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    Teller Quimica inorganica

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    Teller Quimica inorganica

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    © All Rights Reserved
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    Download as pdf
    10 views8 pages

    9e Chap21

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    Vernon Sandoval
    Teller Quimica inorganica

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    © All Rights Reserved
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    ‘The & A blue question or ex that question or oxereiso appoars at th> back ofthis book and a solution appears in Active Learning Questions questions ae designs to be used by group: of students in cas. ‘You isolate a compound with the formula PrCl, * 2KCL From electical condactance tests of an aqueous solution ofthe cm pound, you find that hee ions per formula unit are present and you also notice tht addition of AgNO, doesnot cause a precipi tate. Give the formula for this compound that shows the com- plex ion present. Explain your findings. Name this compound Both Ni(NH2* and Ni(SCN).2~ have four ligands. Te frst is paramagnetic, and the second is diamagnetic. Are the com- plex ions ttraeral or square planar? Explain. }. Which is more likely to be paramagnetic, Fe(CN\ or Fo(H,0).2"? Explain 1. A metal ion in a high-spin octahedral complex has two more "unpaired electrons than the same ion does in a low-spin octa- dredral complex. Name some possible metal ions for which this would be true. vise number indicates that the answer to 1 Solutions Guide, 2s found on PowerLecture. Questions ‘What is the lanthanide contraction? How does the lanthanide contraction affect the properties of the 4d end $d transition metals? Four different octahedral chromium coordination compounds exist tha ll have the same oxidation sate for chromium and. have H,O and CI~ as the ligands and counterions. When 1 mole of each of the four compounds is dissolved in wate, how ‘many moles of silver chloride will precipitate upon addition of ‘excess AgNOs? .. Figure 21.17 shouts that the gis isomer of Co(en):C* is opt cally active while the rans isomer is not optically active. Is the same true for Co(NH),Cly*? Explain A certain frs-rw transition metal ion forms many different colored solutions. When four coordination compounds ofthis mets, each having the same coordination number, are dis solved in water, the colors of the solutions are red, yellow, {green, and blue. Further experiments reveal that two of the complex ions are paramagnetic with four unpaired electrons and the other two are diamagnetic, What can be deduced from {his information about the four coordination compounds? J. Oxalic acid is often used to remove rust stains. What proper ties of oxalic acid allow it to do this? . For the following crystal field diagrams, label each as low spin, high spin, of cannot tll, Explain your answers © He He He ee Oat te © ee 2, 16. ForReview 1015 fonnsa techedal complex ion and Co(CN}~ forms an octaedkal complex in, What is wrong about the following statements concerning cach complexion and the d orbital spit ting diagrams? ‘4, CoCl* isan example ofa strong-feld case having two unpaired electrons. ', Because CN* i 2 weak-feld ligand, Co(CN)* willbe a low-spin case having four unpsiredélectons. ‘The following statements discass some coordination com: pounds. For each eordination compound, give the complex fon andthe counterions, the electron configuration o the tar- ‘von metal, and the geometry af he complex on. 4 CoCl, + 61,0 iss compound sed in novelty devices tht predict in >, Daring the developing process of black-and-white fl, silver bromide i removed from photographie fim by the Jet. The major component ofthe fixer is