无机化学专业英语-(17)[312页]课件

1、Chapter 11 Elements in p - Block1 Introduction2 Halogens 3 Oxygen and chalcogens4 Nitrogen, phosphorus, arsenic, antimony, bismuth5 Carbon, silicon, germanium, tin, lead6 Boron, aluminum, thallium7 Hydrogen and noble gases8 Summary11 Introduction 1-2 Characteristics of elements in p- Block H HeB C N

2、 O F NeAl Si P S Cl ArGa Ge As Se Br KrIn Sn Sb Te I XeTl Pb Bi Po At Rn2outer electron configurations ：ns2np1-6 0 group：ns2np6With their closed-shell electron configurations ns2np6, the noble gas elements of 0 group neither attract nor lose electrons under common conditions.A-IIIA：ns2np15 number of

3、 valence electrons = the highest oxidation number = group numberThe 21 nonmetal elements, each tends to attract electrons to itself to reach the closed-shell electron configurations.31-2 Trends of atomic properties From top to bottom in the same group, r increases, I1, E1 and X decrease. 4Abnormalit

4、y for elements in period 2 high electronegativity value (X) , small radius, no d orbital for use. The electron affinity E1: F Br IX-X bond strengths: F Br ICoordination number CN 4 5Similarity of elements in periods 5 and 6镧系收缩:57La to 71Lu ，the radius of Lu is only 0.11A less than that of La Lantha

5、nide contraction causes the radii of elements of period 6 almost equal to those of elements in the same group of period 5.6中间排异样性Elements in period 4 having 3d10 Compared with elements in periods 2 and 3, the effective nuclear charge (Z*) increase and the radius decrease，which cause bigger Z*/r valu

6、e and bigger electronegativity value. 72Halogens2-1 General properties2-2 Elements2-2-1 Properties2-2-2 Preparations (制备) 2-2-3 Usages2-3 Compounds2-3-1 HX2-3-2 Halides Interhalogen compounds (卤素间化合物) Polyhalogen compounds(多卤化物)2-3-3 Oxides (OF2, ClO2, I2O5) 2-3-4 Oxiacids (含氧酸) /salts82-1 General p

7、roperties Outer electron configuration：ns2np5Oxidation numbers -1 ionic bond, NaFcovalent bond, HFcoordination bond, BF4、AgCl2 +1，+3，+5，+7 when halogen element combine with more electronegative elements, such as ClO2 and polyhalogen compounds. 9Existing form in nature：X, MXnFrom F to I, r increase，w

8、hile I1、E1、X decreaseWith an exception：E1Cl E1F10F2Cl2Br2I2X2/X /V2.87 1.361.090.54X2 oxidizing agent F2 Cl2 Br2 I2 X reducing agent F Cl Br HCl HBr HImp、bp：HF HCl HBr HCl HBr HI 1/2H2(g) +1/2X2= HX (g)fGm(kJ/mol) 273 95 53 1.7E (kJ/mol) 565 431 364 29928Acid strength of HX(aq) HF ：Ka =10-4 HCl HBr

9、H2SO3HNO3 HNO254b. Thermal stability and oxidizing capacity：还原为低价态或单质时，所需破坏的RO键越多，酸越稳定，氧化性越弱。 氧化性: HOCl HClO2 HClO3 HClO4(aq)HOCl HCl + 1/2O2 HClO3 + HI/SO2/Zn/Al Cl + IO3/SO42/Zn2/Al3HClO4 + 55Comparisons：HClO4（aq.）稳定；HClO4 （l.）无色，不稳定HClO4 (aq.)氧化性小；HClO4（ 浓热）强氧化剂氧化性: H2SO4（稀） H2SO3 HNO3（稀） Reducin

10、g capacity (aq.)Acidity 10-24 soluble in dilute acid eg MnS dissolve in HAc FeS dissolve in 0.3MHCl79（3）Preparation FeS + 2HCl = FeCl2 + H2S 用H2O吸 HCl，P2O5干燥 CH3C=SNH2(s) + 2H2 O CH2C=OONH4 + H2S（4）Identification H2S + Pb(Ac)2 = PbS + 2HAc 803-3-2 H2O2Hydrogen peroxidemolecular shapeO： sp3不等性杂化 二面角

