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Gourban Manufacturing Buyer: Hene Kala + Image Credit: Ken EwardiBiografs 1003. by Pearson Education, Ine Pearson Edtication, ever. NI A7ES8 1 rights reserved. No part of ths Rea may be epmend in any form oF ae ac mann persion in waiting Grom the publester The author and publisher of this fodie huve used their best efforts ia Saerne atk These elects inclose the devetopment research, and Saal the cones and prograss:to deter se. THE ing OJ publisher ake bo waraety of any Kind, expressed or imped with regard rogeam) of the documentation contained 48 his wet SRC hae and. publisher sball not be lable im any event for vreall os eemsaquectal damages in-connection wih, Cr arising out of te Tunishing. performance, oc use Of these programs. Prien i the Waited Stas of A 9987654321 ISBN O-23-009790-X Pearson Education Lid, Londan Fearon Edecation Avsralia Ply. Lit. Sxdney 0 Education Sinopore, Pc. id. ron Edecatit North Asia Lid, Hong Kone won Education Canada, 96. Toranto won Fdacactoa le Mexica, S.A. Be CV Peanwon Edicion —tapan, Tak? Tetocation Malaysia, Pte. Ltd Edcatton, Upper Seale River: New Jerseychaptor 12 ter 14 Chapter 16 Chapter 17 Chapter 18 Chapter 19 Chapter 20 Chapter 21 Chapter 22 Chapter 23 Chaptor 24 Chapter 25 Properties of Solutions Chemical Kinetics Chemical Equilibrium Acid-Base Equilbria Additional Aspects of Aqueous Equilibria Chemistry of the Environment Chemical Thermodynamics Electrochemistry Nuclear Chemistry Chemistry of the Nonmatals Metals and Metallurgy Chemistry of Coordination Compounds ‘The Chemistry of Life: (Organic and Biological ChemistryExtaom odotoheeptha menvalat error vrovaed and prdaf-read by at least three chemists fo ensure clenihy Mathematics The work and sovice of Br. Mary Ellen Biggs rans Cannon, University of uinols have been krvaluabe te this rolect TES Y chalenging otis mana, hypos and errors ReNiabl feeP In Plsaee helpus find and ncn ond students in san satan Roxy Wien University f ihn ‘School af Chemical Sciences 6501 S. Mathews Ave, Box AZ Urbane, 1. 61801 owdlson duit ectOo ction of HO ne. aes cunisa phyceal chorge)_(@) phvocel (The aaa chemical change, but ts dapoeition = = physical change) (e) _Toke acvantage of the eetorant water sole ofthe No SHIRES ‘hed wate to rae arse gee is mixture, cofecing ths sand an 6 We Petal aaa aaa ota ck ueporate the water tom the sk to FoRoal= eas ciner me meting pint deren of magnets dffrence betveat is amd SRE cine read reparate ese wo olements. Heatthe mibture Uri M6 SUR STS: eae aart(pouroff te uid uur. OF, use.a magrot to atact the item Palas fearing the sali sultur bering units and Measurement 148 (a) 85 x10*mx— asym ens x iotL = UL = o.5as mi 635 wld iat0 tit =10°L 409 L x 225m 423 <10% m — = 4.28 me? (4.23 pL; 1 mm = 1 uh) rec) 423 mm= SH _1mg 1=10%3 = 0125p (125 49) —1P5 _ = 35 ps(0.035 ns) pts asst pe @ 122 Ge) volume) ares (©) volume (6) density (e) tme ©) length (g) temperatureast s)om*)"" < g.491=8400m 5 519 (07-F 2) =3°C F = 0i5 (755°C) + 32= 1901°F (iv eouid be argued that te result of 8/6 (75) has'S sg Migs =o the fins ower should have 3 sig figs, 1320°F.) e) 15 (- 95°C) + 32=-190°F (win 2g gs, -140°F) i) Kepse+279= 208K, °F = 9/5 (25'C) +32 = 77°F fe) _ mong point= -248.6°C #27315= 24.5 boling paint =-248.1°C 273.15 =27.1K Uncertainty In Measurement 132 Exact: (b).(e) (The numberof students is exact on any aiven day) 1: 140°C. The tempersture can be read to the nearest S0°C and estimated to the naarest E-10°C. Since there le uncertainty in the tens Gig, the measurement has two sgnieant Sgures 4 M3 @4 5 (We (=) 144e10% @) 9755907 — (@) BoD xO ( S78x 10 (@) 34010" (Hh 58 23% 10% (The intermediate resuit has 2 slanficant figures, £0 only the thousand ‘anc hundeed places in the answer are significant) 28 3x 10°-0.01200 « 104] 2.0954= 8.250% 10! (Sinee-cubtraction depends on ecimal places, both numsare must have the same exponent fo determine decimal placesisig fas The intermediate result has + docrral place end 4 sig figs so the ‘anewar has 4 sig figs) (@.004s 20,000.0) + (83x12) = 34x aig igs cee pl 281g fas Mest 2 dis es (45x10) = 762% 10° 3.x figs 0 dec pi 0 der pV sia fie 3a toeand Measurement __ Solutio =2450.4=2.5% 10" ft soa ree (007. oy, 4000 5, 1510 = Sara ey (hostyer 1a 28-79 g total » 290848 5 Toe S118 =s01 630 * paogAs “26799 2500+ 8.1 coins Since coins come in integer numbers, 7 coins are requred. cia comen unit far compatison, inthis case the-er, t1m= 100m 4in= 38m fam=1em ‘The order cf tenath from thortas to longest is 14-4 shoe <57-cm string < 1-1-m pipe Additional Exercises: ‘gold ccn is probably solid solution, Pure gold (element 79) s too soft and too valuable to be used for coinage, x0 other metals are added. However, the simple term "gold cok’ does not give 8 specific indication of the other metais in the mixture |A cup of coffee is @ solution If there are no suspended solids (coffee grounds). Ite a vogeneous matureif there are grounds. If c-2aTor suger are added, the homogeneity of the mixture depends on how tharcughly the components are mixed ‘A wood plank is 2 heterouensous mixture of verious eatuloes combonents. The diferent ora in the mature are visible as wood arain or kricts. ‘The ambiguity fn each of these examples is that tho name of the eubstance does nol provide 9 complete description of the material. We must rly cn mental mages and these vary from person to parson. ‘Ahypothesis isa possible explanation for certain phonomena based on praiminary ipetimantal dato. A theory may be more general, and has 2 signficant body of experimental evidence to support it a theory hag nftsicod the test of experimantation ‘A scentiic law is a summary or statement f natural behavior: if tells how matier behaves. A theory lan explanation of nalural behavior; stternpis to explnin why ‘mater behaves the way i does.er and Measurement solutior The most dens Ha, wil sin: the least dense: cyctohexane, wl figat H,O willbe i the mdla. density = (0568 9 — 14.289)/4 58cm? = 4.67 fem" aSkge 1000@, Ame , tL -asat MSka* Tyg * 1385 * TOOL Vals w P= 4 TQ ern? = 1.0181 = 108 = 1.012 07 = 1.01 8 1 ca torts iden? = 9829 a a56 x 10%@ The sphere weighe 356 hg or 785 pounds. The students untkely tobe able fo cary the sphere ase of towene = 58.58 9-32.85 725835 ‘volume of teluons = 25.88 9 1mk_s sport Beeta volume of solid = 5.00 mL 30.0916 mL = 19.9884=20.0 mL. density of solid = 52889 = 4.53.91. a Togesa me Pian, Calculate the total stance i riles, the total fie in hours toys Stn 2M = yg" weoan Wf te distence can be meatured lo the nearast yard, or 0.0008 mi, there Is ‘uncertainty in the fourth and probably thd cecimal place, so the total distance ie reported io 3 decimal places and 5 8 fs. [Nota distance = 13 +0108 = 13.108 mpsnd Measurement ofu two distine! spots are seen on thes e separation, ealguate a referonco valve fot aah Spot iste, ince Harwiled by SOVeENE se values he two sete a fityaforent he separation i success) (OBsiea «ratte atece even ne sets ttn wed openio s RAGH EAET ona pe ferent for each expanmant. The values svggested above are independent of the length of paper.) stay (eWay tobe tt pecan and acurae, because the errors er creRy ESSERE Sag ooeeiary weight standard wil be resatant 0 chemical and prysical changes: Wie Cearerearcksy cetated, and weighings arkelytabe made by he some parson. The ‘alate large numberof menauremants is Hkely fe mniize tho affect cf endo A", Re veragewelue. The accuracy and precision of study (b) depend on the verack €) HS poniipants responses which cannotbe carefully contaled. It also depends on the eettot Pircomparabie exile” The percentages are not precice, beceuva te broad definton of tery lacs 2 range of resul (ecaller), The roativel large numbar of Patisonis imemvoe the precaion and accuracy, In general, conioting error and maximizing the rumber of data ponts in = study amoroves precision and aDcurasy,les andlons _ Solutio’ Since tha untnown patties ceflecied in tia oppose he Seana pated by rf) plate. The unknown pati is EeainaiSeteas PT rude ofthe ceiecton t= less then that of the 6 Ea Tre rn ne greater mass than the olecton, The unknown BUSAnaM aaatlas partce of arcater mass than the electron. {@) The dreplets contain diferent chames becaits leetrens on the droplet ¢b) The leeronie charge is Kiel ta be he lowest coramon factor in allthe ebeerved EfarU=S: (@) Assuming this is 60, we calculate the apparent eiecronic cherge from each drop as 1a here may be 1, 2, 9 ©r move sees Ac 460 x10!) 12160 810"C 8: 3.95 = 107/22 458= 104 © 481 x10/3= 160% 10" b. 83t<10/4= 15810" C ‘The reported value isthe average of hate four values. Since-each caloulated charge has. three sianficant gquras. tre average wil also have three significant figures. 