???? ???? Chapter 15 The Boron Family Elements

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???? ????Chapter 15 The Boron Family
Elements

• Boron (B) Aluminum (Al) Gallium (Ga)
• Indium (In) Thallium (Tl)
• ns2np1

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• 15-1 Boron and its compounds
• ??General properties
• 1. ???????Si???????,(?????
• ??),?????3???,??????????
• ???????????????M4B?M2B?MB?M3B4?MB2?MB6??
• 2. ?????,????Na2B4O710H2O,???
• ?Na2B4O74H2O,????H3BO3??
• 3. ????????????,???
• ,?????????????????????

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• ???????
• (1) B2O3?SiO2?????????,Al2O3???,CO2?????
• (2) H3BO3?H4SiO4????
• (3) ?????????????
• (4) ?????????????????,?AlH3????

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• ??The simple substance
• 1. ?????????,??
• ??
• ?????????????
• ,?????????x-??? ,
• ???????????????
• ?????,???B12????
• ??????????????x-
• ???

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• 2. properties
• (1) ????????????,??F2??,?????????,????????,???
  
• (2) ???
• 3SiO2 4B 3Si 2B2O3 (??)
• 2B 6H2O(g) 2B(OH)3 3H2 (??)
• (3) ????????,??H3BO3
• (4) ????????,????
• 2B 2NaOH 3KNO3 3NaBO2 3KNO2 H2O

??
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• 3. Preparation
• (1) ????
• B2O3 3Mg 2B 3MgO
• KBF4 3Na 3NaF KF B
• (2) ??? ???? ??? ???
• a. ???????????
• Mg2B2O5 5H2O 2NaOH 2NaBO2 2Mg(OH)2
  4H2O
• b. ??CO2????,?????
• 4NaBO2 CO2 10H2O Na2B4O710H2O
  Na2CO3

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• c. ?H2SO4????,????????????
• Na2B4O7H2SO45H2O 4H3BO3Na2SO4
• d. ??,??
• 2H3BO3 B2O3 3H2O
• e. ?Mg?Al?????
• B2O3 3Mg 2B 3MgO
• f. ??
• 2B 3I2 2BI3
• 2BI3 2B 3I2 (1000-1300K, Ta wire)

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• ??Compounds
• 1. Boron hydrides
• ???????????????(paraffin),?
• ???(Borane)????????BnHn4,BnHn6,
• ???BnHn8,BnHn10 ?????????B2H6
• BH3?????????B???????????,????????,???????sp2??
  ?????p?

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• (2) Preparation
• a. ?????
• MnB 3H 1/2B2H6 Mn3
• b. ???
• BCl3 3H2 1/2B2H6 3HCl
• c. ???????
• 3LiAlH4 4BF3 2B2H6 3LiF 3AlF3
• 3NaBH4 4BF3 2B2H6 3NaBF4

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• (3) ???????
• ????????,??B2H6
• ????????12?,????
• ???????????(2c-2e),
• B????sp3??,??????
• ?BH2???,????????
• ??,????????????
• H??????????????
• ???,??????

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• ??????????????
• a. BH 2c2e ??
• H
• b. B B 3c2e ???
• c. BB 2c2e ???
• B
• d. B B ??? 3c2e ???
• B
• e. B B ??? 3c2e ???

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• 1957-1959?,Lipsomb.W.N?????????????????,???????
  ?????1976?Nobel????
• ?????????
• ??BnHnm
• s????????????(B-H-B)
• t???????(B-B-B)
• y??????(B-B)
• x??(BH)n(???)?????B-H?????
• ??????
• ????? s x m
• ?????(B) s 2t 2y x 2n
• ?????(B) 2s 3t 2y x 3n

B4H10 (4012)
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• 1957-1959?,Lipsomb.W.N?????????????????,???????
  ?????1976?Nobel????
• ?????????
• ??BnHnm
• s????????????(B-H-B)
• t???????(B-B-B)
• y??????(B-B)
• x??(BH)n(???)?????B-H?????
• ??????
• ?????s x m
• ?????(BH)2s2t2y2x2n 3n(nm)
• ?????(BH)3s3t2y2x2n 4n(nm)

