Chapter 18 ????(I) the transition elements (I)

1
Chapter 18 ????(I)the transition elements (I)
IIIB IVB VB VIB VIIB VIIIB VIIIB VIIIB IB IIB
21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn
39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd 47 Ag 48 Cd
57 La 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt 79 Au 80 Hg
2
??(Introduction)

• ????????d?f???????,??????????????IIIB?VIIIB????,?
  ?8???,??????????,??????????????????????,????Cu2??
  3d9,Au3??3d9 ,?????????????.
• ???????????
• ??? (n-1)d,ns,np ?????
• ???
• 1. ?????? 2. 2??????
• 3. ???????????????????
• 4. ????????????????????????FeO4,???OsO4
• ????????????????,??????????d??,?????p?.

3
1???(Titanium subgroup)
??????????????????,???????????????????????????????
???????????,???EF2,EF3,EF4????,???????????????,???
??????EF2?EF4?????????????????,????????,??Zr?Hf???
?????????.

• ?? Titanium Zirconium Hafnium Rutherfordium
• ??General properties
• 1.Radius
• 2.First ionization energy
• 3.Oxidation number and coordination number
• Ti Zr Hf
• 234 4 4
• TiO,Ti2O3 ZrO2 HfO2
• 4.Occurrence in nature
• rutile (???) TiO2 ??? FeTiO3
• ???(Perovskite)

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???

• ??The simple substances
• Physical properties?????,Ti????,Zr?Hf???????
• Chemical properties
• ????,Ti???????????,???????,???????????????
• ????,??????.
• ????
• ???????
• ? HF ??F-??????

MHx MX4 EO2 H2 1000K
X2 600K O2 500K MB(MB2) M
EC B 1300K C
1300K MN 1000K
Ti(IV)?F-???????????????????
6
???
TiO2 2C 2Cl2 TiCl4 2 CO

• 3. Preparation??Ti?Zr?Hf???????????,?????????
• TiCl42Mg2MgCl2Ti K3ZrF74Na4NaF3KFZr
• ??Ti2I2 TiI4(s) TiI4(g)
  Ti(s)2I2
• ??Their compounds
• 1.4O.S.
• TiO2????????????????
• properties???????,?????H2SO4

?
7
???

• 2.Preparation
• ??Rutile2Cl22CTiCl42CO TiCl4O2TiO22Cl2
• ??(???)
• FeTiO3H2SO4(80?)TiOSO4FeSO42H2O
• TiOSO4??TiOSO42H2OTiO2nH2OH2SO4
• 3.Ti(IV)?????
• TiCl4
• a. preparation
• TiO22Cl22CTiCl4?2CO??TiO2CCl4TiCl4 ? CO2 ?

700-900degC
??.??.??
8
???

• b. properties
• 1?Hydrolysis TiCl42H2O
• 2??????TiCl42HClTiCl62H
• 3???????2TiCl4H22TiCl3(s)2HCl
  2TiCl4ZnTiCl3ZnCl2
• Ti(IV)??????
• a.
• b.TiOSO4H2O
• c.? H2O2

2-
????????????????????????,????????????????(Ch
arge transfer)
9
???

• 2.3O.S
• Preparation
• Properties
• ????4TiCl3O22H2O4TiOCl24HCl
• ?? 2TiCl3(s)TiCl2(s)TiCl4(g) ?
• 2TiCl2(s)TiTiCl4(g)?
• ??????Ti(III)? Ti(H2O)6Cl3(??)
  ????,??????HCl?????Ti(H2O)5ClCl2H2O(??)
• 
  ???

2TiO2H2 Ti2O3H2O 2TiCl4H2
2TiCl32HCl
10
2 ???(Vanadium subgroup)

• ??Vanadium Niobium Tantalum Dubnium
• ??General properties
• 1.Radius
• 2.First ionization energy
• 3.Oxidation number and coordination number
• V Nb
  Ta
• O.S 2345 5 5
• C.N 4,6 7,8
  7,8
• 4.Occurrence in nature
• ???,???,???

11
???

• ??The simple substance
• Physical properties????,???????????,?????????????
  ?????????,??O?H?C???,??????,????
• Chemical properties
• a.????,??????,
• ?,???????????,
• ?????????
• ???
• 4E5O22E2O5
• 4E5F22EF5

12
???

• b.??????????????????
• Nb?Ta???? HNO3-HF ?????,(Ta??????)
• 3Ta5HNO321HF3H2TaF75NO10H2O
• c. V?Nb?Ta????????,??????.
• 4E5O212KOH 4K3EO46H2O
• 3. Preparation
• ???????E2O5????????,????????
• E2O5 5Ca5CaO2E
• K2TaF75Na2KF5NaFTa

??
13
???

