Inorganic Chemistry CHEM 463
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This 24 page Class Notes was uploaded by Gavin Harvey on Friday October 23, 2015. The Class Notes belongs to CHEM 463 at University of Idaho taught by Daniel Stelck in Fall. Since its upload, it has received 22 views. For similar materials see /class/227963/chem-463-university-of-idaho in Chemistry at University of Idaho.
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Date Created: 10/23/15
Valence Shell Electron Pair Repulsion as pussxble 4212mm ausrs hbnd 2Eledmnpausrsphybnd p 5 y u Ex cq 3 212mm pans r spa hybnd amp cw NH 0H1 VSEPR cont d 5 912mm past s dzzhybnd Square pyxamm up my 4 mm k Ex InOSI39 5P3dXZ39W XEFZ 5 F3 may x um I VSEPR cont d IIu awn 3 2 Octahedral Sp d EX SF6 S 3d3 Pentagonal Blpyrarrudal P X IF7 or Distorted Octahedron EX 7er Summary of Rules forVSEPR Lone pairs are stereochemically active 7 Ex NH3 1 quotIIH H 2 Repulsion from lone pairsgttri le 4 39 61 L A Therefore 39 39 A sothat repulsions are minimized ereduce no of 90D interaction Example FIIIuQF With 1p in axial position there are three 90D lpebp contacts F F fl 1790 F quot39vl C With 1p in equatorial position there are only twoe 90D lpebp contacts EXP entauy Si V F F M F J Favored structure 7 distorted seesaw V t o 9S Hybridization up 41 up 3 promotional energy I 4 Summary of Rules forVSEPR Central atom and substituent effects hybridize 3 gt stabilization regained in H With heavier atoms promotional energy is on the order of bond strengths so there is incomplete hybridization Result lune A 39 39 39 39 aui e nrbita U quot closer to 90D disposition of p orbitals Also bonds are longer 7 less repulsion Bon dangleis w EX NH8 1066 H20 1045 PH3 933a st 921u AsH3 9183 ste 910 SbHs 913u HzTe 90 Summary of Rules forVSEPR Central atom and substituent effects cont d Bent39s rule More electronegative susbstituents quotpreferquot hybrid orbitals having less 5 character J quot L39 quotpreferquoth h 39d h39t h 39 character Ex ng CHZFZ CH13 NF3 or2 EX 2 Preferred geometry of PC13FZ places uorines in axial positions which have 51 and p character but no 5 character H7C7H 110112D F7C7F 1119D i041 1083i01 1088 r 0750 1023 compare with NH3 1066 1020 compare with H20 1045 T Cl mc1 0 F Consequences of lattice enthalpies Lattice enthalpy increases With increasing ion charges and decreasing ionic radii Electrostatic 2 Z r parameter E charge dens1ty Some salts consisting of complex ions can decompose to simpler salts eg MCO3s gt MOs C02 g AG kJmOl 1 483 1304 1838 2181 Lattice AH kJmOI l 1006 1783 2346 2693 39 Smau Large quotA change 39 change AS 1750 1606 1710 1721 1 JK lmol l C 300 840 1100 1300 Consequences of lattice enthalpies Cations With high oxidation states are stabilized by small anions eg F and 02 MX 05 X2 gt MX2 Higher lattice energy makes the reaction more exothermic Solubility The free energy change of any process precipitation or dissolution depends on both the enthalpy and entropy changes AG AH TAS Lattice enthalpy Hydration enthalpy Hydration entropy For many salts the solubilities are hard to predict but there are a few simple guidelines for some Acidic cations and basic anions tend to give insoluble salts a All carbonates are insoluble except those of the Group 1 elements and NH4 b All hydroxides are are insoluble except those of the Group 1 elements Sr2 and Ba2 Cross combinations give soluble salts a All nitrates are soluble b Most Na and K salts are soluble Large non acidic cations and large nonbasic anions tend to give insoluble salts 4 Size disparity between cation and anion favors A solub111ty T o E w x 1 5 C AHLO cc 5 r r o m 1 o gt Athdoec 2 m r r 5 C LLl 7 t 200 1OUl 0 100 200 Difference in iHH between anion and cationkJ mor39 Primary and secondary hydration spheres of a hydrated cation MgHZO362 CO3H20282 gt MgCO3s 64 H20 Ion Z2r Hydration no Hydrated radius pm Cst 0005 6 228 Kt 0066 7 232 Nat 00088 13 276 Lit 001 1 1 22 340 Ba2 00268 28 Sr2 00303 29 Ca2 00351 