1.60% 10" G+ 158 * 16" C+ 1.80 x 10% 1.58 x 10° C)/4= 1.69% 107C Inthe scattering experment, most alpha particles, massive positively charged helium nuci pasted directly trough the foil butafew were deflected at large angles. The cture postive ‘charge in the ‘plum pudding! model would not have produced a repulsion strong enough to tact the aipha particles at lags angées. In Rutherfore’s model, the positive cherge in the aici ix concentvaled in the ama nucleus. if an aloha paricie etkee a gold nuclaus diecty, tis defected ata large angie. Modern View of Atomic Structure; Atomic Weights 22 gtk anasniah 2 1m anyon sents im hae wera ae Aligned Rh atome have diameters touching. d= 25% 10cm =25% 10° m 1=10%m Tom Vane e=125" 10213010 m eoum = et 410 Rh atoms v= (Aint 25 «20 mt = 22 £0 me(1.09783) = 2.01566 amu = 1.00783 4 201410 = 3.02193 amu = 2@2 01410) -4 07620 amu The mans ratios ore 1: 4.40823: 189848 0115 15:2] 11 ‘Hie lorgest, Because thar is the greatest chance thet two atoms f sims “abundant isotope wi combine. +4 71s the emallet, bacouse there isthe [east share thal wo ators of NS IERE abundant isctope will eombine. The Periodic Table; Molecules and lons 230 (2) tthlum (meta (0) acanciurn(meta) _(€) germankim (metaloid) (@ yorum (metal) (@)manganeea(metat) 7} gold(meta) ig) feturur (metals) ©. carbon, nonmetal; Si silicon, metallid; Ge, germanium, metasid: Sn in, metal Pb, lead, natal Compounds with the same empirical but diferent moteculer formulas difer by the inleger number of empirical formula units in the respective melecules. Thus, they can hava very (Grterent molegulat structure, size and mass, resuling very different physical properties ‘A molecular formula contains af atoms in welecule. An empircal formula shows the plest rato of aloms in a molecule ot elements in 3 compound. molecular: B,My: empirical BH, molaevar: C,H,,O,: empirical: CHO ws @9ms, Molecules and tons _ Solutio! ave two carbon atom in ther mcleciar bachbeniay 2% In -prepanol one of he H atoms on an cutor (terminal) sien haa been teniens ey an -OH grow. cthancie ocid hae two eathons in its chsin. One of these © Stam {is bound fo two, Care ipo way tat la ehorocteduic of 2 carbo Of WEE amas oar ook tas the C alone rte chain and one of the olay © alamaleliag off the carboxylic neld functions! STOUP, | | 4) motecsar formu: C3H4O; or GHACOOH Additional Exercises 6 @ aged on data accumated inthe Iale eighteenth century on how substances reset sith one another, Dalton postulated the atomic theory” Oak's theory is basad on tre indvisible atom as the smallest unt of an element that can combine with other ements, ‘By determining the effects of electric and magnetic felds on cathode rays, Thamsan meatured the mass-to-charge ratio of the electron. He also proposed the “plum useing” model of the atom in which mest of the epace in‘an atom is occupied by = Gtiuse postive charge in which the tiny negatively charged electrons are imbedded. By cbsering the rate ef fall of oil crops in and out of an electric field, Milian measured the charge of an electron. ‘afr ebsening the scattering of alpha partclas at larg angles when the particles stvek gold fo, Rutherford postulatedithe nuclearstom. In Rutherford stom, most ‘of the maas of the atom i$ Concentrated a small danse regen called the nucleus andthe ny negatvely charged electrons are moving throughempty space aroundthe nucleus Droplet 0 would fel mest slowly, It caries the most negative charge, eo kt would be ‘mest strangly attracted fo the upper (4) plate and most strongly repelled by the lower (plate. These electrostatic forces would provide the greatest opposition to gravity Calculate the fowest common factor Acge4m 104/208 «104 = 133, 1.332 8 490™ 107/288 10+ = 1.58; 1.59 © 286 104/288 107 = 1.00: 1.00"3 Deed 107/288% 10*= 3.00: 3.00%3ns, Molecules ant aso of single gad atom. then divide image of toe golé ator, isrOanu oe gargs to = 3.271 10 colt alow)" G22 10" anu 1939 , 100d om _— 5 e9 x 10% Auatomsin the cube she crepe of atoms in aphaten spheres carrot be eran! nts Gis SEE ve ar cnpty pack. The auoeton is how mich emp apevs/s eee TE ee re toy oto camer. no erp apace ord Tata PH Saad true diameter wil be somenhere in this 3902 Novempty space: volume cubsmumber of atoms = volume of ane ater eam ers Orv J vefabest Oio=4 = eee 50x 107 Avaloms 217610? om" fr (8695 x 10 em*yay "= 3.4 = 10am, d= 2r=6.8 * 10em Maxicusm empty apace: eseume atoms are srenged in rove i all three directions certo are touching aeross their damete’s. Thali, cach atom occupies the volume ‘Grocube with tye alone ciameleras the length ofthe side of the clbe. The number cof aloms along one acoe of the gold cube is ther (680% 10 = 3,909 « 10" = 5.88 = 10" stoms/4.0.em. “The clarmotet ofa single atom is 1.0 cov 80 » 10" atoms = 2.569% 107 = 26% {o°.em “The tiameter of a gold atoms bobween 2.6% 10-* em and 6.8 x 10* cm (26-68 A) ‘Some atemie arrangement must be assumed, since none is specified. The solkd state ls characterized by an orderly arrangement of partcies, soit iant surprising that ior errngement is required to caleviate the density of a sold. A more detailed Gacussion of sold-atate atrvetura and density appears in Chapter 11 in arrangement A the number of stems in 1 em isjust tne square ofthe number that Fi fineaty in 4 em, 106m BoP = ies 2.02 x 10" = 2.0 x 10" atomsiom 4.0 cm? = (2.02 + t0lyF=4.088 « 10"= 4.1 « 10" atomefeen™ foaerangementB, the stoms in the horizontal rows are touching.aiong their diameters, sein sirangement A. The number af Rb atoms in a 1.0.cm row is then 2.0% 107 Rb ‘atoms. Relative to arrangement A. the vertical rows ore offset by 1/2 ef an atom, ‘Atoms in 9 ‘column’ are ne longer touching along thelr vertcal diameter, We must ‘calculate the varical distance occupied by @rew of atoms, which Is now lesan the: ameter of end Rb atomns, Molecules and lens Solutio! nding on the adie of the atom, tne Volume Fete tet and € * 10°" that is, between 1 part in 10° ‘and 8 parts tn 10%. sass of proton = 1 0073 amu {0073 amu ¥ 1.66054 x 10% glamu= 1.6727 = 107 drvonr 9.050% mercun <0.c0 107m Seah ae aa ‘ssuring 2 proton ie a ephore, V= 4i3 TP mab vars 19 oy eee 1 om? alg H.0% 10 Weight iar force ave by te mes fan cbt undet the acolraten dis S00 We Foreign othe Nowon, of ha -ie>- Mazo fe = Fndarartal HAGMAY EST vr sothg, The weight of n abject varen depending on he pastan of the jest rails a ee evariantwith postion. Atomic weight, wi nie oforams, ara ie same gnine meonas on Earth, Cleat, hey are masses ater han weights, fa) There are 24 know inatopes of NI, fram “Ni fo7*N () The Five most abundant isotopes are ya, 57 935940 amu, 68.0775 fy4, $9.930788 amu, 26 223% fey, 69.928346 amu, 3.634% Ni, 6.991058 amu, 1.140% fy, 63,927968 amu, 0.826% Data from Handbook of Chemistry and Physics, 74" Ed. [Data may differ slightly in other editions | ‘Ar, molecule could consiet ot ro atoms ofthe-serne lsctope ar ene atom of each cf the ho diferent isolopes. This Secon paesiblty is twice as tkely as the first ‘Therefore, the socond peak (Wwice 96 large ct peaks t and 3) represents @ Bry molecule containing Gtferent isotopes. The mass numbare of the two isctopes are determined from the masses ofthe two smater paaks. Since 157.836 = 158, the fist peak presente a/"8r-"Br molecule. Pesk 2 161.832 = 162, represents 2 "Br molecule. Peak2 then contains one atom of each isotope, "™ar-"6r, with ‘an approximate mass af 160 amu. ‘The mast of the lighter isotope is 157-836 amu/2 atoms, oF 78.918 amufstom. For the heavier one, 161.832 amul2 aloms =80.916 amu/stam “The inte size cf the twee peaksinhe mass erectumct Br, incicatestheieiatve abundance. The average mass of 2 Br, molecule le {.2588(157 296) +-0.4990(159 834) + 0.2431(16%.892)= 159.79 amu {Each procuct has four signfieant figures and wo cocrnal lace, he newer has ‘we eimai places.)Formula Molecules and tons Denetty, mL. Name Solutio Melting Poin, 1515 Pr phorphong 3807 ‘forge sci, silicon 148s tetrachloride 10 coHo o7ae3 4178 (C.H.0H) Ha. gogaag Hise ‘wage oss es x9H_.9105gHt aS aot gc Toco ge oossagh. xg co7oog Hn ac To0a6 ais biphenyl xoH ass49¢ ae mesitylene : o1agHiige ooersaH. _xaHt dawsye To0ge 10.0839 g Ht g Cie 24:4 combining ratio, dividing the g Hi g C obtained in (b) by 0.083 should indicate the ratio of 1:16 In the other compounds. soluene: ; 0.09589 HH a Empical formulas follow the combining ratios. o.105g HII gS tga OS = 25H: 10 = SHACCH, aeameta se bene ocr tees fete 29H GS 2 4394-4 ae Ho30, GH, 9.09599 H10C © 4 4H 10 ScBsPa HOS = 1.44H: 1e= 0H: 7e=6.H,Stoichiomet Calculation with Chemical Formulas and Equations Balancing Chemical Equations 36 +0, incieates that there are 2 hydrogen atoms and 2 einygon ators bound BY crenicn! bonds inta 2 single molscule (of Pysrogen peraxide). HO Isicabsé 2 cralecues (ot waten, each of which contains 2 hycrogen atons and 1 oya8h atom, “The cornpcaition of the diferent mclecules, HO, and H,0. Is flarent and the physical and chemica’ properties of ine lwo compounds they constitute are very dierent. T= subecrint 2 changes molecular eampocition and thus. propertigs of the compound Tha protic 2 indicate how many melacules (or molt) of the orginal compound are under consideration. No. There ate more Hand O atoms on the reactant side than the product side. The coatfcient 6 before HOM) in the products would balance the-equation. 