11、分子不对称，极性分子，OO单键键长149 pm81unstable 2H2O2 2H2O + O2One of the following factor will speed up the reactionhr ; T 153; OH ;Heavy metal ions Fe、Mn、Cu稳定剂：微量Na2SnO3、Na4P2O7、8-羟基喹啉 act as both oxidant and reductant , mainly as oxidant 1.229V n = 2(2) Properties82 MnO 4- + H+ O2 + Mn2+ + 2 H2O H2O2 + MnO 4-

12、O2 + MnO2+ OH+ H2O (in neutral / basic solutions ） Cl2 = O2 + 2 Cl- + 2 H+ Fe2+ + H+ H 2O + Fe3+ H 2SO 3 H 2O + SO 4 2-+ 2 H+ H 2O 2 + Mn(OH) 2 H 2O + MnO 2 Cr(OH) 4 + OH CrO 4 2- Cr 2O 7 2- + H+ CrO 5+ 5H 2O PbS H 2O + PbSO 4 83 Very weak acid: K 1=10 -12 H2O2 + Ba(OH) 2 BaO2 + 2H2O 84(3) Preparati

13、onsBaO2 + CO2 + H2O BaCO3 + H2O2Electrolysis and hydrolysis of saturated NH4HSO4 solutionsAnode : 2HSO4- - 2e = S2O82- + 2H+Cathode : 2H+ + 2e = H22HSO4-= S2O82 + H2S2O82- + H3+O H2S2O8H2S2O8 H2SO5 + H2SO4 (H2O)H2S2O8 H2SO4 + H2O2 (H2O)S2O82- + 2 H2O = 2 HSO2- + H2O2 (H2SO4)In 1850sIn 190885乙基蒽醌法绿色化

14、学“零排放”实例H2 + O2 H2O2（2-乙基蒽醌/Pd）In 1945Progress in Novel Catalysts for Hydrogenation of 2-Ethylanthraquinone化学工业与工程，2006，23（4）：361-36486Progress in Production of Hydrogen PeroxideThrough Anthroquinone87(4) Usages : oxidantTo bleach wool,silk and paintingsPb（OH）22PbCO 3 + H 2S = PbSPbS + 4 H 2O 2 = Pb

15、SO 4+ 4 H 2O3% H2O2 pure H 2O2 can be used as oxidant of rocket fuels883-3-3 Oxides and Oxyacids of sulfur3-3-3-1 SO2、H2SO3 and their salts3-3-3-2 SO3、H 2SO4 and their salts 3-3-3-3 硫代硫酸钠 3-3-3-4 过硫酸及其盐3-3-3-5 连硫酸及其盐 893-3-3-1 SO2、H2SO3 and their salts(1) SO2:sulfur dioxidemolecular shape：中心S原子 sp2杂

16、化 43Physical property：colorless pungent gas，it is permitted less than 0.02 mg in 1 liter air . It dissolves easily in water，40 L / 1 L H2O , SO2 + H2O H2SO390Chemical property：mainly act as reducing agent SO42-/ SO32- = -0.92 VH 2SO4 / H 2SO3 = 0.17 VH 2SO3 / S = 0.45 VSO3 2- + H + + MnO 4 - SO4 2-

17、+ Mn 2+SO3 2- + H + + Cl 2 ( I 2 ) SO4 2 + Cl - ( I - )91resources： combustion of raw materials containing sulfur S + O2 = SO2 (heat) 3 FeS2 + 8 O2 = Fe3O4 + 6 SO292939495DesulfurizeDry methodWet method CaCO 3(s) 2 + CaO CaSO3 CaCO3 COCa(OH) 2 (aq.) (Na 2CO 3 / NH 3 H 2O) + SO 2 + H 2O 3)2 (Na 2SO 3

18、 / (NH 4) 2SO 3 ) CaSO 3 Ca( HSO96催化还原SO2到单质SSO2 + NH3 = S +N2 + H2O 随着近现代工业的发展，我国SO2的排放越来越严重，已超过美国而成为世界第一排放大国。同时，我国每年需要花费巨额外汇进口数十万吨的硫磺来满足生产需要。因此，将SO2还原为S，具有双重的意义。具有工业化前景的是CO还原法和NH3还原法。其中NH3还原法所用催化剂为浸镍氧化铅，其优点是氨水价格便宜，反应的最终产物是S ，N2和H2O, 硫的纯度高，且无二次污染，无疑是绿色的化学工艺。 97（2）MHSO3、MSO3： 遇H +，放出SO 2受热易分解： 2Na 2

