The Brfnsted-Lowry acid-base

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?5?
???? ????
2

1. ?????????

2. ????????????????
3. ???????????????

1. ????????????

1. ??????????????

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5.1 ?????? The Brfnsted-Lowry
acid-base model
5.2 ????? The Lewis acid-base model
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? ???????????????H
H2SO4 HSO4 H
? ???????????????OH-
NaOH Na OH-
? ??????? H OH- H2O
? ???????????
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5.1 ?????? The Brfnsted -lowry
acid-base model
5.1.1 ?? Definition
5.1.2 ????? Conjugate acid-
base pair
5.1.3 ?????? Brfnsteds
equilibrium
5.1.4 ????????????? Relation
between the molecular structure
and the acidity
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5.1.1 ??
? ??????????????, ?????? ?
??????????????, ??????
????????????????????
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5.1.2 ?????
???(Half reaction)???
??????????,????????,??????????????,?????
???, ?????
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?????????????????????
????????, ?????????????????????????(Ampho
teric substance)?
??????????,???????,????????????????
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????????????? (a) Fe(H2O)63?Fe(H2O)62
(b) Al(H2O)63?Ga(H2O)63
(c) Si(OH)4?Ge(OH)4
(d) HClO3?HClO4 (e) H2CrO4?HMnO4
(f) H3PO4?H2SO4
Solution
(a) ??, ???????, ?O??????, H??? (b) ??,
???????, ?O??????, H??? (c) ??, ???????,
?O??????, H??? (d) ? (e)? (f) ????,????????
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1. ???????
??????????????
? ???,?????????,?????? ? ??????????????????????
??????? ? ??????,??????????????
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2. ???????
? ????????
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? ????????
? ????
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5.1.3 ??????
???????????????
??, ??????????B??B???????, ????????????
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1. ???????????????????????????????????

4. ?????????,????????????? ???????
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???????????????????????,????????????????
??????????HClO4H2O??????????, ???H?H3O?????H3O
?NH3???????????????????????? HBr4H2O??H9O4??????
?, ?????????????????????
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????H????????
Solution
H H 2O?H3O, DH q -761.5 kJ.mol-1
??c(H)10-130 mol dm-3,??? l mol L-1
H ?????????????H ,?????????1070????
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????????????????????,???
??????????HCl?HBr ????? ????
???????????????????????? ???
????????,???????? ?????.
??,???,?????????,???????
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Solution
(1) ???,O2-??????????????
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??????????????????????????pKw14??????????
14???????
?????????????(???????)????????(???????)??????
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5.1.4 ?????????????
?????????????????????,????,???????????????
????????
1. ????????
? ?????????????????,????
?????HB??????,HB??? ,? ??????
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??? NH3 H2O HF ??
0.9 lt 1.4 lt 1.9
NH3 ????????, H2O???, ?HF???????????
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???????????(acidic oxide)???(acid anhydride) ?
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?E??????????, EOH???????????EO?,
???????OH????????(H3O)??, ??????H2O????E?????
???????????(Basic oxide)???(Base
anhydride),??????????????????????????????
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?????, ??EOH???????????, ??????????????(Amphot
eric)???????????????(1.6 2.0)????????????
????????????????
ExOy MnO Mn2O3
MnO2 MnO3 Mn2O7 ???
2 3 4 6
7
?????????????? ?????????????
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??????????????????????
????????????????????????????????????????,????????
???????????,??????????????
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d??????????????
?????????????????????? (??????????????,???????
???????,?????????????) ?
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???????????,????
????????????pH??,?? Fe2?Ce3 ?Al3 ?Cr3 ?
V3???????????.?? H2O2 ? NaOH ?,Al?Cr ? V
?????????,?????????????????.
Solution
???? 3 ??????????????????? pH10
?????Al(?)????,????????????Al(OH)4-,V (?)?
Cr(?) ???? VO43- ? CrO42-,???????? V2O5 ?
CrO3 ???????
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3. ???(Oxoacids)???
??????????OpE(OH)q? p?q??????????OH?
???????????????, ?????????OH??????? 1)
?????????, 2) ??????????
??HOCl?HOI???,?????????
???H2SO4?H2SO3???, ??????????????????????
???OH?????, ??OH?????????????
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Solution
(1) 3?pKa???Pauling?????? ????1
???,???????????????
(2)H3PO4 ????????, pKa??2
pKa??5, ??7 pKa??12?
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4. ??????????????
??????????????????????????
????O2S(OH)2????OH?F,Cl?NH2(??)?????????O2S(F)(OH)
????O2S(Cl)(OH)?????O2S(NH2)(OH)????H3PO3?(H)(O)
P(OH)2???????????,????H2S2O3?(O)(S)S(OH)2
??????????????????????
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????????????????????SbF5,?????????????????
?,???????????
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5.2 ????? The lewis acid-base
5.2.1 ??????? Definition and the
related concepts
5.2.2 ???? Hard and soft acids and
bases, HSAB
5.2.3 ????????? The variety of the
representative lewis acids
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5.2.1 ???????
????????????????????????,?????????????????
??????????????????????????????????????????????????
??,?????20??30??????????????
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1. ??
????(Lewis acid)???????????(Electron
pair acceptor)????????? ????(Lewis
base)???????????(Electron pair donor)?????????
???????????????????????????????
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1. ??????,???????,????????

