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Chapter 3 Molecular Shape and Structure

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Chapter 3 Molecular Shape and Structure 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 CHAPTER 14 THE ELEMENTS: THE FIRST FOUR MAIN GROUPS Beginning of the descriptive chemistry ! ▶ Nanotechnology Æ 1 ~ 100 nm particles Æ Biosensor, Microscopic computers, Artificial bones, Light weight, strong materials Fig. 14.1 The relative abundances of the principal elements. PREODIC TRENDS Congener (동족원소) ex. Li, Na, K, Rb, Cs, Fr 14.1 Atomic Properties Fig. 14.2 Atomic radius Fig. 14.3 Ionization energy Fig. 14.4 Electronegativity Fig. 14.5 Polarizability 14.2 Bonding Trends ▶ Multiple bond formation Æ Depends on the size of atomic radii Ex. Period 2 elements form π -bond (effective overlap of p-orbitals) contrary to Period 3 and heavier elements Fig. 14.6 Overlapping of p-orbitals: (a) Period 3 and heavier elements. (b) Period 2 elements (π -bond) ▶ Periodic trend in bonding of main-group elements Æ Binary hydrides: Formulas directly related to the group number showing typical valences of the elements CH4 (Group 14/IV), NH3 (Group 15/V), H2O (Group 16/VI), HF (Group 17/VII) Fig. 14.7 Chemical formulas of hydrides vs. valences 1 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 ▶ Binary hydrides Saline hydrides (이온성 수소화물): s-block elements, white, high m.p., crystals, portable fuel, H– ∆ 2 K(sg) +⎯H2 ( ) ⎯→2 KH(s) Metallic hydrides: d-block elements, black, conducting powder, portable fuel ∆ 2 Cu(sg) +⎯H2 ( ) ⎯→2 CuH(s) Molecular hydrides: non-metal elements, low melting volatile Brønsted acid NH3, HX, hydrocarbons Fig. 14.8 The difference classes of the binary hydrogen compounds. Fig. 14.9 Hydrogen atoms of a metallic hydride in the interstices of the metallic lattice. ▶ Nonmetal oxides Acid anhydrides: non-metallic oxides HO2 HO2 N25O ⎯⎯⎯→ HNO3, SO32⎯⎯⎯→ H SO4 HO Formal anhydrides of acids: CO ⎯⎯2 ⎯→ HCOOH HYDROGEN 14.3 The Element 89% of all atoms in the universe (Fig.14.1) Present in water and hydrocarbons ▶ Preparation: (1) Electrolysis of water hν (2) Water-splitting reaction: 2 H22O(lg) ⎯⎯→+2 H ( ) O2(g) Ni (3) Reforming reaction: CH42()gg+⎯HO() ⎯→+CO()g3 H2(g) Fe/Cu (4) Shift reaction: CO()gg+⎯H22O() ⎯⎯→CO()g+H2(g) Fig. 14.10 Mass of 10mL water (5) Reducing H+ ions from a strong acid: ≈ Mass of 100mL liquid H2. ++2 Zn(sa) +⎯2 H ( q) ⎯→+Zn (aq) H2 (g) ▶ Properties: Light, colorless, no smell, no flavor, liquefy at 20K ▶ Usage: Rocket fuel, Haber process 2 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 14.4 Compounds of Hydrogen ▶ Ionic hydrides: MH (M+H–) o − o+ E (H2 / H ) =−2.25 V cf. E (Na / Na) =−2.71 V Æ Strong reducing power NaH(sl)H+⎯22O() ⎯→NaOH(aq)H+(g)Å portable H2 supply ▶ Hydrogen bonding O–H : Bond enthalpy = 463 kJ·mol–1 Oδδ−+⋅⋅⋅ H−O : Bond enthalpy = 20 kJ·mol–1 GROUP 1: THE ALKALIMETALS Na+/K+ couple Æ Concerted action and migration across the membrane Æ Consciousness Valence configuration: ns1 3 