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P – Block Elements SYJC P – Block Elements Introduction The p-block elements are placed in groups 13 – 18 . The general electronic configuration is ns 2 np1 – 6. The groups included in the syllabus are 15, 16, 17 and 18. Group 15 Elements Nitrogen family: configuration is ns2np3. The elements of group 15 – nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) bismuth (Bi) All Group 15 Elements tend to follow the general periodic trends: Periodic properties Trends Electronegativity:(the atom's ability of Decreases down the group attracting electrons) Ionization Enthalpy (the amount of decreases energy required to remove an electron from the atom in it's gaseous phase) Atomic Radii (the radius of the atom) increases Electron Affinity (ability of the atom to decreases accept an electron) Melting Point (amount of energy increases going down the required to break bonds to change a group solid phase substance to a liquid phase) Boiling Point (amount of energy increases going down the required to break bonds to change a group liquid phase substance to a gas) Chemical properties Action of air;(high temp arc) N2 + O2 2NO Action oxidizing agents: P4 +20HNO3 4H3PO4 + 20 NO2+4 H20 As4 + 20 HNO3 4H3AsO4 + 20 NO2+4 H20 Action of hot conc H2SO4 P4 +10 H2SO4 4H3PO4 + 10 SO2+4 H20 As4 +10 H2SO4 4H3AsO4 + 4 Sb + 6 H2SO4 Sb2(SO4)3 + 3 Hydrides All form hydrides with formula EH3 ( E = N, P, As, Sb , Bi) oxidation state = – 3 Hydrogen bonding in NH3 The stability of hydrides decrease down the group due to decrease in bond Hydrides comparison Anomalous behaviour of nitrogen N is gas all are solids N diatomic others tetra atomic Forms H bonds in hydrides forms p∏ - p∏ multiple bonds Range of oxidation states -3 to +5 No d orbitals does not form co – ordination compounds Dinitrogen N2 Commercial mtd : BP 77.2 fractional distillation of air Lab mtd: NH4Cl +NaNO2 N2 + 2 H2O + NaCl from azide : 2NaN3 2Na + 3N2 Properties 2 isotopes 14N , 15N 3Mg + N2 Mg3 N2 3H2 + N2 773K /200atm 2NH3 O2 + N2 electric arc/ 2000K 2NO CaC2 + N2 CaCN2 + C Preparation of ammonia Lab method: Ammonia is prepared by heating a mixture of calcium hydroxide and ammonium chloride. 2NH4Cl + Ca( OH)2 CaCl2 + 2NH3 +2 H2O Ammonia is collected by upward delivery as it is lighter than air and dried over quick lime CaO. Manufacture of ammonia Habers process It is manufactured by reacting Nitrogen and hydrogen in the presence of finely divided catalyst at temperatures 700ºC at a pressure of about 200 atmospheres. N2(g) + 3H2(g) 2NH3(g) Alminium Oxide ferric oxide and potassium oxide is added to the catalyst to improve its performance. It makes it more porous and this provides a high surface area to the reaction. The reaction is reversible hence it is not possible to convert all the reactants into Structure of ammonia Reactions of ammonia 1] with air: Ammonia burns in a lot of air (oxygen). The flame is yellow green 4NH3(g) + 3O2(g) → 6H2O(g) + 2N2(g) react with oxygen in excess air, and platinum catalyst to form nitrogen monoxide 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l) 2] reduces : Ammonia reduces heated copper(II) oxide to copper i.e. copper turns from black to brown. 3CuO(s) + 2NH3(g) → 3Cu(s) + 3H2O(l) + N2(g) 3] halogens 3Cl2(g) + 8NH3(g) → 6NH4Cl(s) + N2(g). In excess NH3(g) + 3Cl2(g) →NCl3(l) + 3HCl(g) 4] co – ordination complex Ammonia solution (Ammonium hydroxide) contains hydroxyl ions with metal ions precipitates of the hydroxides are formed. Hence a blue precipitate forms when aqueous ammonia is added to copper II sulphate solution. The precipitate dissolves in excess ammonia forming a deep blue solution. Cu(aq)2+ + 2OH-(aq) Cu(OH)2(s) Cu2+(aq) + 4NH3(aq) → Cu(NH3)42+(aq) Iron(II) is (Fe2+) forms a dirty green precipitate with Reactions Its aqueous solution is weakly basic due to the formation of OH- ions, NH3 + H2O ———→ NH+4 + OH- With sodium hypochlorite in presence of glue or gelatine, excess of ammonia gives hydrazine 2NH3 + NaOCI ——→ NH2.NH2 + NaCI + H2O With Nessler’s reagent (an alkaline solution uses Uses of ammonia It is used in the manufacture of fertilizers e.g. Ammonium sulphate. It is used in softening water. It is used in making nitric acid. It is used in making plastics. NITRIC ACID Lab method NaNO3 + H2SO4 → 2 HNO3 + NaHSO4 Large scale 4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g) Nitric oxide is then reacted with oxygen in air to form nitrogen dioxide. preparation Structure of HNO3 Properties 1] dilute 3 Cu + 8 HNO3 → 3 Cu (NO3)2 + 2 NO + 4 H2O 2] concentrated Cu + 4 HNO3 → Cu (NO3)2 + 2 NO2 + 2 H2O 3]non – metals C + 4HNO3 → CO2 + H2O +4NO2 4] metals With hydrocarbons 1. with benzene conc H2SO4 C6H6 + 2HNO3 C6H5 NO2+ 2H2O 2. With toluene conc H2SO4 C6H5 CH3 +3 HNO3 C6H2 (NO2)3 CH3 + 3H2O 2,4,6, trinitro toluene 3. With phenol Oxides of nitrogen a) Dinitrogen monoxide N2O b) Nitrogen monoxide NO c) Dinitrogen