Section 1: General Trends in the p-Block Elements 1.1 Atomic and lonic Size + Trend across a period: Atomic and ionic radii decrease from left to right due to an increase in nuclear charge pulling electrons closer to the nucleus. ‘+ Trend down a group: Atomic and ionie size increases due to the addition of new electron shells = Example + B(85pm) ~ C (70 pm) ~ N(65 pm) ~ 0 (60 pm) ~ F (50 pm) + N=» 0% >F (Anions are larger due to electron-electron repulsion) Diagram: Periodic table size trend chart 1.2 Metallic and Non-metallic Character ‘+ Metallic character: Increases down the group; decreases across the period. + Group 13: 8B (non-metallic) ~ TI (metallic) + Group 15: N (non-metallic) Bi (metallic) ‘= Explanation: Due to increasing ionization energy across the period and decreasing Ionization energy down the group. Diagram: Graphical trend showing metallic to non-metallic vansition. 1.3 Melting and Boiling Points ‘= Varies irregularly across the groups due to different types of bonding (metallic, covalent, van der Waals). ‘+ Group 14 shows highest metting/boiling due to strong covalent bonding (C, Si). 1.4 lonization Enthalpy + Increases across the petiod (more protons attract electrons more strongly). + Decreases down the group (outer electrons are farther from nucleus). ‘= Group 13 Anomaly: Ga > Al due to poor shielding by electrons. 1.5 Electron Gain Enthalpy + Definition: Energy change when an election is added to @ neutral atom, + Becomes more negative across a period, less negative down a group. = Chlorine > Fluorine (F has smaller size, more repulsion),1.6 Electronegativity * Increases across a period, decreases down a group. © Order: F > O> Cl>N>Br>1>S>C>P>H 1.7 Allotropy + Elements lke ©, 0, §, P, Sn show allotropy. + Carbon: Diamond (tetrahedral), Graphite (planar layers). + Phosphorus: White, red, black forms. Diagrams: Structures of diamond and graphite. 1.8 Inert-Pair Effect + Tendency of s-electrons (ns?) to remain non-bonding in heavier p-block elements. * Seen in Group 13 and 14, especially TI() and Pb(II) more stable than +3/+4. + Cause: Poor shielding by d-and forbitals ~ ns? electrons are held tightly. 1.9 Diagonal Relationship + Beryllium-Aluminium, Lithium-Magnesium + Similarities due to: + Similar size * Charge density * Electronegativity 1.10 Anomalous Behavior of First Element of Each Group + Dueto: + Small size + High electronegativity + High ionization enthalpy + Absence of d-orbitals + Examples: + B#AI,C#SiN2PSection 2: Structure, Bonding and Properties (Acidic/Basic Nature, Stability, lonic/Covalent Nature, etc.) 2.1 Structure and Bonding in p-Block Compounds a. Nature of Bonding + Covalent bonding is dominant in p-block compounds. ‘+ Elements use sp, sp#, sp?, sp*d, spd? hybridization depending on their group and oxidation state Examples: + NH, — sp? + BF = sp? + SFy— spi? + PC, - sptd Diagram: Structures showing molecular geometry: trigonal planar (BF,), tetrahedral (CH.), ‘trigonal bipyramidal (PCI,), octahedral (SF). b. Acidic and Basic Nature + Actoss a period: Basic — Amphoteric -- Acidic = Down a group: Acidic character decreases, basic character increases. Examples: + Group 15 Hydrides: NH, (basic) > PH, (weakly basic) > AsH, (neutral) + Group 16 Oxides: SO, (acidic) » SeO, (acidic) > TeO, (amphoteric) c. Stability + Stability of