Phosphorus (P) Phosphorus Atomic Number Phosphorus Atomic Mass Phosphorus Group Number Phosphorus Period Number Phosphorus

Relative Abundance : 15 : 31 : 15 (V A) :3 : 11

Phosphorus Electronic Configuration : [Ne]3s23p3

Phosphorus is second number of the "Nitrogen family" with group number 15 and period number 3. Phosphorus is mostly used in match industry. Occurence of Phosphorus phosphorus being an active element, it is not found free in nature. Phosphorus occurs as phosphate in the rocks and in the soil. The important minerals of phosphorus are i. ii. iii. Phosphorite - Ca3(PO4)2 Flourapatite - 3Ca3(PO4)2.CaF2 Chlorapatite - 3Ca3(PO4)2.CaCl2

Other than this, phosphorus is essential constituent of bones, teeth etc. Bone ash contains about 80% of calcium phosphate. Properties of Phosphorus: 1. Phosphorus is a non-metal. 2. Phosphorus though a solid can also convert easily into vapour state. 3. The atomic radius of phosphorus (1.10 ) is higher than nitrogen (0.74 ) and lower than the rest of the family members 4. The first ionisation energy of phosphoprus (253.9 kcal) is lower than nitrogen (336) due to its own bigger size than nitrogen and higher than the rest of the family members 5. Electronegativity of phosphorus (2.1) is lower than the nitrogen but higher than the rest of the members. 6. Phosphorus can exist in discrete tetratomic tetrahedral molecule i.e. P4. 7. Phosphorus can exists in number of allotropic forms like

i. ii. iii. iv. v. vi.

White or yellow phosphorus Red phosphorus Scarlet phosphorus - Black phosphorus - Black phosphorus Violet phosphorus

8. Phosphorus can show oxidation state of -3 to +5

Extraction of Aluminium Aluminium Atomic Number: 13 Aluminium Electronic configuration: [Ne]3s23p1 Aluminium being very reactive does not occur free in nature. Aluminium is obtained from bauxide ore. The bauxide ore is generally contaminated with ferric oxide and silica. The extraction of aluminium from bauxide ore involves the following three steps. 1. Concentration of the ore 2. Electrolytic reduction of Al2O3 3. Electrolytic purification of aluminium 1. Concentration of bauxite ore: Following methods are used for concentrating the bauxide ore: a. Baeyer's process: This method is mainly applied when ferric oxide is present as chief impurity. The crushed ore is first heated at moderate temperature so as to convert ferrous oxide into ferric oxide. It is then digested with concentrated solution of sodium hydroxide in which aluminium oxide dissolves forming soluble sodium meta aluminate while ferric oxide and silica remains insoluble and settle down. Al2O3.2H2O + 2NaOH 2NaAlO2 + 3H2O

The filtrate containing sodium meta aluminate solution is agitated with freshly precipitated Al(OH)3 when sodium meta aluminate undergoes hydrolysis to precipitate Al(OH)3 when sodium meta aluminate undergoes hydrolysis to

precipitate Al(OH)3. NaAlO2 + 2H2O NaOH + Al(OH)3

The precipitate is washed, dried and heated to get Al2O3. 2Al(OH)3 Al2O3 + 3H2O

b. Hall's process: Bauxide ore is fused with sodium carbonate, Al2O3 combines with sodium carbonate forming sodium meta aluminate. The fused mass is extracted with water where Fe2O3 and SiO2 remains insoluble in the residue. Al2O3 + Na2CO3 2NaAlO2 + CO2

The solution containing sodium meta aluminate is warmed to 50-60oC and CO2 is circulated through it. Al(OH)3 separates out as precipitate. 2NaAlO2 + CO2 + 3H2O 2Al (OH)3 + Na2CO3

The precipitate is filtered, washed, dried and ignited to get Al2O3. c. Serpeck's process: This process is used when silica is present in considerable amount of bauxide ore. The ore is mixed with coke and heated to 1800 C in presence of nitrogen, when aluminium nitride is forms. Al2O3 + 3C +N2 2AIN + 3CO

