GENERAL CHEMISTRY CHEM 162
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This 31 page Class Notes was uploaded by Carmela Kilback on Wednesday September 9, 2015. The Class Notes belongs to CHEM 162 at University of Washington taught by Staff in Fall. Since its upload, it has received 24 views. For similar materials see /class/192605/chem-162-university-of-washington in Chemistry at University of Washington.
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Date Created: 09/09/15
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4 Chem 162A Feb 27 2006 LectureJenekhe Chapter 20 Transition Metals and Coordination Chemistry 201 The Transition Metals A Survey Vanadium metal center and in solution as 202 The FirstRow Transition VZaq V3aq VOZaq and VOZaq Metals left to light 203 Coordination Compounds 204 Isomerism 205 Bonding in Complex Ions The Localized Electron Model 206 The Crystal Field Model 207 The Molecular Orbital Model 208 The Biological Importance of Coordination Complexes Figure 181 The periodic table A 8A ii 3A 4A 5A 6A 7A 9 Li Be B C N O F Ne I Mg Al P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Se Br Kr Rb Sr Y Zr N1 M0 Tc Ru Rh Pd Ag Cd In Sn I Xe Cs Ba La Hf Ta W Re 03 Ir Pt Au Hg Tl Pb Bi Rn Fr Ra Ac Rf Db Sg Bli Hs Mt Ds Uuu Uub Uuq Lanlllanidcs Ce Pr Nd Pm Sm Eu Gd l Tb Dy Ho Er Tm l Yb l Lu ACUnidCS l Th l Pu U I Np I Pu lAm l le Bk 1 Cl Es Fm Mdl No Lr Figure 1239 Special names for groups in the periodic table Alkali Nnhic mum plies IA Ir Mku inc llnhvgcu I i canquot 7 U 2 mm 3 m A 6A 7A if 7 Tmnsilion clcmcms Figure 1239 Special names for groups in the periodic table cont d JA 4 5A nA 7A Noumme Mcmls l Mclzllluulx Figure 201 Transition elements on the periodic table llrhlm minuunll elemcnu Sc 139 V Cr Mn Fe Co Ni Cu Zn l Y Zr Nb Ma T Ru Rh l d Ag Cd Liv in Tu W Re 05 It PI Au Ac39 Rf Db 5g 13h H MI I Uuuluma I lilllL L ltalmtiun clement Limllmunln C P Nd Pin 5m i Eu id n Dy Ho ht Tm Yb Lu l A lllllldtv T Pa 0 Np Pu Am m m I Fm Md l Bl TB Some Transition Metals Important to the U S Economy and Defense TABLE 20 Some Transition Metals Important to the US Economy and Defense Percentage Metal Uses Imported Chromium Stainless steel especially for parts exposed to 91 corrosive gases and high temperatures Cobalt Higlitemperatur alloys in jet engines magnets 93 catalysts drill bits Manganese Steelmaking 97 Platinum and Catalysts S7 palladium 201 A Survey of the Transition Metals 7 Recall the Representative Elements Groups 1A 7 8A Chemical similarities occur Within the vertical groups NaCl KCI all ionic compounds RbCl CsCl Large changes in chemistry across a given period as the number of valence electrons changes Eg Na Mg Al Si P S Cl Ar NaCl MgCl2 AlCl3 PCl5 Ionic lt gt Covalent molecules increasing metallic character decreasing ionization energy gt Transition Metals Similarities Within a given period as well as Within a given vertical group gt this huge contrast with the representative elements is due to the fact that the last electrons added to the transition metal elements are inner electrons d electrons in d 7 block transition metals f electrons in the lanthanides and actinides 7 the inner d and f electrons cannot participate in bonding as readily as the s and p electrons Characteristics of the transition metals 7 typical metals metallic luster high electrical and therm al conductivities Differences in Physical Properties among the transition metals can be large 7 Eg W tungsten mp 3400 C vs Hg mercury mp lt 25 C 7 hard and high strength vs soft Fe iron and Ti Cu Au Ag 7 ready rxn W 02 to form oxides vs no rxn With 02 Cr Ni Co Al Fe Au Ag Pt Pd Ionic compounds With nonm etals 7 Often more than one oxidation state Eg FeCl2 FeCl3 2 3 7 the cations are often complex ions species in which the transition metal ion is surrounded by a number of ligands Molecular model The C0NH3 63quot ion Nig3 3 C 7l NH a 2 r Week7W3 9304 3 to NH3 The CoNH363 ion mqu knuvx Ligands are molecules or ions that behave as Lewis bases ie have a lone pair of electrons Most compounds of the transition metals are colored i the transition metal ion can absorb visible light Many transition metal compounds are paramagnetic 7 because they contain unpaired electrons r r g gt Electron Configurations See Section 1213 302 an Cry F yy 795MB The 3d orbitals begin to fill after the 4s orbital is complete eg Sc Ar4s23d1 Ti 4s23d2 Y 4sl3d3 See Table 202 Cr 4s13d5 I Mn 4523d5 4s13dquot1 exceptions to 4s23dn electron configuration Cu 4s13d10 Zn 4s23d10 for most elements of the firstrow transition metals 4s23dn has a lower energy than 4s13dquotl except chromium and copper The 4s and 3d orbital energies are very similar Table 202 Selected Properties of the FirstRow Transition Metals IAaLE 202 Selected Propenies oi the rusmow Iransition Metals l rupurn Scamlmm 39nmumm Vanadium