (ii)Holmer signals, (iii)Radio therapy (P 32) ,(iv)Smoke screen during wars (v)Alloys like phosphor bronze (Cu+P+Sn). Safety Matches-The tip of the safety match stick contains a paste of antimony sulphide(Sb2S3), charcoal,K2Cr2O7 (or KCIO3, Pb3O4) and glue.To ignite, the tip must be rubbed on a rough surface. The rough surface is prepared by coating a paper with a paste of r.p, Sb 2S3, powdered glass and gum.On rubbing the tip of the stick on the rough surface, heat is generated due to the friction which is enough to start the reaction between r.p and the oxidizing agents (K2Cr2O7, KCIO3 and Sb2S3).As a result the tip burns. Why is W.P more reactive than R.P-W.p is soft, highly reactive element with low m.p, while R.P is hard and much less reactive, having high m.p. These remarkable diff between the 2 forms can be explained in the light of their molecular structure. W.P is made up of tetrahedrally arranged P 4 units where P-P-P bond L is 60 which is less than the normal bond L 90 occuring with 3Px,Py,P2 orbitals of P and hence the P 4 molecule is under considerable strain which confers high reactivity and less stability to the molecule. Solid W.P P4 discrete molecules are held by weak vanderwaals forces i.e. why it is soft.

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Red P occurs with tetrahedrally arranged P 4 units, joined in a chain of infinite no. of P 4 units.As every bond formation is an energy releasing process, when infinite no.of P 4 units are bonded together.A large qyantum of energy is released , hence R.P becomes more stable and less reactive.

N2 and P belong to the same group in the periodic table, but N 2 is a gas while P is a solid at ordinary temperature:-N2 molecule is diatomic. Due to the smaller size of the Natoms it can undergo sidewise overlap between. Two N atoms. Thus, 2 N atoms are linked to each other by 16 and 2 bonds.The discrete N 2 molecules are held together by weak Vanderwaals forces. On the other hand, as P atoms are bigger, sidewise overlap is not possible, and hence multiple bonds are not found between. 2phosphorus atoms. As a result the P molecule consists of 4-P atoms. The 4-P atoms in the molecule are arranged at the 4 corners of a tetrahedron and linked to each other by strong single covalent bond. The forces acting among the P molecules are called vanderwaal's forces is directly and to the molecular wt. As mol.wt of N2 is much less than that of P4 , the force acting between the N2 molecules is much less than that of P 4 (i.e. v.waals forces are much strong).Thus P4 is a solid and N2 is a gas at ordinary temp. Spontaneous oxidation of phosphorus vapour in air- Cold Flame-Some W.P taken in a r.b flask covered with glass wool-CO2 passed to remove air P vapours come out in

contact with air a greenish flame is produced at the mouth of the exit tube.This flame does not burn paper or match stick and so it is called cold flames.Cold flame is produced by the spontaneous oxidation of W.P vapours by the oxygen of air.

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Nitrogen Group W.P has a strong affinity for O2-fire under waterW.P melts when it is heated to 60 a strong affinity for O2.

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in a water bath.On passing O2 gas through the

molten mass of W.P, the molten P ignites,and burns under water.This proves that P has HYDRIDES OF PHOSPHORUS-PH3 and phosphorus dihydride (P 2H4) are the best known hydrides of P.

PHOSPHINE
(A) PREPARATION(1)By heating white P with conc. soln of NaOH (KOH) in an inert atm. of CO 2 or coal gas. P4+3NaOH+3H2O=PH3+3NaH2PO2 6P +4NaOH+4H2O=P2H4+4NaH2PO2 2P +2NaOH+2H2O=H2+2NaH2PO2 The evolved gas escapes out of water and comes in contact with air, it inflames spontaneously with a bright flame forming a vorten ring of white smoke rising up in air (The white smoke due to own of PH 3 by O2 Purification (1) P2H4 is removed by passing through a U-tube kept in a freezing mixture.P2H4 condenses as a liquid white PH 3 passes out.PH3 may be dried by passing over solid KOH or P2O5.. (2)By action of water or mineral acids on metallic phosphidesCa3P2, AlP on being treated with boiling water or mineral acids yield phosphine. Ca3P2+6H2O=3Ca(OH) 2+2PH3 2AlP+3H2SO4=Al2(SO4)3+2PH3. (3)By action of strong alkali on phosphonium salts-Phosphonium iodide on being heated with 30% soln of NaOH or KOH yield pure PH 3.The pure PH3 id dried by P2O5 and is collected on Hg. (P4+2I2+8H2O=2PHI+2HI+2H3PO4) PH4I+KOH=KI+PH3+H2O. (4) From phosphorus acid-Phosphorus acid on being heated yields By action of nascent H2 on P:6H2SO4+6Zn+P4=4PH3+6ZnSO4.