sodium thiosu- fate. The equation for the reaction is: ‘AgBrls) + 2Ne,S,03l0q) —> Na{Ag(S,0,)al(ag) + NaBr(ag) «Inthe production of printed circuit boar forthe eles- ‘monic industry thin layer of copper is laminated onto an insulating plastic board, Next, citeait pattem made of a chemically resistant polymer is printed on the board ‘The unwanted copper is removed by chemical etching, and the protective polymer is finally removed by so vents. One etching reaction is CulNH),Cl,(aq) + 4NHy(aq) + Culs) —> 2Cu(NH) Clay) ‘Assume these copper comple fons have tetrahedral geometry, . When concentrated hydrochloric acid is added toa red solo- tion containing the Co(tf;O)e* complex ion, the solution tums blue as the tetrahedral CoCL? eomplex ion forms. Ex- plain this color change ‘Tewahedral complexes of Co** are quite common, Use a d-rbitl splitting diagram to rationalize the stability of Co! tetrahedral complexions ‘Which ofthe following ligands are capable of linkage isomer ism? Explain your answer. SCN", Ny", NO3”, NH-CH,CHNH,, OCN™ I> Compounds of copper(l) are generally colored, but com- pounds of copper) are not. Explain. Would you expect ‘CakNHL).Cl to be colored? Explain, - Compounds of Se are not colored, but those of TH and V"* sre, Why? Almost all metas in nature re found as ionic compourds in ‘ores instad of being in the pure tare. Why? What must be done to 4 sample of ore co obtain « metal substance that has desirable properties? 2. What causes high-altitude sickness, and what is high-altitude seclimatization? |. Why are CN and CO toxie to humans? | ASSRIR SSO 1016 Chapter 22_Transition Metals and Coordination Chemistry Exercises inthis section similar exercise Transition Metals and Coordination Compounds ‘Write electton configurations for the following metals. aN BCd GZr a Os 22, Write electron configurations fr the following fons. a Nig Zit and Zt bce d, O8* and Os 3, Wie electron configurations for each ofthe following. a. T,TH,TH —b, Re,Re, Ree, Ir fe" 1 244, Waite electron configurations fr each of the following. a CACPCPb Cu,Cutcu oe VV “What isthe electron configuration forthe transition metal ion {nach of the following compounds? a. KolPe(CN)al b. (Ag(NH):ICI . (NiGLO)Be> 4. [CHHLONODIT 126, What is the electron configuration for the transition mot jon() in each of the following compounds? a (NHDaIFe(HLO)-CLd by (Co(NH),NHACH_CHNH)l2 ce NaI TaFs} 4, (P(NHL)llfPt) Pt fos +2 and +4 oxidation states in compounds. Fi Molybdenum is obtsined as a by-product of copper mining ot is mined directly (primary deposits are in the Rocky Mountains in Colorada). In both eases itis obtained as MoSs, which is then converted to MoO, The MoO; can be used directly in the ‘production of stainless steel for high-speed tools (which ee- Counts for about 85% ofthe molybdenum used). Molybdenum, tan be purified by dissolving MoOs in aqueous ammonia ard ‘crystallizing ammonium molybdate, Depending on conditions, tier (NB4):Mo;0; oF (NH4)¢Mo}03«° 4H0 is obtained. a. Give names for MoS; and MoO by. What isthe oxidation state of Mo in each ofthe cort- pounes mentioned above? 28, Titanium dioxide, the most widely used white pigment, oscars naturally but fs often colored by the presence of impurtis, ‘The ehloride process is often used in purifying rile, a min- «eral form of titanium dioxide. fa. Show that the unit eel for rutile, shown below, conforms to the formula TiO. (Hint: Recall the discussion in Sec tions 10.4 and 10.7.) ‘The reactions forthe elorde process are 2TI0,(9) + 3C19) + ACL) 222, 2TIC(y) + COxlg) + 2C0(9) TIC (e) + Ox(e) 22S Ti0,G) + 2CL(6) [Assign oxiation sates to the elements in both reactions ‘Which elements are being reduced, and which are being ox- dized? Identify he oxidizing agent and the reducing agent in cach reaction. 