B4H10 (4012)
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• s x m ?
• ? s 2t 2y x 2n ?
• 2s 3t 2y x 3n ?
• ? ??s t n
• ? ??t y n m/2
• x m s
• t n s
• y s m/2
• ? B2H6 (2002) (styx) B4H10 (4012 )

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????????2c2e B-B?????????????????? ??????????3c2e
B-B-B???,??4????3c2e?,??2????????????????????4?3??
????????4?2.5c2e?(?????????)??????2?B-B?2?B-B-B?
4620 (SEP12, nido-,????)
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Wade rule
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• 1971????????K.Wade????????
• ???????????,???????????
• ????????,????Wade??,????
• ???????????????????????
• ????????????
• ??b??????????,n??????,
• ? bn1????? bn2?????
• bn3????? bn4?????

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• ????????????,?????????
• ???? (CH)a(BH)pHqd-
• CH?????,BH?????,S?????,
• P?????????
• ???????????M3a2pqd
• ??apn,?M2naqd
• ??bn1/2(aqd)
• ??BnHn2- a0,q0,d2,
• ??bn1,?????

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• ???
• ??Wade??,???????????
• ??
• B6H62-,B9C2H11, B9C2H112-,B4C2H6,
• B3H3-,B10H14,B10H15-,B10H18,B3C2H7,
• B10CpH11,B9SH11

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B6H62-
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• (4) ??
• a. ???? ????????????,???
• ????,?????
• B2H6 3O2 B2O3 3H2O
• b. ?????(??????)
• 2NaH B2H6 2NaBH4
• c. ???????,????,????????
• d. ???????????,??????

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• 2. ???(Boron halides)
• (1) Preparation
• 3CaF2 B2O3 3H2SO4 2BF3? 3CaSO4
  3H2O
• B2O3 3C 3Cl2 2BCl3 3CO
• (2) Properties
• a. hydrolysis
• 4BF3 6H2O 3H3O 3BF4- B(OH)3
• BCl3 3H2O B(OH)3 3HCl
• b. ????
• 4BF3 Na2CO3 2H2O 3NaBF4 NaB(OH)4
  2CO2?

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• 3. ????
• (1) B2O3
• a.????
• B2O3 3H2O 2H3BO3 (???)
• b.???????B2O3??????????
• ????????
• CuO B2O3 Cu(BO2)2(??)
• NiO B2O3 Ni(BO2)2(??)
• c. ?NH3??,??(BN)n

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• (2) H3BO3
• a. ????,???????,OH??????
• B(OH)3 H2O B(OH)4- H
• ????????,???????????????????
• b.????
• 2NaOH 4H3BO3 Na2B4O7 7H2O
• Na2B4O7 2NaOH 4NaBO2 H2O
• c. H3BO3??????????????????
• d. H3BO3?????????
• B(OH)3 H3PO4 B(PO4) 3H2O

?
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• (3) ??????????
• a. (BO2)33-
• ??,
• ?KBO2,NaBO2???
• b. (BO2)nn-
• ZigZag Chains ,
• ?Ca(BO2)2 ,LiBO2?

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• c. ??

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• c. ??
• ???????????????,?????B
• ??????????????????????
• ???????????
• ?????????,?????????,?
• ???????????????

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• 15-2 Aluminium and its compounds
• ??????,?????
• Al2O3?????,a- Al2O3????,????,
• ????????????(SiC), a- Al2O3???
• ????(2100K),?a- Al2O3??Cr3??,??
• ????????- Al2O3??????,??
• ??,?????????????

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• ?AlF3???,Al????????Al2Cl6?,Al
• ???????
• Cl Cl
  Cl
• Al Al
• Cl Cl
  Cl
• Al2Cl6???,??AlCl3???????
• 2Al 3Cl2 2AlCl3
• 2Al 6HCl(g) 2AlCl3 3H2(g)

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• ??(zeolites)
• ??Mx/n(AlO2)x(SiO2)ymH2O
• ????????,?SiO4?AlO4????????
• ??
• ????????????????????????
• ????????,????????????
• ???????????????,??????,?
• ??????(?),?8?????6?????????
• ?ß??