compounds depends on + Size and charge of central atom + Bond energies + Oxidation state Examples: + H,P0, > H,PO, > H,PO; (based on oxidation state of P) + HNO, is more stable than HNO,d. lonic vs. Covalent Character + Fajan's Rules: Covalent character increases with: + Small cation size * High cation charge * Large anion size Example’ * AICI, (covalent) vs NaCl (ionic) * PbCI, (less covalent) < PbCl, (more covalent) e. Oxidation and Reduction Behavior + Many p-block elements show variable oxidation states. + In general: © Group 13:+3,+1 * Group 14: +4, +2 * Group 15: 3,+3,+5 + Group 16: -2, +2, +4, +6 © Group 17: -1, +1, +3, +5, +7 Example: + In HNO,, Nis in +5 oxidation state. * INNO, Nisin +2. f. Hydrolysis and Action of Heat + Hydrolysis: Many p-block halides hydrolyze in water. + BCI, +3H,0 — B(OH), +3HCI + SiCl,+2H,0 - SiO. + 4HCI + Thermal Stability: Down the group, thermal stability of hydrides decreases. + NH > PH; > ASH, > SbHaNext Subsection: Hydrides of p-Block Elements We'll now cover hydrides group-wise as mentioned in the syllabus. 2.2 Hydrides of p-Block Elements Hydrides of Group 13 (Boranes and Borohydrides) Types: 1. Electron-deficient hydrides: Incomplete octet (e.g., BpH.) 2. lonic hydrides: e.g., LiIBH, 3. Covalent hydrides: e.g., BH; Boranes: © General formula: ByHp+s (nido), BaHpse (arachno), ete. * Diborane (B,H,): « Contains two bridging hydrogen atoms. * 3-center 2-electron bonds. Diagram: Structure of diborane showing banana bonds. Borohydrides: e NaBH,, LiBH, are reducing agents. » Reactions: « NaBH, +H,0 — NaBO, + H,t « Used to reduce aldehydes/ketones to alcohols.Hydrides of Group 14: Carbides and Silicates A. Hydrides of Group 14 Elements These are tetrahydrides (general formula: MH,) for lighter members (6, Si) and unstable, polymeric or unknown for heavier members (Ge, Sn, Pb). Element Hydride Nature Stability c cH, Covalent Very stable Si si, Covalent Less stable Ge GeH, Covalent Unstable sn ‘Sn Covalent Highly unstable Pb No stable hydride - Very unstable Trends: + Down the group, thermal stability decreases. + Covalent character Is maintained. + They react with oxygen to form oxides and water. Reactions: © CH,+20, - CO, +2H,0 «SIH, +20, ~ SiO, + 2H,0 B. Carbides Definition: Binary compounds of carbon with a less electronegative element (usually a metal or metalloid). Types: 1. Salt-like (Ionic) Carbides: e.g. CaC., MgsCs + CaC,+H.0 ~ CaHs + Ca(OH), 2. Covalent Carbides: e.g. SiC (carborundum) + Extremely hard, used as abrasive. 3. Interstitial Carbides: e.g. TIC, WC + High melting points, good conductivity. Diagram: Bonding in CaC, showing acetylide ion C.*C.Si Defin ites. nition: Salts containing anionic SiO,* units. ‘Types of Silicates (based on structure): 1 2 3. 4. 5 Orthosilicates ~ S10," (isolated tetrahedra) .. Pyrosilicates ~ Si,0,*- (two tetrahedra linked by one oxygen) Chain Silicates (Inosilicates) ~ (Si0,)"="~ Sheet Silicates (Phyllosilicates) - mica, tale Framework Silicates (Tectosilicates) - quartz, feldspar Structure Diagram: Tetrahedral structure of SiO, and chain linkage in silicates. Uses: Zeolites in ion-exchange Silicones for lubricants/sealants Silica in glass and ceramics Next: Hydrides of Group 15 (N and P) Hydrides of Group 15: NH3, PH3, ASHs, SbH,, BiH, Compound Nature Stability Basicity smell NH, Strong