08 rite the balanced equation fr the reaction, 2H, +O > CHOH ‘The combining ratio of CO is 21. Mw have 8 H, meleculns, 4(CO molecules are required for complete reaction. Alternatively, you could examine the atom ratios in the formula of CH,OH, but the balanced equation is most direct. e ® © 0 @ G14) + fo) 7 2L4M5) TiN + 2H,0() > T0,i) + 4HCIaa) BiHLNO,() > 2NG) + Og) + 44406) CapP.lo} +8H,0l) + 3CalOH) fe) + 2FH(0) ANOH)ss) + 3HCIO,aq) -» AUCIO.)aa) + 34,0 24gNO,faa) + NB,S0.faq) > Ag.S0,\0} * 2NaNO;'eq) BN Hug)* NOV) > 44,0(0) + BN)ichiometry Solutio 1 FW=11105-1) +295.5) #21140) + 6(10) = Some i sere 108 6.01% Cigh0=: FIV = 18(1210)-+ 24(1,0) + 2180) =272.0 amu Dams » 490 = 78.4% CoaHeNOg: F= 10(12.0)* 27¢1.0) + 1(140) +9116 0) = 805.9 aml wo 18020)eM , 400 = 708% 305. 0ame com FI = 1412.0) + 2(18.0) = 44.0 om 12.0 am aoamu HOH: FW= 1(12.0)+ 41.0) + 10160 me= = 10 12.0.ame Rema eye FIV = 2012.0) + {1 0) =30.00mu %c 00> 375% wece 242018 4 yop =an0% CRUNH: FW = 1(120)+ 1182.1) +2(14 0) + 401.0) = 76.4 ama 120 BML x 499= 15.6% The Mole 322) mae t#29 — (@) 6.0221621 10%, Avogadro's number 3.24 30% 10" H,0; molecules contains (4 sloms x 0.5 mal) = 2 mol atoms 52 g O,comistns (2 atoms * 4 mol) = 2 mol atoms 2.0 melCH, contains (S atoms x 2 mol) = 40 mal atoms 250 muilin = 250 » 40" = 2.50 10" peonte scorn soe , $1. 55.002. 10" exe $247 10%%pernen Zeon Wi pods TOE 2.50% 10" people iporscrichiometry 10" Catone: 08 10" Haters « 21100 10° 210» 16H, moloeles contre ied miele Ra om 10% moieedes 0 « 104 el Cas motar mass = 19{12.01) +26(4,008) +2(46.00) = 26841 = 228,49 $827 Or = 9.0527 9 CxHa Os 25 #107 9CaHaOe* 10 10 mol Gata aasge 6.022 10"? moteciies. 1:95 « 10-9 mol GyH0, x £922 210" GyHn0; molecules 95 + 10% mol GH0; om 8x10" Empirical Formulas 338 ‘the box cortaina 4 € atoms and 16 H atoms, a0 the empirical formula of the hystocarban is CH, tthe molecular formula of tho hydrocarsonis the eaine ax the empirical forms, the osctanis’ box would contain 4 CH, molecules and § 0, molecules. At this si9g, youneve no basis for knawing whether arnt hare mightbe a hysrocarbon molest pet fran Cli, that has this same empirical formula, Mtums out, however, thal there: re rons. In general, the molecular formula of a substance does not have to be identical wit is empincal formula Calculate the simplest retio of motos. 0.404 met k/0.082=2 0.052 mol ¢/0.052 = 0.586 mol 010.052 = 3 Tha empirical famula ie KCO, Calculate moles of each element present, then the simplest ratio of moles sangn~ LDASD. 300,i0) + 44,049) CH.CH,COCH,) + 1172 O49) > 4C0x%9) + 41400 the fuse transformed to H,0 fn the producas: TIBRSSGIETS (CyH, and CH,CH,COCH, (CaP) Both vil produce the same amount of sO: na combuation reaction, af H woth most rot Hitnol fuel wil produce the ost wave 8 nal Hm! fuel, 8015 mol of ether fuel 5 mo! C,H,0H yl produce less HO. CihlaOuloa) > 20,H,0H(en) + 260,f5) (0400 met CHuCa* 19 Hu 750 0GHOH* sg a7goFLOH FBIM Oe = 14.7 9 CH Oe ma C.H.0F 4401 960, x 2 =7.18 C0, STE CHLOE Troi CO, a 375= 9.38 mol O, zomalO, | 320090, S009GHn* spect, om: =17590, 1.00 gal C,H, 37954 , 1o00mL , asa20 ‘oat tL TnL = 25195-26210" 9 Catyy 26mdd, | 320050, 251859 CM, pp seetty ImaAGH, 1700, 9175.49 = 918% 10°90, Pian Calculate 2 “mole ralio" between nitroglycerine and total males of gas 18 mol gas, 4 mol nit: 29 total mol ges. Soive, Zango Amotnee se le es asaso=a 4Solutic o.a50 mal Aor», «2724S = 9.675 met H, 80, noel le Only 0'580 rol H,S0, available, 4NOV) + SH.O'9) Fallow the aspraach in Sample Exerose 3.18 tw 9,1921= 0.132 mol NH, 225 01M os 1melO, 2.789 0,6 20s = 9.4972=0.197 mol Oy 320090, mmol NH, 0.1472 mel, « “TOTS = 0.08575 = 0.0838 mot NH equ More than 0.0838 mol NH, fs available, so O, isthe liming reactant ate REO MOINS « S0.018N2 = 281 fr Se > ‘BNO produced 0.1321mol NH, -€.088 mal NH, eeacted = 0.0389 = 0.038 mel NH, remain 17.03 ght. WS 20.852 9 NH, remain 0.1972malO,* 0,038 mel NH, * Trai Nh Pian. Whe balanced equation; determina limiting reactant, catulate amounts of excess, ‘rpactant remaining and products, based on Imnting reactant Save. H,S0,(aa) + PBIC,H,O,).{a9) > PD5O,(8) + ZHCH,0,(2a) 4 mal H,80, 7509 1,80, «Oe og 0765 mo OHE0.* sore arr sg, TOOTS =O.OFES mal HS, 1 ot POICH,O.). 7.509 Pb ‘ae SPMCHOD: * Ses gPIE HOR 023088 = 0.0231 rol PC,H,0,), 1 mel H,50,:1 mol PD{C.H,O1)» $0 PDIC-H.O;), i the Imiing reactant. (© mel PE(C;+,0.}, (0.07685 -0.028086) = 0.0530 mot H.S0,, 0.0231 mol PSO. (0.923086 = 2) = 0.0961 mo! HEH/O, are present after reactionhiometry o(14.0) + (4.0) # 1(32.1) +4(160)= 1924 Smal sent (2(14 09192 41 100= 212% NHNO,: FW =2(14.0) +4(1.0) +2016 0 %N=[2114.0)60.0]« 100 26.0% ney) CO: FAV =2(14.0) + 4(1.0) = 1120) + 1(16.0) =60.0 ama = (2(14.0)60.0) x 100 = 46.79% N iy Fwy 1¢14.0) + 301.0) = 17.0 S4n= [140770] » 100 = 82.40 _ 5228 t0%'g _ , 6OI21» 10 mateciles = 3217 gimol penal Tovecule penieila S Tal £0 g hemoglobin (ham) contains 3.40 x 10" a Fo. 1oDghem _,, SS.85gFe , 4molFe = 657.x10' ginol hemoglobin Sa0<102 gfe TmolFe | tmorem Pian Assume 100 g, calculate mole ratios, empsical formula, than molecular formu from. reolar mass, Solve smote st2eC* Doge 568 mol C; SS40.568 6.84 mol Hy 6.8170 568 sgn ima 5 158g = RN, = 4.13 moh 1.130.568 = 2 90890 = 17919. «o.s68moiO: o.ssai0 0568-1 76008 The enpiccal formula is CgHN.0. FW = 78 amu (or), Since the malar mass is 176, the ‘empiteal and molecular formula ave the same, Cy'/nh0. Since al the C in the vanllin must be present in the GO, prodveed, get a C from g CO, 1 maico, pas ncox-! oe argco; Since ale H in vaniin must be present nthe HO produced, ge gH fom g HO AmolHO ._amaM_ , 1000GH . oonsg= GEgHO* imat,O imay ee TOES eN Get 90 by eubtaction. (Since the analysis was performed by combustion, an unspecified amount of, was @ reactant. and thus tal the On the GO, and H,0 produced came from, vaniin) 1.05 9 vantin- 06839-00589 osogH,o=oichiometry Calculate the tot from gH.©. Calculate mole ratioe and the emit ergcox 10000» IIS x az01g oas7 9c e 1mol 0, Wc 2 7339 CO; * x = 1201 9C=0.20090 O733.960:* Teor geo, | Tmo Total mass Cis 02009 + 02009=0.400 aC ima , amet , 1.00804 99503 9H 945094,0* Teno imdHO Iman (Gince nycrocaibons contain only the elements C and H, gM can also: be Obtaies by subtraction: 0.450.g sample -0-400g C =0.050.9H) oaoogex ae 0.0333 mall; 0.0333 / 0.0333: 0.0503 gH« —1MOlH. 49 g409 mel; 0.0499/00333 - 15 1.008 aH ‘Mutbptying by # faetor of, the emprical formula is CH ‘Mass is conserved. Tetal mess products -mass sample = (0487 g CO +0733 9 CO; + 0.450 a H,0 -0.450 g sama For complete combustion, 0487 g CO must be converted 10 CO, 2601g) + Oya} > 200,60) tmaco , 1madO, 320050, 2B01ge " 2maeO tmdo, 0.467 gCO* 202679 The jotal mass of B, required for complate combustion fe 12009 + 0267 g= 1.407 30> Ni(@) +39) > 2NH(9) Determine the moles of N; and Hz required to form the 2.0 moles ef NH, presant after the reaction hse stopped. mel NH, 20 mol NE, * = 3.0 mol H, actediometry Soluti 1.82% 10°94 100 = 828% (a) parenat yield 25 «10a fe Exercises S278 pass of A > molAg > Ag atome 1049gAg « _LmOlAg 6.022% 10 atoms) Temag WTSTOAR Tmo = 5.5562 « 107 = 5056 « 10 Ag atoms Pan. volume of Ag cube Salva: (1.000}* em? Ag em? Ag 4.000 en? cube volume, 74% is occupied by Aa alors 0.7400 cm? = volume of 856 = 10" Ag atoms a.7a00em? _ 4.2636 x 199 = 4.264% 10 cn? / Agatom Babee» 10 Agatoms Since atomic dimensions ae uoualy given in A, we wl shew tis conversion. Qasim’. a gcatagsiem Tem 0" ears we: P= slam r= @viany* 1.284 «10 em? y= (3% 12.806 A (any! = 1.4449 = 4.485 A lan. We ean proceed by writing te ratio of masses of Ag to AgNO, whore y is the atomic mass cf nktegen Solve: Aa» 9634095 = Rand, 107 BoB - KISSD) ¥ ‘Solve for y to obtain y = 14,0088. Thisis to be compared with the currenily accepted value oF 14.0087. (3) Pfam Caleuiste the ig of air nthe roor and then the mass of HCN required to produce adose of 300 mg HCN/kg air Solve: $2Rx 15M = 8.0R= $440 = 4.4% 108? of ait in the room inf, @s4emP , 00011893", 110 4.42 Tin? tem air 1000; 248 kg air BomgHEN 40.72 ta ais = SOTAHEN . tg ay i Tag ar” To00m aNSe Aqueous Reactie and Solution Stoichiometry Electrolytes no. Electriyie aaltione conduit electricity because the dissohedions cary charae INo¥ah the solution