Silica is reduced to silicon and volatilises off at this temperature SiO2 +2C Si + 2CO

AIN is hydrolysed with water into aluminium hydroxide. AIN + 3H2O Al (OH)3 + NH3

The precipitate is filtered, washed dried and ignited to get Al2O3. 2. Electrolytic Reduction of Pure Alumina The electrolysis of pure alumina involves two difficulties. i. ii. Pure alumina is a pure conductor of electricity. The fusion of temperature of pure alumina is about 2000oC and the metal formed vaporises at this temperature. (boiling point of Al is 1800 C).

To remove this difficulties, cryolite (Na3 AlF6) and Fluorspar (CaF2) is added which reduced the fusion temperature to 900 C and makes ir good conductor of electricity. The

electrolysis is carried out in an iron tank lined inside with carbon which acts as cathode. The anode consists of carbon rod dipped in the fused mixture of electrolyte. The fused electrolyte is covered with a layer of coke. On passing current, aluminium is discharged at cathode. Aluminium being heavier than electrolyte settles down in the bottom and is periodically tapped out. Oxygen is liberated at anode. It attacks carbon rods forming CO and CO2. Mechanism: AlF3 from cryolite ionised as AlF3 Al3+ + 3FAl

At cathode: Al3+ + 3eAt anode: 2FF2 + 2e-

The liberated fluorine reacts with alumina to form AlF3 and O2. Al2O3 + 3F2 2C + O2 C + O2 2AlF3 + 3/2O2 2CO CO2

Refining of Aluminium by Hoope's Electrolytic Method The electrolytic cells consists of an iron box lined inside with carbon. The cell consists of three layers which differ in specific gravity. . a. b. The upper layer is of pure aluminium which acts as cathode. The middle layer consists of a mixture of the fluorides of Al, Ba and Na. The lowest layer consists of impure aluminium which acts as anode.

On electrolysis, aluminium is deposited at cathode from the middle layer and an equivalent amount of aluminium is taken up by the middle layer from the bottom layer (impure aluminium). Therefore aluminium is transferred from bottom to the top layer through middle layer while the impurities are left behind. Extraction of Lead Lead Atomic Number: 82 Lead Electronic configuration: [Xe]4f144d106s26p2 Lead is extracted from galena (PbS) involving the following steps:

1. Concentration: The crushed, powdered ore is concentrated by the froth floatation process. 2. Reduction: The concentrated ore is reduced in two steps: a. Roasting: The concentrated ore is roasted in reverberatory furnace, where the ore is partially oxidised. 2PbS + 3O2 PbS + 2O2 2PbO + 2SO2 PbSO4

b. Smelting: After roasting, the temperature of furnace is raised and air supply is reduced. Some more concentrated galena is added. PbS reacts with PbO and PbSO4 forming lead metal. 2PbO + PbS PbSO4 + PbS 3Pb + SO2 2Pb = 2SO2

Molten lead is drawn off from the lower part of the furnace. c. Purification: Lead obtained from furnace still contains Bi, Sb, Cu, Fe, Ag, etc. as impurity. These impurities can be removed by the following processes. i. Softening process: The impure metal is melted on the hearth reveberatory furnace in a current of air. The base metals are oxidised and float over the surface of the molten mass as scum, which is removed. Desilverisation: The removal of silver is done by Parke's process or Pattinson's process. Electrolytic refining: The desilverised lead is further purified by electrolytic method. On passing current, pure lead is deposited on the cathode. The less electropositive metals like Ag, Au, Sb etc. collect below anode as anodic mud while more electropositive impurities like Zn, Fe, Ni etc. go into the solution.

ii. iii.

