“Transition” metals
过渡 金属的特性
? 变价性
? 配合物
? 颜色
? 磁性
From highly reactive metals of
the s block to the much less
reactive metals of Group 12
and the p block,
Trends in Physical Properties
? All the d-block elements are metals,
? Most,good electrical conductors,
? Most,malleable,ductile(延展 ),lustrous(光
泽 ),silver-white in color,
? Generally,higher melting and boiling points,
例外, Hg,low melting point,Liquid(RT)
Cu,red-brown and Au,yellow,
原子半径 （ d区元素,pm）：相似性；
镧系收缩（ lanthanide contraction）
(From 224pm for Ba to 172pm for Lu)
La-Lu
Scandium through Nickel
Scandium,Sc
Isolated in 1937,a reactive metal,
1) Sc react with water about as vigorously as
Ca does,
2) The small,highly charged Sc3+ ion is
strongly hydrated in water (like Al3+),the
resulting hydrated ion is about as strong
a Bronsted acid as acetic acid,
Titanium,Ti
Light,strong metal (vital in
airplane),Resistant to corrosion,
Ores,ilmenite (钛铁矿 ),FeTiO3
Rutile(金红石 ),TiO2
Ti requires strong reducing
agents for extraction from its
ores,Ores +Cl2→ TiCl 4
TiCl4(g) + 2Mg(l) 700° C→
Ti(s) + 2MgCl2(s)
TiO2 brilliantly white,nontoxic,stable solid used as white pigment
in paints and paper,Semiconductor in the presence of light,used as
electrode in photoelectrochemical cells,BaTiO3,piezoelectric(压电 ),
S + O2 → SO 2; 植被分解和火山爆发；燃油和煤 (电厂 )
H2S(g) + 3O2(g) → 2SO 2(g) + 2H2O(g)
酸性氧化物
SO2(g) + H2O(l) → H 2SO3(aq)
还原性 和 氧化性
SO2(g) + Br2(aq) → Br -(aq) + SO4-(aq)
2SO2(g) + O2(g) △ → 2SO 3(g),slow reaction,catalyzed V2O5
SO3(g) + H2O(l) → H 2SO4(aq) 酸雨（ Sox,Nox,H2O）
H2SO4,无色腐蚀油状液体； 强酸，脱水剂，氧化剂。
SO3(g) + H2SO4(l) → H 2S2O7(l) (Oleum,发烟硫酸 )
化肥（ 2/3）,石化产品，染料，清洁剂。
SO2,SO3,H2S(IV)O3,H2S(VI)O4
Chromium,Cr (the name comes from chroma,Greek for color)
Bright,lustrous,corrosion-resistant metal,
FeCr2O4(s) + 4C(s) △ → Fe(s) + 2Cr(s) + 4CO(g) or
Cr2O3(s) + Al(s) △ → Al 2O3(s) + 2Cr(l) (thermite 铝热 process)
Cr metal,mostly,used in steelmaking and for Cr plating,
CrO2,a ferromagnetic materials used for coating,chrome”
recording tapes because they respond better to high-frequency
magnetic fields than do conventional,ferric” (Fe2O3) tapes,
2CrO42- (aq) + 2H+(aq) → Cr 2O72-(aq) + H2O(l)
Cr2O72-(aq)+14H+(aq)+6e- → 2Cr 3+(aq)+7H2O(l) Eo= +1.33V
(NH4)2CrO4热分解
（火山实验）
Manganese,Mn
Gray metal that resembles iron,Rarely used alone,much less
resistant to corrosion,Important component of alloys,In
steelmaking,it removes S,
3MnO2(s)+4Al(s) △ → 2Al 2O3(s)+3Mn(l)
(thermite 铝热 process)
MnO2,a brown-black solid used in dry cells; as a decolorizer to
conceal the green tint of glass; as the starting point for other Mn
compounds,
KMnO4,a widely used strong oxidizing agent in acidic solution,
Also as a mild disinfectant (消毒剂 ),
Rational synthetic reactions to MnO2
?MnSO4 + (NH4)2S2O8 → MnO2 nanobelts
?MnSO4 + NaClO → MnO2 nanorods
?MnSO4 + H2O2 → MnO2 nanorods
?2KMnO4 +3MnSO4 → 5MnO 2 nanowires
?Mn2++2OH- → Mn(OH)2 → MnO(OH) nanowires
?NaMnO2 → MnO2 nanotubes
1-D nanostructures in Manganese dioxides
Iron,Fe
The most widely used of all the d-metals,The most abundant on
Earth as a whole,and the second most abundant metal in Earth’
crust (Al,No,1 metal),Hematite(赤铁矿 ),Fe2O3; magnetite(磁铁
矿 ),Fe3O4; pyrite(黄铁矿 ),FeS2,
Fe2O3(s)+3CO(g) △ → 2Fe(l)+3CO 2(g)
(Fe/kg requires ca,1.75Kg ore,0.75Kg coke,0.25kg limestone.)