19、H SO 3 = Na 2 S 2 O 5 + H 2 O 4Na 2 SO 3 = 3Na 2 SO 4 + Na 2 S遇强还原剂时： 2H + + SO3 2 + 2H2S = 3S + 3H2 O SO2 + 2CO = S + 2CO 2 ( t = 500 , ) 2SO2 + 2NaHg = Na 2 SO 2 + 2Hg 2Na 2 HSO3 + Zn = Na 2 S 2 O4 + Zn(OH) 2氧化 ： SO4 2983-3-3-2 SO 3、H 2 SO 4 and their salts SO 2（g）+ O 2 2SO 3（s，colorless，volatile）

20、（1）SO 3Molecular shape：properties：strong oxidant Fe/Zn + SO 2 = FeSO 3 / ZnSO 3 4P + 10 SO 3 = P 4O 10 + 10 SO 2 2KI + SO 3 = K 2 SO 3 + I 2Usage ：They are mainly used for preparing H 2 SO 4 SO 3（s）+ H 2 O = H 2 SO 4 H = -133 KJ/mol 99（2）H 2 SO 4 ( 市售浓H 2 SO 4 9698%，d=1.84g/cm 3,18M ) 结构： S: sp 3不等性

21、杂化，与两个O 形成两个键。 具双键成分：与另两个O形成两个配键（S0）；O的P电子与S的空轨道形成dp键 性质： strong acid Ka 2 = 1.0 10 -2 H 2 SO 4 H + + HSO 4 -strong oxidant Zn + H2 SO4(concentrated) = ZnSO 4+SO2 (g)+ S(g)+ H 2S(g)Cu + H2 SO4(concentrated) = CuSO4 + SO2(g)+ H2O + S C + H2 SO4(concentrated) = CO 2 (g)+ SO 2 (g)+ H2O100absorbing wate

22、r dehydration C12H2 2O11 = 12 C + 11 H2 O C 2 H 5OH = C 2 H 4 + H2 O HCOOH = CO + H2 O 101（3）sulfate Most of sulfates are easy to dissolve in water, while some slightly dissolve, such as CaSO4, SrSO4 ,PbSO4 , BaSO4. easy to form hydrateCuSO45H2O胆矾 bluestoneFeSO47H2O绿矾 copperasKAl(SO4) 2 12H2O明矾 alum

23、CaSO 42H2O 石膏 gesso/gypsumNa2SO410H2O 芒硝 Glaubers saltZnSO47H2O皓矾(NH4) 2 SO4FeSO46H2O Mohr salt 102 thermal stability8e,A,A sulfates are stable， not decomposetransitionmetal sulfates MO + SO3（heat）2MO 2M + O 2CuSO4 CuO + SO3 Ag 2 SO4 Ag 2O + SO3（heat）酸式盐 2NaHSO4(s.) Na 2SO 4 + SO32NaHSO 4(s.) Na 2 S

24、O 4 + H 2 O（high temperature） 103（4）焦硫酸：x SO3 + H 2SO4 (concentrated) H 2SO4x SO3H 2S2O7 ( colorless crystal solid ) 2H 2SO4碱性 Fe2 O3 + 3 K2 S2 O7 = Fe 2 (SO4)3 + 3 K2 SO 4两性 Al2 O3 1043-3-3-3 硫代硫酸钠（1）Preparations：S + O2 SO2 （ignite）Na 2 CO 3 + SO2 Na 2 SO 3 + CO 2Na 2SO3 + S Na 2S2O3 （ boiling ） pH

25、 4.6105（2）Properties： Decompose with H + ：S2O32 + 2 H + H2S2O3 S+ SO2 + H2Oreductant：S2O32- + Cl2 = SO4 2- + 2 Cl 2S2O32- + I2 = S4O6 2- + 2 I - ligand：AgBr + 2 S2O3 2- = Ag2S2O3（white）AgBr +2S2O3 2-(excess） = Ag(S2 O3)2 3- + Br - 1063-3-3-4 过硫酸及其盐：Properties Strong oxidantS2 O8 2-/ SO4 2- = 2.01 VC

26、u + K2 S2 O8 = CuSO4 + K2 SO 42 Mn 2+ + 5 S2O8 2- + 8 H 2 O = 2 MnO 4 - + 10 SO4 2- + 16 H +（catalyzer Ag+）instable 2 H2 S2O8 = H2 SO4 + 2 SO3 + O2（heat up）2 K2 S2O8 = 2 K2 SO4 + 2 SO3 + O2 （heat up） 107 3-3-3-5 连硫酸及其盐连二硫酸：H 2 SO 3 + MnO 2 = H 2 S 2 O 6 连三硫酸：K 2 S 2 O 3 + SO 2 = K 2 S 3O 6(s) 连四硫酸：2

