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by: Carmela Kilback


Carmela Kilback
GPA 3.92


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Class Notes
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This 33 page Class Notes was uploaded by Carmela Kilback on Wednesday September 9, 2015. The Class Notes belongs to CHEM 312 at University of Washington taught by Staff in Fall. Since its upload, it has received 34 views. For similar materials see /class/192591/chem-312-university-of-washington in Chemistry at University of Washington.




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Date Created: 09/09/15
Fission yield disuibu on for 135U for a thermal spectrum of neutrons thermal reactors as well as for 14 MeV neutrons trom nuc1eartusron of deutenum and mum tn 1 Ftssml39 ytetn m an no t 0 we MussnumDLr The total hssron yreld for an the rsotopes adds up to 200 per cent re ecung the tact that two fmgments are produced m each trssron event The relauvely hrgh trssron yrelds of 1370s and Ensn therr halfrlwes of about 30 years and the tact that Cs and 5139 are chemrcauy srmuar to K and ca respectively an combme to make these two radronucudes very h zar ous to humans The same r true for 1311 wrth rts halfrhfe of 8 days and rts af mty to the thyrord gland http lluNwxcsurscope orgdownloadpubsscopesotchaptero1 htmltttrgl 1 p orbital 3 1 orbital dx2y orbital fxy orbital dyz orbital Figure Ll Angular wave functions of x p d and an fcrbilal showing signs of the wave functions in different lobes and indicating nodal planes with dark planes or solid lines From hemiml Srruuure and Bonding by R L DcKock and H B Gray Copyrighl 39tquot 1980 by Bcv1amin39Cuminings Publishing Company Reprinted by permission d rcation ranion d2 2 ranion or d 12 ranion V XrAuin 3 V ZO39S 80 V2 ranion rcation ranion V2 1 ranion rcation 0414 ranion rcation rcation lt 0414 ranion anion repulsion is the same as above but cationanion attraction is reduced Unfavorable V4 1 0 3 amid mt VA 75 39 rcation gt 0414 ranion anion repulsion is reduced while cationanion attraction is maximized if M a 07g A 3 I Fine E i B i 12 Z 51 quot39Ptrrhapr an HMO gentlcmca39 wnufd ITde lling ma usl what If i5 Dut id flu winder that yam Find 50 a mdivc Covalent Bonding A bond in which each atom contributes one electron to form a shared pair of electrons AB Alt9 OB a Alt gtB Difference in electronegativity is typically small Pure covalent bonds occur between nonmetallic elements eg HH HCl CHEM312 Winter 2005 VI Bonding in Solids Covalent Radius Half of the distance between two identical atomic nuclei bound by a covalent bond Similar general periodic trend as for ionic radii CHEM312 Mnter 2005 VI Bonding in Solids Bond Dissociation Energy BDE The energy required to break one mole of gaseous bonds to form gaseous atoms A39Bltggt A39ltggt B39ltggt Indication of strength of bond Often reported as mean bond energy BDE of a specific bond will depend on molecule BDE of SiSi Si2H6 226 kJmol391 Si2CH36 322 kJmol391 Can be used to estimate reaction enthalpies