中级无机化学翻译2.docx
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中级无机化学翻译2.docx
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中级无机化学翻译2
第一章
1.4指出下列物质在液氨中的酸碱行为(写出反应方程式):
CH3CO2H,NH2CONH2,CH3CH2OH,NaH
1.4Pointedoutthatthefollowingsubstancesinacid-basebehaviorinliquidammonia(writereactionequation):
CH3CO2H,NH2CONH2,CH3CH2OH,NaH
参考答案:
CH3CO2H为强酸CH3COOH+NH3→CH3COO--+NH4+
NH2CONH2为弱酸NH2CONH2+NH3≈NH4++NH2CONH-
CH3CH2OH为弱酸CH3CH2OH+NH3≈NH4++CH3CH2O-
NaH为强碱NaH+NH3→NH2-+H2↑
1.4指出下列物质在液氨中的酸碱行为(写出反应方程式):
1.4Pointsoutthefollowingmaterialinthesodaacidliquidammoniabehavior(writearesponseequation)
CH3COOH,H2NCONH2,CH3CH2OH,NaH
解:
CH3COOHstrongacidCH3COOH+NH3=CH3COOˉ+NH4+
H2NCONH2weakacidH2NCONH2+NH3=NH4++NH2CONHˉ
CH3CH2OHweakacidCH3CH2OH+NH3=NH4++CH3CH2Oˉ
NaHstrongsodaHˉ+NH3=NH2ˉ+H2
1.5指出下列物质在100%H2SO4中的酸碱行为(写出反应方程式):
HNO3,CH3CO2H,HClO4,C2H5OH,H2NCONH2,SO3
1.5Pointedoutthatthefollowingsubstancesinacid-basebehaviorin100%H2SO4(writereactionequation):
HNO3,CH3CO2H,HClO4,C2H5OH,H2NCONH2,SO3
参考答案:
HNO3为碱HNO3+2H2SO4→2HSO4-+NO2++H3O+
CH3CO2H为碱CH3COOH+H2SO4→HSO4-+CH3COOH2+
HClO4为酸HClO4+H2SO4≈H3SO4++CH3COOH2+
C2H5OH为碱C2H5OH+2H2SO4→CH3CH2HSO4+HSO4-+H3O+
H2NCONH2为碱H2NCONH2+H2SO4→HSO4-+H2NCONH3+
SO3为碱SO3+H2SO4≈H2S2O7
H2SO4+H2S2O7≈H3SO4++HS2O7-
1.8Pleasewritedownthechemicalequationofthefollowingreactions.
(1)Potassiumamideandanilinehavereactionsinliquidammonia.
(2)InjecthydrochloricacidintoconcentratedsulfuricacidandconcentratednitricacidsolutiontogetNO2Cl.
(3)Boricacidisdissolvedinsulfuricacid.
1.9Inliquidammonia,whatistheconcentrationofammoniumion?
1.9intheliquidammonia,whatistheconcentrationofammoniumion?
Answer:
2NH3=NH4++NH2-K=1.0*10-33
[NH4+]=K1/2=3.16*10-7(MOl/L)
1.12estimateroughthevalueofPKaabouteachofthe
Followingacids?
Answer:
1.phosphitepka1=2pka2=7
2.nitricacidpka1=-3
3.Percholoricacidpka=8
4.Periodatepka1=2pka2=7
1.12粗略估计下述各酸的pKa值
1.12AroughestimatethefollowingthesourpKavalue
解:
(1)H3PO3m=1pK1=2pK2=pK1+5=7
(2)HNO3m=2pK=-3
(3)HClO4m=3pK=-8
(4)H5IO6m=1pK1=2pK2=7
第二章
2.1Determinethefollowingmoleculesorobjectsbelongpointgroup
(1)SiHDBr2TetrahedralCspointgroup
(2)SiFClBrITetrahedralC1pointgroup
(3)SiH2Br2TetrahedralC2vpointgroup
(4)PCl3ThreesidesofvertebralC3vpointgroup
(5)OPCl3ThreesidesofvertebralC3vpointgroup
(6)CO2LinearD∞hpointgroup
(7)P4O6TetrahedralTdpointgroup
(8)Mn(CO)5IOctahedralC4vpointgroup
(9)LetterTandZ
TC2vpointgroup
ZC2hpointgroup
(10)ApieceofchalkC∞vpointgroup
2.1确定下列分子或物体所属的点群(Surethefollowingmolecularorobjectpointsofsubordinate)
2.3指出下列分子或离子所属的点群,并写出他们所含有的对称元素(Pointoutthefollowingmolecularorionpointsofsubordinate,andwriteouttheirsymmetryelement
2.8WhichpointgroupPtCl42ˉbelongto?
Drawitsstructure,marktheelementsoftheseoperations(eachoperationmarkone).
2.9Knownfollowingmolecularpointgroup,drawtheirstructures.