A healthy adult human body contains ca,3g of iron,mostly as
hemoglobin(血色素 ),Close to 1mg is lost daily(in sweat,feces,
hair),must be ingested daily,Iron deficiency,in reduced transport
of oxygen to the brain and muscles,an early symptom is chronic
tiredness(持续疲倦 ),
Blast furnace
(鼓风炉 )
CaO(s)+SiO2(s)
→CaSiO 3(l)
CaO(s)+Al2O3(s)
→Ca(AlO 2)2(l)
6CaO(s)+P4O10(s)
→2Ca 3(PO4)2(l)
Slag(炉渣 )
矿，焦碳，石灰石
炉渣
Basic oxygen process
（炼钢）
A blast of oxygen and
powdered limestone is
used to purify molten
iron by,respectively,
oxidizing and
combining with the
impurities present in it,
Cobalt,Co
Oren are often found in association with copper(II) sulfide,
Silver-gray metal,used mainly for alloying with Fe,
Alnico(磁钢 ),an alloy of Fe,Ni,Co,Al,
Cobalt steel are hard enough to be used as surgical(外科 ) steels,
Co(II) oxide is heated with Si and Al to produce a blue pigment
used to color glass and ceramic glazes,
We need cobalt in our diet(食物 ),for it is a component of Vitamin
B12,
CoCl2 + (NH4)2S → CoS
CoCl2 + NaOH → Co(OH) 2
Co(OH)2 +H2O2 → Co(OH) 3
NiO
NiCl2 + (NH4)2S → NiS
NiCl2 + NaOH → Ni(OH) 2
血红蛋白
配位化合物
? 配合物的结构
概念 (中心原子、配体、配位键、配位数、配
位层、螯合、八面体、四面体、四方形，命名 )
异构 (结构异构,立体异构 )
? 晶体场理论
配体对 d电子的作用 (能级分裂 )
配体对配合物 颜色 的影响
dn配合物的 电子结构
配合物的 磁性
(http://www.chem.purdue.edu/gchelp/cchem/)
Ligand = Lewis base
Metal atom or ion =
Lewis acid
chelate
(命名口诀：先无后有，先阴后中，先 A后 B，先少后多。 )
Linkage isomers 键合异构
NCS-,异硫氰酸根
SCN-,硫氰酸根
亚硝酸根
硝基
Geometrical isomers 几何异构
Identifying optical isomerism
红宝石晶体
配体对配合物颜色的影响
?o = h?
?o = hc / ?
? = hc / ?o
? = hc / ?o
Spectrochemical series Complementary color
?
增
加
配位化合物
? 配合物的结构
概念 (中心原子、配体、配位键、配位数、配
位层、螯合、八面体、四面体、四方形，命名 )
异构 (结构异构,立体异构 )
? 晶体场理论
配体对 d电子的作用 (能级分裂 )
配体对配合物 颜色 的影响
dn配合物的 电子结构
配合物的 磁性
配位平衡及其移动
? 配位平衡及平衡常数
? 配位平衡的移动
配位平衡与酸碱平衡
配位平衡与沉淀平衡
配位平衡与氧化还原平衡
配合物之间的转化与平衡
过渡 金属的特性
? 变价性
? 配合物
? 颜色
? 磁性
From highly reactive metals of
the s block to the much less
reactive metals of Group 12
and the p block,
Trends in Physical Properties
? All the d-block elements are metals,
? Most,good electrical conductors,
? Most,malleable,ductile(延展 ),lustrous(光
泽 ),silver-white in color,
? Generally,higher melting and boiling points,
例外, Hg,low melting point,Liquid(RT)
Cu,red-brown and Au,yellow,
原子半径 （ d区元素,pm）：相似性；
镧系收缩（ lanthanide contraction）
(From 224pm for Ba to 172pm for Lu)
La-Lu
Scandium through Nickel
Scandium,Sc
Isolated in 1937,a reactive metal,
1) Sc react with water about as vigorously as
Ca does,
2) The small,highly charged Sc3+ ion is
strongly hydrated in water (like Al3+),the
resulting hydrated ion is about as strong
a Bronsted acid as acetic acid,
Titanium,Ti
Light,strong metal (vital in
airplane),Resistant to corrosion,
Ores,ilmenite (钛铁矿 ),FeTiO3
Rutile(金红石 ),TiO2
Ti requires strong reducing
agents for extraction from its
ores,Ores +Cl2→ TiCl 4
TiCl4(g) + 2Mg(l) 700° C→
Ti(s) + 2MgCl2(s)
TiO2 brilliantly white,nontoxic,stable solid used as white pigment
in paints and paper,Semiconductor in the presence of light,used as
electrode in photoelectrochemical cells,BaTiO3,piezoelectric(压电 ),
S + O2 → SO 2; 植被分解和火山爆发；燃油和煤 (电厂 )
H2S(g) + 3O2(g) → 2SO 2(g) + 2H2O(g)
酸性氧化物
SO2(g) + H2O(l) → H 2SO3(aq)
还原性 和 氧化性
SO2(g) + Br2(aq) → Br -(aq) + SO4-(aq)
2SO2(g) + O2(g) △ → 2SO 3(g),slow reaction,catalyzed V2O5
SO3(g) + H2O(l) → H 2SO4(aq) 酸雨（ Sox,Nox,H2O）
H2SO4,无色腐蚀油状液体； 强酸，脱水剂，氧化剂。
SO3(g) + H2SO4(l) → H 2S2O7(l) (Oleum,发烟硫酸 )
化肥（ 2/3）,石化产品，染料，清洁剂。
SO2,SO3,H2S(IV)O3,H2S(VI)O4
Chromium,Cr (the name comes from chroma,Greek for color)
Bright,lustrous,corrosion-resistant metal,
FeCr2O4(s) + 4C(s) △ → Fe(s) + 2Cr(s) + 4CO(g) or
Cr2O3(s) + Al(s) △ → Al 2O3(s) + 2Cr(l) (thermite 铝热 process)
Cr metal,mostly,used in steelmaking and for Cr plating,
CrO2,a ferromagnetic materials used for coating,chrome”
recording tapes because they respond better to high-frequency
magnetic fields than do conventional,ferric” (Fe2O3) tapes,
2CrO42- (aq) + 2H+(aq) → Cr 2O72-(aq) + H2O(l)
Cr2O72-(aq)+14H+(aq)+6e- → 2Cr 3+(aq)+7H2O(l) Eo= +1.33V
(NH4)2CrO4热分解
（火山实验）
Manganese,Mn
Gray metal that resembles iron,Rarely used alone,much less
resistant to corrosion,Important component of alloys,In
steelmaking,it removes S,
3MnO2(s)+4Al(s) △ → 2Al 2O3(s)+3Mn(l)
(thermite 铝热 process)
MnO2,a brown-black solid used in dry cells; as a decolorizer to
conceal the green tint of glass; as the starting point for other Mn
compounds,
KMnO4,a widely used strong oxidizing agent in acidic solution,
Also as a mild disinfectant (消毒剂 ),
Rational synthetic reactions to MnO2
?MnSO4 + (NH4)2S2O8 → MnO2 nanobelts
?MnSO4 + NaClO → MnO2 nanorods
?MnSO4 + H2O2 → MnO2 nanorods
?2KMnO4 +3MnSO4 → 5MnO 2 nanowires
?Mn2++2OH- → Mn(OH)2 → MnO(OH) nanowires
?NaMnO2 → MnO2 nanotubes
1-D nanostructures in Manganese dioxides
Iron,Fe
The most widely used of all the d-metals,The most abundant on
Earth as a whole,and the second most abundant metal in Earth’
crust (Al,No,1 metal),Hematite(赤铁矿 ),Fe2O3; magnetite(磁铁
矿 ),Fe3O4; pyrite(黄铁矿 ),FeS2,
Fe2O3(s)+3CO(g) △ → 2Fe(l)+3CO 2(g)
(Fe/kg requires ca,1.75Kg ore,0.75Kg coke,0.25kg limestone.)