CHEM312 Winter 2005 VI Bonding in Solids BDE of Homonuclear Bonds A39Altg 2A39ltggt AHrcnBDE eg CI2g gt 2 CIg AHrcn BDE 244 kJmol391 CHEM312 Winter 2005 VI Bonding in Solids Periodic Trends of BDE Homonuclear Table 65 ElementrElcmenl Covalent Bond Fnergies uan from Wulfsberg a Single Sigma Bond Encrgivs Unusually weak bonds Hill 4 Li7 Ll Evils 7 g m cox a NaiNz Vigng 57 1 m N a nil 070 CM GJ 1 In 49 Hm I a R b R h Sp r In In g x l mu a E LsiLs 43 r In In reases left to n ht across a erlod Note that horizontal trend is not as reliable CHEMZMZ Wlnler2005 Vl Bondlngm SOlldS Periodic Trends of BDE Homonuclear 300 EE Grp w 250 3 200 E 5 1 150 100 50 5 G a I i 355 l 2 3 4 5 6 7 I Row 300 0 BE Grp v1 250 E E Gp7VII 395 200 E g i 3 150 4 3A 1 39 1 t 100 50 1 G I 1 2 1 4 5 6 7 CHEM312 Winter 2005 V VI Bonding in Solids ROW Periodic Trends of BDE NN 00 and FF HOOH H2NNH2 and FF have weak bonds Small covalent radii Have lone pairs lt gt lt90 er NN FF 1 39 HH HH Lone pairs repel each other Also have electrons in antibonding orbitals CHEM312 Winter 2005 7 VI Bonding in Solids Periodic Trends of BDE Homonuclear Table 65 ElementrElcmem Cowlem Bond Fnergies ILmeH a Single Sigma Bond Fncrgiu HiH 4 LPLI Bcg z B Fit NiN 070 r I 105 mm 29 J40 I67 H 15 in gr 7 Sn75n 4 H10 6 I T H9 L 7CE 417M 3 Hh Na Mg Al Si CI r CHEMIMZ Wmter 2005 V Bondmg m Sohds BDE vs Bond Length A LOO i50 200 250 300 400 r T Shorterbonds 88 generally have higher 8 BDEs 2300 72 61 TA Relationship also true for heteronuclear bonds l l 4lJLLLLLJ 100 150 200 250 300 Bond length pm Figure 65 Relation between bond length and bond energy For bonds between like atoms The upper line is for Group l4IVA elements only the lower line is for other 5 and p block elements Reprinted with permission from J E Huhcey and R S Evans J lrmrg Nucl Chem 32 383 l970l Copyright by Pergamon Press I970 CHEIVIJ I4 Winter AUUD VI bondlng In solids Polar Covalent Bonds and Bond Cleavage Electrons are not equally shared between nuclei Electrons tend to be localized towards the more electronegative nucleus 5HF 5 A B39 Heterolytic cleavage Basis for Hard and Soft AcidBase AB HSAB Principle CHEM312 Winter 2005 VI Bonding in Solids A B Homolytic cleavage Periodic Trends of BDE Polar Bonds F Cl CC 347 gt NX3 283 313 CSI 301 CGe 242 PX3 490 326 In kJmol1 ASX3 484 322 be3 440 315 BiX3 393 274 In the p block quot1 kJmC For elements with no lone pairs BDE decreases down a group For elements with lone pairs the value of the Period 2 element is smaller than for Period 3 CHEM312 Winter 2005 VI Bonding in Solids BDEs of Polar Covalent Bonds NaX ng2 AIX3 Six4 PX3 sx6 Can XF 477 513 583 565 490 284 n1249 n3172 n5142 X 304 264 234 184 n1 208 Polar covalent bonds are generally stronger than nonpolar covalent bonds Ionic contribution to bonding CHEM312 Winter 2005 VI Bonding in Solids CHEM312 Winter 2005 VI Bonding in Solids Bond Dissociation Energy BDEs of Polar vs NonPolar Covalent Bonds Heat of Atomization AH atom The enthalpy change when 1 mole of a substance is converted to gaseous atoms Estd state EQ AH atom 12 F2 F 9 BDE F2 gt 2 Fm CHEM312 Winter 2005 VI Bonding in Solids Pauling s Equation Ionic contribution BDE EX 12BDE EE BDE XX 965XX E2 Covalent contribution Electronegativity eg BDE HCI 12432 240 965220 31612 336 889 425 kJmo1 Actual BDE HCI 432 kJmo391 CHEM312 Winter 2005 VI Bonding in Solids Using BDEs to Estimate Reaction Enthalpy Clg BDE ClF F g 249 kJmol391 AHatom AHatom 122 kJmol391 79 kJmol391 05 05 AHlrcn 122 79 249 AHlrcn 48 kJmol391 CHEM312 Winter 2005 VI Bonding in Solids Self Test Estimate BDE OH quot29 0395 c2g H39O39Hg AHrcn 242 kJmoI1 AHat0mH 218 kJmoI1 AHatomO 249 kJmoI1 What is the 0H bond strength CHEM312 Winter 2005 7 VI Bonding in Solids Self Test Estimate BDE OH 2Hg 919 BDEOH AHatom AHatom 218 kJmo1 249 kJmol391 quot29 0395 c2g H39O39Hg AHrcn 242 kJmo1 AHrcn 2 x AHatom AHatom 2 x 39BDE 242 2 x 218 249 2 x BDE OH 2 x BDE OH 242 436 249 927 kJmol1 The average OH bond strength is 4635 kJmol1 CHEM312 Winter 2005 VI Bonding in Solids Hard and Soft AcidBase Principle HARD BASES Table 8 Hard and Sun Acids and Rm Mm urn2n wtnl a Lc is thud H c 03 l 57 Hdld and Ham L Elds 0 ME Bordcrhnc LU L3 Junk lv 1 hr 39 Cr Mn mu m 4 3x N mu 1 LR 10 I Jh 54 Lb 16 I K1Yll I Mim 19 10 NYE Rb Sf Ar Nb Mn C I d 1kg Ld 3952 093 l 22 I K L 2139 LUquot 3 V I 7U 93 IN C Ba Lu Hf V RC 0 39I Hg TI I H79 H89 127 339 230quot IFquot I 132 In 11I60 LIIHW 30 1UUH 4L39133 B I SOFT Agms 1 RA 7 1quot Immmmc Acids L C Pr Nd I m Sm Eu d I b In Er Tm b 1quot I39ll LI1 H4 H7 1 135 L14 L25 AU TI Pa U Np Am 1 BR Cf F l lll Md ND J 13 I 5 LIX I 5 13 I I 1 1 I L3 13 HAIR MACIDS Run r I 39 CHEM312 Winter 2005 VI Bonding in Solids Hard and Soft AcidBase Principle HASB SAHB lt gt HAHB SASB Property Hard Acids Hard Bases Soft Acids Soft Bases XP 07 16 34 40 19 25 21 30 Ionic small small large large Radius Ionic h h low Charge lg CHEM312 Winter 2005 VI Bonding in Solids Useful Background for Chemistry 312 A working knowledge quotI know where to find itquot of Freshman Chemistry and some Organic Chemistry Including A Interpreting the Periodic Table 1 groups and rows e g Sr is in Group 2 5th period or row 2 regions of the periodic table metals nonmetals etc 3 Orbitals s p d f energy s fills before p etc shape of s and p orbitals 4 electronic configuration Sr 1s22s22p63s23p63d104s24p65s2 or Kr5s2 5 stoichiometry of simple compounds from electronic configuration e g why are the stoichiometries SrC12 and B2S3 B Chemical Bonding 1 Lewis Dot structures the quotoctet rulequot eg for NH4 or C02 2 Hybridization eg N in NH3 is sp3 hybridized C in C02 is sp hybridized 3 Shapes of molecules hybridization and VSEPR theory e g NH3 is pyramidal and C032 is planar 4 Resonance structures e g Lewis structures for S02 acetate 5 Electronegativity eg Cs 08 H 22 F 40 6 Covalent vs Ionic bonding eg NaCl vs C12 7 Polarity of chemical bonds relationship with electronegativity eg H Cl vs Cl Cl 8 Oxidation states eg N 3 in NH3 and NH4 B3 in B203 C States of matter solids liquids and gases D Chemical reactions h 1 Balancing reactions balance atoms and charge