trioxide N2O3 d) Nitrogen dioxide = NO2 Phosphorous Exist in three allotropic forms- white, red and black. White phosphorous burns in air with faint green glow, phenomenon is called chemiluminescence. P4 + 5O2--> P4O10 Reactions of phosphine Reaction with chlorine PH3 +4CL2 PCl5 + 3HCl Reaction with CuSO4 CuSO4 + PH3 Cu3P2 + 3H2SO4 Reaction with mercuric chloride HgCl2 + PH3 Hg3P2 +6HCl Reaction to form phosphonium salts HBr + PH3 PH4 Br Phosphorous trichloride: Preparation Dry chlorine when passed over heated white phosphorous, gives phophorous trichloride. P4 + 6Cl2 4PCl3 It is also obtained by the action of thionyl chloride (SOCl3) with white phosphorous. P4 + 8SOCl2 4PCl3 + 2S2Cl2 + 4SO2 Properties PCl3 + 3H2O H3PO3 + 3HCl PCl3 + Cl2 PCl5 3CH3COOH + PCl3 3CH3COCl + H3PO4 3C2H5OH + PCl3 3C2H5Cl + H3PO4 3AgCN + PCl3 P(CN)3 + AgCl Phosphorous Pentachloride: Preparation Prepared by passing excess of chlorine gas over white phosphorous: P4 + 10 Cl2 4PCl5 Properties PCl5 + H2O POCl3 + 2HCl POCl3 + 3H2O H3PO4 + 3HCl PCl5 PCl3 + Cl2 C2H5OH + PCl5 C2H5Cl + POCl3 + HCl CH3COOH + PCl5 CH3COCl + POCl3 + HCl 2Ag + PCl5 2AgCl + PCl3 Oxyacids of phosphorous a.Hypophorphorous H3PO2 b.Orthophosphorous H3PO3 c. Orthophosphoric H3PO4 oxyacids pyrophosphorous acid H4P2O5 Pyrophosphoric acid H4P207 oxyacids Hypophosphoric H4P2O6 Group 16 Elements . Oxygen family: Group 16 of periodic table consists of five elements – oxygen (O), sulphur (S), selenium (Se), tellurium (Te) and polonium (Po). Their general electronic configuration is ns2np4. Electronic configuration general periodic trends: Periodic properties Trends Atomic Radii (the radius of the atom) increases Electronegativity:(the atom's ability of Decreases down the group attracting electrons) Ionization Enthalpy (the amount of decreases energy required to remove an electron from the atom in it's gaseous phase) Electron Affinity (ability of the atom to decreases accept an electron) Melting Point (amount of energy increases going down the required to break bonds to change a group solid phase substance to a liquid phase) Boiling Point (amount of energy increases going down the required to break bonds to change a group liquid phase substance to a gas) Oxidation state Their general electronic configuration is ns2np4 The most common oxidation state is – 2. The most common oxidation state for the chalcogens are −2, +2, +4, and +6. Chemical properties Reaction with air: S + O2 SO2 with acid[ only oxidizing acids] s + 6hno3 h2so4 +6no2 +2h2o With alkali 3S +6 NaOH Na2SO3 +2 Na2S + 3H2O reactions with non - metals 2S + C CS2 S + H2 H2S S + 3F2 SF6 reactivity 1. The metallic character increases as we descend the group. Oxygen and sulphur are typical nonmetals. Selenium (Se) and Te are metalloids and are semiconductors. Polonium is a metal. 2. Tendency to form multiple bond decreases down the group. Example O=C=O is stable, S=C=C is moderately stable, Se=C=Se decomposes readily and Te=C=Te is not formed. Formation of Hydrides All the elements of group 16 form hydrides of the type H2M (where M= O, S, Se, Te or Po). The stability of hydrides decreases as we go down the group. Except H2O, all other hydrides are poisonous foul smelling gases. Their acidic character and reducing nature increases down the group. [ less energy to break M – H bond ] All these hydrides have angular structure and the central atom is in sp3 hybridised. H – M – H Bond angle decreases Formation of Halides Element of group 16 form a large number of halides. The compounds of oxygen with fluorine are called oxyfluorides because fluorine is more electronegative than oxygen (example OF2). The main types of halides are 1. Monohalides of the type M2X2 2. Dihalides of the type MX2 3. Tetrahalides of the type MX4 4. Hexahalides of the type MX6 Formation Of Oxides Group 16 elements mainly form three types of oxides. 1. Monoxides: Except Selenium (Se), all other elements of the group form monoxides of the type MO (Example SO) 2. Dioxides: All the elements of group 16 form dioxides of the type MO2 (Example SO2) 3. Trioxides: All the elements of the group form trioxides of the type MO3 Anomalous behaviour of oxygen O is gas all are solids. O diatomic others poly atomic. O2is paramagnetic others diamagnetic. Forms H bonds in hydrides, alcohols and carboxylic acids. forms p∏ - p∏ multiple bonds. oxidation states -2 and +2 only with F others +2 and +6. Forms ionic compounds. dioxygen Preparation of o2 thermal decomposition of oxygen rich compounds Potassium chlorate will readily decompose if heated in contact with a catalyst, typically manganese (IV) dioxide (MnO2) . 2 KClO3(s) → 3 O2(g) + 2KCl(s) 2 KNO3 → 2 KNO2 + O2 2 KMnO4 ==> K2MnO4 + MnO2 + O2 oxides Preparation of oxygen using hydrogen peroxide The decomposition of hydrogen peroxide using manganese dioxide as a catalyst also results in the production of oxygen gas.
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