rom one etectrace to the oiher). though H.0 melezuiee are elacticaly neural, ther fan unequal sibution of sistane frovgheutihe molecule. There ate more electrons naer O and fewernear H, giving We O Sra drive molecule « padial negative charge and the H end of the molecule @ partial postive charge. onic compounds are compacad of postvely ard negatively charged Ions, 17s purtaty poste endeo! HO molecules are ntrocta othe negativaians (anions}in the sold ein tha partaty negative ends are attrectedto the posivelons (cations), Thus, both cations hd anions in an lonie ald ore surtounded and seperated (dissolved) by H20 molecules. fa) Mah(ac) >MaM(aq)+2I'(an) —_(B)._ANOSIy(aa)-> Al*(aa) + 9NO> (2a) {@) HOI0,{aa) 9 HXea)+ Crag) —_(@)_(MHY,8Ox60q) > 2NH, faa) + SO." (28) Both AX and BY are weak electclyies, becaues some butnot all melecies jonize when they disaohe. BY will bo the beltor conductor of efecifcty because it produces more ions Pet mole of dissolved solute (a) acetone (nonelectrtyiey: CH,COCH,(aa) melacules only; hypechlereus seid (WeBle ‘elecirolyte}y HCIOaq) molecules. H’{aq), CIO" (aq); ammonium chloride (sirong iectroyte): NH,'(aq), Crfea) HCl, 0.2 mol solute particles: HCIO, between 0.1 and 0.2 mol panicles: CHLOCH,, 0.1 mal of sclute particles Precipitation Reactions and Net lonic Equations 412 According i Table 41 (a) NUOH), insoluble (©) _PRSO, insoluble, PA is an exception to soluble sulfates (©) BRNO), souRie (APO, Insohible fe} AgOiH,Oy solsbleSolution -souton dove conde some olay, bit e551 a factory electrahta) tye unknown aohuta must be 2 week olactoN “The weak electrolytes feos oe nena HPO sien test ade) MuHa HPO, Haro: wesk (e) HNO; sheng (6) KOH: ston croc: non fe) CaSO¢ stong (0. Cutts Ne HC.H,0,(2q) + KOH(eq) > Ke,H,0,lea) + H,000 (oq) + OFF oq) -* H,O00 ‘GxO#,(2) + HNO, fea) > CHNO,)faa) + 34,000 ‘eyOH)(s) +3H(aa) > 34,010 + OP") ca(OM{aq) + ZHCIOIaq) > Ca(CI0),(aa) + 2H.00) OF (ea) + Hea) > HO. ¢200,{s) + 2HNO,(aay > Ca(NOs)(aa) + H.019 + CO,(0) 2kfaq) * CaCO) +H,0() + 6OuG + CaCO) 5) + 2HBriag) 3 FeBrfox) + #503) 2i(0@) + FeSis) > HeSI6) + Fe™(o5) Kc0faq) + HOM) = 2KOH(aq}, molecular, O* (a5) + H,0() > 20H (aa), net lente teste: (Hf ion acceptor) O (20), act; (H" on dover) H,Ofaa); spectator: KC Oxidation-Reduction Reactions 435 Coeidaion and reduction can anly occur gather, not separately. When a metal reacts with uygen the metal aiomslore aeetons and he cxygen aloe gain elecrens, Free electrons ce not exist under normal conditions. If electrons are lost by one substance they must be alned by another, and vice vores. pininum and gold are caled the noble metals because they are especially unreactive and ‘iticulttoeadize. The slkali and alkaline earth meials are called active because they are very ouily exiszed anc chemically eacive. as Oo OH OS | 6 (e)ae-base reaction (B) _‘sxedation-reduetion reaction; Fe is rectuced, C is oxidized (c) _paeeiptation reaction (@)—_oxidaton-seauction neaction; Zn ig oxkized, N in reducedeous Reactions _ ago. X980MIE 5 q(4'5g solo) = 29)gsoue DeomolsoKte 4.Sasclute The result has 2 89 figs: 22.5 rounds to 23g tolste oases, rolsdise = 0.189 MNO, ‘Lsolution OrsoL = art KONO sls 04251. = 1.06% 107 mol KMNO Mant; 9255mol HCL = 2.20 «10% Lor 220.mt TG mol HOV © (ae ie tn symbol or malar mass int manual.) 12.5.9 Cn} i Amel (NH,).SO, 4 250.9 (NH),SO.% ere x 50. INHISO6% 57 zg (NiO, | 250.7 = 0.0756 MI(NH),S0, msl CuSO, a $00 aCuS0.* ss gqGuS0, - 0587 mo CIS, x or = 162ml solution 0.10:mct NaCt250 mL = 0.40 me! NaCl'1090 ml.= 0.40 M NaCl 045 MKCI-<0.10 ANAC, < 0.40 mol NaCl in 250 mL Naci> Na+ Cr; 088Mx 0040 | =0014 mel Cr cach, > Co + 2Ch 0.25 Mx 0.025 L = 0.00625 mol CaCl, x 2= 0.0125 = 0.013 mai cr “The NaCl selution has slightly more meles Cr. re, 0.100. Mx 20.01mL + 0.500 M1 # 10:0-mb a8 293 4H" Cr: eoncentraian Gr = concentration H"= 0.253. Cr Nor, 20300» 180M)

. 9.300 Mx 150m yp, 9.2004 «1.0m Bam OOM gmReactions Solutio! ex(oH)ien) > BaChiag) + 24,00) 9101 mst BOM. oso0t Belo, * STUER Tess, (OH, 9.0842 , or 842 mL He ein 180,09) + 2NeOH(eq) > Na,SOaa) #24000) sae Tmonsor , IMSS. , 0.200 9 NSOH™ Zy09 gNAOH ” ZmoINSOH = 0.0200 Lor20.0 mt H,50, so! (20) + Na,SO\(aq) > BeSO,s)+ 2NaGliea) ae mq = 0.752 gNa,S0.* a5 co nie.5O, trol = 00048 MBSCl, (@ — 2HCXaq) + CafOtfac) > CaCl(aa) +2H,00) ic) , Amd CaIOH), , 74.106 C0104) rine! x 22S mol HG . AMSEAEM » — CR ea a Brave” ima Ca(OH), 329 Ca(OH), TmolHEH,O, _ 60.05 HCHO; mot tia molNiBOH » go3a5t* = Tima NeOH ~ 1molHC,H,O, 247 g HCHO, in 2.50 mb 1.00 gt vinegar * = ca at = 82.3. g HG,H,O/at ‘The balanced equation forthe tration is ‘Sr{NO,},fa9) + Na,CrO,(aa) > SrCrO,\s) + 2NaNOs(e9) Beginping with 2 0.100 | eampla, we can do the folowing conversions: volume soin-> gSX(NO.}s > mol Sr(NO,}; > moi Na,CrO, > vot Na,CrO, soln TEBGEUNO. | LmelSHNOS | tmp! Ne,CrO, 2190 Lact = ets DIsisdn ~ BBgSMNO,, imo SIND), * gprs maneao, 1th Neoraces 474 (a) HND,{ag) + Mars) > NaNO,foq) + H,000cous Reaction nyt 4.289"90) 6:02" (0=) > A0,050.(0) whl aia Exot & Cxtaa) +.€,0,+ (aq) > CoC,0.6) white ream Expt 6 Actteq) + Cr oe) -> ADCs) white pect “The stver cans of bath ions are insaluble, : wri wt 6) The calcium sail of Cro, soluble (Expt 3) {G,0¢" aq) is insoluble (Expt §). Thus, chromate sate ‘appear more soluble Enh ‘oxalate salts 2H tac) + SO," (aq) > H,80,(a9); sulfureus acid ¥480,(aq) > H,O(0 + 80a); sulfurdioxida sree boiing point af S0,(g) fs -10°C. Webs a. gee at room lamperaire 128° C3 tet pressure (1 atm), Na,S0.faq) + ZHCiteq) > ZNeCKoa) + H.00 + $0.9) 50;-(eq) + 2H (aa) > 1,010 + 50(0) fy Ag,SOxfs} + ZHCKaq) > ZAGCKS) + H-010+ Sia) ‘Ag.80,() + 2H'(at) * 2cr(aq) > ZAgCK) + H.O(H + 80.0) KHSO,(s) + HCliag) > KClaa) + H,O(0 + S00) KHSO,(¢) + H'f2q) > fea) + H.0t) + 80,69) ZnSO,(an) + ZHCKaq) > ZnC,faa) + H,0() + 50.10) S0,*(eq) + 2H'(aa) > H.0(0 + S0,(9) 32 2 Nitya) + 50xla}—> 4NO(a) + 6H,O0) (a) tedox seaction (b) N isoxibized, © is reduced 2NO\e) + 04a) —= NOs) (e) redox reocton B) Nitouied 0 is reauces a GhDua) * HON) > HMOJaR)* NOI). (@) FOdoxreacon tb) Ne ovtand (NO, 3 HNO, Nis reauced (NO, “+ NO}. A reaction where the seme ent eset ocsiad and reduced iw ealedeaproportion (@) Bog) +Zn(a) > ZT eq) * Zea) “The coefficients are required because the number of jectrons lost by Zn (Ze) must ‘equal he number of electrons gahied by TI" (2 * 1e°). “This reaction dose not indfcate the positicn of Thon the activity series in Table 4.5. Ail reactions in Table 45 involve oxidation of an elemental metal to a metal ion or ‘compound. This reaction does not produce TI metal and thus cannot be compared te the other reactions.ueous Reactions Hou faq) > CAHLO* (ae) + 24,010 TrelHiCHO, vex ome molNaOH 1.0, aes 1022621 NaOH « Ni ma NO” CORRE RyGOR = 6.05855 M HCHO, 8b snot O¥¢ rom NaOH(sq) * mo} OH" trem ZOH)e) = me Fem Hr vel "= MEL HBr= 0-500 NTHEr 0.400 L HB 0.200 mol HP rel OFF ftom NaGH = M NaGH x NBOH = 0.800 M NaOH * 0.0885 L NaOH = 0,08825 = 0.0988 ral OF smci OF worn ZajOH)(s) = 0.200 mol H'-0.04825 mo} OH fora NaOH = 0.15075 = 0.4181 mol OFF from ZKOH) jpolZnOH}, _ 98.419 2104} nOHe., SRA ZRENE 749g zniornh zmton —_1moenGH 9.15075 mel OF = Integrative Exercises ass (a) At theequivaionen point cf tition. mai NaOH added = mol H’ present for an acid with 1 acitic ) 26 (ot sn acid win | ace hyeronen) ___ 020534 __ = 498 gfe! 0.40084 0.01501. hes Assume 100 g of so tmal & 7os9C™ 5.68 mol) $88/147~4 smal Set mol H: BAIT AT <4 7.008¢H 5.89 gH™ 235 go LO = 4.47 mol 0; 147114724 The empirical fermiia i CHO. 38 <2: me molecilarformuain 2 the erpieal formula “The molecular formula ia GH,Os 495 BaPaq) + SOF(aq) 3 BaSOU8) 0.4123 ano, x T3988 rt SaIsEts ~ 0205 a8 9884 499 = 928254988 4 100 = ‘gsample Bo gsample i oe30 mOBE = 9.94 182 ME Aat(aa) + OF (ae) > ADIGE 25.00 ml sea water * maze %Cr= @ = 0.0e258L* 1.0259 = _oasziza: smo! OFF In table!