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Nitrogen Group Properties of PH 3 (A)Physical Properties(i)Colourless gas having the smell of decaying fish. (ii)It is heavier than air and sparingly soluble in water. (iii)It is highly poisonous. (iv)It can be liquefied at -87 (v)Pure PH3 is stable in air, but it catches fire when heated to 150 PH3+2O2=H3PO4.(P2O5+H2O) (B)Chemical Properties-

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(1)Action on oxygen-Pure PH3 is not inflammable in air or oxygen at ordinary temp.It burns in air or O2 when heated to 150 2PH3+4O2=P2O5+3H2O. (2)Basic character- PH3 is feeble basic though it is neutral to litmus.It forms unstable phosphomium halides with halogen hydracids.Its basic nature is exhibited by the formation of these salts. PH3+HCl=PH4Cl 35 , PH3+HI=PH4I A mixture of PH3 and dry HCl does not react at atmospheric pressure but if cooled to or under 18 atm. Pressure at 15 , white cubic crystals of PH 4Cl are deposited. Phosphonium salts react with strong alkalis like NaOH or KOH to liberate pure PH 3. PH4I+NaOH=NaI+PH3+H2O. with mild explosion yielding P2O5.

(4)Action on Cl2-PH3 ignites spontaneously in Cl2 yielding PCl3 and PCl5. PH3+3Cl2=PCl3+3HCl PH3+4Cl2=PCl5+3HCl (5)Reducing property-(a)PH3 is more powerful reducing agent than NH 3.It forms a black ppt. of Cu3P2 (copper phosphide) when it is passed through CuSO 4 soln. 3CuSO4+2PH3=Cu3P2 +3H2SO4. (b)PH3 reduces AgNO3 to metallic silver. At first PH 3 reacts with AgNO3 producing yellow addictive compound,which is decomposed by water to give black ppt. of metallic Ag. PH3+6AgNO3=Ag3P.AgNO3+3HNO3. (yellow addictive compound) Ag3P.3AgNO3+3H2O=6Ag+3HNO3+H3PO3. EDUDIGM 1B Panditya Road, Kolkata 29
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Nitrogen Group (c)PH3 reduces N2O and NO to N2 (electric spark)

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Will O-the wisp-PH3 frequently contains traces of diphosphine (P 2H6) and P2H4 which causes it to catch fire spontaneously .This is the origin of flickering light called will-othe-wisp , seein in mashes. (6)Formation of addictive compounds-PH3 forms addictive compounds when it is passed through a soln of CuCl2 or AlCl3. Cu2Cl2+PH3=Cu2Cl2.PH3 .AlCl3+PH3=AlCl3.PH3 (7)Absorbant-PH3 is completely absorbed by a mixture of water and bleaching powder 3Ca(OCl)Cl+3H2O+PH3=PCl3+3Ca(OH) 2+3HCl Tests of Phosphine-(i)PH3 may be identified by its smell of decaying fish.(ii)PH 3 may be detected by the formation of black ppt. of Cu 3P2 when it is passed through CuSO4 soln. Structure The lp is present in pure s orbital.The H-P-H bond L is 92 in PH3.