Extraction of Magnesium Magnesium Atomic Number: 12 Magnesium Electronic configuration: [Ne]3s2 Magnesium is highly electropositive and strong reducing agent. Therefore it is extracted by

electrolysis of their fused metal halides containing alkali metal halides. The function of alkali metal halides is a. To lower the operating temperature. b. To increase the electrical conductivity. 1. From Magnesite: (MgCO3) The magnesite ore is calcinated into magnesium oxide. MgCO3 MgO + CO2

Magnesium from magnesium oxide is obtained either by thermal reduction or electrolytic reduction. The magnesium oxide is dissolved in a mixture of molten fluorides of magnesium, bairum and sodium. The electrolysis is done by using carbon rods as anodes suspended in molten mass and cast iron rods as cathodes at 650oC. The magnesium is obtained in molten state. 2. By Electrolysis of anhydrous magnesium chloride: Step 1: Preparation of anhydrous MgCl2 1. From carnallite: (KCl.MgCl2.6H2O) Carnallite can not be dehydrated by heating alone. Because the water of crystallization reacts chemically with magnesium chloride to form oxychloride and finally to magnesium oxide. MgCl2.6H2O MgCl2.2H2O Mg2OCl2 MgO

So, carnallite is heated in a current of HCL gas and air. MgCl2.6H2O MgCl2 + 6H2O

2. From MgO: Chlorine is passed over red hot mixture of MgO and carbon. MgO + C + Cl2 MgCl2 + CO

3. From Dow's process: Sea water containing magnesium compound is treated with calcium hydroxide when magnesium hydroxide get precipitated. It is dissolved in dil. HCL. The solution on concentration gives hydrated magnesium chloride, which is hydrated as

Electrolysis of MgCl2 Anhydrous magnesium chloride is fused with NaCl and anhydrous calcium chloride in the ratio of 35% (MgCl2); 50% (NaCl) and 15% (CaCl2) to lower the fusion temperature and to increase the conductivity. The mixture is electrolysed at 700oC in presence of an inert gas to protect it from reaction of N2, O2 and CO2 present in air. Magnesium is discharged at cathode. Magnesium being lighter than the fused mass floats on the surface from where it is removed periodically. Extraction of Silver Silver Atomic Number: 47 Silver Electronic configuration: [Kr]3d104s1 Silver occurs in native state as well as in combined state. Silver is extracted from Argentite ore (Ag2S). Cyanide process: This process is also called Mac Arthur Forest Process. The process involves the following steps: 1. Concentration of ore: The crushed and fine powdered ore is concentrated by froth flotation process. 2. Cyanidation: The finally powdered concentrated ore is treated with dilute solution (0.4 to 6%) of sodium cyanide in presence of a current of air to form sodium argentocyanide. Ag2S + 4NaCN 2Na[Ag(CN)2)] + Na2S

The air blown in converts sodium sulphide to sodium sulphate thus shifting the equilibrium to right side. 4Na2S + 502 +2H2O 2Na2SO4 + 4NaOH + 2S

The soluble sodium argentocyanide is separated out by filtration. 3. Recovery of Silver: Zinc powder in finely divided state is added to clear filtrate to precipitate Ag as a dark amorphous mass.

2Na[Ag(CN)2] + Zn

Na2[Zn(CN)4] + 2Ag

4. Refining: Silver obtained by the above method is contaminated with impurities of lead, copper and gold. Impurities are removed by: Electrolytic Refining: Pure silver is obtained by the electrolysis of AgNO3 solution containing 10% HNO3 and using the impure silver as anode and pure silver plate as cathode. During electrolysis copper passes into solution as copper nitrate while gold collects as anodic mud. Silver is deposited at cathode. Anode : Ag Ag+ + eAg

Cathode : Ag+ + e-

Note: Same process can be applied for gold as well. Extraction of Zinc

Ores: Zinc Blende, ZnS Calamine, ZnCO3 Zincite, ZnO 1. Concentration: Powdered Zinc Blende is concentrated by froth floatation process. 2. Roasting: 2ZnS + 3O2 3. Reduction: ZnO + C Zn + CO 2ZnO + 2SO2