= mal H’ total - mol H' reacted wity NaOH mo! H*fotal 0,600 M MC x 0.0500 L = @.9250 mol H’ tosh ral Ht w/MaOH = 0.288 NaOH » 0.0900 L =01007880 = 0.00788 mol OFF 0.00788 mal H* ral OFF in tblet = 0.0250 - 0.00788 = 0.01712 = 0.0171 mal OH in biet mess (Mo(OH), + AKOH},) = 500 ma x 0.950 "478 mg=0.475.0 aMgOHh=< gANOH) = 0.475 -x x 2mol OH x__,_2molOH _ = mot OH fram MatOH} BESO MgO, 101 Mg(OH nae 75 =x 3molOH, 3 x = ral OH" from Al Sete eR oY oe 2x | 14e5-a% #25 3% 9.01712 mol Big - AEG FE soorra mal or 156.00 + 631065 -174.06% 4 ovr $5.32(78.07) Bie “$894 x77 8082- 83.106 = S2178=-52 x= 0.27849= 0.275 g Mg(OH),; 0.479 -0.275 = 0200.9 AKOH), (Gticly speaking, both masses have2 cig fige because ihe difference (78-8311) has 1 decimal place end 2 sg figs) ‘mol HC: initial mat NH, from air= mol HEL remainisg = mol NaOH required for ration se 4 «0.0131 L =1703 x 10% =7.70 * 10 mol NaOH =7,70 * 10" mol HCI roman,' ml . YW Thermochemistry eof Energy fe) ThaFnatc energy of ball decronesé' at Tveoves Nee. 8 BEEESTES per and opponee party kina energy is changed ine patents @ASTRI “The potential energy ofthe hall Increases 2s itrmaves Niche srre heavier pot would go hail ag Righ oethe twanis ball At the apex of We Seer. a vital Knee aneroy has bean changed into potental etary. Te vanities af the enange in potential energy is m g Ah, which ie ena! > the ener sen imperted tothe bal. the same amount of aneray is Impared tf bel wit twice the mass, m daubles 60.2971 half as large: Plan Conver io > kg. rife -> mis. Solve. $501 = 490.84 = 434 ko 1.609% , 1900m , the tr in Tk min , = 12 m= 12 430.84 kg * (50.398) mi . ia provonionsl to, so if epaad decreases by 2 factor of 2, kinetic energy decreases by a factor of 4 rakes stop a meving vahicle, so the kinetic energy of the motorcycle & primarily transfered to trcton between brakes and whesls. and somewhat to deformation of the tre and fiction between the tre and road, Analyea Gover: ‘the A watt= 1 is; Twat es = 1. Find: conversion factor for joules and knh. Flan. kwh > wh wa Pd ooo, 0mm thw teh =38 = 10 ‘Sone. 4 kwh “Thesenergy s0urce of 100 watt ight bulb is lectrical current from household wiring. Current pauses rough and heats s tungsten ftarent (thin wite) in the bulb. The siargy i radiated fn the form of heat and visible ightae 524 the, my hermochemistry Solutio’ e andw is negatwe, Be = +800 1 - 4Zzds qi negative and wm essenaly zero, BE= 31404 “Tne procens fs exothermic. qi negative ond is zero, QE = B65: “ihe process i= SsOhetTIeS a]= 0 (0) Ae be pactve tor ha areas fH REET lee tf wi greater than the magnitude of BE wil be, negathre for this. preoass HI magntuce of@ i= greater tran the magnitude Off «OQ, _ FO:22 56 gro opposiely enarged parisien, the sign of is negalve: tha Goes! articias, the greater the macitude of Ey. The polenta energy becomes less negative othe particles ae separated (rincreases) ‘ne forthe process fs posve; the intemal enaray of the system (nereasen 65: ‘oppostely charged paricies are separated. Were le done on the system to seperete ho particles sow is poslve. We have nie Greet Knowledge of the change In, except tha jt cannot be large and negalve because overall AE =q + is postive Independent. Potential energy is # state inction Dependent, Some of the energy released could be employedin performing Work, 35 is done in the body When sugar is metabaiized; heat is not 8 state function. ‘Dependent. The werk accomplished depends on whether the gasoline i “ead in 29 erpine bumed i an apen flame, ar in somo other manner. Wort is not a stata function When a process eccurs undor constant extemal pressure. the enthalpy change (AH) ‘squats the amount of heat transferred. GH = 9, State functions are particularly uneful because they are totally dafined by the current conditions (slate) of the system, not the hisiory of how the aysiem rived at is current state. Changes to siale functions, lke AH ean be eaiculated trom knowledge finial and final atates, without details of how the change takes place. AH=a, Ifthe eystern sbaorts heat. 9 and AH are postive and the enthalpy of the ‘systom Increases.ne OH=AE + APY). " coon For ths racton, there sre 2 mol of gaseous product sr Te var or ACPA) iw negate. Since aH = A= + AlFMy we nrpeare that BH wil be sriier or more negative ven AE -ye gas # tha system, 11518 J of heat is added, a decreases the overall eneegy of the system, 59 ews e506 5-127 J = 4990 4. OH Gite) > TCHAD OH = 2103 CH) > SCAG) BH = 3(+210) “The exotnerric reverse reagtion fe rove likely to be theemagyti cHHala) aH 4/3 CeHelo) 49 CHAO tree reactant fn the higher enthabpy gas phase, the overall AM forthe reaction M&S a smller positve value, Calorimetry ‘The specific heat of water to four significant figures, 4.104 JigK, wil be used in many of tha folowing exereses; temperature units of Kand *C willbe used interchangeably 5.44 Analyee. Bath objects are heated t> 100°C. The two hot objects are placed in the some Srotnt of coké water atthe same temperalure. Object A rales the water temperature mare than ebject'®. Plan. Appiy ne definkion of heat capecty to Neating the water and heating te objects to determine which object has the greater heat capacity. Solve: a) Both beakers of water contain the same mass of wales, so they beth have the same eat capacity. Object A raices the lemperature af is water more than object B, so pore heat wes trensiered trem object than from object B. Since both cbjects were hosted tothe same lemperalure italy. object A must have absorbed more heat to reach the 103° temperature. The greater the heat espaciy of an object, the greater the hes! required to produce a giren rise in terngerature. Thus, object A haa the: (eater heat capacity.hermochemistry Hees’s Law 556 Head's Law | « eoreequance of the fac Trolopendent of path, we can describe a procoss Dy any seis 8 ‘overal process and AH for the process ie Yor dHe+zKd he sam of te BH values for the SIePS: an| = #105 a = ‘ne process of fonring Z can be described as ¥ fering X and X forming 2 No. Any temperature change le accompanied by = change in hes Comparing ectonk and enthalpies of reaction at diferent tomperaures doesn lake ine ‘coount the change in heat to 09 ftom one temperature te the olher. BH(G) +3200) > 34,010) Om > 320,99 Tis) + Of) > SHO) NOG) > NAad+ 2.015) NO,ig) 9 NO(G) + 12 GB) N{@) + OX@) 7 2NOG NOG) + NOUa) > SNOIG) Enthalpies of Formation bH= 572-4896 bs) aH = 867.710 BH = 112-1632 Kd) V2(413.4 ks) a= 180.7) BH=tS57K 554 (@) Tables of AH) ate uxeful because, accarding to Hess's aw, the stancard enthalpy ‘of ary reaction can be calcufated from the standard enthalpies of formation for he resetants and products aH, _,= BAH, (preducts)- DAH, (reactants) ‘The standard enthalpy of fomation for any element in its siandard state is zero ‘Elements in thai standard states ae the reference pointer the enthalpy of formation acai.vemistry _ Solutio! ico 8,4 the combustion of B.H, produces Bs 38) th heat of combustion of 8,H, m adation to dato GMenI IA Ee Ua calculation of the hat af fermion of ByHy she combustion roncton ix: 8/0 + 60,(0) -» 52 6.030) Fay 614 (4B(e) + 30410) > 28,0.(8)] ait = 574(-2508 01) 944 [2H(a) + xa) > 24,0001 = 9/4 (871.7) 28,0512) + 92H,0() > BiH + 8OK—) BH = -Mheat of combustion) ose Sane cant meutb beste contour RANT 264 tama tierce measure te heat of orbuaon of Ee! s00(a) + 4H,(@) + Cute) formation eyble) + 12049) 9 1060,) + 44.000 combustion, AH! = S454 ka ni], = 10nH) Coy) +44H, HOM-AH, Cal - TRAM, Orf@) 5154 = 10-394 5 ks) + 4285.83 1) - OH C\H4(5) - 1210) ‘BH, Cghy(s) = 10(-988.5 kl) + 4(-285.83 hl) + 515A Ke = 7d Check The result has 0 decimal places because the heat of combustion has 0 Secimal places, Foods and Fuels: 5250 Fats are appropriate fo {uel storage because they are insoluble in water (and bay ffuide) and have » high tye value. combustion analysis ix a poor measure of the fuel valve af proteins, since the products of protain combustion in the body are diferent than tha products of Combustion in 2-calorimeter. That is, we ave not measuring AH for the reaction that ‘cccurs in the body, ok! sz cc) Bataxt x gprsion «Soren! * “SBE Frten CCaleuate the fuel value in a pound of M&M candies soite 2 eases eed 320.9 carbonyarate ® JTS —— = Sank) = 5-4 10" Md 21g pron s HL = ser een ae Topeen, ae ‘otal fuel valve = S68 hd + S440 Kd + 987 barmochemistry Solutio 5.5 dascibes enemy changes to the systems Spel Tatar energy ofthe system is manifested 2s heat transfer EWES that an equal but opposite ehange occur tothe BUTOUnEINaS BE wr a ncton eometrres depends an patente sre aati UNS FASE cree tincton =o AH for ha two pathways leading tthe eame change of is pictured in er 510 mat be to ear. However, not te same for both, OM SRGRs 7 must bo tat BH + qfor these pathways. The condition for AH = a, (eter hen constant pressure) a amen posebie workon or by te ayaten it pressue-rcume work, Cia UST: paing dove in Bs scenario nt peasurewoiume work, 90 AH 7a, even ROUBR His SO changes occur at eonstan! pressure ae ae x 421.0 gGu(30.1°6- 190.470) =-22749=-927 * 10° Tre negative sin indicates the 3.27 « 10° J are lest by the Cu Black. Aiba jena gh.o = Bttreras eh sats IS “The positive sign indicates that 3.14 * 10 J are gained by the H.0. “The difference in the heat lost by the Cu ard the heet gained by the water is 278 « 10° J 3.198% 107 J=0.137 « 10° = 1 « 108. The: temperate change of the calorimeter is 50°C. The Nest capacity of the calorimeter in aM ie 0.137 10? dx 1 = 27.4910 aoe Since gu. ls known ta 4 dec. place, the diferenca has 1 dec. place and the resuithas 1 sig 8g. i teria rept rr (} and yar ed. Cope 2221S Be 1d = 4 10M. aig" 3.278 = 10's = SEE x ss0.9 96 AY=5.20"G; T,=28.1°C 522°C = 303% From the mess of benzoic acid that produces a certsin temperature change, we can ccsicuate the heat capacity of the calcrimeter. 