27、 Na 2 S 2 O 3 + I 2 = Na 2 S 4O 6 + 2 NaI 连五硫酸钠： 5Na2S2O3 + 6 H + = 2 Na 2 S 5O 6（s）+ 6 Na + + 3 H 2 O H 2 S 5O 6 = H 2 SO 4 + SO 2 + 3 S1083-3-4 硫的含氧酸的卤素衍生物HCl+SO 3 (发烟硫酸，H 2 SO 4xH 2 O)=HSO 3Cl（氯磺酸， colorless liquid ）HSO 3Cl + H2O = H 2 SO 4 + HCl SO 2 + Cl 2 = SO 2 Cl 2 氯化硫酰，硫酰氯，sulfuryl chloride

28、, colorless liquid SO 2 Cl 2 + H2O = H 2 SO 4 + 2 HCl SO 2 + PCl 5 = POCl 3 + SOCl 2 亚硫酰氯，thionyl chloride, colorless liquidSOCl 2 + H2O = SO 2 + 2 HCl 1091104 Nitrogen, phosphorus, arsenic, antimony and bismuth4-1 General properties4-2 Nitrogen and its compounds4-3 Phosphorus and its compounds4-4 A

29、rsenic, antimony and bismuth1114-1 General propertiesOuter electron configuration：ns2np3随r,I1、X减小，E1无规律 Oxidation numbers-3、3、5-3：N与活泼金属， Li3N Na3N Mg2N3 为离子型NH3 , PH3 ，AsH3 为共价型氢化物。3、5大多形成共价型化合物，3只与F、NO3、SO42才有可能形成离子型化合物，如AsF3、SbF3、BiF3、Bi(NO3) 3、Sb2 (SO4) 3另外：NH2NH2（联氨，-2），NH2OH（羟氨，-1），HN3（叠氨酸，-1/

30、3），N2O（+1），NO（+2），NO2（+4）112（3） 6s2惰性电子对效应随r增大，3 还原性减小，稳定性增大；5 氧化性增大，稳定性减小，NaBiO3 (s)强氧化剂。As3+ Sb3+Bi3，还原性逐渐减弱As5+ Sb5+Bi5，氧化性逐渐增强5 NaBiO3+2 Mn2+14 H+=5 Bi3+3 Na+ + 3 MnO4- +7 H2OBi3+ Xe4f14 5d10 6s2Bi (V) Xe4f14 5d10 6s0113（4）随r增大,非金属向金属完整过渡 HNO3 强酸H3PO4中强酸， Ka1= 103 , 108 , 1013H3AsO4 中强酸，Ka1= 103

31、 ,107 ,1012Sb(OH) 3 两性Bi(OH) 3弱碱（5）作中心体时，N的配位数为4，例NH4+；其余为6， 例PCl6 114N2P4(6)存在形式1154-2 Nitrogen and its compounds氮元素的循环1164-2-1 N2 Preparations Liquefy air Decompose of nitrogen salts, heatNH4Cl + NaNO2 = NH4NO2 = N2+ H2O(NH4)Cr2O7 (s) = N2 + Cr2O5 + 4 H2O 2 NH3 + 3 CuO = N2+3 Cu + 3 H2OBa(N3) 2 =

32、Ba + 3 N22 AgN3 = 2 Ag + 3 N2(叠氮化银，白色固体，不溶于水，遇热分解) 117Applications 用作保护气（有机合成反应，金属有机）致冷剂：液氮mp.= -210 ，bp.= -198制NH3、HNO3、NH4+、炸药 118Properties inactiveThere are only several metals that can react directly with dinitrogen in air. For example, Li、Mg、Ca、Sr、BaLi + N2 Li3N（RT）（其余A元素不能直接得）Li3N + H2O Li(OH

33、) + NH34 Mg + 3 N2 = 2 Mg2N3 （heat ） Mg2N3 + H2O Mg(OH) 2 + NH32 B + N2 = 2 BN(原子晶体，结构与石墨相同)Al + N2 Si + N2 Si3N4 （T 1473）*过渡金属氮化物TiN VN ZrN NbN TaN 高熔点，高硬度，做工程材料、功能材料 1194-2-2 NH3 / NH4+ saltsAmmoniaPreparations2 NH4Cl + Ca(OH)2 = CaCl2 + 2NH3+ 2 H2O （heat ）(NH4)2SO4(s) + CaO(s) = CaSO4 + 2 NH3+ H2