• ??Their compounds
• 1.5O.S.
• V2O5
• a.?? 2NH4VO3V2O52NH3?H2O
• b.??
• V2O5 ????,?????????.
• ???? V2O5 6NaOH2Na3VO43H2O
• ?pHlt1?????V2O52H 2VO2 H2O
• ?????V2O56HCl2VOCl2Cl2?3H2O

?
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• (2).????????
• V(V)?????
• VO2 H ???
• VO3 VO4 V2O7 OH ???
• b.?????????
• (1).pH??,?????????(?????) ???
• (2).???????????.
• VO43-?????
• ?????lt10-4M?

4-
3-
-
-
16
???

• c.
• d.

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???

• 2.4O.S (VO2,VCl4)
• VO2????,
• ????4VO22KOHK2V4O9H2O
• ???VO22H VO H2O
• VCl4???VCl4H2OVOCl22HCl
• 3.2,3O.S.
• (1)VOV2O5H2 ?VO
• VO????V(H2O)6 ??
• (2)V2O3????V(H2O)6
• (3)VCl3 ??VCl3 ?VCl2 (g)VCl4(s)
• ??????3KCl VCl3 K3V2Cl9

2
2
3
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3 ???(Chromium subgroup)

• ??Chromiun Molybdenum Tungsten Seaborgium
• ??General properties
• 1.Radius
• 2.First ionization energy
• 3.Oxidation number and coordination number
• Cr Mo W
• O.S 0123 45 45
• 456 6 6
• 4.Occurrence in nature
• ???Fe(CrO2)2 ???MoS2
• ???(Fe,Mn)WO4 ???CaWO4

Cr ??????Cr(NO)4 (-4) Cr( NO)2(CO)3 (-2)
19
???

• ??The simple substance
• 1.Physical properties bcc??(body-centered
  cubic),????????Cr------W??,??????????????,???????.
  ???????,??????????

20

???

• 2.Chemical properties
• (1)Reactions with acids and bases
• ??????????????????????????????
• ?????,??????,??(????),?????????????????????,?Mo?W
  ???????????????? W???H3PO4,??H3P(W3O10)4???,????
  ?HNO3HF?????,???????????
• W2HNO38HFH2WF82NO4H2O
• E3NaNO32NaOHNa2EO43NaNO2H2O
• (2)Reactions with non-metals
• ????,????????Cr?Mo?W?????????
• ??

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???

• 4Cr3O22Cr2O3 2Mo(W)3O2Mo(W)O3
• 2Cr3X22CrX3,2Mo5Cl2(??)2MoCl5
• 3.Preparation
• (1)CrAluminothermyCr2O32Al2CrAl2O3
• (2)Mo,W
• (3)??Fe(CrO2)24CFe2Cr4CO

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???

• ??Their compounds
• 1.2O.S
• (1)?????
• 4Cr(H2O)62O24H 4Cr(H2O)3 2H2O
• Cr(OH)2??,Cr ?????????Cr3???
• (2)Mo,W(II)??????????????
• MoCl2?Mo6Cl8Cl4 ? Mo6Cl12?????

2
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???

• 2.3O.S
• (1)Cr2O3,nH2O
• a.??4Cr3O22Cr2O3
• Cr33OH- ? Cr2O3nH2O
• Na2Cr2O7SCr2O3Na2SO4
• ???(NH4)2Cr2O7N2Cr2O34H2O
• (NH4)2MoO42NH3MoO3H2O
• b.??
• (i)Cr2O3????,???,???????????????(????),???????????
  ??????
• ??Cr2O33K2S2O7Cr2(SO4)33K2SO4

??CrO2- (AlO2- , ZnO22- )
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???

• (ii)
• ????????CrO2 ?????,??H2O2??
• ??????Cr2O7 ?????.
• (2)Cr2(SO4)3???(???????????????
• Cr2(SO4)318H2O
• Cr2(SO4)36H2O Cr2(SO4)3
• ?? ???
• 3SO2H2SO4K2Cr2O723H2OK2SO4Cr2(SO4)324H2O
• ???M Cr(SO4)212H2O

-
2-
I
25
???

• (3)Cr(III)????
• Cr2S3,Cr2(CO3)3????????.
• (4)Cr(III)????
• a. Trans-dark green blue violet
• Cr(H2O)4Cl2Cl2H2O Cr(H2O)6Cl3
  Cr(H2O)5ClCl2H2O (pale green)
• ???????,??,???pH?
• b.Cr(NH3)63 ?NH3 ????????,????????
• Cr(NH3)6Cl33H2O Cr(OH)33NH4Cl
  3NH3? ?????????????.
• c.Cr2Cl93-?W2Cl93-????

HCl
HCl
??
??
26
???

• 3.6O.S.
• (1)MO3(CrO3-poisonous!)
• a.??2Mo3O22MoO3
• K2Cr2O7H2SO4K2SO42CrO3H2O ?????????.
• b.??
• (i)CrO3 ????167C??????????
• ?WO3,MoO3??
• CrO3?Cr3O8?Cr2O5?CrO2?Cr2O3
• (ii) CrO3 WO3 MoO3????,?H2WO4
  H2MoO4???????????????,???????????
• EO3 2OH EO4H2O
• (iii)CrO3?????,???????????????