5, When 6 M ammonia is added gradually to aqueous copper) nitrate, a white precipitate forms. Te precipitate dissolves as nore 6 M ammonia is added, Write balanced equations to ex plain these observations. (fin: Cu** reacts with NH to form, CugNH? 30, When an equeoes solution of KCN is added to solution con- taining NP" ions, a precipitate forms, which redissolves on ad tition of more KCN solution, Write reactions describing what happens inthis solution. [ints CN isa Brpnsted-Lowy base (i, = 10°) anda Lewis base.) Tir Coder aqueous solution ofthe following coordination com pounds: Co(NH)h. PUNFL da, N6sP, and CNH. I Tiqueovs AgNOS i added to separate beakers containing sol thos ofeach coordination compound, how many moles of ABL ‘vi precipitate per mole of transition metal pesen? Assume that each transition metal on forms an octahedral complex 32. A coordination compound of cobalt contains four ammo- tia molecules, ane sulfate on, and one chloride ton, Adon tf aqueous BaCh, solion to an aqueous solution ofthe com pound gives no peep Addition of aqueous AgNOs tt Equeous solution of the compound produces white preci tate. Propose «structure fr this coordination compound 35, Name the following complex ions nes erie tala ah ae cere Lene 34, Name he falling complex ios a. Ru(NH3)CP* b, Fe(CN) . Mn(NH;CH,CH;NH;);?* d. Co(NHs)sNO,?* = Name the following coordination compounds & NICN f CANHCL" & Fe(C,0,);" 1, Co(SCN)H.O)," a (CoNH)ACL a. K{PICl] b [ColOylls ——& [Co(NH,) CIC, & KlPCh) £. (Co(NH)(NO3)3} 36, Name the following coordination compounds. 4 (CHHO)sBrIBe, — e. [Re(NH,CH,CH.NH)(NO2RICI , Nay(Co(CN)g] ad. (P(NH)LN(Pa] A. Give formula for the following. potassium tetrachlorocobaltst(it) 1b, aquatricarbonylplainumD bromide «. sodium dicyanobis(oxalato}ferate(11) 4. vvismminechloroethylenediaminechromium(I iodide ‘38, Give formulas for the following complex ions . tetrchloroferratett) ion 1, pentaamminesquaruthenium(t) ion « tetracarbonyldihydroxochromium(I) ion 4. amminetrichloroplatinate(t) ion aw geometrical isomers of each of the following complex a, Co(Cs00} (80 Ir(NHs)sCl b. PUNE 4. Crteny(NE ah” 49, Draw structures of each of the folowing . cis-dchlorothylenediamineplatinum(t) 1. transdchlorobis(ethylenediamine)obal) « cirteraamminecioranitrocobalt() ion 4. rrans-otrsaminechloronittocobali() ion . trans-diaquabis(ethylenedinsine}eopper() ion = Tie carbonate ion (CO#*) can ato iter a monodentate or a bidemate ligand, Draw a pictur of CO; eoowinatng toa ‘metal on 8 8 monodentate nd as bidentate ligand, The car Sonate fn can also act as abridge between two metal ions Draw a picture of a COs ion bridging between two metal «Amino acids ean at as ligands tonard tansicion metal ions, ‘The simplest amino acid is glycine (NH,CH;CO3H). Draw a seructure of the glycinate anion (NHCHjCO,”) acting as @ bidentate ligand. Draw the srictual isomers ofthe square lana complex CUINH,CH;CO>), .. How many bonds could each of the following chelating ands form with a metal ion? 2 acetylacetone (acacH), a common igand i organometal- lic catalysis as eben lat ons poe Crp eingzo — ForReview 1017 1. diethylenetriamine, used in a variety of industrial processes: NH, —CH,—CH,—-NH—CH,—CH,—N# salen, a common ligand for chiral organometallic catalysis: 4. porphine, often used in supesmolecular chemistry as well, «as cataysis; biologically, porphine isthe basis for many diferent types of porpbyrin-containing proteins, includ- ing heme proteins: 44, BAL isa chelating agent used in treating heavy metal poison- ing I ats asa bidentate ligand. What type of linkage isomers se possible when BAL coordinates to metal ion? CH.