34、O （heat）N2 + 3 H2 = 2 NH3 Harber 和Mittasch 等开发成功Fe catalyst（Fe3O4），high temperature / high pressure)工业合成氨的单程转化率,即氨的合成率只有15 %25 % ,大部分气体需循环,增加了动力消耗。要提高催化剂的活性和单程转化率,就必须降低反应温度。120氨合成催化剂研究的总发展趋势就是开发低温高活性的新型催化剂,降低合成氨反应温度,提高氨的平衡转化率和单程转化率。20 世纪30 年代Zenghelis 和Stathis 钌的氨合成催化活性。1972 年Ozaki 等发现,钌为活性组分、金属钾为促进

35、剂、活性炭为载体的催化剂对氨合成有很高的活性,在常压下的活化能为6911 kJ / mol ,打开了钌催化剂研究之先河 。之后,日本、俄罗斯、英国、美国、意大利等国的学者,投入大量精力到钌催化剂的研制以取代铁催化剂。121PropertiesColorless, pungent gas, easily dissolves in water.Weak base，Kb =1.8105氨水，NH3 + H2 O NH4+ + OH （ 0.1M ；1.34%）与酸反应，得相应铵盐：均易溶，热不稳定铵盐的热分解 NH3 + 酸 （heat ）NH4Cl = NH3 + HCl (NH4)2SO4 =2

36、 NH3+ H2 SO4 (NH4)2CO3 = 2 NH3+ CO2 + H2 ONH4NO3 = N2O (g) + 2 H2O NH4NO3 = N2 + O2 + H2O （high temperature）NH4NO2 = N2 (g) + 2 H2 O(NH4)2Cr2O7 = N2 + Cr2 O3 + 4 H2O2 NH4ClO4 = N2 + Cl2 + 2 O2 + 4 H2O122Remove small amount of NH4+ in a solution by adding acid: NH4+ + HNO3 + HCl = N2 or N2 O (heat) I

37、dentification of NH4+ by Nessler reagent：K2 HgI4 / KOHNH4+2HgI42-+4OH- = Hg2ONH2I(红棕色)+7I-+3H2O123as a ligand providing electron pair：Ag(NH3) 2+、Cu(NH3) 42+CaCl2 (s) + 8 NH3 = CaCl2 8NH3 124as a reductant in Redox reactions：4 NH3 + 5 O2 = 4 NO + 6 H2 O（Pt，500）4 NH3 + 3 O2 (pure) = 6 H2 O + 2 N22 NH3

38、 + 3 CuO = 3 Cu + N2 + 3 H2 O（heat ）2 NH3 + 3 PbO = 3 Pb + N2 + 3 H2 O（heat）NH3 + Cl2 = N2 + HCl2 NH3 + 6 Cl2 (excess) = 2 NCl3 + 6 HClWhen it encounters strong reductants, NH3 acts as oxidizing agent.2 NH3 (l) + 2 Na = 2 NaNH2 + H22 NH3 (l) + 3 Mg = Mg3N2 + 3 H2125A、Ca、Sr、Ba的液氨溶液具强还原性，蒸干得金属；且导电，如Na

39、(NH3) x+126ApplicationsNH3易蒸发，rHm大，是致冷剂（臭味） 制HNO3制氮肥，(NH4) 2 SO4、(NH4) 3PO4制塑料、医药品、涂料127 4-2-3 联氨（肼）、羟胺、叠氮酸（氢氮酸） NH2NH2NH2OHHN3结构性质无色，高度吸湿性，介电常数比 NH3（l.）大，其盐溶液可导电二元弱碱N2H5 , Kb1 = 106N2H62 Kb2 = 1015不稳定，白色固体 NH2OH (288K) NH3 + H2O + N2 + NO 弱碱 Kb = 109无色液体一元弱酸 Ka = 105128性质提供孤电子对，作配体Pt(NH3)2(N2H4)2Cl