Cllmumlln Mumm lron Clllmh 1mm Copper 2m Atomic 11 21 23 14 1i 5 17 25 19 so numlm am 45141 mm 493 451W 48 4534139 431w 4634 4513 m I47 3l no IS 24 m gt24 12x m iummmn i m39rgik s CValuml Fim 574 7 7 764 5mm 141 mm ism mm 131quot llurd 1931 3095 7 3065 7 ductiun 712 7091 7mg 7044 4113 7023 pountult m Cmumnn 415 an 17 ans am my 1 11 gt2 v m 4 4 5 5 47 mm Melting 1397 1572 17m wuu 1244 1531 I495 1455 um 4w puini Cl 199 449 595 710 743 736 S3 590 2492 714 39mcal 1 J m 2 17 14 14 97 17 cumlwivmvi l m mun nulcr4nw Hum my 1 m Nnili rruluuimi M F 7 7gtMicuxyilm Nahumnlixrvllvrumlshx39 i gr unlparul mm m Mum 7 u mlm m HH Iw ligh Electron con gurations of ions of the rstrow transition metals 7 the energy of the 3d orbitals is signi cantly less than that of the 4s orbital Eg Sc 4s23d1 Sc 3d1 Ti 4s23d2 Ti 3d1 Zn 4s23d10 Zn 3d10 7 these ions do not have 4s electrons since the 3d orbitals are lower in energy Oxidation States and Ionization Energies Various ions formed by losing electrons Eg Ti 7 Ti Ti Ti 4s23d2 most common See Table 202 7 to the right of the row the higher oxidation states are not observed because the 3d orbitals become lower in energy as the nuclear charge increases making electrons dif cult to remove Zn 7 Zn Zn3 Zn5 Zn1 etc 7 NOT OBSERVED 4s23d10 observed See Figure 202 Figure 202 plots of the first red dots and third blue dots ionization energies for the rstrow transition metals Cr Mn Ft Cu gt Standard Reduction Potentials The potential of the halfreaction M6 gt Mm ne characterizes the reducing ability ofthe metal MEL 1 r a 2n Relative Redmng Abvlmes a me irsHZaw Transmon Mam m Aqueous Summon Remain this is the reverse ofusually V tabulated halfreactions and the potentials are opposite in sign to tabulated Values in Table 20 Since by de nition 5 7 0 for 2H 39 2 all the rstrow transition metals except copper can reduce H ions to hydrogen gas in 1M aqueous solutions of strong ac39 5 Ms J 2Hltaqgt a H2 N 2 Ha gt The 4d and 5d Transition Series Comparison of the atomic radii of 3d 4d and 5d elements See Figure 203 general decrease in size in going from le to right across each series signi cant increase in size from 3d to 4d 4d and 5d metals are very similar in size gt this is due to the lanthanide contraction lanthanide series elements between lanthanum La and hafnium H lling of 4f orbitals Which are in the interior of the atoms do not affect size of the 5d elements 4d and 5d transition metals though not as common as 3d metals have some very useful properties Eg The platian group metals 7 Ru Os Rh lr Pd and Pt 7 are Widely used as catalysts in many industrial processes Figure 1228 The orbitals filled for elements in various parts IA Group m Illa M J m m M m quot Figure 1231 The positions of the elements considered in Example 128 Group A 8A I m a 1 2 2x 2 3 317 539 PM 4 4 34 I 4p a i 1 4111 cm I V 5 3 6w 1Lz Hf 511 1 7 6p 7 7s Ra1Ac 611 1 7 1 1 1 14f 1 1 1 1 1 1 1 1 1 1 WI 1 1 1 1 1 1 Figure 203 Atomic radii of the 3d 4d and 5d transition series Atomic radii 11m Isl series 3d 2nd mm 44h 3nd crim 1511 An Alomic number Figure 201 Transition elements on the periodic table Mm mum mm ii t m m n x x 0 I n Atng Lammuulcw C n Nd I m 5 Eu 4 Tl iDy m i rr r t z 1 ya Lu l39m Md N Ir 1 N Equot 202 The FirstRow Transition Metals gt Highlights of some properties or chemistry of the 10 3d transition metals Scandium Sc gt 3 oxidation state in compounds eg ScC13Sc203etc gt most of its compounds are colorless and diamagnetic Titanium Ti gt fairly abundant 06 by mass ofthe earth s crust gt low density high strength high mp 1672 C excellent structural material jet engines Boeing 747 jetliners etc gt titanium IV oxide or titanium dioxide TiO2 is the most commo d comp oun hite pigment used in many producm paper paint linoleum plastics cosmetics etc Vanadium V The most common oxidation state is 5 as in V205 orange mp 550 C and VFS YABLE 1M Cxldallcn states and Species In Vanadium m Aqueous Solution Oxidation 5 mn u Vmudmm Vt 39Lilowt vo v39 391 Y4 3 71 c v1 4m mlcli Figure 204 Titanium bicycle 4 Chromium Cr 7 Main ore is chromite FeCrZOA 7 FeCrzoW 4 c s 7 4 co g Fe 5 2Cr Ferrochro added directly to iron in steel making process common oxidation states in compounds 2 3 n 2 chr n hromium IV oxide conc sulfuric acid cleaning solution 5 Manganese Mn 7 The only member ofthe 3d metals that can exist in all oxidation states from 2 to 7 7 Manganese VII ion MnOA39 permanganate ion a strong oxidizing agent in solution me ad TABLE 205 Typical Chromium Compounds Oxlduion Exnlllplm or Compounds lx Imlngcn 1 mxl 3 1 0 gro OHlx llvlllcgreclll 0V clan c Ix CI39U l ml L Manganese 4 E n s daliun Slate Oxidation 5mm of e o Some Compounds ol in Its Mast Common Oxi 5 Examples ol Compounds MnlOHl lpmkl MnS salmon V uun l MnO dark brown KMnOo purple
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