2.9Giventhefollowingmolecules(ions)belongtowhichpointgroup,drawtheirstructure.
(1)B(OH)3C3h
(2)Cr(en)3D3
(3)Co(gly)3C3
(4)Mn2(CO)10D4d
(5)AlleneD2d
第三章
3.1Trytoestimatethegeometriesandelectronicstructuresofthesefollowingcoordinativeions.
[Co(CN)6]3-(diamagnetism):
octahedron,Ohstrongfield,lowspin,t2g6eg0;
[NiF6]4-(2singleelectron):
octahedron,Ohweakfield,highspin,t2g6eg2;
[CrF6]4-(4singleelectron):
octahedron,Ohweakfield,highspin,t2g3eg1;
[AuCl4]-(diamagnetism):
planesquare,D4hfield,eg4a1g2b2g2b1g0;
[FeCl4]-(5singleelectron):
tetrahedron,Tdfield,e2t23;
[NiF6]2-(diamagnetism):
octahedron,Ohstrongfield,lowspin,t2g6eg0。
1、Describethestructureandelectronstructureofthefollowingcoordinationion.
[Co(CN)6]3-(diamagnetism)[NiF6]4-(twounpairedelectron)
[CrF6]4-(fourunpairedelectron)[AuCl4]-(diamagnetism)
[FeCl4]-(fiveunpairedelectron)[NiF6]2-(diamagnetism)
5、Whichonesarehigh-spinstateinthefollowingcoordinationion.
Mn(H2O)2+6Fe(H2O)3+6Co(NH3)3+6Co(H2O)2+6
CoCl2-Fe(CN)4-6
3.5Thefollowingcationswhicharehighspinconfiguration?
(a)Sixhydratedmanganese(Ⅱ)cation;(b)Sixhydratediron(Ⅲ)cation;(c)Sixammoniacobalt(Ⅲ)cation;(d)Sixhydratedcobalt(Ⅱ)cation;(e)Fourchloridecobalt(II)anion;(f)Six-ironcyanide(Ⅳ)anion.
Theanswer:
Wateristheweak-fieldligands,it’ssplittingcanbelow,that(a),(b),(d)arehigh-spinconfiguration.
Cyanideisthestrong-fieldligands,it’ssplittingcanbehigh,that(f)islow-spinconfiguration.Amineisamediumstrengthligand,haveagreatersplitcoordinatedwithcobaltions,that(c)islow-spinconfiguration.
FourcobaltIIchlorideanionisTetrahedralgeometry,becauseoftheregulartetrahedronsplitinsmaller,so(e)ishighspinconfiguration
3.8Thefollowingcations,whichmayproduceJahn-Tellereffect?
(1)Six-ironfourcyanideanion
(2)SixhydratedironDivalentCation
(3)Hexahydratecadmiumtrivalentpositiveions
(4)Sixammoniacobalttrivalentpositiveions
Theanswer:
(1)Cyanideisthestrongfieldligand,low-spin,it’selectronicstructureist62geg0,t2gisfullfilled,itdoesn’tproduceJohn-Tellereffect.
(2)Wateristheweak-fieldligand,high-spin,it’selectronicstructureist42ge2g,it’st2gtrackisasymmetricoccupy,itdoproduceJahn-Tellereffect.
(3)Wateristheweak-fieldligand,it’selectronicstructureist32geg0,it’st2gtrackissymmetricoccupy,itdoesn’tproduceJohn-Tellereffect.
(4)Ammoniaisastrongfieldligand,low-spin,it’selectronicstructureist62geg0,it’st2gtrackissymmetricoccupy,itdoesn’tproduceJohn-Tellereffect.
3.8下列离子中,哪一种可能产生john-teller效应?
Thefolleringwithionin,whichonemayproducethejohn-tellereffect?
3.14Co2+的四面体配合物比Ni2+的相应的四面体稳定,但是Ni2+的弱场正八面体配合物都比Co2+形影的正八面体配合物稳定。
请通过计算说明原因。
Co
(2)iontetrahedroncomplexesisstableerthanNi
(2)ion,butNi
(2)ionweakfieldareoctagoncomplexesisstablerthanCo
(2)ion.pleaseThroughthecalculationofthereasonwhy.
P137
3.5:
Thefollowingcomplexioninthosebelongingtoahighspinconfiguration?
(a):
[Mn(H2O)6]2+;(b):
[Fe(H2O)6]3+;(c):
[Co(NH3)6]3+
(d):
[Co(H2O)6]2+;(e):
[CoCl4]2-;(f):
[Fe(CN)6]4-
Solution:
H2Oisweakfiled,so[Mn(H2O)6]2+、[Fe(H2O)6]3+、[Co(H2O)6]2+arehighspin.NH3isstrongfiled,so[Co(NH3)6]3+islowspin.Cl-isweakfiled,so[CoCl4]2-ishighspin.CN-isstrongfiled,so[Fe(CN)6]4-islowspin.