40、2以还原性为主B N2 / N2H4 = - 1.15VA NH4 /N2H5 = 1.27VN2H4(aq.) + AgNO3 4Ag + N2+ H2ON2H4(aq.) +2X2 4HX+N2N2H4(l.) + 2H2O2 (l.) 4H2O + N2N2H4(l.) + O2 (g) 2H2O(l.) + N2 (g.)(CH3) 2NNH2+O2 H2O+ N2 + (CH3) 2O以还原性为主 B N2/NH 2OH = 3.04 V 2NH2OH + 2AgBr = 2Ag +N2 + 2HBr + 2H2ON3卤离子AgN3白色固体，难溶制备2NH3(过量) + ClO N2

41、H4 + Cl+ H2ON2H4 + HNO2 = HN3 + 2H2O(低温)用途有机合成129 4-2-4 HNO3 / nitrateS2P33个sp2pNsp2杂化130 4-2-4 HNO3 / nitrate4-2-4-1 HNO3Preparations 催化氧化法4 NH3 + 5 O2 4 NO + 6 H2 O2 NO + O2 = 2 NO23 NO2 + H2 O = HNO3 + NO NaNO3 + H2 SO4 = NaHSO4 + HNO3 (393 - 423K) structure：N 2s22p3 NO3- 的对称结构比HNO3稳定,氧化性NO3- 浓HN

42、O3 稀HNO3 溶有NO2，NO2起传递电子的作用机理：NO2 + e- = NO2 NO2 + H+ = HNO2 HNO3 + HNO2 = H2 O + 2 NO2 HNO3通过NO2获得还原剂的电子133王水：V HNO3：V HCl = 1：3 氧化+配位Au + HNO3 + 4 HCl = HAuCl4 + NO+ 2 H2 O3 Pt + 4 HNO3 + 8 HCl = 3 H2 PtCl6 + 4 NO + 8 H2 O （4）用途 制炸药、染料、人造纤维、塑料、底片、硝化1344-2-4-2 Nitrate Easy dissolve in water Easy to

43、decompose when heatedFor active metal nitrate： NaNO3 = NaNO2 + 1/2 O2Mg Cu： Mg(NO3) 2 = MgO + 2NO2 + 1/2 O2 Mn(NO3) 2 = MnO2 + 2 NOFor metals more inactive than Cu： AgNO3 =Ag + NO2 + 1/2 O2 Hg(NO3) = 2 HgO + 2 NO2 2 HgO = 2 Hg + 1/2 O2135136NO3-的鉴定：棕色环NO3- + 3 Fe2+ + 4 H+ = 3 Fe3+ + NO + 2 H2OFe2+ +

44、 NO = Fe(NO) 2+1374-2-5 HNO2 nitrous acid /nitrite4-2-5-1 HNO22HNO2 N2O3+H2O NO2(g)+NO (g) + H2O 蓝棕HNO2不稳定，易分解138（1）Preparation：NaNO2 + HCl = NaCl + HNO2 (blue)（2）PropertiesWeak acid，Ka =104，quite unstable which can only exist in very dilute solution. It is easy to decompose. mainly as an oxidant2 N

45、O2 + 2 I + 4 H + = 2 NO + I2 + 2 H2 O （氧化性强）5NO2 + 2MnO4 + 6H+ = 5NO3 + 2Mn2+ + 3H2 O （还原性弱）NO2-as a ligandCo(NO2) 3(NH3) 3 三亚硝酸根三氨合钴（）1394-2-5-2 Nitrite colorless solids which easily dissolve in water poisonous, carcinogen 1404-2-6 Treatments of NOX (NO、NO2 as principal components)4 NH3 + 6 NO = 5N

46、2 + 6 H2 O （CuO-Cr2O3）8 NH3 + 6 NO2 = 7 N2 + 12 H2 O 1414-3-1 Elements4-3-1-1 PropertiesP4，white phosphor, whose radius is larger than nitrogen, has little tendency to form bond.Nonpolarity, Activ：unstable,self-ignite,preserve in water;Poisonous, cause death ( be fatal at 0.1g)4-3 Phosphorus and its

47、 compounds142P的氧化物P原子O原子P4O6 P4正四面体的6个P-P键打开，各结合1个O, 形成6个P-O-P键（桥氧）P4O10在P4O6基础上,每个P原子结合1个O原子143P4 + 3 O2 = P4O6 P4O6 + 2O2 = P4O10 P4O6 + 6 H2O(cold) = H3PO3 P4O6 + 6 H2O (hot) = 3 H3PO4 + PH3P4O10 + H2O = (HPO3)n mixturesP4O10 + 6 H2 O = 4 H3PO4（HNO3，heat ）2P + 3Cl2 = 2PCl3 PCl3 + Cl2 = PCl5PCl5 +