eg 2 Na C12 gt 2 NaCl 3 Ca2 2 HPO42 gt Ca3PO42 2 Ht p 2 Simple thermodynamics what are AG AH and AS 3 Simple electrochemistry what is a half reaction what is the redox potential Equot 4 Relationships between AG E and equilibrium constants AG 2 nFE AG 2 AH TAS AG 2 RT1nKeq w Black Group 1l Acidic solution Basic solution 70 828 1 H20 quot2 4mm LI gt LI 72 7H Na 7 gt Na 72 93 K 39 H K 72 92K Rb gt Rb 73026 Cs i gt Cs s Block Group 2 Acidic solution Basic solution 3 0 2 m 4 07 Bequot Be A 71356 26X7 Mg mg MglOH M9 2 37 Ca1 gt Ca 2 7 0 Sr 7 74gt Sr 72m Baz gt Ba 4 916 Ra Ra 1 Block Group 13III Acidic solution Basic solution 3 0 3 o rug3n 4 m BIOH2 gtB BDHI B V 5 72 am Ali Wgt Al Ana 4 AI 41 GaoioH gt Ga 1 1 0 4444 41126 L24 n gtln Hln mo 9 BH 70333 m Anna T39 gt11 gtTI 03972 1 Block Group 14IV Acidic solution 4 2 u 72 4 701 I4 70029 137 0533 COgtHCOOH gtHCHO 0 gtCH30H cm UW4 Iquot 5 7 0132 Basic solution a 4mm 7 AJM 4 4 245 co gtHCOILHCHO gtcnoni um I Mr C p Block 39 Group 14IV continued Acidic solution Basic solution 4 3 0 4 2 0 701w z 7109 n c SIOz E quaan 70x0 GeOAOH gtGe 6902 370 G 0225 Ge mm Md 6 my 1 rw siloquotgtu W Silo MM Sn Salami pK U 3 snooir 39 39 5n lwhite black Sn v15 Sn 4mquot h 5 not mm W 012 Pb Phoz 014 PM 77 um Pb red mu Pbso p Block Group 151V Acidic solution 5 4 1 2 1 9 71 2 4 125 4m mm 1 1 0 9 7 15 NogtNO gtHNoz gtNo gtNio 094 I 07 Basic solution l 4m 17 quot01 936 N20 y 1 6 u x07 ml 0 Is L77 347 l 41 2 39 gtN gtNH30H39gtN1HJNHI 4105 I 15 7 m 004 1 404 073 l r quot039 N0 Nlog Nz NH1OH4gtNIH HgtNHJ 05 u 41 P Block 39 Group 15V continued Acidic solution 5 4 1 0 3 70933 0 3x0 70499 075in 7n um HFOgtHP1CI gtMPCI gtHPO gtP gtPHa 7n 27 7n m 0 me A 0 2m 0 225 may quot7w i ms w u ISU 5bo gt szo who m 51 0 5amp9 A 2 l1l7 my n 37 n Basic solution 5 3 1 ii 7 7 7i 12 7 v 7 7 Poi Poi 1 s quotInquot 2 05 n 039 Phi 7 7x in 67 70 38 7i 7 AsOi Z A ASH 7 39 7 u 7 3 smoHgtsuom quotM S39 1 K Sbquot 707452 Bizo gtBi p Block Group 16Vl Acidic solution 0 125 15 y mof l 695 L753 02 gt H202gt H20 L229 6 5 4 2 0 72 7 0 153 7 0 369 0400 06510 0114 9450 gtszo mso 3quot 2 OJSK 0500 L96 slur gt so s 4 A u 71 2 w 15 74 7 l Sear quot5203 0 Q n quot8 I193 4 057 70 74 7 n1 H1790 4 l T i 2T9 LS I39gt39 0 Tmz Basic solution 0 7 3 AU 0 20 0 v 0 U649 1857 o gtHo 0H mm 5 4 2 f 71 2 8037936 so 7 D 376 r 0742 D 476 a gt m 5202 003 c n 4m c 4 m e L07 DJ2 084 l 445 v f1gz no r quot7 11 Block Group 17VII Acidic solution 0 7 5 2979 HF 7 5 4 3 lt1 4 l 175 Clo 1 HM LbSo Clo mm n r I Ixr Him mm H I 1e30 i 1355 H 1458 7 B39O 853 n n 1447 HPquot 1604 alzurf 1 165 B39 Bulaqli H5 5 Im I I m m L44 77 le 0535 I 0536 wnh Bum should be used In aH pram51 calculauons 11 Block Group 17Vll continued Basil solution n I 2365 Fg gt F 7 5 4 3 1 0 1 4x48 1 m CIo l rm o m V Mm um 1353 v m m z w r xuu u 5x4 1025 0492 0455 I ms 1 V a 4 gtBr Br n a 0760 3920 0 15 0 42 0535 17 Hlei 39 gtI 0 a p Block Group 18lVll Acidic solution 3 396 4 2394 2 12 HXe0aq gtXeOzaq gtXeg 118 T Basic solution HXuO39quot H f 19


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