
Chapter 14 Elements in d- Block过渡元素分类d区:IIB_VIB, VI-第四周期:第一过渡系第五、六周期:第二、三过渡系(性质相似)f区:镧系元素La(57)一Lu(71)钢系元素Ac(89)—Lr(103)
1 Chapter 14 Elements in d- Block 过渡元素分类 d区:ⅢB—ⅦB,Ⅷ— 第四周期:第一过渡系 第五、六周期:第二、三过渡系(性质相似) f 区:镧系元素 La (57)—Lu (71) 锕系元素 Ac (89)—Lr (103)

14-1General Property14-2 Titanium(钛副族)14-3 Cr Mo W(铬副族(锰)14-4Manganese14-5(V)Fe Co NiPt14-6
2 14-1 General Property 14-2 Titanium (钛副族) 14-3 Cr Mo W(铬副族 ) 14-4 Manganese (锰) 14-5 Fe Co Ni (Ⅷ) 14-6 Pt

14-1 General Property1. Valence electron configurations(n-1)d1-8ns1-24d10Pdwith exception:Pt 5d96s1W 5d46s2有可变的氧化数,+2直至与族数相同的最高氧化数;相互转化,氧还反应
3 14-1 General Property 1. Valence electron configurations (n-1)d1-8ns1-2 with exception:Pd 4d10 Pt 5d96s1 W 5d46s2 ◼ 有可变的氧化数,+2直至与族数相同的最 高氧化数; ◼ 相互转化,氧还反应

Stability同周期,从左至右,氧化态升高后再降低Eg,VIBMn7+ Fe3+ Co3+ Ni2+同族,自上而下,元素氧化数的可变性趋向于减小高氧化态趋于稳定(与p区相反)Cr20,2-、Cr042-strong oxidizing agentMoO2-、WO42-weak oxidizing agent当与羰基、亚硝基、联吡啶等配体配合时,可皇现低氧化态+1、0、-1、-2、-3
4 Stability 同周期,从左至右,氧化态升高后再降低, Eg, ⅦB Mn7+ Fe3+ Co3+ Ni2+ 同族,自上而下,元素氧化数的可变性趋向于减小, 高氧化态趋于稳定(与p区相反) Cr2O7 2- 、CrO4 2- strong oxidizing agent MoO4 2-、WO4 2- weak oxidizing agent 当与羰基、亚硝基、联吡啶等配体配合时, 可呈现低氧化态+1、0、-1、-2、-3

2. Atomic radi同周期从左至右,半径减小,在接近IB时增大:同族从上而下,半径增,第五周期~第六周期3. Physical properties of elements--- similar密度大,硬度大,熔沸点高第三过渡系金属具有特别大的密度:从左至右金属的熔点升高文下降例:VIBCr熔点最高,硬度最大Mn、Tc反常低3385℃,W、Re熔点最高
5 2. Atomic radii 同周期从左至右,半径减小,在接近ⅠB时增大; 同族从上而下,半径增,第五周期 ≈第六周期 3. Physical properties of elements - similar 密度大,硬度大,熔沸点高 第三过渡系金属具有特别大的密度; 从左至右金属的熔点升高又下降 例 :ⅥB Cr熔点最高,硬度最大 Mn、Tc 反常低 3385℃ ,W、Re 熔点最高

4. As central elements to form complexes价键理论::(n一1)d nsnp能级相近且为空轨道,可以杂化成键,例 Co(II) sp3杂化 Co(SCN)42-Ni(II) dsp2杂化 Ni(CN)42-CFSE:Fe、Co、Ni形成配合物的能力最强
6 4. As central elements to form complexes 价键理论:∵(n-1)d ns np能级相近, 且为空轨道,可以杂化成键, 例 Co(Ⅱ) sp3杂化 Co(SCN)4 2- Ni(Ⅱ) dsp2杂化 Ni(CN)4 2- CFSE: Fe、Co、Ni形成配合物的能力最强

5.水合离子、配离子大多有颜色BlueRedPurpleGreenYellowOrangeWavelength/nm400500600700Co0200002500015000Wavenumber/cm-Figure Visiblespectrumof Ti(H,O)3+ solution
7 5.水合离子、配离子大多有颜色 25000 20000 15000 Wave number/cm-1 400 500 600 700 Wavelength/nm Purple Blue Green Yellow Orange Red Absorptivity 0 25000 20000 15000 Wave number/cm-1 400 500 600 700 Wavelength/nm Purple Blue Green Yellow Orange Red Absorptivity 0 25000 20000 15000 Wave number/cm-1 400 500 600 700 Wavelength/nm Purple Blue Green Yellow Orange Red Absorptivity 0 Figure Visible spectrum of Ti(H2O)6 3+ solution

dl-d9离子有色,d轨道上有1~5个未成对电子的水合离子,常具有不同的颜色原因:成单d电子d-d跃迁,吸收可见光中的某些光而显色d°、d10无色,例:Sc3+ La3+ Ti4+Zn2+ Cd2+ Hg2+ Ag*
8 d 1 -d 9离子有色,d轨道上有1~ 5个未成对电 子的水合离子,常具有不同的颜色 原因:成单d电子d-d跃迁, 吸收可见光中的某些光而显色 d 0 、d 10无色 , 例: Sc3+ La3+ Ti4+ Zn2+ Cd2+ Hg2+ Ag+

14-2 Titanium14-2-1General Characteristics14-2-2Titanium14-2-3Compounds of Titanium
9 14-2 Titanium 14-2-1 General Characteristics 14-2-2 Titanium 14-2-3 Compounds of Titanium

14-2 Titanium14-2-1 General CharacteristicsValence electron configuration22 Ti 3d24s2147pm 0.63%40 Zr160pm72 Hf158pmDue to the lanthanide contraction, the sizes of Zr and Hfare almost similar and these elements have almost identicalproperties in the element as well as in the combined states.Oxidation number: Ti (): Ti(H,O)3+紫;Ti(IV):无色、抗磁Due to the presence of a single electron, the Ti (IⅢI)10stateformscoloredandparamagneticcompounds
10 14-2-1 General Characteristics Valence electron configuration 22 Ti 3d 24s 2 147pm 0.63% 40 Zr 160pm 72 Hf 158pm Due to the lanthanide contraction, the sizes of Zr and Hf are almost similar and these elements have almost identical properties in the element as well as in the combined states. Oxidation number:Ti (Ⅲ):Ti(H2O)6 3+紫; Ti(Ⅳ):无色、抗磁 Due to the presence of a single electron, the Ti (Ⅲ) state forms colored and paramagnetic compounds. 14-2 Titanium