28.28 Kd gttg TTS es78Kurcemistry Solutid ac.Hla) 2 CHAD ‘AH, = AH; QyH4{0 38H, G3Hia) = 490K - 32287: esp = 091.9 since te acta a exother (ia negate), the produit tml arid a less enthalpy than the resctats, 3 moles of C:H,(0) sofihe “The uel value cf svestance i he amount of heat (is) praauced When TS eaaeereia Lured. Caculate the most heat of combustion ckifmal nd tea lis to rd lg of fuel yHiia) + 82 O,f9) > 2600) + H,000 aH, = 20H; CO,la) + AH, HOM ~GH, CHa) -82AH, O-C0) 4290.5 ksmel CoH G.HAg) + 1512 0,66) > 56Oxia) + 3H,0K0 aH, = 64H COUG) + 34H; 11,0(-BH, CyH(t)- 15/2 AH, 0,60) = (9985 ks) +9¢-285 69 k))- 48.0 ks ~ 18/2 (0)= -9287.5 kitmal CoH ima Got ind Calle yy gon =42 kilo G.H,0c) * 0,0) > 8CO,(0) + 5HL010, big, = 8H, COG) + 68H, HLOW)-AH; C4H0,(6) -60H, Oo) (389 5) + 9-288 89) (1272 4) - 60) = 2803 nol C00 CyHhs0.(e) +1200) > 1200404 14,00 AA... = 1288, COJe)* 14H, HOW -A4, CaH0,,(5)- 1208, Oe) 12(-395.5 kd) + 14(-285.83 ks) - (-2221 kJ) -12(0) + 5645 kiymol CHO, _ rages, AGH 155545 THES, SHanCuTGT Becca 7 Oe TSO elt) seishs IAC HMO 18400 ag Tra Hay” HASTE EA, TEC aad,” BOHen Tal valu The svecage fuel take of catbohyimlss (Betton 6.) fe 17 kilo, Theee we Ccarbonycrates have (uel values (16 Ki/g) slightly loner but in tne wath this average, (fis ectopic catatonia) orc ale he arecamochemistry eneigy of he system, +E; Works dona te the NaCl PY IPs lee Sine at coe cdwalen are pat of the system, the nat amount of work ieaalas ate De = q and bon ore postiwe The cissobing proceos EIR Sta crete ‘aimospheric pressure, so OH = a and BHie sito posta * “eve his conclusion, carrycutthe dssaliion of NaCl A consiont pressure catia: Pee bin Lt HO, ecard he impetus, eal 0.1 mot NaCl and Gases compat: card the final emporalure. (AH i postive, tha tamperature wl P=7=220 eye) Ag'fan)* tis) > Aol) + U"(04) aH = aH, Liaa)- AM, Asr(@a) 278.5 kd ~ 105.90) =-3844 Kd Fe(a) +2Nar(a)-> Fe™(oq) + 2NaCe} it = aH, Fe*(aq) 26H; Nav(ead = 57.85 k)- 26-2404 kJ) = 4982.3) 2k(s) + 2H,0(9) > 2KOH(aq) * Hig) aH = 2H, KOH(aq)=28H, HO) =2(-482 4 kd) 21-285 69 Kd) =-963-4 6 eathermic reactions are more lia tobe favorable, eo the first and third reactions shouldbe favorable and the sacond reaction should be unfavorabe: nine activity series of metats, Table 4.5, aay matal can be axicized by tha cation of ‘= metal Below @ on the table, ‘Agé is below LL 20 the fret reaction wil onc ‘Nat is above Fo, 60 tha second reaction wil nt occu Gray in #0) is below K, 29 the third reaction wil OeUF. “These predictions agree with those in pat (c) an =a, NaNO,fax)+ At H,0(9- BH, HNO.taq)- BH NaOH(2q) (OH = 448.2 bi) -285.B3 kd - (-206.8 bi) -(-469.6 KJ) = ~55.8 kel sata rat poten ail) Oe ae HO ea BH = 407.1 ns 205-83 1) - (4072) (4008 Kd) 56.1 Kd AH '= AM, Nilod) + OH, Na‘(aq) +4, H,0(0 -8H, NH/(aq) BH, NaOH(ad) 80.29 kJ = 240.1 bed - 285.83 bel - (-192.5 kJ) - (468.6 kJ) = 4 1d Hriea) + OFF (ea) > 1,01) 1 the net onc equation fr both reactions ‘The Ai’ valves forthe fet we reactions ae nearly identical, -65.9 ki and 56.2 Wd “The specaioronsby defiition do rot change during the course ofa reaction, $0.4H™ Is me enhaipy change forthe net onic \quation. Sinve the rat two ceases have the wma net ionic equation, tis nal surprising Mat thay have the same AM,‘ai sample = 195 185 kd ~59.965K! «(311 7 2 = 42.8 = 41.4 « 10% KC unit asrgsampe Crust -rhe hydrocarbons inacrendhx C with empiri! forniaa CH are Cot at ia ‘substance AH, fmol AH CH unit GHio) 267K sak Ho) ezok 138K eH 400k) Bath sma 11 10% “The ealeulated value of AH /GH unit for the sample & 2 good match with seetyione: Gris) CHa) > Cla) + 4HIg) () reaction given CH Ya) > Cle) © 2H, (l0 revorsect formation ‘ino citerences are: the slate of C in the products; the chemical form atoms oF atomic molecu, of Hin the products AH'= aH) cfg) + ait, Hig) BH CHL). 718.4 kd + (217,96) kd - (74.8) ks = 1588.0 6d ii BHY= AH, CH,=-¢78.8) k= 748K “Tha rather large diflerence in OH" aluee & due to the enthaipy sifference betwean aniated gaseous C atoms and the order, bond array of C atoms in graphite, Cis): ad the enthalpy Aerence between iaaled H atoma and H, molecules, In other ‘wards. the ofocence in the enthalpy stored in chemical bonds in Cia) and Hla) ‘vergut the corresponding isciated storms chia) + 4F(g) + CFJg)+4HFig) HY = 1072. Sk “The SH" value for this reaction wes calculated in Solution 5.6, 0.21509= 0.215 mol CH, 12297 ee SF“ SE 000F: 9321 mol Fy “There are fewer mol F; then CHy, But 4 mol F, are required for every 1 molof CH, reacted, so clearly Fs the liming reactant 16TO5Ks o.cs211 mal F, = 43.48==13 5 kJ heat evolved, *6TOSKS = 3490-135 ks hoatesumed that fight feel is quantized, that ihe: mils centre ight i dct proportional tke feauens =H ent surface nas less than the threshold anergy. ne ele=tion i the photon nas energy equal ot areaar than the hvenild nee ve any excess energy bacores the Kinetic energy of the sleet 2996 10%, 1 sere E= hen 6.626 moo -8 = 2 Teen Tie =52am07d 805410" 533x104 w 26.028 103-5 « 25% THOS = 267 «10s Beas x 10 as 42 « 10" m: the radiation fs nares bul near the vsble 60 AM, 6.628.210 Jeg x — as4=t0™ J pe coonao Seg = Seta 10> “the Fld photon nas about 88 times more energy than the AM phoion. 405 = 1085 y __Amot_ 8.220 x 10-7 =68.22 x10" Jiphoton mal Or, 6.022 = 10 photons. eye = SEASONS, 290810 Mm —3.4g « 10% m=242 0m B20 x10" 4 ve: ‘Accowding to Figure 6.4, the is ultravolat radiation, ea7~ 1 J+s , 2.908% 10'm Ean = elk = 4350" 10% m 13 471510" =4.47 10 Jpneten 4a715« 104 , Bx 10! photons , 00s , 60min AAT £1073 photons , 005 , OMIM tgo4n10* =4x 10% Ih e2 248404 <4 10% JI 71 phaton tein” TR 4a 103 $6281 10 Jes 652610 Jos , 7.908 x10'm 4751075 s @ veEM= = 5.5556 ™ 10" =6.85 « 10°45" Oy k= hee 50 x 107 m=450 om eh an ben= SEM =10" +8 , 2000 10%m 25x 107% =4.53% 10° 885 107m 3 ee EE E4525 "10% J-441 «107 rs lectronic Structure x; a= pve SEER IOS (5.626 » 10% Jos 52.998 = zie 19" JN 8) densom > 110M = 4.056% 10% m; this e's ntheinared ‘orion nia wan n= [ar rte vl and wR n= 2 arene ate Hae a tit am oo tot Krow the met vale OFty, Casein cas seavelenath with n.=3 (14=4), Ithis is leas than 4085 nm 0? 3: seze= 10. 98 * 10 mis — 4.975 x 10% m = hole = ae 218% 10%*0(118 ~ 156) “This wavelength Is shorter han 4.055 «10% m,e0.n,> 5 yn, 4 und sole for asin Solution 631 3 ne yng ~ 5828210 sxsomeie = |ae aetex 109 4.055 «10% ma 2.18= 109 Bnd my; change mass to kg and velocity to rn's rmose of muon = 7on8 «97900 210% ga TAF = 4.8638 m1 = 188% a 0 9x 19 = 1.88 10™ ko 4s ——t x __18__ 3.87 410°" m {e838 10" hg BED x1 rvs =397A 4084% 10%" ig (backeinside cover of text) 6626 «10 kgem?es 5 0 kas * A 18 — 2423010? or @1004% 10% kg 593* 10% iS an 710m ‘Since atomic radi and interatomic distances are on the order of 1-8 A (Section 2.9), ho ‘wavvelengih cf thi electron s comparable tothe size of atoms. 123210" m *nn ¢ otbital, there ae (0 1) nodes. ‘The 2p, efital has one rode (he yz piane pasting throug # The 38 orbeal has 2 nodes. nucleus ofthe stom), The nodes in p orbitals are planes. 2s = 2p <3e< 4d < Se. In the hydiogen atom, orbitals wih degenerate end onergy increaxes with increasing 7 vali. the same n value are Many-Electron Atoms and Electron Configurations ase ® ‘The electron with the grester average dislanes from tha nucleus feels # smallar stiraction for the nucleus and is higher in energy. Thus the 3p is higher in energy nan 36 Because thes @ largorn value, a $e election has 2 greater average distance from the Chlorine nucleus then a2p electron. The 3selectron experiences & smalls attraction forthe nucleus and requires lees energy te remove front the ehipnne stem. “The Pauli exclusion princinte tates that no two electors can have the same four guanium mumbers ‘An alterale stalement of the Paull exctusion principle is thet single nrotal ean hold “a maximum of two elections, Thus, the Pauli principle limits the masium number of electrons in a main shall and its subshals, which daiermines when @ new row of the periedic table begins. 