Uses:-(i)PH3 is used in producing thick smoke screen. (ii)It is used in preparing Holmes signals-A mixture of CaC2 and Ca3P2 is packed in a Sn vessel having holes at the top.This is thrown into the sea near a rock water enters the vessel and reacts with Ca 3P2 and CaC2 to produce PH3 and C2H2. Ca3P2+6H2O=3Ca(OH) 2+2PH3 CaC2+2H2O=Ca(OH) 2+C2H2 PH3 gets ignited when it comes in contact with air and ignites acetylene.The light of the burning gases indicates the position of the rock to the approaching ships. Convert PH3 to P :-

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M.P and B.P of PH3 is much less than that of NH3-The mol wt. of PH3 is double than that of NH3 , but PH3 boils at a much lower temp.than NH 3.This is due to the existence of inter molecular H2 bonding among the molecules of NH 3. Because of the higher electronegativity and smaller size of N2 atom as compared to those of P, NH3 molecules are able to get associated but H 2.Bonding, as a result of which the effective mol.wt of NH3 becomes much higher than that of the discrete molecules of PH3.So, greater amount of heat energy is reqd. to break these H2 bonds among NH3 molecules. B.P and m.p of NH3 > PH3 ( where no association is present).

NH3 is a much stronger base than PH 3-The basic character of a compound depends on its tendency to donate its lone pair of electrons to the proton of an acid.Both N and P in NH3 and PH3 contain a lap of electrons.Due to the strong electronegativity small size of N-atom , it has a strong affinity for electrons.So, the bond pair of the N-H bonds in NH3 are drawn towards the N 2 atom.As a result the electron density around the N 2 atom in NH3 becomes very high which exerts a repulsive force on the electrons in the N 2atom.But P is much less electronegative and so its ability to donate its lp more freely to a proton is much less than N-atom in NH3 .So, NH3 is more basic than PH3.

Properties 1.Colour and smell

NH 3 smell.

PH 3 of decaying fish. Heavier than air. Sparingly soluble in water. litmus.Forms phosphonium

Colourless gas having a pungent Colourless gas having smell

2.Density 3.Solubility 4.Basic Prop.

Lighter air. Highly soluble in water. blue.Ammonium salts (NH4Cl)

Basic in character.Turns red litmus Feebly basic.No action on

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Nitrogen Group salts (PH4Cl) 5.Action on Cl 2 (a)Excess NH3 8NH3+3Cl2=N2+6NH4Cl (b)Excess Cl2 NH3+3Cl2 NCl3+ 3HCl NCl3+3H2O=NH3+3HOCl. 6.Combustion support combustion,but

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Ignites spontaneously in Cl2 to form PCl3 and PCl5 which undergoes hydrolysis. PH3+3Cl2=PCl3+3HCl PCl3+3H2O=H3PO3+3HCl. burns not form P2O5.2PH3+4O2=P2O5+3H2 O. support

Not combustible and does not A combustible gas but does with a yellow flame in an atm. Of O2 combustion,burns in O2 to 4NH3+3O2=2N2+6H2O

7.Redn.prop

Reduces metallic oxides at high A temp.3CuO+2NH3=3Cu+N2+3H2O

strong

redn

agent ,

reduces AgNO3 to metallic Ag at ord temp. 6AgNO3+PH3=Ag3P.3AgNO


3+3HNO3

Ag3P,3AgNO3+3H2O=6Ag +3HNO3+H3PO3 8.Action on metallic Precipitates metallic hydroxides on Precipitates salts being treated with their salts FeCl3+3NH4OH=Fe(OH) 3 +3NH4C l 9.Physiological action 10.Decomposition A non-poisonous metallic metals or on phosphides

being treated with the salts of Cu,As, Au etc. Highly poisonous gas in a

It decomposes into its elements It decomposes at 440 under electric 2NH3 N2+3H2 phosphorus. 2PH3=2P+3H2

sparks sealed tube into H2 and red

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Oxides of Phosphorus
(i) (ii) Phosphorus trioxide (P2O3) (ii)Phosphorus pentaoxide (P 2O5)