4. Purification: Impure Zinc obtained above contain impurities of Pb, Fe, Cd, As etc. This impure Zinc is known as spelter. Firstly, Cd is distilled off at 800 C and then electrolytic purification is done using impure Zn as anode and cathode consists of sheets of pure Al. Pure Zn is scrapped off from Al-sheets. Extraction of Tin

Tin: Atomic Number: 50 Electronic configuration: [Kr]4d105s25p2) Tin is extracted from cassiterite ore. The extraction involves the following steps: a. Concentration: The crushed and powdered ore is washed with running water, which removes lighter siliceous matter. Wolframite is removed by electromagnetic separator. b. Roasting: S and As are removed as their volatile oxides. Iron and copper pyrites are converted into their oxides and sulphates c. Washing: This ore is then washed with hot water to dissolve out copper sulphate and iron sulphate. The lighter ferric oxide is washed off while the concentrated tin stone sinks to the bottom. It is called black tin. d. Smelting: Black tin is mixed with carbon and smelted in a reverberatory furnace. The ore is reduced to the metallic state while SiO2 is removed as slag. SnO2 + 2C CaCO3 Sn + 2CO CaO + CO2 CaSiO3 (Slag)

CaO + SiO2

Molten metal is cast into ingots or blocks. It is known as block tin and contains about 99.5% of metallic tin. e. Purification: The metal is purified by: i. Liquation: The easily fusible tin melts away and less fusible impurities (Fe, W, S, As) are left behind. Electrolytic refining: In this method, impure tin is made anode and a thin sheet of pure tin is made the cathode. Electrolyte consist of H2SiF6, tin sulphate and sulphuric acid. On passing current, tin is dissolved from anode and gets deposited on the cathode.

ii.

Blast Furnace The smelted ore is introduced in the furnace by lowering the cup and cone arrangement and at the same time furnace is lit and a blast of hot air is sent upwards through the Tuyeres. On the basis of variation in the temperature, there are four zones where different chemical changes occur.

a. Combustion zone: this is lowest part of furnace where the temperature is about 1500 1600 C. C + O2 CO2 + C b. Reduction zone: 2Fe2O3 + CO Fe3O4 + CO Fe + CO 2Fe3O4 + CO2 3FeO + CO2 Fe + CO2 CO2 H = -97 kcals 2CO

Iron formed is called sponge iron. In this reduction zone heat is also evolved due to which CO partially decomposes. 2CO CO2 + C

c. Slag formation zone: This is the central zone where the temperature varies from 8001000 C. CaCO3 CaO + CO2

Impurities in the ore are reduced to Si, P and Mn, respectively. P4O10 + 10C SiO2 + 2C MnO2 + 2C 4P + 10CO Si + 2CO Mn + 2CO

These are partly absorbed by iron and partly by slag. d. Zone of fusion: This zone is above combustion zone. The temperature ranges between 1200-1500oC. The spongy iron melts at 1300 C and collects at the bottom of hearth. The slag being lighter floats over the molten iron and prevents oxidation of molten metal. The slag and molten metal are removed from their respective holes. The molten metals is run into moulds and is allowed to solidify. Iron obtained from the blast furnace is called pig-iron. It contains 93% iron, 5% carbon and rest silicon. The pig-iron is remelted and cast into moulds. This is known as cast iron.

There are three commercial varities of iron depending on their carbon content. i. ii. iii. Cast iron - most impure form, containing carbon from 2.5 to 5%. Wrought iron - purest form of iron, containing carbon from 0.25% to 0.3%. Steel - most important commercial variety of iron, containing carbon from 0.25 to 2%

Periodic Table and Periodicity History 1. Doebereiner discovered group of three elements having similar properties and called them triads. The atomic mass of the central element was the arithmetic mean of the atomic mass of other two elements e.g., Li, Na, K 2. Newlands law of Octaves: He arranged elements in their increasing atomic weights of the elements and properties of first element was found to be similar to that of eighth element. 3. Lother Meyer plotted graph between atomic volumes and atomic weight of the elements. Elements with similar properties had the similar position on the curve. 4. Mendeleev stated that "Physical and chemical properties of elements are periodic function of their atomic weight". Only 57 elements were known at that time.