base Very stable Strongest Pungent PH, Weak base Moderately stable Weak Rotten fish ASH, Neutral Less stable Very week Garlicsike SbH, Neutral Unstable Weak Unpleasant BiH, Decomposes Highly unstable Negligible - Trends: Thermal stability decreases down the group. Reducing character increases down the group. Bond angle decreases: NH, (107°) > PH (94°) > AsH, (92°) Reaction: Diag NH, +HCI -. NH,CI (acid-base reaction) ram: Pyramidal shape of NH, showing lone pair on nitrogen.Hydrides of Group 16 (0 and S) Overview: The general formula is HaE (where E = 0, S, Se, Te, Po). These are covalent and volatile compounds with varying physical and chemical properties, Hydride Name Physical State Ho Water Liquid Hs Hydrogen sulfide Gas Hse Hydrogen selenide Gas H,Te Hydrogen telluride Gas H,Po Hydrogen polonide Unstable Trends in Group 16 Hydrides: Property Thermal stability Acid strength Bond angle Boiling point Hydrogen Bonding in Water Stability Highly stable Moderately stable Less stable Very unstable Highly unstable Down the Group Trend Decreases (H,0 > H,S > H,Se > H,Te) Increases (H,0 HCl > HBr > HI + Reducing Power: Increases down the group — HI is a strong reducing agent, Reactions: + HI+H,SO, ~ |, +S0,+H,0 + HF +Si0, ~ SiF, +H,0 (used for glass etching) Diagram: Hydrogen bonding in HF.2.3 Oxides and Oxoacids of Nitrogen, Sulphur, Phosphorus and Chlorine This section involves understanding Oxidation states of central atoms Acidic/basic/amphoteric nature Structure of molecules Reactions (including redox behavior) A. Oxides and Oxoacids of Nitrogen Oxides of Nitrogen: Oxide Formula Oxidetion State of N Nature Nitrous oxide NO 4 Neutral Nitric oxide No 2 Neutral Dinitrogen trioxide N,0; 8 Acidic Nitrogen dioxide No, 4 Acidic Dinitrogen tetroxide N,0, 4 Acidic Dinitrogen pentoxide N,0; +5 Strongly acidic Structures & Notes: + NO: odd-electron molecule (paramagnetic). * NO,: planar, bent molecule with unpaired electron (brown gas). + N.O,: anhydride of HNO,. Reactions: + N:O;+H,0 — 2HNO, + NO+0, — NO, Diagram: Structures of NO, (bent), N,O5 (bridged structure)Oxoacids of Nitrogen: Acid Formula Oridation State Hyponitrous ac HNO, “ Nitrous aia HNO, #8 Nite acid HNO, 6 Key Reactions: + HINO, ~ NO+NO, + H,0 (on heating) + HINO, + Cu — Cu(NO,), + NO, +H,0 (oxidizing acid) B. Oxides and Oxoacids of Sulphur Oxides of Sulphur: oxide Formula Oxicstion State Sulphur dioxide 50, “4 Sulphur trioxide 80, + Structures: ‘+ SO, Bent molecule (sp? hybridization), lone pair on S. + SOs: Planar trigonal (sp? hybridized), symmetrical Reactions: + 80, +H;0 ~ H,S05 + 80, +H,0 ~ H,SO, Oxoacids of Sulphur: Acid Formula Oxidation State Sulphurous acid H.S0, 4 Sulphuric acid H.S0. +6 Pyrosulphuric acid H.S:0, +6 Thiosulphuric acid H,8,0, Mixed (+2, +6) Petoxomonosulphuric acid H,S0. +6 Diagram: Structure of H,S0, and $0,. Strength/Nature Weak acid Unstable, weak acld Strong monabasic acid Nature Acidic Acidic Features Weak acid Strong dibasic acid Inoleum Unstable Contains -0-0- groupC. Oxides and Oxoacids of Phosphorus Oxides: Oxide Formula Oxidation State Nature Tetraphosphotus hexoxide PO, cc Acidic Tetraphosphotus decoxide PO, 45 Acidic Reactions: + P,Q, +6H,0 = HPO, Oxoacids of Phosphorus: Acie Formula Oxidation State Properties Hypophosphorous eld HPO, “ Monobesie Phosphorous acid H,P0, “8 