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• O O
  O
• O Si O Al O Si
  O
• O O
  O

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???
Zeolite A
Zeolite Y
Zeolite ZSM-5
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?????
Discovered in 1992, mesoporous materials are
porous materials with regularly arranged, uniform
mesopores (2 nm to 50 nm in diameter). Their
large specific surface area, as high as 1,000
m2/g, makes them useful as catalysts or
adsorbents.
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Zeolites. Zeolite is a Greek word that means
boiling stone, because naturally occurring
zeolites are minerals that absorb water that
subsequently boils when heated. Zeolites are
microporous, crystalline aluminosilicates
consisting of three components framework
tetrahedra, cations, and adsorbed molecules.
Depending upon the framework and cations, the
adsorbed phase feels a local electrostatic
environment ranging from nonpolar to extremely
polar. Three important zeolite framework
topologies are shown in Figures. The
technological importance of these materials
cannot be overstated. For example, it is
estimated that the monetary value of zeolitic
catalysis to petroleum cracking over the past
several decades is in excess of 100 billion
dollars. Zeolites are also used as molecular
sieves for separating chemical mixtures, as ion
exchangers and filters, as environmentally safe
detergents, as desiccants for new coolant
systems, and as hydrocarbon traps for new
cold-start catalytic converters. Mesoporous
sieves show promise for separating biomolecules
and may be useful for making optical electronic
materials with substantial quantum confinement.
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• 15-3 Gallium subgroup
• ??General properties
• (?????)
• Ga,In?????3,Tl?????1
• ??The simple substances
• 1. Ga?In?Tl????H???,???????
• Tl?HCl?????Passivated??,??????????TlCl,???Tl??,?
  ???Tl????????????
• 2. Ga???, In?Tl????????,????
• 2Ga 6H2O 6NaOH 2Na3 Ga(OH)6 3H2

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• ??Compounds
• 1. 3 O.S.
• (1) Oxides ?????
• Ga2O3 In2O3 Tl2O3 ?????
• 
  ????
• M2O3 6HCl 2MCl3 3H2O
• Ga(OH)3??????,Ga2O3?Al2O3????
• Ga(OH)3 3OH- Ga(OH)6 3-
• Ga(OH)3?????,?Al(OH)3??

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• (2) Sulfides
• Ga2S3(??)????
• Ga2S3 6H2O 2Ga(OH)3 3H2S
• 2TlCl3 3Na2S Tl2S? 2S?6NaCl
• In2S3(??)???(NH4)2S?M2S?
• (3) Halides
• TlBr3?TlI3????,?????TlF3?TlCl3
• ?? Tl3 3I- TlI I2

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• 2. 1 O.S.
• (1) Ga?In?1??????,?????
• 3Ga2O Ga2O3 4Ga
• 3Ga2S Ga2S3 4Ga
• 3In(aq) In3 2In
• In2S(??)?????,??????H2
• In2S 4H 2S2- 2H2? In2S3 (??)
• (2) Tl?1?????,??TlF?,??TlX????,?Ag??

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• Tl3 2Tl 3Tl 4Tl O2 2Tl2O
• TlOH???,???????H2O?CO2,??
• ???
• ???????????????????
• ?Tl2Cl4 , Tl4Cl6?????Tl?2?,?????
• ?? TlI TlIIICl4 TlI3 TlIIICl6

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• ??????
• ?????????
• 1. ??
• (1) ??
• a. ???????,???,???
• b. 18????,182????,??????????
• ??? Zn2?Hg2?Bi3?Fe3??????8????????
• (2) ??? NF3????,PF3???CF4?CCl4??
• ?,?SiCl4??(nd ???)
• 2. ????????

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• ??????
• 1. ??????
• SnCl2 H2O Sn(OH)Cl? HCl
• 2. ???????
• AlCl3 3H2O Al(OH)3 3HCl
• 3. ??????
• PCl5 4H2O H3PO4 5HCl
• 4. ?????
• 3SiF4 4H2O H4SiO4 2H2SiF6

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• ??????
• 4. ?????
• Fe3 H2O H Fe(OH)2 Fe2(OH)24
• 5. ????
• 2 XeF2 2H2O 2Xe O2 4 HF
• 6.??
• 6XeF4 12H2O 2XeO3 4 Xe 3O2 24 HF
• BrF3 H2O HBrO3 HBr HF
• 3I(NO3)3 6 H2O 2HIO3 HI 9 HNO3