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北京化工大学:《无机化学》课程电子教案(教学课件,2011)Chapter 13 The p-block elements(Ⅰ)

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§13.1 Outline on the p-block elements § 13.2 The elements of boron family § 13.3 The elements of carbon family
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Chapter13 The p-block elements(I X$13.1 Outline on the p-block elements X$13.2 The elements of boron family X 13.3 The elements of carbon family

Chapter13 The p-block elements( Ⅰ ) § 13.3 The elements of carbon family § 13.2 The elements of boron family §13.1 Outline on the p-block elements

13.1 Outline of the p-block elements 蹋 1 18 IA 2 1314 15 16 17 0 IIIA IVA VA VIA VIA He Li Be B 3 S 7 N 0 F 4 6 8 9 Ne 1011 12 3 Na Mg IIIB IVB VB VIB VIB 四 IB IIB Al Si P c1 Ax K Ca Sc Ti Cx n Fe Co Ni Cu Zn Ga Ge As Se Bx K 5 Rb Sx YZ红 Nb Mo Te Ru Rh Pd Ag Cd In Sn Sb Te I Xe 6 Cs Ba Lu Ha Ta Re Ix Pt Au Hg Pb Bi Po At Rn E Ra Lz Rf DSghs Mt 镧系 La Ce Pr Nb Pn Sm Eu Gd Tb Dy Ho Ex Tm Yb 钢系 Ac ThPa卫u如Cm Bk Cf Es Em Md

§13.1 Outline of the p-block elements

General features in properties of p-block elements The properties of p-block elements show secondary periodic trends when descending in the same groups. 1The p-block elements in the 2ed row (i.e.,B,C,N,O,F) are abnormal in many ways compared to the other elements of the corresponding groups (only having 2s,2p orbits) Example:1)形成配合物时,配位数最多不超过4;2)第二 周期元素单键键能小于第三周期元素单键键能。 EN-N)=159E(0-0)=142EF-F)=158 EP-P)=209E(S-S)=264 E(C1-CI)=244 N,O,F原子半径小,成键时N-N,O-O,F-F键长短,未参与成键 的电子间排斥作用大,削弱了共价键的强度)

① The p-block elements in the 2ed row (i.e., B, C, N, O, F) are abnormal in many ways compared to the other elements of the corresponding groups (only having 2s, 2p orbits) Example: 1)形成配合物时,配位数最多不超过4;2)第二 周期元素单键键能小于第三周期元素单键键能. General features in properties of p-block elements ‹ The properties of p-block elements show secondary periodic trends when descending in the same groups. E(N-N)=159 E(O-O)=142 E(F-F)=158 E(P-P)=209 E(S-S)=264 E(Cl-Cl)=244 (N,O,F原子半径小, 成键时N-N, O-O, F-F键长短, 未参与成键 的电子间排斥作用大, 削弱了共价键的强度)

2 The p-block elements in the 4th and 5th rows show differ- ences (the insertion of d block)compared to other rows Example:The oxidizing power of HBrO3 and HBrO are stronger than that of other haloid acids(HCIO3,HIO3 and perhaloid acids (HCIO,HsIO). E9(C103/C12)=1.458V Ee(BrO;/Br,)=1.513V E9(I03L2)=1.209V Ee(C104/C103)=1.226V Ee(BrO4/Br03)=1.763V E(H,I06/103)=1.60V

② The p-block elements in the 4th and 5th rows show differ￾ences (the insertion of d block) compared to other rows E (ClO3 /Cl2 ) =1.458V − (BrO3 /Br2 ) =1.513V − E (IO3 /I2 ) =1.209V − E (ClO4 /ClO3 ) =1.226V − − E Example:The oxidizing power of HBrO3 and HBrO4 are stronger than that of other haloid acids (HClO3, HIO3) and perhaloid acids (HClO4, H5IO6). E (H5IO6/IO3 ) =1.60V − E (BrO4 /BrO3 ) =1.763V − −

3 The properties of last three p-block elements in the same group (elements in the 4th,5th and 6th rows) change soft-progressively (the insertion of d-block and f block). K Ca2+ Ga3+ Ge4+ AS5+ r/pm 133 99 62 53 47 Rb+ Sr2+ In3+ Sn4+ Sb5+ r/pm 148 113 81 71 62 Cst Ba2+ T13+ Pb4+ Bis+ r/pm 169 135 95 84 74 more obvious less obvious

③ The properties of last three p-block elements in the same group (elements in the 4th, 5th and 6th rows) change soft-progressively (the insertion of d-block and f￾block). K+ Ca2+ Ga3+ Ge4+ As5+ r/pm 133 99 62 53 47 Rb+ Sr2+ In3+ Sn4+ Sb5+ r/pm 148 113 81 71 62 Cs+ Ba2+ Tl3+ Pb4+ Bi5+ r/pm 169 135 95 84 74 more obvious less obvious

having various oxidation numbers Outer electron configurations:ns2np1~5 Example:The oxidation numbers of chlorine are+1,+3,+5,+7,-1,0。 Inert electron pair effect(惰性电子对效应): The compounds of ELEMENTS of low oxidation number are more stable than those of high oxidation number when descending in the same groups 同族元素从上到下,低氧化值化合物比高氧化值化合物变得更稳定

Outer electron configurations : n s 2 n p1 ~ 5 Example :The oxidation numbers of chlorine are +1 ,+3 ,+5 ,+7 ,-1 , 0 。 Inert electron pair effect (惰性电子对效应 ) : ‹ having various oxidation numbers The compounds of ELEMENTS of low oxidation number are more stable than those of high oxidation number when descending in the same groups 同族元素从上到下,低氧化值化合物比高氧化值化合物变得更稳定

Example: Si(II)Pb(IV) electron configurations are [Xe]6s2 (inert electron pair effeet )for Pb(II)and [Xe]for Pb(IV),respectively. Large electronegativity,forming covalent compounds

Example: Si(II) Pb(IV) electron configurations are [Xe]6s2 (Inert electron pair effect )for Pb(II) and [Xe] for Pb(IV), respectively. ‹ Large electronegativity, forming covalent compounds

13.2 The elements of boron family 13.2.1 Outline on boron family ©13.2.2 The elemental substances of boron family 13.2.3 The compounds of boron -*13.2.4 The compounds of aluminum

§ 13.2 The elements of boron family *13.2.4 The compounds of aluminum 13.2.3 The compounds of boron 13.2.2 The elemental substances of boron family 13.2.1 Outline on boron family

13.2.1 Outline on boron family Boron family (IIA):B,Al,Ga,In,TI Valence electron configuration:ns2npl Electron deficient elements:number of valence electrons number of valence orbits Electron deficient compounds:number of electron pairs in bonding molecular orbits number of valence orbits(即:还有空的成键轨道), 雨林木风1 Example::BF3,gBO3。 B:2S22p1 HBF is not electron deficient compound

13.2.1 Outline on boron family Boron family (ⅢA):B,Al,Ga,In,Tl Valence electron configuration:ns2np1 Electron deficient elements: number of valence electrons < number of valence orbits Electron deficient compounds: number of electron pairs in bonding molecular orbits < number of valence orbits(即:还有空的成键轨道). Example:BF3,H3BO3。 B: 2S22p1 HBF4 is not electron deficient compound 雨林木风1

幻灯片9 厢林木风1 B:2S22P1,其1个s轨道和2个P轨道与3个F配位后还有一个空的p轨道

幻灯片 9 雨林木风1 B:2S22P1,其1个s轨道和2个P轨道与3个F 配位后还有一个空的p轨道 webuser, 2010-11-25

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