4 |2 2 *Outer-chell electrons” are thase bayond the previous neble-a8s or core electron configuration, “Unpsired electrons” are elections nat eccupy efbtais Sngly. That is. when there is nly one electron in av orbital, this electron is “unpaired.” ASiotomhas 4 cutershall electrons: 38°35" Two ofthern (those in the degenerate’ 3p orbitals) are unpaired2.63 10% Jno = 263 kulimol 200% 10°) , 1m phot 321 1° = 3.22 = 10" Jipheten mot 022.10 photons fe 6828 10 dss « 2.008 « 10! mS 5966 407m 5 3a2i< 10" within tne visble prion of the electromegnetis ra-orange light, Red light. with ‘have suffeient eneray 10 iiate he 5.98 «107 m= 598 nm is well spoctrum and corresponds to yelow or yell wavelengths neor 0: greater than 700 nn, does nek sleciran transfer and darken the fim hie" is hydrogen-tike because itis a one-electron partici, An Ha stom has Kwa: clestrons, The Behr model is based on the interaction of a single electron with the: pucleus, but dees not accurately account fcr addtional interactions when wo or more electrons are present. Divide each energy by the smallest value to th the Integer relationships He 2161928 = 10 He" 872% 10%248= 10 LP (ex tors «toto: Z=3 “The ground-state energies are in the ratio of 1:49, which ls alsa the rao 2% the ‘square of the ruclear charge for each parice “The ground state eneray for hydrozer-the parties is E=R,Z'. (By definiton, n= 1 forthe ground state of a one-electron (6) Z=8 fore, Ca -218x 10") (GF =-785 «1094 Plan, Change keV to Welectran Calculate v from kinetic energy. A= nadia « 0000 , 964851 10005, ___t mat wey" Vevernod” TK” 6.022% 10" otsctrons 320% 10% Ee mela = 26m v= (BET 703% 10° = 1.70 « 10" mis vyo( 2220210 egantet) perverer aa 6525" 10> es Lege’? Se =42re10%m= 427) BAGS = 10 hig * 1.709 = 10" nl fail: Structure: solutic ni-compounds of the ype MCh and MO, the Oat Is Batis oe COMPU OF ee Te iat 4 occa ae ¢ Hf. {xeyss°4 “Sc, similarly foes its four: he conplte at eves “cicating that the neutral arome have (os tlectans beyond its Krcore conniguration. {Gb.and 84 eloctione, but rot eloctrons from # vide ss neutral compound, Each oxide ion, ©; caries a2: charge. Exch metal ex448 8 aan etal ion oricne mst adopt atta postive charg ects WRI aia Shag: or he odie lw hv the comocend. The ttle tet” al Cag Sees clon of haute rata lore the postive charue Of seen Millay xe, and the correspending lecron configuration of the meta on. nas tt TAI ce na! 2+ TAN Se Widex’ 3+ TAT Te pardastac? a+ Ad frase 5+ IAN cr tAle'ad® 6+ IAN Each meta atom loses al valence) electrons beyend the Ar core configuration. {9 {cO_ £6.0, end V,0, where the meta! ions have odd charges, two matal ons are sre to produce a neutral oxice potassium oxide i, calcium oxide Wi scandium(tt)) oxide: te. tlankum (Mpexidev. vanadium (V) oxide. vi, ehrorrium(V) oxide {Roman numerals are required 1o epecly the charges on the wansition motal ions because more than ona stable lon ay exist) Recall that AH, = Oforelements in ther standard states. in these reactions, Mis) and Hig) are elements their slandard stator i K0l8) + Hyg) * 2kis)+#,016) AM" =AM, HO(G)+24H, Kis) GH K,O(s)- OH, Hata) Ht = 241.62 + AO) - (969-2 6) -0 = 1214 Ca0is) + Hy) > Cate) + HL0 ANY = 6H) H/0(@)* aH) Cafe) AH; Cais) -A1, H.l9) ‘BHP = 244.82 id +0 (895.1 bd) -0= 303.360 TiO.ie) +2H4(q) > THs) + 24,010) AM" =2BH, H.O(g) + aH) Tis) -AH, TiO9)-2aH HG) = 21:281.82) +0 -(-836.7)-2(0) = 456.1 hd Vi04s) + His) +240) +508) Ht = SAH, H,0(@) +244, Vis)- BH, V,O\6) 54H, His) += 5.241 82} + 2(0)- (150.6) 5(0)= 3415_ Periodic Prope of the Elements eriodic Table; Effective Nuclear Gharge 72 @ -tne verifcation ofthe existence of meny new sl temic weights spurred interest in a clossiicatir yrotoa that certain chemical and physical ‘Hlements are arranged by increasing atone weia provided @ commen properly on which to Bane # slarvents Moceley realized that te characte Xray roquantiesemited by Soen Meet arrested toa uniaue iniege!thathe-aasgnad io each clement, We Aad kno TiS Maeper asthe omic pumbe, tne rember of protons inthe nucleus ofan Sm. srecral some weight nereasen:as atomic number increases, bul ther are 3 GW Rrceions. I elements re arnged by increasing atomic nuiber, © few eneming contradicions In the Mendelev tale (tie postion of Ar and K or Te and I} ste eliminated. Eecrostatc attrection for tho nuceus lowers the energy of an electron, while ‘ectron electron repuisions increase this energy The concept of effective nuclear Charge alana uso model this increase in the oneray ofan electron as asmraller net sxiraction to # nucleus wih a smaller positive charge. Zye In Be (or any element), the 1s exectrons are not shicided by any core elecirens, se they experience a much greater 2,,than the 2s electrons, Za = 2-H of core elecions = 13 -10= +3 ‘an estimate ot 2, based on the assumption in part (2) will abvays be lower than the ‘ralue based on detaled calculations. Secause outer ciesirons have same probabilty ‘f being in the core, the core sicirons are never 100% effective at shielding; the numberof core electrons represents en upper Smit fo S, hg

Be ruclaus causes the size of panicles with ike charge 0 eo: paste? ea” FaP> (Art, The 4s vale elecirons 1) TE EE ania ar Hor the nucleus tan te Sd olecrons) 60's 8 iOS; UE a cers gre the 26 oti, in Fe af let One omlal Tusk conta 9 =! aeerne, Removing ene election to form Fe™ sgnifeanty reduces, TEP, Inneouing the ruciat charge expeerced DY each ofthe, ciner dgirsi=r an decreasing the size of thejon. Fe> Fe” > Fo™ ‘The order of rat is Ca > Ca” > Mag, 20 the torgest sphere is Ca, the intermectate one is Gi ©. @ Oy) ® 6 and te smaest is Ng ica) Ca, Ge (0) SE, Ar (a), Co™, Fe Gies =a) te” (O) AHMG) > RNa) # te mz ‘The effective neclear charges of Li ond Na are similar, but the outer electron in Li has 1s walle value and is closer to the nucieus than the outer electron jn Na, More ‘conrgy is needed to overcome the greater atvaction ofthe L lesion forthe nucleus,of the column, tsa 9081, reves ports of the halopens Increase going dvr the COMMAS toe temperat _Atbalogene form lori: compound wih Na: trey hee ine generis formula BK: The compound formed by AL wil have we formula NAA ‘pe, they (atleast partially) tose electrons: TPIS Terme onizalion anorgy the mare resctve ths ‘the average sistance of va Outer electvons experience a smal ‘and eaciviy towards tuoring ‘yimen the neble gases react with 142r is related o ization areray, the al noble-gaselement. Maving down the far the outer electrons fram the nucleus =e ‘sraction forthe nucleus, ionization anes} increases. Xeis most ractve toward Foe pxvough thas relehoy arg sageive siectron affniy, Cl debe nk Pav STATE ores remove cecrane ft eter steve ou F tas: tne OE ema ain im of Fstoms, which can approach the elton cious of et UIE BESS more closely than Cl ators. iia) + H0¢) > Helieg) + HOCKa) faa(s) + H,(a) > BaHA0) 2Lite) + S(6) > LLSI8) Mats) + FG) > MOF.(6) (6) +2F.(@) > SF9) 0, oxygen; Op az0ne ‘Fluorine can remave electrons from silica glass (5i0,) according % the reaction SO{2) + 2Fig) > SFAG) + Oxi). Thus, fuorine ges would “dizsoNe” the glans cconiainer, This process is also known as etching. Additional Exercises 72 co) © ‘eka - aluminum is galium (Ga), Z= 24. From the Handback of Chemistry and Physics, 74th edition, the physica! propertios of Ga are ‘atomic weight = 62.82 g/mol mp-= 2878°C density = 5.808 g/mL (s) bp. = 203°C = 6.085 g/mL () ‘oxide = Ga,0,, Ge,0 ‘The stomic weight, density and formula of oxide all agree ‘with Mendeleev's predictions. Gallum does have a law mehing point and a high Bolling point. “Sereadiy with H,O: Fr (It has the lowest OPtzaHen! jes wo nerron the range of chosces: an Pion. Use qualitative physical (oulk) proper ficelarent. Solve patch meting point snd density toidenbty the spect lo s0 this Hordress varies widely in metals and nonmetal cuctty indicate that the element Is: ‘The rvlatively high density, appearance 2nd probably less metalic than copper arcs c on he block of nine main groue elements aoa errand Phe rosa posobity Paoeuee ie iaac ca ‘comparison Srandard. ‘The meting point ofthe fwe laments Closes! 19 FY A wh goserte fe, 168:1°C: $n.252°03 Se M0 S°O: BLgT Ean tea best wate i In. To cari ta (erica, the oral OFS 73 gm, iso 2 good match Ip properties ofthe unknown ek@rnent sacerdcto'weto the comet balan esd quanon, det. toe Fi Salsa produc om the mass data, assuring the unknown is In 508g oxide -420gIn=08800 14:20 g In!114.82 ginal = 0.0966 ro! In, 0.03860. 