P2O3
(a)Preparation-P2O3 is prepared by burning white P in a limited supply of air. P4+3O2=2P2O3. Some P2O5 is also formed.The vapours of these two oxides pass through the condenser when the vapours of P2O5 are arrested by the plug of glass wool and the vapours of P 2O3 pass out and condense to a solid mass in the cooled bottle under the U-tube.P2O3 is purified by distilling in inert atmosphere. (b)PropertyPhysical Properties(1)At ordinary temp. P2O3 is white, crystalline and waxy solid. (2)Its m.p is 23-8 (3)It is soluble in water and in organic solvents like C 6H6, ether,CS2 etc. (4)It inflames in contact with alcohol. (5)It has a smell like that of a garlic. (6)V.D=110 and depression of freezing point in C 6H6 corresponds to P4O6. Chemical Properties(a)P2O3 is an acidic oxide.It dissolves in cold Water to produce phosphorus acid P2O3+3H2O=2H3PO3 (b)With hot water it yields phosphine and phosphoric acid. 2P2O3+6H2O=PH3+3H3PO4 (ii)Oxidation-P2O3 is readily oxidized by air or O2 to P2O5 P2O3+O2=P2O5 (iii)Decomposition-P2O3 decomposes at 400 phosphorus. to give phosphorus dioxide and red

Structure From V.d measurement the molecular formula of P 2O3 is P4O6.The 4-P atoms are situated at the 4 corners of a tetrahedron.Each of the six O atoms is linked to 2 P EDUDIGM 1B Panditya Road, Kolkata 29
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atoms by single covalent bond by the formation of 6 non-linear P-O-P arrangements .All octets are comp. The P-P bonds are absent .An unused lp is left on each P-atom.

(iv)Reaction with Cl2-P4O6 burns spontaneously in Cl2

Phosphorus pentaoxide (P 2 O 5 )
Preparation(i)P2O5 is prepared under white or red P is burnt in excess of air or O 2. P4+5O2=2P2O5. White clouds of P2O5 settle down as snowy white soft power called flower of phosphorus. The P2O5 thus produced contains P2O3 is small quantity.It is sublimated in a current of dry ozonized air over platinized asbestos., when P2O3 is oxidized to P2O5 and the sublimate is collected in a cooled receiver. (ii)P2O5 from orthophosphoric acid-

(iii)White P on being heated with CO2 at 100 (b)Properties Physical Properties

yeilds P2O5

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(i)At ordinary temp. P2O5 is a soft white powder.It becomes crystalline like snow when cooled.(ii)It sublimes at 250 to light at low temperature. Chemical Properties (i)P2O5 is an acidic oxide. (a)With cold water it reacts with a hissing sound to yield metaphosphoric acid. P2O5+H2O=2HPO3. (b)With excess of boiling water it gives orthophosphoric acid. (ii)Reaction with alkalis-P2O5 reacts with alkalis forming phosphate and metaphosphates. 6NaOH+P2O5=2Na3PO4+3H2O 2NaOH+P2O5=2NaPO3+H2O. (iii)Affinity for water-P2O5 has a great affinity for water. It is a strong drying agent because of its power to abstract the elements of water from other compounds. Thus, it can dehydrate conc.H2SO4, HNO3,HClO4 yeilding SO3, N2O5 and Cl2O7 and P2O5 itself being converted to metaphosphoric acid. H2SO4+P2O5=SO3+2HPO3. 2HNO3+P2O5=N2O5+2HPO3. 2HClO4+P2O5=Cl2O7+2HPO3. Thus, SO3, N2O5, Cl2O7 are the anhydrides of H 2SO4,HNO3 and HClO4. P2O5 can dehydrate ethyl alcohol to produce ethylene. C2H5OH+P2O5=C2H4+2HPO3. (iv) Reaction with coke-At 1500 it is reduced by coke to give white phosphorus. .(iii)It exhibits phosphorescence after a short exposure

Structure V.D measurements show

P4O10.4 P atoms are situated at the 4 corners of a

tetradron. Each of the six O atoms is linked to 2P atoms by single covalent bond by the formation of six nonlinear P-O-P arrangements and each of the 4 O atoms is linked to each P atom by co-ordination bond no. P-P bonds. Imp note-The bonds on the corners are much shorter than a single bond and are in fact double bonds.These EDUDIGM 1B Panditya Road, Kolkata 29 Covalent bond