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 14.5 The Group 1 Elements ▶ Preparations: Electrolysis of molten rock salt (Downs process): Cathode: 2 Na+(melt) + 2 e– Æ 2 Na(l) Exposing molten KCL to sodium vapor: 750oC KCl(lg) +⎯Na( ) ⎯⎯→NaCl(s) +K(g) ▶ Properties: soft, lustrous, low m.p. & b.p. Fig. 14.11 (a) Li (b) Na (c) K (d) Rb & Cs Fig. 14.12 Melting points(oC) of alkali metals. ▶ Usage: Li-6 as a source of tritium (T) in thermonuclear weapons 64Li +⎯n ⎯→+T He Lithium-ion batteries 14.6 Chemical Properties of the Alkali Metals ▶ Strong reducing agent Å small E o values 2 Na(sl) +⎯2 H22O( ) ⎯→+2 NaOH(aq) H (g) Fig. 14.13 Reactions with water: (a) Li (b) Na (c) K 4 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 ▶ Reaction with ammonia : ▶ Reaction with oxygen Electrons released from the metal fill the cavities formed by ammonia molecules. Æ ink-blue metal-ammonia solution Fig. 14.15 Lithium oxide(LiO),,Sodium peroxide(Na2O2), Potassium superoxide(KO2) Fig. 14.14 Sodium-ammonia solution 14.7 Compounds of Lithium, Sodium, and Potassium ◆ Lithium, Li Properties: Small size of Li+ ion Æ high polarizing power Æ forms bonds with high covalent character Æ strong ion-dipole interaction forming hydrates Usage Ceramics, lubricants, medicine Li CO : bipolar disorder (조울증,躁鬱症) Fig. 14.16 An evaporation pond for brine from salt 2 3 lakes. (Blue dye for increasing heat absorption.) Lithium soap: high m.p., used in high-temp lubricant H-bomb, Li-Batteries ◆ Sodium, Na Sodium compounds: Low cost, high solubility in water ► NaCl: Used in producing Cl2 and NaOH ► NaOH: Soft, waxy, white, corrosive solid Produced by electrolysis of brine − 2 Cl (aq) + 2 H2O(l) electrolysis − ⎯⎯⎯⎯⎯→+Cl22(g) 2 OH (aq) +H (g) ► NaHCO3: baking soda sodium hydrogen carbonate (sodium bicarbonate) Fig. 14.17 A diaphragm cell for the electrolytic − production of NaOH from brine. HCO3 (aq) +→HA(s aq) ⎯⎯→ − A (aq) ++H2O()l CO2 (g) ↑ Swelling of batter 5 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 ◈ Kitchen Chemistry ▶ Baking powder = baking soda + acid salts (both high and low T) + corn starch High T (slow-acting) acid salts: sodium aluminum sulphate, AlNa(SO4)2·12H2O sodium aluminum phosphate, NaAl3H14(PO4)8·4H2O or Na3Al2H15(PO4)8 sodium acid pyrophosphate, Na2H2P2O7 Low T (fast-acting) acid salts: cream of tartar (or potassium hydrogen tartrate), KC4H5O6 monocalcium phosphate (or calcium acid phosphate), Ca(H2PO4)2 Corn starch: absorbs moisture ► Na2CO3·10H2O: washing soda Å alkaline 2+ 2− 2+ Ca (aq) +⎯CO33(aq) ⎯→CaCO (s) Å removing Ca ions from water ► Na2CO3, Soda ash Æ source of Na2O in glass industry ◆ Potassium, K Minerals: Carnallite, KCl·MgCl2·6H2O; Sylvite, KCl Usage: Fertilizers ∆ 2 KNO3(s) ⎯⎯→2 KNO2(s) +O2(g) Å less hygroscopic (흡습성,吸濕性) ☺ Safety matches (1855) – Johan Lundstrom (서전,瑞典, 1815-1888) match head: KNO3 + Sb2S3 + Pb3O4 + K2Cr2O7 rubbing surface: sand paper + red phosphorus + Sb2S3 GROUP 2: THE ALKALINE EARTH METALS 6 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 14.8 