—sH I CH-SH Chon BAL ‘FE Draw all geometrical and tinkage isomers of Co(NH)(NO2)s. 46. Draw all geomettical and linkage isomers of square planar PUNE) SCN) Fi Acetylacetone, abbreviated acacH, is a bidentate ligand. It loses a proton und coordinates a§ acac™, as shown below, ‘where M is transition metal: ‘Which of the following complexes are optically active: cis: {Cr(aeac) (FO), wans-Crfacse)(H:O), and Cxacae)s? 48, Draw all geometrical isomers of PUCN)sBr.(H.0)s. Which of| these isomers has an optical isomer? Draw the various optical 1018 Chapter 21 Transition Metals and Coordination Chemistry Bonding, Color, and Magnetism in Coordination Compounds Match the crystal eld diagrams given below with te follow {ng complex ions. CNHSCEY CoN Ha iBrst Fe(H0},* (assume strong fietd) (assume weak field) ae Oe te te 50, Match the crystal field diagrams given below withthe follow- ing complex ions. Fe(CN —-Mn(H,0)2* @ a O =e Si, Draw the d-orbitl sping diagrams fo the octahedral com- plex ons of each ofthe following. 2 Fe (high and iow spi) >. Fe (igh spin) NF 452 Draw the drial splitng diagrams forthe octahedral com plex ions ofeach of the following a. Zet* 1. Co* thigh and low sin) eT @. The Cet," ion isknowa tohave four anpaired electrons. Does the F-ligand produce a tong o weak field? S54, The Co(NH\2” ion is diamagnetic, but Fe(HL.O),?* is pare rmagreti. Explain 35. How many unpaired electrons are in the following complex a Ru(NEly)e* (low-spin case) B, Ni(H,O),* ©. Ven) ‘56, The complex ion Fe(CN)s” is paramagnetic with one an- paired electron. The complex ion Fe(SCN),*~ has five un- paired electrons. Where does SCN” le inthe spectrochemical series eative to CN"? Rank the following complex ions in order of increasing wave- length of tight absorbed. Co(HH,0),4*, ColCN), Coly Colen)!* 58. The complex ion CuO}? has an absorption maximum at around 800 nm, When four ammonias replece wate (Cu(NH))(H,0).*, the absorption maximum shifts t around 6600 nm. What do these results signify in terms of the relate field splitings of NH, and H,07 Explain, The following test tubes each cont complexion Fr each complex ion, predict the predominant color of light absorbed, Ifthe complex ions are Cr(NH)?", Cx(H,0)", and Cr(sO,Ci,*, what is i identity of the complex ion in each est ube? (in: Reference the spectrochemical series) (60. Consider the complex ions Co(NHs).*, Co(CN}2", and CoF,'. The wavelengths of absorbed electromagnetic radi tion for these compounds (in no specific order) are 770 am, 440 am, and 290-nm. Match the complex ion to the wave- length of absorbed electromagnetic radiation, ‘The wavelength of absorbed electromagnetic radiation for CoBr.?” is 3.4 10-® m, Will the complex ion CoB” ab- sorb electromagnetic radiation having a waveleng longee or shorter than 3.4 X 10°F m? Explain, (62. The complexion NiCl,*~ has two unpaired clectons, whereas Ni(CN)_" is diamagnetic. Propose structures for these (wo complex ions. ‘62, How many unpaired electrons are present in the teuchedral fon FeCl"? (64, ‘The complex ion PACI?~ is diamagnetic, Propose a structure for PAC, Metallurgy 6S, A blast furnace is used to rede iron oxides to elemental ton. The reducing agent for this reduction process eatbon monoxide a. Given the following das Fe,046) + 3CO(¢) —> 26) + 300) an = ~284T 3Fe,0,(0) + COl@) —> 2F2,0,6) + COMg) aw” = —298) Fe0,(5) + CO(g) —> 3FeO(s) + COx(g) AN? = 18K determine AM fr the restion FeO(9) + COls) — Fels) + Ox.) b. The CO; produced in bas fornace during he redusion process actually can oxidize ron ito FeO. To eliminate this reaction, excess coke is alded to convert CO; into CO by the reaction CO,(g) + C(s) —+ 2C0(g) | | | | Using data from Appendix 4, determine A¥* and AS for this resetion. Assuming AW" and AS" do not depend of temperature at what temperature isthe conversion ection of COs into CO spontaneous at standard conditions? 66, Use the data in Appendix 4 forthe following a, Caleuate APP and AS" forthe reaction 3Fe,0,6) + COls) —+ 2Fes04(9) + COs) that occurs ina blast furnace. ‘Assume that AH" and AS” are independent of tempereture Calculate AG? at $00.