0366 0.889 0/16.00 ginol = 0.0550 mol O;0.0550/0.0388 = 1.5 tuanpiying B52 produces an intaget rao of 2 Te: SO and's Graig ct De Te balanced equation is 4 In(e) +30a) 2219.08) ecording to Faure 72, the element In was discovered betwoen 18431868, The investigator who fist recorded ths dala in 1622 coulé have bean the fatto dacover In Integrative Exercises: 795 @ oh 2.052 « 10"" «= 2052 = 107 He 2.908% 40" mis — g 526 « 10" He 3358410 m 2o08 19's = 20.69% 107 Hz 14367 10% mjodic Properties ola) > Herta 16° 1, = Eone-Ey# 24.23 eV 1075 eV = 10.48 = 10.5 00 sous ov x 284854) 24.07 x t0*kitmal jos ov x SS3958 = 1.0 From Figure 7.10, edie (1) appears 10 have the nization <°ef3 ‘closest to that of Hg, approximately 1000 ki/mot ata) > Na‘(a) + 16° (enzation enerey of Na) Clg) + te” > CHa) (electron afinity of CD Wag) + CQ) > NaI) *CHa) (BH =T, (Na) # &(G8) = 1496 ta “940 d= #147 KS, endothenmic “The reaction 2Nate) + ©1,(g) > 2NaCi(s) involves any more sleps than the rearton roar (a) One mpotiant diferencoisthe pecucion of NaCl) versus NSC) npioneation NaCl) >» NaCi(s) is very exotheric and isthe step that causes the Tractor of the elernants in thor staadard states to be exothermic, white the Ges: phase reaction ie endothermic. feo fom, fw =263A- 144A 1494 0s) + BHB(aq) > 2BiBr,(ad) + 34/00) £210, e colon acid solutions bucouse il acts a a base and undergoes and-base reactions tka the one in pat (b). Its Insoluble in base because it cannot act a8 an ‘acd. Thus, BLO, is.a basic oxide; the axide of a meizl Based on the proparties of Its oxide, Bris characterized as a metal i peejsetersc™op®. Gi has Soler electrons in the 6p and 6s subshels. fal S clectrons pareipate bonding, compounds such as BiF, are possible. Aico, Bi has Stange enough atomic radus (1-49 A) and lewenergy orbitals. avaliable 10 ‘Secommodate more than four pars of Bonding eecirers ‘The high fonizaton energy and relaliely large negative electron affinl of F, coupled ‘wth its smal atomve radius, make it the most election withdrawing of the halogens, GIF, forms Eecause F has the greatest lendency to aiiret lectrone from Bi. Also, the small atomic radius of F reduces repuisions between neighboring bonded F atoms. The srong electron withdrawing properties of Faze also the Feason that only F compounds of Xo are known (Selon 7,65),emical Bonding Soluti or-N < P-Br fr {0(C=0) + 4DIF-F) - 401C-F)-4010-F) = 2(988) +4(155) -4(485) - 4(180) = 482K te more oxygeh ata beund to carbon, the ls eveherile fe Feeraod Rl sens Additional Exorcises 4.70. (6) Latico energyis proparfendl te Q,0,/4. For each of these compouncs, 2,031= the ‘Same. The anion Fr is present i each compound, but the jon radius ofthe e=llon increases going from Be to Ba, Thus, he value of 6 (tne cation-anion separation) increases and tne ratio 0,0,/ 4decreases. This is reflected in tho decrease in latice energy going trem BeH, to Bal, ‘Again, 0,2, for Zab; is the same 8 that for the ether compounds in the series and the anion ig H™ The latice energy of ZnH,, 2670 kd, & closest to that of MgHy. 2791 ki. Ths ionic rade of Zn s similar to that of Mg™. 99% 10" JefcouP (.s0~10 GF _ a-pasay x10 «708% 10" J (0.97 - 1.96) «10m ‘The sign of E ls negative because ene of the inerseting ions ie an anion; this san tractive interacton, Ons moar basis: 7.058 10-* 6022 ¥ 10% = 473. 10° =-473 Kd 5 Cee CS ett 10") 39> 10%Jem (241.804 10" GF 13+ 18) 10 gs Ona molar basis: -1.87 = 10° J ==1.87 x 104d Rh (KiJSe%4d?. In order to achiave the electron configuration of Kras.2 positveion, Rh would have tolose its Ss valence electrons and alleven 4d sioc\rone resulting in a Rh" an. Ths) 4g elecitovs are closer to the nucleus than n'=5 elections and are incompletely shila from,Shemical Bonding Solu! Lse the method detailed ip Section 8.5, A Cfoser Look 19 eleciranetativity values From Figure 8.6, the elecronegsthty paar: of Fis 4.0and of C15 30. F has 4.0/9.0 +40) = 0.87 of he charge of the bonding & Pa Chas 301 (3.0 +40}= 043 of the charge ofthe bonding & Pale “This amounts to 0.57 # 2e= 1.140.0n|F or 0.140 more than a neutral atom. This implies: “a-0-14 charge on F and +0 14 charge on Cl Jen! radus of Fic 0.71 Aand of Clis.0.99-4. The F-Olseparaion, From Figure 7.5, the coval ie 1704 p=arz0 te x 15081076 5 4.704 410. Clearly, this method is approximate. The the meseured value of 0.28 D. (0) Mar, 76° pairs a2e, 1e"pars FOonCi=7-(6* 122) Fooncl=7-10+ 172653) =o " “The oxidation number bf C) is +1 in C1O-and +7 in CIO. “The definition offormal charge aesumes that li bonding pairs of eleetrans.are equally shared by the two bonded atoms, that all tonde are purely covalent. The definition cfoxidation number assumes that the mors eleetronegalive element in tha bond gets all ofthe bonding wlactrone, that the bonds are purely ionic. These two cefintions. represent the hwo exaremas of how oleeiron density Is distributed between bonded ‘atoms. In CIO- and CIO, Cl the less electronegative element, £0 the oxation numbers have a higher postive value than tha fermal charges. Tho true daserigton of the sleciron density distribution i somewhere Between the extremes indicated by formal ‘ekatge and axiéation number has o Lewis struchire with an expanses eetot of electrons srouns the eantral | cannot accommadaa an axpandad octet because itis too small and has no available aerevais in ta valence shedsical Bonding 1.75 ne sum of the bonding temic ofthe 5S distance in (1.02) pha half tthe 0-2 tar ie 1784 ving tthe resonance stustres or 0, (ene Solston 8 Se eee naa oat so, ts rerodata beurer a cOubl ond 25H PoP ee aes Soo ics opntennny stone tn an &-O soe Cord Saeaima ag Sher 27 &" pal sy : “The sbeorved 8-0 bond distance. 1.48, #simiartodhatin SO, 1.43 A, whieh can be descrbad by resonance structures. showing both single and double 8-0 Bonds Thus, 8,0 must have resonance structures wih both single and double S-O Bonds. “The sinicture with the $0 bend has 5 e~paire about this S atom, To the extent thet this resonance form contribules to the te structure, the & atom bound to © has moro than an ectel of elactrons arcund Integrative Exercises ane ® S4(s) > Sr@) BH; Sta) (4H, S18) SXg) > Srig) +16 1st Sr(g)> SPQ) tte 1,8 Chia} + 2Cile) 22H, Clip) (1G) 20\g) +25" + 2cr1@) 2501 SeCife) F Seis) Clo) -OH, SIC, Sexe) > SPQ 2c) Ke ax) Srou(e)= AM) Sxfg) + 1150+ L180) +28H, Clio) +2E(C)- AH, SIC, (BH, SrCl(s) = 164.4 kl + 549 fl + 1064 kl +2(124.7) hd + 26-940) Ka - 2927 204 ks Assume 1009. rol s4s2g¢~— "l= 1.208 mal C; = SC ane ©; 1.209) 4200=4 simol ees 94 * To0898 B16 mol; 1.816 /1.200=15 8430 9 lx LE = 1614 melt 1.8149 2001.8 imal Naan go eo a, Fee g = 1.200 mal 0; 1,208 14.208 1.0 ‘Muttptying by 2 10 obtain an integerchertical Bonding Assume 100 9 ezotg boxe 4510 mol Ba: 0.4518 / 0481810 wr si83 a76 90 xl = zrio maine 2710 /0AstE 88 re empirical formula BEN, Bs hasan ric charge of 2; 30 STs Trea oa te balance fe chore. Tha forute'ef oach aside 0 te “The eft strctire minimizes formal charges and is probably the mafn Sanirinor tact) ni: KSS24™% nl) = KeISS!4a; Incl) Rr [Nona of these are noble-ges configurations. “The ionic radius of In? in compaund C wil b= smallest Removing successive lectrons from an alom reduces election repulsion, increases the effective nucieat ‘charge exnenenced by the valence electrons and decreases the Fonic radius, The higher the charge on @ cation, the smafer the rad Lattice energy is directly related to the charge on the lone and inversely related tothe interionic distance. Only the charge and sizeof the In varies in the three compounds, ing) fr compound A has the smallest. charge and the largest ionic radius, £0 compound A has the smallest lattica enargy anc the lowest meting port Inll) in ampound ¢ has the greatest charge and the smallest ionic radius, so compound C has the largast lates energy and highest melting pointular Geometry Soluti| molecular geometry x finear electron-domain Lewis structure geometry trigonal bipyramicot cinhedra! (oh, eotaw (ss) square pyramidal (ep), eae plana (2D: ws onal planat (\r}, trigonal pyramidal (tp). ttishedral (ts), tigonel binyramicel (top), Via “T-shaped (1) Becton \olesniler Maiecue Volence Lows an eae orion elocirons s colt no 16 1 Ca 0. Sor Se. Shepe fi hes § electran domsins, co A misst be in or below tna third row of the periods table This elimhates Ge and C. Assuming each F atom has 3 nenbanding elctron domains and forms enly single bonds with A. Amulet have BF pairs on each F atom rave bean amited for lan The three nonbonded electron Are raloh -A€ (aquaria) ange felges!n PF and emails i Sai re ec nontoraing domatesin the equatrat plane mereesen, the cI ‘back the axial Acebends, decmasing the F (aa) “AF (equsicsia) bond encies Polarity of Pelyatomic Molecules sizz WO ware tneer, H-O“H, the two 0-H bond polo would Cancel wld BE PAE a a poald va tro. Since HO is pkey, the O-Hi and pois cannct be deci pees to each other the molecule cannot be liner. gat (@) For a molecule win polar pends te be nonpaler, the polan Bonds el Bs (eymmianrealy) amangad 80 thet the bond dipoles cancel, lh most asee, ronbonding e- domisins must be sbcent fom the central atom, Sqyare planar structures may net meat the second condition. ‘Ad linear 6~ domain gecmatry (eds). Inear molecular geamety 9a) \vigeral bipyramidal eda, linear mg ‘ABy trigonal planar edg, trigonal planar mg 'ABe tetrahedral dg, tetrahacral mg: octahedral ede, square planar mg Polar, AEN> 0 (b) _ Nenpolar, the molecule is Hear ‘and the bond dipoles eancel Le s: 3. Nonpolar, in a syinmatricat Polar, although the bond dipoles are trigonal planar structure essentially zero, thors % an unequal [Exercise (8.12 (bj. the bend ‘charge distrinution due to tha nonbonded election pair on P ® A> oe Polar, square pyramidal molecuiat geomeiry, bond dipoles do nat eancel