The Group 2 Elements st nd –1 Fig. 14.18 1 - and 2 -ionization energies (kJ·mol ) of alkaline metal elements. Fig. 14.19 Alkaline earth metals: (a) Be, (b) Mg, (c) Ca, (d) Sr, (e) Ba. ◆ Berylium, Be Mineral: beryl, 3BeO·Al2O3·6SiO2 Æ emerald (beryl + impurity, Cr3+) Preparation: Electrolytic reduction of molten BeCl2 Usage: Construction of missiles and satellites Window for X-ray tube Rigid Be-Cu alloy (Be added in interstitial sites of Cu metal) Æ nonsparking tools (preventing explosion) Fig. 14.20 Emerald (녹주석,綠柱石) 5월 탄생석, ‘청순,淸純’ for oil refineries and grain elevators ◆ Magnesium, Mg Seawater, Minerals (dolomite, CaCO3·MgCO3) o Chemical reduction: dolomite Æ MgO ⎯ferro⎯⎯⎯⎯⎯silicon, 1200 C→ Mg Ca(OH)2 HCl Electrolysis Electrolytic reduction: seawater ⎯⎯⎯⎯→ Mg(OH)2 ⎯⎯⎯→ MgCl2 ⎯⎯⎯⎯→ Mg Burns vigorously in air, Reacts with water, CO2, N2 Usage: Airplane, automobiles Å light and tough Mg metal ◆ Calcium (Ca), Strontium (Sr), Barium (Ba) Preparation: Electrolysis ∆ Thermite process with Al: 3 BaO(ss) +⎯2 Al( ) ⎯→+Al23O (s) 3 Ba(s) 7 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 Reaction with water: Be does not react with water. Mg reacts with hot water. Ca reacts with cold water. Ca(sl) +⎯2 H2O( ) ⎯→ 2+− Ca (aq) ++2 OH (aq) H2 (g) Colors of burning flames Ca (orange-red), Sr (crimson), Ba (yellow-green) Fig. 14.21 A gentle reaction of Ca with water. 14.9 Compounds of Beryllium and Magnesium ◆ Beryllium − 2− Reaction with a base: Be(sa) ++2 OH ( q) 2 H24O(l) ⎯⎯→+Be(OH) (aq) H2(g) beryllate ion Beryllium compound: Æ Very toxic 2+ Æ Be (strongly polarizing, small) Æ forming BeX4 unit Æ Chloride 600−800o C BeO(ss) + C( ) + Cl22(g) ⎯⎯⎯⎯→+BeCl (g) CO(g) Be in BeCl2 : Lewis acid Æ accepts electron pairs from neighboring Cl atoms Æ Forming a chain of tetrahedral BeCl4 units in solid ◆ Magnesium Forming ionic compounds Energy generation in living cells Æ Contraction of muscles ► MgO Æ obtained by heating hydroxide or carbonate Æ refractory (내화성,耐火性) m.p. 2800oC, cf. refractory index (굴절율) Æ good conductor for electricity Æ poor heat conductor Æ used for an insulator in electrical heaters ► Mg(OH)2 Æ basic Æ Forming a white colloidal suspension, “milk of magnesia” Å stomach antiacid Reaction with acid Æ MgCl2 (purgative,설사제下劑) 8 2009년도 제2학기 화 학 2 담당교수: 신국조 Textbook: P. Atkins / L. Jones, Chemical Principles, 4th ed., Freeman (2008) Chapter 14 ► Antiacid, MgCO3 Æ causing ‘belch’ due to CO2 ► ‘Epsom salt’, MgSO4·7H2O, Æ purgative 2+ Mg prevents absorption of water by intestine ► Chlorophyll (엽록소,葉綠素) Capturing solar energy and channel it into photosynthesis 2+ Mg keeps the plane of ring rigid Æ preventing the loss of energy into heat 14.10 Compounds of Calcium ► CaCO3 Colored marble due to impurity of iron cations Minerals: calcite (방해석,方解石), aragonite (산석,霰石) ► CaO (quicklime,생석회) ∆ CaCO32(ss) ⎯⎯→+CaO( ) CO (g) 2+ − CaO(s) +⎯H2O(l) ⎯→+Ca (aq) 2 OH (aq) Å highly exothermic reaction Å Fire ! ∆ CaO(ss) +⎯SiO2( ) ⎯→CaSiO3(l) Å low m.p.
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