A healthy adult human body contains ca,3g of iron,mostly as
hemoglobin(血色素 ),Close to 1mg is lost daily(in sweat,feces,
hair),must be ingested daily,Iron deficiency,in reduced transport
of oxygen to the brain and muscles,an early symptom is chronic
tiredness(持续疲倦 ),
Blast furnace
(鼓风炉 )
CaO(s)+SiO2(s)
→CaSiO 3(l)
CaO(s)+Al2O3(s)
→Ca(AlO 2)2(l)
6CaO(s)+P4O10(s)
→2Ca 3(PO4)2(l)
Slag(炉渣 )
矿，焦碳，石灰石
炉渣
Basic oxygen process
（炼钢）
A blast of oxygen and
powdered limestone is
used to purify molten
iron by,respectively,
oxidizing and
combining with the
impurities present in it,
Cobalt,Co
Oren are often found in association with copper(II) sulfide,
Silver-gray metal,used mainly for alloying with Fe,
Alnico(磁钢 ),an alloy of Fe,Ni,Co,Al,
Cobalt steel are hard enough to be used as surgical(外科 ) steels,
Co(II) oxide is heated with Si and Al to produce a blue pigment
used to color glass and ceramic glazes,
We need cobalt in our diet(食物 ),for it is a component of Vitamin
B12,
CoCl2 + (NH4)2S → CoS
CoCl2 + NaOH → Co(OH) 2
Co(OH)2 +H2O2 → Co(OH) 3
NiO
NiCl2 + (NH4)2S → NiS
NiCl2 + NaOH → Ni(OH) 2
血红蛋白
配位化合物
? 配合物的结构
概念 (中心原子、配体、配位键、配位数、配
位层、螯合、八面体、四面体、四方形，命名 )
异构 (结构异构,立体异构 )
? 晶体场理论
配体对 d电子的作用 (能级分裂 )
配体对配合物 颜色 的影响
dn配合物的 电子结构
配合物的 磁性
(http://www.chem.purdue.edu/gchelp/cchem/)
Ligand = Lewis base
Metal atom or ion =
Lewis acid
chelate
(命名口诀：先无后有，先阴后中，先 A后 B，先少后多。 )
Linkage isomers 键合异构
NCS-,异硫氰酸根
SCN-,硫氰酸根
亚硝酸根
硝基
Geometrical isomers 几何异构
Identifying optical isomerism
红宝石晶体
配体对配合物颜色的影响
?o = h?
?o = hc / ?
? = hc / ?o
? = hc / ?o
Spectrochemical series Complementary color
?
增
加
配位化合物
? 配合物的结构
概念 (中心原子、配体、配位键、配位数、配
位层、螯合、八面体、四面体、四方形，命名 )
异构 (结构异构,立体异构 )
? 晶体场理论
配体对 d电子的作用 (能级分裂 )
配体对配合物 颜色 的影响
dn配合物的 电子结构
配合物的 磁性
配位平衡及其移动
? 配位平衡及平衡常数
? 配位平衡的移动
配位平衡与酸碱平衡
配位平衡与沉淀平衡
配位平衡与氧化还原平衡
配合物之间的转化与平衡