5. Modern periodic Law: Moseley stated that physical and chemical properties of elements are periodic function of their atomic number. 6. Bohr given long form of periodic table. Long Form of Periodic Table There are 7 periods (Horizontal rows) and 18 groups (vertical columns) 1st period : Very short period (only two elements H11 and He42) 2nd period : Short period (8 elements 3Li - 10Ne) 3rd period : Short period (8 elements 11Na - 18Ar) 4th period : Long period (18 elements 19K - 36Kr) 5th period : Long period (18 elements 37Rb - 54Xe) 6th period : Longest period (32 elements 55Cs - 86Rn) 7th period : Incomplete period (26 elements 87Fr - 112Uub) In the long form of periodic table elements can also be classified as: a. s-Block Elements: Elements of group 1 and 2 having general electronic configuration ns1-2 ns1 - Alkali metal (Li to Cs) Fr is radioactive ns2 - Alkaline earth metal (Be to Ba) b. p-Block Elements: Elements of group 13, 14, 15, 16, 17 and 18 having electronic configuration ns2 np1-6. Elements of group 18 are also called as inert gases. c. d-Block Elements: Also called as transition element having electronic configuration (n1)d1-10 ns1-2 (except 46Pd) d. f-Block Elements: Also called as inner transition element, having electronic configuration (n-2) f1-14 (n-1) d0-1 ns2. It includes 4f or lanthanoid (Ce to Lu) 5f or actinoid (Th to Lr) The elements are broadly divided into three types i. ii. iii. Metals comprise more than 78% of the known elements. Non-metals are less than twenty (C, N, P, O, S, Se, H, F, Cl, Br, l, He, Ne, Ar, Kr, Ar, Kr, Xe and Rn) Elements which lie in the border line between metals and non metals are called metalloids. (B, Si, Ge, As, Sb, Te, Po, At)

Periodicity is observed in a number of properties which are directly or indirectly or linked with electronic configuration.

Effective nuclear charge increase across each period and remain almost constant down the group. Zeff = Z where 'Z' is nuclear charge is shielding effect

Atomic radii (is generally taken as covalent radii) n = Principal quantum number of outer orbit It generally decreasing across a period and increases down the group. It is of three types i. ii. iii. Covalent radius Metallic radius van der Waal radius

Order: van der waal's radius > Metallic radius > Covalent radius Ionic Radii

Cationic radii is smaller than anionic radii for some atom. Cationic radii < Atomic < anionic radii Elements of 2nd and 3rd transition series belonging to same group are similar in size and properties due to lanthanide contraction. Ionisation Enthalpy is the energy required to remove the most loosely held electron from the gaseous isolated atom

Ionisation enthalpy generally decreases down the group.

Successive I.E of an atom have higher values. IE1 < IE2 < IE3 ....... Electron gain enthalpy is the enthalpy change taking place when an electron is added to an isolated gaseous atom of the element. The Ist electron gain enthalpy of most of the elements is negative as the process is exothermic. Electron gain enthalpy becomes more negative from left to right in a period and less negative from the top to bottom in a group. Successive electron gain enthalpies are always positive. Electro negativity is the tendency of an atom to attract the shared pair of electron towards itself in a molecule. 1. Electro negativity increases across the period and decreases down the groups. 2. Metals have low electro negativity and non-metals have high electro negativities. 3. Application of Electro negativity 1. Percentage ionicity = 16 (XA ~ XB) + 3.5 (XA ~ XB)2 2. For oxides Xo ~ X element higher the difference more basic the oxide In formed when H-atom of one molecules combines with the electronegative atom of other molecule by dipole-dipole interaction (N, O, F and electron cloud exhibit H-bonding) Type of H-Bonding 1. Intermolecular H-Bonding: Formed between H and electronegative element of two different or same molecule

It increase the boiling point, solubility in water and viscosity. 2. Intramolecular hydrogen bonding: Formed between H and electronegative element present in the same molecule.