°C for this reaction. 77. tron is preset in the earth's crust in many types of minerals ‘The iron oxide minerals are hematite (Fe,Os) and magnetite (Fe,0.). What is the oxidation state of iron in each mineral? ‘The iron ions in magnetite are a mixture of Fe and Fe** ions. What isthe ratio of Fe” to Fe? ions in magnetite? The for- sma for magnetite is often written as FeO Fe,Os. Does this make sense? Explain (8. What roles do kinetics and thermodynamics play in the effect that the follosvingresction has on the properties of see? 3Fe + CFC TS Giver is sometimes found in nature as lange nugeets; more often ts found mixed wih other metals an their oes. Cy nide on soem ved to extrac the sive by the following re exon that occu in basi solution: gl) + CN“(ag) + Ox6@) > AgICN)= Cad) Balance tis uation by using the hal-esction metho 70, One ofthe cassie methods for the determination of the man- ganese content in steel involves converting all the manganese to the deeply colored permanganete ion and then messuring the absorption of Light. The ste! is frst dissolved in nite ‘si, proacing the manganese) ion and ittogen dioxide 8. This solutions then weacted with an aie soliton con- tsining periodate ion; the products are the permanganate and fodate fons, Waite balanced chemical equations for both of those steps Additional Exercises Acetylacetone (see Exercise 43, part), abbreviated acacH, is ‘bidentate ligand. I loses a proton and coordinates a aeae™, 18 shown below: ‘cy _Acetylacetone reacts with an ethanol solution containing 9 salt ‘of europium to give a compound that is 40.1% C and 4.1% H ‘by mass, Combustion of 0.286 g ofthe compoure! gives 0.112 ‘21,03, Assuring the compound contains only C, H, O, and Ex, determine the formula of the compound formed from the reaction of scetylacetone and the europium salt. Assume that the compound contains one europium io.) ForReview 1019 172. The compound cisplatin, PiNH);Cls has been studied exten- sively as an antitumor agent, The reaction forthe synthesis of cisplatin is K,PACI,(aq) + INE, loa) —> PUINH:CLO) + 2KClleq) ‘Write the electron configuration for platinum ion in cisplatin. Most d® transition meal ions exbibit square planar geometry. ‘With this and the name in mind, daw the structre of cisplatin “73. Use standard reduction potentials to calculate €°, AG*, and (a: 298 K) forthe reaction that is used in production of gol 2Au(CN);“(ag) + Za(s) —> 2Au()) + Zn(CN)-"Caa) ‘The relevant half reactions are Au(CN)," +e" —> Au + 20N"-€*= -0.60¥ Za(CN) + 20° —P Zn ACN B= 126 7A, Until the discoveries of Alfred Werner, it was thought that ex bon had tobe presen ina compound forit tobe optically activ. ‘Were prepared the following compound containing OH ions as bridging groups and separated the optical isomers a Draw stctres ofthe two optically active Isomers ofthis compound. ', What are the oxidation states ofthe cobalt ions? ‘c. How many unpaired eleetrons are present ifthe complex isthe low-spin cas? H I 9, \ cof CotNH Is | | Cs A | 0 | 1 L \a ‘75, Draw all the geometrial isomers of Cr(en)(NHy)sBrCl* ‘Which ofthese isomers also have an optical isomer? Draw the 176. A compound related to acetylacetone is 1,1, acetone (abbreviated Hit): uoroaceryl io crccnscom, Hila forms complexes in a manner similar 10 acetylacetone. (Gee Exercise 47.) Both Be®* and Cu’ form complexes with fa having the formula Mita). Two isomers are formed for each metal complex. a, The Be complexes ae tetrahedral. Draw the two iso= ‘mers of Be(fa), What type of isomerism is exhibited by Be(tfay? b, The Cu? complexes are square planar. Draw the to isomers of Cutfa)- What type of isomerism is exhib= ited by Cultta)? 