3.8:
ThefollowingcomplexioninwhichapossibleJahn-Tellereffects?
(a):
[Fe(CN)6]4-;(b):
[Fe(H2O)6]2+;(c):
[Cr(H2O)6]3+;(d):
[Co(NH3)6]3+
Solution:
(a):
CN-isstrongfiledligands,[Fe(CN)6]4-islowspin,andelectronicstructureist2g6eg0,soitisnotJahn-Tellereffects
(b):
H2Oisweakfiled,[Fe(H2O)6]2+ishighspin,andelectronicstructureist2g4eg2,soitisJahn-Tellereffects.
(c):
H2Oisweakfiled,[Cr(H2O)6]3+ishighspin,andelectronicstructureist2g3eg0,soitisnotJahn-Tellereffects.
(d):
NH3isstrongfiled,[Co(NH3)6]3+islowspin,andelectronicstructureist2g6eg0,soitisnotJahn-Tellereffects.
3.14:
Co2+tetrahedralcomplexesthantheNi2+correspondingtetrahedralcomplexesstability,butNi2+weakfiledareeightsurfacecomplexesarebetterthanthoseofCo2+eightsurfacecorrespondingisstable,pleasebycalculation.
Solution:
intetrahedralCo2+complexesashighspin,andtheelectronicstructureise4t
(2)3.CFSE=-0.6△t*4+0.4△t*3=-1.2△t.
intetrahedralNi2+complexesashighspin,andtheelectronicstructureise4t
(2)4.CFSE=-0.6△t*4+0.4△t*4=-0.8△t.
SoCo2+complexesarestable.
IneightbodiesCo2+complexesashighspin,andtheelectronicstructureist2g5eg2.CFSE=-0.4△o*5+0.6△o*2=-0.8△o.
Ineightbodies,Ni2+complexesashighspin,andtheelectronicstructuret2g6eg2.CFSE=-0.4△o*6+0.6△o*2=-1.2△o.
SoNi2+complexesarestable.
3.20AccordingtotheCrystalsfieldtheoryandthenatureofthelistions,Writetheirdelectronconfigurationstructureandcalculateitsmagneticstrengthμ.
coordinationion
pairingenergy
P/cm
Δ/cm
delectronconfiguration
magneticstrengthμ
[Co(NH3)6]3+
17800
23000
(1)
(2)
[Fe(H2O)6]3+
26500
13700
(3)
(4)
Key:
(1)t2g6eg0
(2)0(3)t2g3eg2(4)5.92
3.22Contrastcomplexes[Fe(H2O)6]SO4和K4[Fe(CN)6]:
(a)Separatelythemisloworhighspincomplexes;
(b)Drawtheircenterofmetalionsdelectronconfiguration;
(c)ClculatetheirLESErespectively;
Key:
(a)[Fe(H2O)6]SO4ishighspincomplexes;K4[Fe(CN)6]islowspincomplexes;
(b)TheFe2+of[Fe(H2O)6]SO4electronconfigurationist2g4eg2;
TheFe2+ofK4[Fe(CN)6]electronconfigurationist2g6eg0;
(c)[Fe(H2O)6]SO4:
LFSE=-0.4Δ*4+0.6Δ*2=-0.4Δ
K4[Fe(CN)6]:
LFSE=-0.4Δ*6+2P=-2.4Δ+2P
3.22Comparethecomplexes[Fe(H2O)6]SO4againstK4[Fe(CN)6]
(a)Separatelydeclarewhethertheyarelowspinorhighspincomplexes.
[Fe(H2O)6]SO4ishighspincomplexes;K4[Fe(CN)6]islowspincomplexes。
(b)Drawouttheircentermetalions’delectronconfiguration.
[Fe(H2O)6]SO4Fe2+t2g4eg
2;K4[Fe(CN)6]Fe2+t2g6eg0。
(c)SeparatelycalculatetheirLFSE
[Fe(H2O)6]SO4:
CFSE=-0.4Δo×4+0.6Δo×2=-0.4Δo
K4[Fe(CN)6]:
CFSE=-0.4Δo×6+2P=-2.4Δo+2P
第四章
4.2 Why excessive metal Mn, Tc, Re and Co, Rh, Ir easy to form more nuclear carbonyl compounds
4.2 Why transitionmetal Mn, Tc, Re and Co, Rh, Ir easy to formmultinuclear carbonyl compounds?
Answer:
Thismetalsatomicnumberisodd,Sotheycannotformdualisticmononuclearcarbonyl compounds.Ifnot,thevalenceelectronofthemetalsareinconformityruleEAN.
4.5 For the following stable compounds in the patent X value
Mn(CO)xI Co(CO)x(NO) (η5-C5H5)Fe(η6-C6H6)x+ Fe(CO)4 x-
4.6Trytoexplainfollowingexperimentresults
(1)Twoferroceneoniumionisakindofstrongoxidant
Thecompoundowns17Electroni
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