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double bonds are diff. in origin from the usual double bond. The second bond in P=O is formed by p back bonding. A full p orbital on the O atom overlaps sideways with an empty d orbital on the P-atom. Thus it differs in 2 respects:- (1) A o orbital overlaps with a (P 4O10) d orbital, rather than p with p. (2)Both electrons come from one atom, and hence the bond is a dative bond. Comparison between:P 2 O3 waxy solid. 2.It smells like that of garlic. 3.M.P=2308 4.Soluble in water and organic solvents. 5.It is an acidic oxide. (i)Cold water (ii) Hot water 6.Not a dehydrating agent. 7.Highly poisonous. or O2. P 2 O5 becomes cooled. 2.It is odourless. 3.Sublimes at above 250 4.It is soluble in water. 5.Acidic oxide. (i) Cold water (ii) Hot water 6.Dehydrating agent. 8.It is oxidized by air or O2. crystalline like snow when

1.At ordinary temp. it is a white crystalline 1.At ord. temp it is soft white powder

8.It is oxidized to P2O5 when exposed to air 7.Non-poisonous.

P 2 O3 1.White crystalline waxy solid having low m.p. 2.Highly poisonous. 3.Has a smell like that of garlic. 4.Not decomposed at ordinary temp.

N 2 O3 1.At ord. temp it is a brown gas. 2.Not so poisonous. 3.Smells like nitric acid. 4.Decomposes at ordinary temp. 5.Acidic oxide, gives nitrous acid with N2O3+H2O=2HNO2.

5.Acidic oxide gives H3PO3 with cold H 2 O. water.

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Chlorides of phosphorus
(i)PCl3:- 2P(red)+3Cl=2PCl3 3PCl5+2P=5PCl3. PCl3 fumes in moist air because of the formation of HCl by hydrolysis. 1.PCl3+H2O=H3PO3+HCl 2.PCl3+Cl2=PCl5. 3.SO3+PCl3=POCl3+SO2 (phosphorus oxychloride) 4.2H2SO4+PCl3 HSO3Cl+HPO3+SO2+2HCl (chlorosulphoric acid) (5)Replacement of (-OH) group by (-Cl) in org compounds :-

(ii)PCl5:- (1) (2) Hydrolysis:PCl5 fumes in moist air due to the production of HCl by hydrolysis. (3) With SO2:- SO2+PCl5=POCl3+SOCl2 chloride) (4)Replacement of (-OH) group by (-Cl):(phosphorus oxychloride and Thionyl

Oxyacids of Phosphorus- (1) Phosphorus acid (2)Orthophosphoric are must imp. (1)Phosphorus Acid- (a)Preparation-(1) By the hydrolysis of PCl3By dissolving PCl3 in cold water. PCl3+3H2O=H3PO3+3HCl. The aq. Solution is evaporated at 180 whwn HCl is removed, crystals of H 3PO3. (ii)By the action of oxalic acid on PCl3:- A mixture of oxalic acid and PCl3 in being heated yields phosphorus acid.

(iii)By action of cold water on P 2O3:- P4O6+6H2O=4H3PO3.

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(b)Properties- H3PO3 is a white crystalline solid.It is hygroscopic substance.Its m.p is 74 .Soluble in water. (i)Decomposition-Crystals of H3PO5 on being heated at 300 and orthophosphoric acid.(Disproportionation) (ii)Oxidation-Slowly oxidized by atmospheric O2 to H3PO4 in presence of I2 catalyst. (iii)Acidic nature-H3PO3 in its aq.soln behaves as a dibasic decompose to give PH3

acid.Inspite of the presence of 3-4 atoms, only two are replaceable. As a result two series of salts are given by H 3PO3 e.g. sodium dihydrogen phosphate (NaH2PO3) and disodium hydrogen phosphate (Na 2HPO3)>.The 3rd H-atom being nonreplaceable , Na 3PO3 is not known . Na3PO3 though looks like an acid salt is actually a normal salt as there is no replaceable H- in it. (iv)Reaction with PCl5:- H3PO3+3PCl5=PCl3+3POCl3+3HCl (v)Reducing action-H3PO3 is a strong reducing agent. (a)It reduces mercuric chloride to mercurous chloride.