17. Would it be beter use octahedral Ni? complexes or ocahe- ral Ce* complexes to determine whether a given ligand isa sirongefleld or weakcfild ligand by measuring the number of unpaired eleewons? How else could the relative ligand field strengths be determined? 1020 Chapter 21_Transition Metals and Coordination Chemistry 78, Name the following coordination compounds a. NalNi(C-0)s] b, K,{CoCi fe. (CuNF)JS0, 4. [Cofen)ySCNICIICL Give formulas for dhe following, a, hexakis(pyridine}eobaltI) chloride >, pentsammineiodochromium( li) iodide . is(ethylenediamine)nickeKID bromide 4, potassium tetracyanonickelate(II) €, tetrzamminedichloroplatinum(V)tetrchloroplatinate(t) 1. The complex fon Ru(phen);** has been used as probe forthe struetute of DNA. (Phen isa bidentate ligand.) 8, What type of isomerism i found in Ru(phen)?"? i, Ru(phen)s!* is diamagnetic (s ae all complex ions of Ru"). Draw the erytal field diagram for the d orbitals in One) Carbon monoxide is toxic because it binds more strongly to iron in hemoglobin (Hb) than does O;. Consider the following reactions and approximate standard free energy changes: Hb +0;—+ HBO; AG*= 70K Hb+CO—+ HbCO AG’ = -801 Using these data, estimate the equilibrium constant value at 25°C for the following reaction HBO; + COM*HDCO + 0; For the process Co(NH).CP* + Cl” —> Co(NH).C* + NH ‘what would be the expected ratio of esto sans isomers inthe product? 86, Phen = 1,10-phenanthrolin ST. 2, ChemWork Problems ‘These riulticoncept problems (end sedition] ones ate found i actively online with the same typ of sssistonce a sident weuld get from a instructor, 83, In which ofthe following isare) the electron confguration(s) comet fr the species indicated? a Cu [arist3d? b Fe (arpad® Co [Ard ala [array fe PEt [Xe}4p5dh Which ofthe following molecules exhibits) optical isomerism? a. cis PUNHY;Ch b trans-Nilen):Br, (en is ethylenediamine) 88, Which ofthe following ions isare) expected to form colored © els-Nifen),Br; (en is ethylenediamine) él eee [ da Jor d™t Lo & etal equa complex ions? 2 bc c. Ma A ‘The folonng tele indices the mamber of uapsted e. trons in the ery la dpa for some eompleen Ch it the table by cling each species s weak eld fel, orinufcteat infomation a Unpalred Species Electrons Clasiteation Fe(CNs) o coc? 3 Fe(Hs0)* 5 aE Fe(CN ° ‘Which of the following crystal field diagram(s) i(are) comet forthe complex given? a Zn(NH)2* (tetrahedral) ae te AR te te . Ma(CN)2* (stone field) Het Ni(CN)2* (square planar, diamagnetic) Sad + athe Which ofthe following statements) is(are) rue? ‘a. The coordination number of a metal ion in an octahedral ‘complex ion is 8, , Alltetzahedral complex ions are low-spin, The formula for triaquatriamminechromium(If) sulfate [CxH.0),(NH,)sh( 80.) 4. The electron configuration of Hf2* ‘€. Hemoglobin contains Fe". is Xe" Challenge Problems 48. Consider the following complexion, where A and B represent ligands ‘The complex is known to be diamagnetic. Do A and B produce very similar oF very different crystal fields? Explain, ‘90. Consider the pseudo-octahedral complex it of Cr"*, where A and B represent ligands Ligand A produces a stronger crystal field than igand B. Draw an appropriate crystal field diagram for this complex ion (as~ sume the A igands are on the zis) 91, Consider the following data: Col + > Co CoP + 3en —> Coen)? Co +3en —> Colen);* kK where en = ethylenediamine 4, Caleulate &* forthe hal-reaetion B= 182V 15 x 10 = 20 x 10” Colen))* +e” —> Colen)** ', Based on your answer to pasta, which is che stronger oxi- izing agent, Co! or Cofen)s"? Use the crystal field model to rationalize the result in part b 92. Henry Taube, 1983 Nobel Prize winner in chemistry, has stud- fed the mechanisms of the oxidation-reduction reactions of teanstion metal complexes. fn one experiment he and his stu ents studied the following reaction CHB1,O}2* (ag) + Co(NH)

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