-
2-
27
???
2-
2-

• (2)H2CrO4,CrO4,Cr2O7????
• a.?????? Ka14.1
• b.??????
• 2H 2CrO4 Cr2O7 H2O K1.2X10
• ????????????????????
• ?????????????,??????????????????????,?????.
• ???????
• c.?H2O2??????????

14
2-
2-
?? ???????,???50C,??Na2HPO4??,??????,????
?????.
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???

• d.?(?)???????,???????????2(NH4)2MoO43Zn16HCl2M
  oCl33ZnCl2NH4Cl8H2O
• ??????????.
• e.???
• ???????,?,?
• ????????????.
• f.?S ????????
• Na2WO44H2SNa2WS44H2O (????WS3??)
• (NH4)2MoO43H2S2HClMoS32NH4Cl4H2O
• (4)CrO2Cl2
• a.?????,???????,?CCl4,CS2??,????.
• b.??CrO32HCl(g)CrO2Cl2H2O
• K2Cr2O74KCl3H2SO4(?)2CrO2Cl23K2SO43H2O
• c.??
• ??CrO2Cl2H2OH2Cr2O74HCl

2-
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4 ???(manganese subgroup)
????????????,????????????????1925?(?????????)
,??????????????,???1937?,????????,??????????,???
?????????

• ??Manganese Technetium Rhenium Bohrium
• ??General properties
• 1.Oxidation number
• ????Mn(NO)(CO)4
• 2.Coordination number ReH9
• 3.Occurrence in nature
• ???(MnO2),Pyrolusite
• Re???????,?????????

2-
Mn Tc Re O.S
0123 4567 7
7 C.N 4,6 7,8,9 7,8,9
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???

• ??the simple substance
• 1.Physical properties
• ?????????????(??????),???????
• (Re??????W),???(Re???????????
• ?),?????????(?Mn,Re???)
• 2.Chemical properties
• (1)??????????,??????????,??????HNO3?????????,????
  ????????,?X2?B?C?Si?O2?P?????4ReO22Re2O7
  3Mn2O2Mn3O4
• (2)????Tc?Re???????????
• Mn2H Mn2H2? 3E7HNO33HEO47NO?
  2H2O
• (3)????MnH2OMn(OH)2H2?,Tc,Re??
• (4)???????????,????????????????
• Mn4KOH3O2 2K2MnO42H2O

??
35
???

• 3.Preperation
• (1)Mn 2MnSO42H2O 2Mn2H2SO4O2
• MnO2Si MnSiO2
• (2)Re 2NH4ReO44H2 2ReN28H2O
• 4.Usage
• ??????,???????????????.
• ??????????????.
• ??Their compouds
• 1.0O.S E2(CO)10
• (1)Structure and formation of bonds
• (2)Reactivity Mn(CO)522Na 2NaMn(CO)5
• Mn(CO)52Br2
  Mn(CO)5Br

??
36
???
eg ? ? t2g ? ? ?

• 2.2O.S.
• (1)Mn(H2O)6 ???
• (2)MnO????,?????? Mn2 MnS ????
• (3)?????,Na2S2O8,PbO2,NaBiO3??? ?
• (4)?????? MnCl2Na2O2 MnO22NaCl
• 3MnSO42KClO312KOH 3K2MnO42KCl3K2SO46H2
  O

??
37
???

• 3.4O.S ?Mn(H2O)64 ??,??MnO2?????????,?K2MnF6
• (1)preperation ????MnCO3???,?????
• (2)properties
• a.??????????
• 2MnO2 4HCl(?) 2MnCl2Cl22H2O
• 2MnO2 2H2SO4 2MnSO4O2?2H2O
• b.?????????
• 3MnO2KClO36KOH 3K2MnO4KCl3H2O
• 2MnO23PbO26HNO3 2HMnO43Pb(NO3)22H2O

??
38
???

• 4.6O.S Mn?????,?Re?????
• Properties
• a.????
• ??????
• ReCl63ReCl620KOH 2KReO4 ReO2 18KCl
  10H2O
• b.
• c.

39
???

• 5.7O.S.
• Mn(VII) Mn2O7,?MnO3F?? Re(VII)?ReF7,ReOF5,ReO3F??
• properties ?MnO4-??
• a.MnO4-???,????????
• b.???? hv?????,???????????
• 4MnO4-4H 4MnO23O22H2O
• c.
• d.

?????????????,????????? KMnO43H2SO4 K
MnO3 3HSO4 H3O ??????????????,???Mn2O7(?????),
?????CCl4????Mn2O7 ??CCl4???????.

-


40
???

• (3)Preperation
• a.?MnO2????KMnO4
• ???MnO2O24KOH2K2MnO42H2O
• ??? K2MnO42CO22KMnO4MnO22K2CO3
• ?????66.7
• b.???
• Anode
• Cathode
• ?????

??
?????100