(b)H3PO3 reduces CuSo 4 soln to metallic Cu and AgNO3 soln to Ag

(c)H3PO3 colour of acidified KMnO4 soln colourless manganous salt. 2KMnO4+5H3PO3+3H2SO4=K2SO4+2MnSO4+5H3PO4+3H2O. (d)H3PO3 reduces SO2 to S. 2H3PO3+SO2=S+2H3PO4 (e)It reduces I2 to hydroiodic acid I2+H3PO3+H2O=2HI+H3PO4

decolourises

the

pink

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Nitrogen Group Structure

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H3PO3 is a strong redn agent because of its tendency to go to +5 state from +3 state by reducing agent. Although the formula H3PO3 suggests that it is a tribasic acid, but its dibasic and Na2HPO3 is a normal salt because only two H-atom linked through O-H bond are replaceable. The 3rd atom which is directly linked to the P-atom cannot be replaced by any metallic radical.

Phosphoric (Ortho) Acid- (H3 PO 4 )


Preparation:(i) By the action of conc. HNO3 on red phosphorus:-

(v)By hydrolysis of PCl3 by water-PCl5+4H2O=H3PO4+5HCl (ii)From Bone ash:- Bone ash or mineral phosphate is digested with 60% H 2SO4 in a lead lined cast Fe tank, by heating the mixture by means of steam. (iii)By heating a mixture of powdered minerals phosphate, silica and coke in an electric furnace:- (Large scale)

CO (iv) By dissolving P2O5 in hot water- P4O10+6H2O= Properties:Physical Properties (1) is a glassy crystalline solid. (2) Its m.p is 42 . (3)The crystals of orthophosphoric acid absorb moisture from air producing a syrup y liquid. (4)Highly soluble in water. EDUDIGM 1B Panditya Road, Kolkata 29
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Nitrogen Group Chemical Properties:(i)Action of heat-:-

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(ii)Acid Property- HPO3 is a tribasic acid as all the 3 H atoms present in it are replaceable. It produces 3 series of salts- phosphates(a)Primary phosphates- Sodium phosphate H3PO4+NaOH=NaH2PO4+H2O (b)Secondary phosphate-di-sodium hydrogen phosphate. H3PO4+2NaOH=NaHPO4+H2O (c)Tertiary phosphate- sodium phosphate (3-H-atoms replaced by metallic radical) H3PO4+NaOH=NaH2PO4+3H2O The aq. Soln of tertiary phosphates are alkaline in nature due to hydrolysis. Action of heat- (a) (Normal tertiary) resist heating) (b) Inspite of the presence of the 3 replaceable H atoms orthophosphoric acid behaves as a dibasic acid- Although the molecular structure of orthophosphoric acid shows the presence of 3-OH groups, it behaves as a dibasic acid in its solution. The pKa values are:-

(i)On titration with NaOH solution H 3PO4 behaves as monobasic acid with methyl orange at the stage of NaH 2PO4. H3PO4+NaOH=NaH2PO4+H2O The pH at eq pt = orange) (ii)It is a dibasic with phenopthaliam at the stage of Na2HPO4:H3PO4+2NaOH=NaHPO4+2H2O. pH at the eq. pt= = phenopthaliem) EDUDIGM 1B Panditya Road, Kolkata 29
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(close to range of methyl

(close to range of

Nitrogen Group

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(iii)Direct titration of H3PO4 as a tribasic acid is not possible with any indicator, as the 3rd dissociation const. is very small.Hence the reaction, H3PO4+3NaOH=Na3PO4+3H2O, does not take place in aq. Med.This explains why H 3PO4 behaves as a dibasic acid in aq.med inspite of the presence of 3 OH groups in its molecule. However , indirect titrations of H 3PO4 excess of CaCl2 soln is added when a white ppt of Ca3(PO4)2 is formed.The filtrate contains HCl which is titrated by NaOH soln using phenopthalein indicator.

(iii)Action on silver nitrate-A yellow ppt. of silver phosphate is obtained when H 3PO4 is treated with AgNO3. (iv)Action on BaCl2- Barium chloride gives a white ppt. of barium orthophosphate in neutral or slightly alkaline soln.

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