3. It increases volatile nature, decreases boiling point and solubility. Modern Concept of Covalent Bonding Valence bond theory: Formed by overlapping of half filled atomic orbitals. Main Characters: 1. 2. 3. 4. Greater the overlapping higher the strength of the bond. Electron density is maximum between the two atom where overlapping takes place. p-orbitals will form stronger bond than s-orbital. When overlapping of orbital takes place along their axis the bond formed is (sigma) bond. 5. When overlapping of orbital takes place laterally or sidewise the bond formed is bond. Oxygen (O) Oxygen Atomic Number Oxygen Atomic Mass Oxygen Group Number Oxygen Period Number Oxygen Relative Abundance :8 : 16 : 16 (VlA) :2 :1

Oxygen Electronic Configuration : [He]2s22p4

Oxygen is a most abundant element on earth. Oxygen is 46.6% by weight in the earth's crust. In atmosphere, oxygen is present 21% by volume. Oxygen is the first member of "Chalcogen family". Properties of Oxygen 1. Oxygen is a gas while other family members are solids. 2. Oxygen molecule is diatomic while the other family members exist in polyatomic ring form.

3. Oxygen is non-metal whereas metallic character increases down the group. The nonmetallic character of oxygen is due to its high value of electronegativity. 4. Oxygen molecule is highly stable due to higher bond energy of multiple bonds. 5. The atomic radius; atomic volume and density of oxygen are lower than rest of the family members. 6. The ionisation energies of oxygen due to its smaller size is very high compared to that of the other family members. 7. Oxygen is highly electronegative member of its family. It is the second most electronegative element after fluorine (4). 8. The melting point -219 C and boiling point -183 C of oxygen are lower than that of other family members. 9. Oxygen mostly exhibits oxidation state of -2. Oxygen do not have d-orbital hence can't show +4 +6 oxidation state while other family members can. 10. Oxygen reacts with metal to form basic oxide. K + O2 2Mg + O2 KO2 (Potassium super oxide) 2MgO (Magnesium oxide)

11. It reacts with non-metal to form acidic oxide. C + O2 S + O2 4P + 5O2 CO2 SO2 P4O10

12. It reacts with some metals to form amphoteric oxides (acidic as well as basic) 4Al + 3O2 2Be + O2 2Zn + O2 2Al2O3 2BeO 2ZnO

13. It reacts-with some non-metals to form neural oxide C + O2 N2 + O2 CO 2NO

14. It acts as oxidising agent. It is trequired for combusion. It is used for roasting of sulphide ores. CS2 + 3O2 2ZnS + 3O2 Sulphur (S) Sulphur Atomic Number Sulphur Atomic Mass Sulphur Group Number Sulphur Period Number Sulphur Relative Abundance : 16 : 32 : 16 (VlA) :3 : 16 CO2 + 2SO2 2ZnO + 2SO2

Sulphur Electronic Configuration : [Ne]3s23p4

1. Sulphur is the sixteenth most abundant element on earth crust. It constitutes 0.034% by weight of the earth's crust. 2. Sulphur is the p-block element and is the second member of "Chalcogen family" after oxygen. 3. The group number of sulphur is 16 and period number is 3. 4. Sulphur is the mostly used in manufacture of SO2, H2SO4, fire works, medicine. Properties of Sulphur 1. Sulphur exist as staggered 8-atom ring S8 molecule. Each sulphur atom is in sp3 hybridised state. 2. Sulphur is a non metal. 3. The atomic radius, atomic volume and density of sulphur is higher than oxygen but lower than rest of the family members. 4. Electronegativity of sulphur is lower than that of oxygen but higher than rest of the family members. 5. Melting point and boiling point of sulphur are higher than the oxygen due to its bigger size than oxygen but lower than rest of the chalcogen members

