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Chapter 20 The Representative Elements: Groups 5A Through 8A 20.1 Group 5A Elements The Nitrogen Family ns2np3 valence electrons configuration Nitrogen can exist in many oxidation states. N and P are nonmetallic. As and Sb are metalloid. Bi is metallic. Bi and Sb tend to be metallic But no ionic compounds containing Bi5+ and Sb5+ are known BiF5, SbF5 and SbCl5 are molecular rather than ionic G 5A elements can form molecules or ions that involve 3, 5 or 6 covalent bonds to the G 5A atom NH3, PH3, NF3, and AsCl3. They all behave as Lewis base. All G 5A elements except N can form molecules (MX5) with 5 covalent bonds. The ability of G 5A elements to form bonds decreases dramatically after N. This is why N exists as N2 molecules; while other elements in the group exist as larger aggregates containing single bonds: P4, As4, Sb4 The Molecules of the Types MX3, MX5, and MX6 Formed by Group 5A Elements The Structures of the Tetrahedral MX4+ and Octahedral MX6- Ions 20.2 The Chemistry of Nitrogen Since N2 molecule contains a triple bond, most binary compounds (except NH3) containing N decompose exothermically to the elements In the preparation of NH3 from N2 and H2, too much energy is needed to disrupt the N≡N bond. Thus, though K (106) is high the reaction is very slow at room temperature. Haber process is used to prepare NH3 (high pressure, high temperature and a catalyst are needed) Nitrogen fixation: The process of transforming N2 to other nitrogen containing compounds Nitrogen fixation can be carried out by: Haber process (ammonia can be applied to the soil as a fertilizer) High temperature combustion process in automobile engines. NO produced is converted into NO2 that with moisture is concerted into NO3that reaches soil. Natural. Lightning produces the energy that disrupt N2 and O2 molecules producing reactive N and O atoms that attack other molecules to form nitrogen oxides that convert eventually to NO3 Nitrogen-fixing bacteria that reside on the root of nodules of plants such as beans and peas. This converts N2 to ammonia and other nitrogen containing compounds. Denitrification: return of N element to the atmosphere as N2 gas. Bacteria changes NO3- to N2 The Nitrogen Cycle Some Common Nitrogen Compounds 20.3 The Chemistry of Phosphorus Chemical properties of P are significantly different from N for the following reasons: Nitrogen’s stability to form much stronger bonds Grater electronegativity of N Larger size of P atom Availability of empty valence d orbitals on P White phosphorus exists as P4: very reactive and bursts into flames on contact with air. It is commonly stored under water Black P and Red P are network solids (a) The P4 Molecule Found in White Phosphorus (b) The Crystalline Network Structure of Black Phosphorous (c) The Chain Structure of Red Phosphorus P is essential for plant growth Soluble phosphate fertilizer is made by treating phosphate rock with sulfuric acid to make superphosphate of lime, that is a mixture of : CaSO4. 2H2O and Ca(H2PO4)2. H2O A reaction of NH3 and P produces NH4H2PO4 a very efficient fertilizer 20.4 The Group 6A Elements The valence electron configuration is ns2np4 Non of these elements behaves as a metal They achive the noble gas configuration by adding 2 electrons to become 2anion G 6A elements can form covalent bonds with other nonmetals Due to the presence of empty d orbitals (except O), they form molecules in which central atom is surrounded by more than 8 electrons: SF4 and SF6 Group 7A ns2 np5 valence electron configuration. All nonmetals Reactive. Not free in nature. Found as halide (X-) ions. Astatine radioactive with t1/2 = 8.3 hrs for its longest living isotope Very high electronegativities (4, 3, 2.8, 2.5 and 2). Ionic bonds with metals and covalent bonds with nonmetals in low oxidation states & polar covalent in metals in high oxidation states. Hydrogen Halides HCl is the most important acid. HF is used for etching glass. SiO2(s) + 4HF(aq) SiF4(g) + 2H2O(l) X H–X Bond energy (kJ/mol F Cl Br I 565 427 363 295 2O X ( g ) H X ( aq) Ho Ho (kJ/mol) (J/mol.K) -510 -159 -366 -96 -334 -81 -291 -64 Go (kJ/mol) + 102.4 90 53 23 Group 8A n2p6 configuration; Un-reactive. He. Component of the sun. Present in natural gas (from decay of radioactive elements). Used as Coolant and a rocket pressurizing gas. Ne. Used in Luminescent lighting. Ar. Used as a non-corrosive atmosphere in light bulbs. Xe & Kr form compounds with O and F.