2 . ??????????????
Solution
1. ???? BeCl2,CO2,CO,Hg(NO3)2,SnCl2
???? PH3,CO,SnCl2
2. ??? ??? ??? ???
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2. ???????
? ????????????,??Fe(H2O)63?
Cu(NH3)42??Fe3???Cu2???
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? ?????????????????8????,
??????????????????? SiF4 ?
?????,???2?F?????? SiF62?
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? ????????????????8????,? ??????????????????
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? ?????????????????????? ?????????????????,?
??I2? ???????????????????????
(CH3)2COI2? ???????(TCNE)?p???????
????
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3. ?????????
?????????????(Complex formation
reaction), ??????????????,??????????(Non-coordinat
ing solvent)??????,?????????????,?????????

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A B B AB B ????
??????????(Displacement
Reaction)?????????????????????,??
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???????????(Metathesis
Reaction),?????Metathesis????,???????????????,
??????????
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???????? Lewis ??? ? BrF3 F
BrF4 ? (CH3)2CO I2
(CH3)2CO-I2 ? KH H2O KOH
H2
Solution

• ? ?(BrF3)??(F )??
• ? ?????I2??,???O????????? ?I2???? ??????
• ??????(KH)???(H )?????(H )????H2?
  KOH???KOH????(OH- )???? ??(K )???????

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5.2.2 ????
1. ??
????????,??????????????????
???,?????,??????
2. ??
? ?????(?)????????,?????? ??????????(Hard
acids),????? ??????????(Soft acids)???, ???
????(Hard bases)???(Soft bases)?
? ????????????,????????? ????
? ????????????
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3. ????????(???????)
4. ?????????
?????????? ??????????
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??Hg2??F?I?Kf?????,??Hg2?b??????Pb2?
Kf ?????????,???????,??Pb2????????Zn2???????Hg2
?Pb2??,?a???????Al3???????Zn2???????????
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??????
?Ag??, ?????????????????,
????????Hg2(??)????????S2-(??)??,
????????????????Se??S?????(????????????),
???Hg????????????????, ????????????Se??,
??????????S?????Hg2???????, ??Se2-?????????,?????
???????????
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?????????
???(C2H5)3Si-I AgBr?(C2H5)3Si-Br
AgI ??, ????????, ???????????? - ??????????
????????
AgF42-?FeO42-?OsO4??Ag(2)?Fe(6)? Os
(8) ??? F ?O2 ????????????? ??????????????,
???????
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???HSAB???????????
Solution
????????????????????????????????????,?????
???,??????,???????????????,??????,??????????,????
??????
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Ni?Cu?????????,?Al?Ca???????????????????HS
AB ????????
Solution
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5. 2. 3 ?????????
1. ?????
? B? Al????????? Lewis ??????? BX3 ? AlX3
????????,?????????? p ????? Lewis ??????
??????????????????
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? BX3 ?????????????
BF3ltBCl3 lt BBr3
? BX3????????????,????????
????????????????
????????,???????????????
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2. ?????
? ?BX3 ??,AlX3 ????????????? Al ????? B
??,p???????????,? ?Al ???????? Al ???
? Cl ?????,?? ??? ???? (self acid base
complex)?
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3. ?????
? Si????????,????????? ???? ??? Lewis ???
SiX4 (g) 4HF (aq) SiF62 (aq) 2
H2F (aq)
? SiX4 ?????F? I?????? ???? SiF4gtSiCl4
gtSiBr4 gtSiI4
4. ??
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? 1962?, Olah G A ?(CH3)3CF???? SbF5 ,? 1H
NMR???????????????
(CH3)3C-F SbF5 (CH3)3C SbF6
? ????????Lewis?
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? SO3 ?Lewis??????? SO3 ????H2SO4 ? ?????
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