6. Catenation property is more pronounced in sulphur as compared to rest of the family members. 7. Sulphur can exhibit the range of -2 to +6 oxidation state due to availability of vacant dorbital. 8. Sulphur reacts with acid where it itself gets oxidised. S + 2H2SO4 (Conc.) S + 6HNO3 (Conc.) 4S + 6NaOH 3SO2 + 2H2O H2SO4 + 6NO2 + 2H2O

2Na2S + Na2S2O3 + 3H2O

9. Sulphur undergoes reduction in presence of hydrogen. H2 + S 10. Cl2 + 2S 11. C + 2S 12. 2As + 3S H2S S2Cl2 CS2 As2S3 2H2S + SO2

13. 2H2O (steam) + 3S (boiling) Oxyacids of Phosphorus: i. ii. iii. iv. v. vi. Hypophosphorus acid - H3PO2 Phosphorus acid - H3PO3 Orthophosphoric acid - H3PO4 Metaphosphoric acid - HPO3 Hypophosphoric acid - H4P2O6 Pyrophosphoric acid - H4P2O7

a. Phosphorus acid - Orthophosphorus acid - H3PO3 Preparation: i. Phosphorus trichloride when reacted with water gives phosphorus acid. PCl3 + 3H2O ii. H3PO3 + 3HCl

Phosphorus trioxide (P4O6) on reaction with water gives phosphorus acid. P4O6 + 6H2O 4H3PO3

Properties:

iii.

Phosphorus acid disproportionates to give PH3 and H3PO4. 4H3PO3 3H3PO4 + PH3

iv.

Phosphorus acid is a disbasic acid. H3PO3 H2PO3H+ + H2PO3H+ + HPO3-2

v.

Phosphorus acid on reaction with phosphorus pentachloride gives phosphorus oxychloride. H3PO3 + 3PCl5 PCl3 + 3POCl3 + 3HCl

b. Orthophosphoric Acid - H3PO4 Preparation: i. Phosphorus when treated with nitric acid gives H3PO4. P4 + 20HNO3 ii. iii. iv. 4H3PO4 + 20NO2 + 4H2O

Calcium phosphate on reaction with sulphuric acid gives H3PO4 Ca3(PO4)2 + 3H2SO4 2H3PO4 + 3CaSO4

Phosphorus on reaction with excess of oxygen gives oxide which on further reaction with hot water gives orthophosphoric acid. P4 + 5O2 P4O10 4H3PO4

Properties:

v.

Orthophosphoric acid is a tribasic acid and forms series of salts. Primary phosphate - NaH2PO4 Secondary phosphate - Na2HPO4 Tertiary phosphate - Na3PO4

vi.

2H3PO4

H4P2O7 + H2O

vii. viii.

H3PO4

(HPO3)n metaphosphoric acid

+ H2O

H3PO4 on reaction with BaCl2 and AgNO3 gives precipitate. 3BaCl2 + 2H3PO4
White ppt

Ba3(PO4)2 + 6HCl Ag3PO4 + 3HNO3

3AgNO3 + H3PO4 ix.

(yellow)

On heating H3PO4 in presence of nitric acid with ammonium molybdate, a canary yellow precipitate of ammonium phosphomolybdate is formed. (test of Po43- ion) H3PO4 + 21HNO3 + 12(NH4)2MnO4 12H2O (NH4)3PO4 . 12MoO3 + 21NH4NO3 +

Oxyacids of Nitrogen: a. Nitrous acid - HNO2 b. Nitric acid - HNO3 c. Hyponitrous acid - H2N2O4 a. Nitrous Acid: HNO2 Preparation: i. By dissolving N2O3 in water N2O3 + H2O 2HNO2

By action of acid on metallic nitrites NaNO2 + HCl ii. NaCl + HNO2

By oxidation of NH3 NH3 + 3H2O2 HNO2 + 4H2O

Properties:

iii. iv.