Dibasie Orthophosphoric acid ———+H,PO, 6 Tribesi, moderately strong Pyrophosphore acid HP.0, + Dibacie Metaphosphorc eid (HPO), 45 Polymer of HPO, units Diagram: Structure of H,PO,, showing three replaceable protons. D. Oxides and Oxoacids of Chlorine Oxides of Chlorine: oxide Forrula Oxidation State Nature 3 Dichlorne monoxide c.0 4 Acidic Dichlorine trioxide 10, 8 Acie Dichloine ttvonide a0, “4 Acide Dichlorine pentoxide a0, 6 Acidic Dichlorine heptoxide 1,0, a AcidicOxoacids of Chlorine: Acid Formula Hypochlorous acid HCIO Chlorous acid HClO, Chloric acid HClO, Perchloric acid HCIO, Reactions: Oxidation State Acid Strength +1 Weak acid 4g Unstable +5 Strong acid +7 Very strong acid © Cl,+H,0 = HCI + HCIO (disproportionation) e HCIO, ~ H++ClO,- Diagrams to include in notes: « Lewis structures of SO2, NO, HNOz, HySO4, HCIO4, P2010. ° Graph showing acid strength trend across oxoacids.2.4 Peroxoacids of Sulphur and Halogen Compounds A. Peroxoacids of Sulphur ‘These acids contain the -O-O- (peroxo) linkage and sulfur in the +6 oxidation state. ‘They act as strong oxidizing agents due to the peroxo group. Types of Peroxoacids of Sulphur: Name Formula Structure Highlights Peroxomonosulphuric acid (Carols H,S0, (One ~0-0- linkage, one ~OH group acid) Peroxodisulphurle acid (Marshalls H,S,0, Two -0-O- groups, symmetrical acid) structure 1. Peroxomonosulphuric Acid (H,SO;) © Preparation: H,S0, + H,0, + H2S0, + HO + Structure: Contains one peroxide (-0-O-) bond and one -OH group. + Oxidation state of S:+6 * Strong oxidizing agent. 2. Peroxodisulphuric Acid (H,S,0.) + Preparation: 2H,S0, + H,0, — H,8,05 + 2H,0 © Structure: ‘Two tetrahedral SO, units connected via a peroxide bridge © Used in: * Bleaching + Polymerization initiator * Cleaning electronic parts Diagram: Clear illustrations of H,S0; and H,S,0, with -O-O- bondsB. Halogen Compounds 1. Interhalogen Compounds Definition: Compounds formed between two different halogens (X and Y), where X is less electronegative than ¥. General Formula: + AX, AXs, AXs, AX (A = larger halogen, X = smaller one) Compound Formula Geometry Hybridization cr, AX Tehaped opid err AX, ‘Square pyramidal spd iF, AX, Pentagonal bipyramidal spar Properties: + Covalent and volatile + Strong oxidizing agents ‘+ More reactive than individual halogens Reactions: © CIF +H,0 HF +HCIO +0, 2. Pseudohalogens Definition: Non-halogen polyatomic species that mimic halogen chemistry. Exemple Formula Resembles cyanogen ™, ch, Thiocyanogen (son), Br, Aride Ne Halide ion (Cl ete) Properties: ‘+ Exist as diatomic molecules or polyatomic anions: ‘+ Form halide-ke salts and acids. Example Reaction: ‘+ Ag+ CN> ~ AgCN (analogous to AgCI)3. Polyhalide lons Definition: lons that contain more than one halogen atom (usually in combination with a halide ion and a halogen molecule). lon Structure Formation Triiodide ion Ie bh Io Tetrabromide ion Bry Br + Br, Bry = Bry Properties: * Exist in solutions of halogens with halide salts. © I, is linear (I-I-I) Diagram: Linear structure of |,~, showing delocalized bonding © Quick Summary Chart: Class Example Key Feature Peroxoacids H,SO., H,S,0., -0-0- linkage, strong oxidizers Interhalogens CIF,, BrF Mixed halogens, hypervalent Pseudohalogens (CN),, No~ Behave like halogens chemically Polyhalides I>, Bre Extended halogen halide ions