29 M g2t 00465 36 Cd2 00549 39 Zn2 00599 44 Crystal Defects 0000000000 0 000000000 00 39ob39o39o39ob39do39o 39 quot 0 o 39 0 00000000 a 0000 o 20102210uniqoiohm td 4 1 f l T l T l a b c d e f g h a Interstitial impurity atom b Edge dislocation c Self interstitial atom d Vacancy e Precipitate of impurity atoms f Vacancy type dislocation loop g Interstitial type dislocation loop h Substitutional impurity atom Metals Semiconductors amp Superconductors 1g E 1039 U Q Superconductor 2 1 ti 3 39U C o 0 10 Semiconductor 10 l 1 10 100 1000 TK Metals are Viewed as a lattice of cations held together by a sea of free electrons a fermi sea Properties of bright lustrous appearance 111633133 high electrical conductivity high thermal conductivity malleability Band Formation Most antlbon dmg em g m 3 Intermediate L16 I I gt orbitals Most antibonding 7 7 g 39 V 39 K I 1 1quot lr l gt A Q 139 f g LLI quot 1 l f g p Most bondinrgquot 1 2 3 4 5 6 7 8 9 10 11 12 20w Metals Li 11 Ben T Empty band Empty p band gt5 9 a E LIJ Empty levels 39 F39ll d b d lt7 Ferml eve 1 e S an Occupied levels Intrinsic Insulator 39 C Semiconductor diamond Si or Gen Antibonding MOS Band Gap 500 k mole Band Gap 70 100 k mole Bonding MOS Fermi Level El corresponds to the highest occupied energy at T0 HOMO energy 1 Femerxrac distnbuuon P E 7E 1039 e F 1 population P of the valence band mums Cmauc on am some mums have analgy ahmm mo Fem We r E Noseemcmmmmmm NW Imam WWW band a 0K SW19 N NE quotwe E JVS39QY can mach me canduclmn hand and above the Farm MM and Wave 9 5 conmbme Ia elecmc current no mums enemy sates m the harm as Doping in semiconductor p type 0 GD 0 O Q 7Felm lava P Type Doping in semiconductor n EXCESS ELECTRON Extrinsic Semioonducto p39ype mam km W m Eunice awmxmma SnmGendwtdwithPmAs camp ypeCu10F FeSCul Olhzrnlype zo 1710 Density of States 3 gt Energy gt Energy gt Density of states Dequot Sity 0f States Metal Semimetal Conducting Polymers Nobel Prize in Chemistry 2000 Hideki Shirakawa Alan McDiarmid Alan Heeger W M x x Copper metal transpolyacetylene cis polyacetylene P olyac tylene dop e d with Ast P olyac etylene dope d with I 1 m m S N X Liqmd mercury X I P 01 p phem ane polythiophene polypyrrole doped with ASP Poly pyrrole doped w h Ii NQN N2CgtZN l H H Y 39Y X P 0131 amhne emeraldim Loga thmic conductivity ladder locating some metals and conducting polymers polyaniline Ieucoemeraldine y 1 emeraldine y 05 and pernigraniline y O pn Junction Depletion region Djfinscd electrons e G 9 ptype G Q Q G D G G G G Q Q 9 G lt9 9 i i pu junction Barrier potential electric eld Electron diffusion across a pn junction creates a barrier potential electric field in the depletion region 0 ooo 2 ooog ooo To Reversed bias pn Junction Minority carrier flow n side p side Widened depletion region llllle External battery Only minority carriers can move freely Foward bias pn Junction Narrowed depletion region 999 999 I39r External battery Lower potential barrier so that majority carriers can diffuse across the junction Light Emitting Diodes Forward bias at a p n junction forces minority carriers across the junction This causes electrons to fall into vacant holes radiatively giving off light Common LED materials GaAs Eg143 eV gt Near IR GaPN Eg 225 eV gt Yellow GaPZnO Eg 225 eV gt Red GaN SiC ZnO AlN gt Blue UV Ohmic contacts Figure 51 Injection of minority carriers in a forwardbiased pn junction leading to spontaneous emission of photons Light output nr substrate Dielectric layer 10 Common LED materials GaAs Eg143 eV gt Near IR GaPN Eg 225 eV gt Yellow GaPZnO Eg 225 eV gt Red GaN SiC ZnO AlN gt Blue UV Superconductors Key words Type I and II superconductors BCS theory and Cooper pairs Meissner effect Resistance 01 Nunsuperconductive K T v C K 46 Superconductor Temperature ll Type II superconductor YBaZCu30H 17117111 Mijller and Bednorz 71986 m Ndan39l30 GlanlCu307 YBalCuJO7 31392 I439II70ls TmBnlCllzo Yan239n30 httpsnpercouductoxsorg Hgnsno23 2c 2c 3ox33 HgBalCazCuJOs IinghC 