It is a weak acid and does not exist in free state. 2HNO2 NO + NO2 + H2O (Vapour phase)

3HNO2 v.

HNO3 + H2O + 2NO (Aqueous solution)

Oxidising property 2HNO2 H2S + [O] 2NO + H2O + [O] H2O + S H2SO4 Fe2(SO4)3 + H2O SnCl4 + H2O 2KOH + l2

SO2 + H2O + [O]

2FeSO4 + H2SO4 + [O] SnCl2 + 2HCl + [O] 2Kl + H2O + [O] vi. Reducing property HNO2 + [O] HNO3

K2Cr2O7 + 4H2SO4 + 3HNO2 2KmnO4 + 3H2SO4 + 5HNO2 Br2 + H2O + HNO2 vii. H2NCONH2 + 2HNO2

K2SO4 + Cr2(SO4)3 + 3HNO3 + 4H2O K2SO4 + 2MnSO4 + 3H2O + 5HNO3

HNO3 + 2HBr CO2 + 2N2 + 3H2O

b. Nitric acid: HNO3 Preparation: i. By heating sodium nitrate with conc. sulphuric acid. 2NaNO3 + H2SO4 ii. 2HNO3 + Na2SO4

Birkeland - Eyde Process N2 + O2 2NO + O2 3NO2 + H2O 2NO 2NO2 2HNO3 + NO

iii.

Ostwald's Process 4NH3 + 5O2 2NO + O2 3NO2 + H2O 2NO2 2HNO3 + NO 4NO + 6H2O

Structure:

Properties: Anhydrous acid is a color less fuming liquid. It usually acquires yellow color due to its decomposition by sunlight into NO2. 4HNO3 4NO2 + 2H2O + O2 6H2C2O4 + 5H2O

C12H22O11 + 18[O] Reaction with Metals

iv. v. vi. vii.

Mg + 2HNO3 (dil) 3Mg + 8HNO3 (conc.)

Mg(NO3)2 + H2 3Mg (NO3)2 + 4H2O + 2NO 3Cu(NO3)2 + 4H2O + 2NO Cu(NO3)2 + 2H2O + 2NO2

3Cu + 8HNO3 (cold and dilute) Cu + 4HNO3 (cold and conc.) [Ag, Pb and Bi also react as Cu]

viii. ix.

6Hg + 6HNO3 (dilute) Hg + 4HNO3 (conc.)

3Hg2(NO3)2 + 4H2O + 2NO Hg(NO3)2 + 2H2O + 2NO2

x.

4Zn + 10HNO3 (very dilute)

4Zn(NO3)2 + NH4NO3 + 3H2O 4Zn(NO3)2 + N2O + 5H2O

xi. xii.

4Zn + 10HNO3 (dil) 4Fe + 10HNO3 (very dilute) 4Sn + 10HNO3 (dil.) Fe + 6HNO3 (conc.) Sn + 4HNO3 (conc.)

4Fe(NO3)2 + NH4NO3 + 3H2O

xiii.

4Sn(NO3)2 + NH4NO3 + 3H2O Fe(NO3)3 + 3NO2 + 3H2O

xiv.

xv.

H2SnO3 + H2O + 4NO2

Reaction with non-metals, metalloids and compounds xvi. xvii. xviii. xix. xx. xxi. xxii. xxiii. xxiv. C + 4HNO3 S + 6HNO3 l2 + 10HNO3 B + 3HNO3 As + 5HNO3 Sb + 5HNO3 SO2 + 2HNO3 2Hl + 2HNO3 CO2 + 4NO2 + 2H2O H2SO4 + 6NO2 + 2H2O 2HIO3 + 10NO2 + 2H2O H3BO3 + 3NO2 H3AsO4 + 5NO2 + H2O H3SbO4 + H2O + 5NO2 H2SO4 + 2NO + O2 2NO2 + 3l2 + 2H2O 3Fe2(SO4)3 + 2NO + 4H2O

6FeSO4 + 3H2SO4 + 2HNO3