39n 0 TlBazCazCuJOW lennzcazcuzom 5HgDJBgt12 111010 NUSPIJMSIzmlc pg TllBHZCHCIIlO6 Tmazc j CllJOll ImaZCa39uzo 11213qu6 138 Kr record holder 1337135 K 125126 R 1237125 K 94A K 133 http sup erconductors org Fluorite vertex linked CuO4 squares Mng mm mm 7 Tc39 K 43 79 r u A an 7 quot7 WM 77 r 7 Qquot Ease E lt J o 0quot 39 1 E EI 9 E 5 g 4n 2 2n n n m 4H n an mu Tempemture K Homonuclear Diatomic Molecules cont d sz mpg Ming Mnlaculal 0mm hadiminns we Unpaue Bundenergy DxarDr Band Length MDlecule Eledmns NE BDnds electmns H mmquot Faramagnehc pm 112 2 1 0 43200 D 7412 H92 4 o o L12 6 1 o 105 D 2672 592 B o o 52 1o 1 2 33 F 1539 c2 12 2 o 932 D 131 N2 14 3 0 91169 D 1093 q 15 2 2 49359 F 1207 F2 12 1 o D 1413 N82 20 o o Bond Order Length and Enthalpy Relationships 1 2 C1 0 I 2 Bond order Bond order 325 The mvrllatinn at bond strength 18 Th mmlation af bond mm and and hand man band 01mm kw m m points is the Sam 5 m g 325 Bond Strength vs Bond Length 1000 800 f 600 T E 3 0 CC 0 400 0 CN 0 C0 6 NN 200 o 00 0 l l l l I I 110 120 130 a 140 150 160 ReA 327 The correlation of bond length and bond strength The key for the points is the same as in Fig 325 Ultraviolet Photoelectron Spectroscopy UVPES Provides information about the energies of the molecular orbitals their ordering and Whether ionization of electrons from the MOs affects bonding in the molecule Kinetic energy Sunpk Ejected electron i gt 7quot Kinetic energy f hv l o photoelectrnn l 7 Number of electrons Cylindrical c I H source hv hv 2122 cV F1 Dclecmr 39H Multiplier 2121 Counrcr I m H Analyzer Volug H cps Chan Rccordcr EK hU39I UVPES of N2 Electrons emitted Schematic photoclecuon 20quot l a l1rI 00 gt 5 E N states 0 la 2 s l quot39 E3 a 5 u J 13979 g 3 gt I N2hv gtN2 39 10921039u2177u 2og2 12IUu2l ITu 2crg 2201 e i I lozlou2im320m211quot e quot2 399 103200011m 2092 22H e L00 125 gt 1Ua 10quot2117u 2a2 Zu e InmmuciaudisunceX FranckCondon principle An electronic transition occurs very quickly relative to the time required for the nuclei to move appreciably Dinitrogen Vibrational evels N I eV N2 309 167 eV 11u HTU E O5454 20 188eV u 313 The UV photoelectron spectrum of N2 The ne structure in the spectrum arises from the excitation of vibrations in the cation formed by photoejection ECU E O7137 Heteronuclear Diatomic Molecules Sam ll E06505 I40 160 394 I80 4 no uunnl 4 q q u quot ou 5 quot u 2 J r 1 u 6 1 ur a 5 3 0 8 I 9 6 0 Z 7 6 I I C 0 1 w I a r and E E i o u a quotn u Tquot u 0 U A n l u c 3 N 2 a u 3 u w quot0 ix quot u n 0 IF lquotl391 l 9 a u 4 o 0quot 4o 3 1 a f c Auuawlhuum vuV 5 oll ln ow w 6 o E mainly H q 4 V I I v f I I s II 2 W F 2 x X B y O O vA x t C gm 3 0 11 C s III gt O 1 gt s II 2 3 S k I 2 II PWA m y B II C B X B m E x x I W x VC I x A I I I l A II S Iw I mY it vC 1 X 1P i I I I I 1P Hls Molecular Orbitals of Linear Chains Molecular Orbitals of Cyclic Molecules Simplst Example 113 Pnlynuclear Mnlemles HF a many draw a 1mm do mum in urns moleculz A as 9 gt 25 9 g 15 a 150quot 6D 4 A Orbital combinations NH3 MO Diagram 00 88 0 18a391ScNp ls 2 3 N Nitrogen orbitals X quot Sb c py ZPZ O lsa lsb 13C sz 2S 0 6 O O l 0 g G O O H d G o e i y rogen roup orbital c9 6 o o 6 ol 0 1 Node 1 5 2p 3 O Node ls exxi X g 0 o o e a 1 xZ 1 1 12 6 Sa S 12 isa 2 Sb SC LLI39 o a o o o O 0 1 N3 1 2 quot u 0 Sa 1sb 1sc O O Nitrogen atomic Molecular Hydrogen SALCS orbitals Orbitals More Walsh Dlagrams from Gimarc B Acc Chem Research 1974 7 384 g 3 quotmy lb Inquot E d a6 ab l AH r 2 In 2 ea linear Bent Figure I Qualitative MO correlation diagram for linear and bent f I f AH molecules Changes in geometry which increase inphase overlaps between AO39s lower the MO energy Tolruhodrul Squuro Planar rd D h 6 a n Figure 3 Molecular orbital pictures for AH4 in tetrahedral and I 39 squareplanar genmezry Io lay Planar Dan Pyramidal C3V 4 Figure 2 Qualitative M0 correlatinn diagram for an All male cule in planar and pyramidal shapes
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