48、 4 H2O = H3PO4 + 5 HClPCl5 + H2O ( insufficient) = POCl3 + 2 HClP + 5HNO3 = H3PO4 +5 NO2 (g)+H2O2P + 5H2SO4 = 2H3PO4 + 5SO2(g)+2H2O4P + 3 KOH + 3 H2O = PH3 (g)+ 3 KH2PO2144P4O6化学性质 (2) 热水中歧化-磷酸和膦P4O6 + 6H2O（冷）= 4H3PO3(1) 冷水中生成H3PO3 （亚磷酸）145偏磷酸 焦磷酸 正磷酸脱水性，可使H2SO4, HNO3脱水： P4O10 + 6H2SO4 = 6SO3 + 4H3P

49、O4 P4O10+12HNO3=6N2O5+4HPO3P4O10是实验室常用的干燥剂P4O10有很强的吸水性，是效率很高的优良干燥剂，与水反应，可形成：P4O10化学性质 1464-3-1-2 Preparations2 Ca(PO4) 2 + 6 SiO2 + 10 C = 6 CaSiO3 + P4 + 10 CO（1173-1713K，电弧炉中熔烧还原）SiO2 + CaO = CaSiO3 It is an exothermic reaction. Add SiO2 to decrease reaction temperature.4-3-1-3 UsagesMake fire bom

50、b and fog bomb4P + 5O2 = 2P2O5 , P2O5 + H2O fogPrepare H3PO41474-3-2 Phosphoric acid/ Phosphates4-3-2-1 Phosphoric acid （1）PreparationsP + 5 HNO3 (concentrated) = H3PO4 + 5NO2 +H2OP4O10 + 6 H2O = 4 H3PO4（HNO3，heat up）In industryCa2(PO4)3 + 3 H2SO4 = 3 CaSO4 + 2 H3PO4Ca3 (PO4) 2 + 2 H2SO4 + 4 H2O =Ca

51、(H2PO4) 2 + 2 CaSO42 H2O 148（2）Structures等电子体：ClO4、SO42、PO43、SiO44 50e-（3）properties中强酸，三元酸 Ka=103 , 108 ,1013无氧化性，无挥发性（高沸点）PO43配位体Fe3+ + 2 PO43 + 3 H+ = H3 Fe(PO4) 2 or H Fe ( HPO4 ) 2 149 溶解性 水解性 稳定性正盐 A、铵盐易溶， 其余难溶（Li除外） pH 12 稳定磷酸氢盐 A、铵盐易溶， 其余难溶（Li除外） pH 9-10 加热得焦、偏磷酸磷酸二氢盐 均易溶 pH 4-5 加热得焦、偏磷酸2、磷酸

52、盐150 4-3-2-3 Identification of PO433Ag+ + PO43= Ag3PO4(yellow) Ag3PO4 + HNO3 dissolveMg2+ + NH4+ + PO43 = MgNH4PO4（white）3 NH4+ + 12 MoO42 + 24 H+ + PO43 = (NH4) 3PO4 + 12 MoO3(yellow) + 12 H2O1514-3-3 P ()的其它含氧酸焦磷酸：2 H3PO4 H2O H4P2O7 三磷酸：3 H3PO4 2 H2O H5P3O10（NaPO3）n 格式盐：处理锅炉用水核糖核酸：RNA脱氧核糖核酸：DNA腺苷三

53、磷酸：ATP (adenosine triphosphate)腺苷二磷酸：ADP (adenosine diphosphate) Adenine:腺嘌呤152H3PO4磷酸H3PO2次磷酸H3PO3亚磷酸与氮氧物种不同，四面体方式成键是磷氧物种的一个特点153 4-3-4 Phosphorous acid / Hypo-phosphoric acid 亚磷酸 次磷酸 结构 H3PO3 H3PO2 性质 无色固体，易溶 无色固体，易潮解，有毒 二元酸 Ka=10-2 , 10-7 一元酸 Ka=10-2 还原剂 强还原剂 4 H3PO3 =3 H3PO4 + PH3 HPO32-/H2PO2 =

54、 - 1.565V HPO32- + 2 Ag+ + H2O H2O + H2PO2- + Ni2+ = 2 Ag + PO43- + 3 H+ = HPO32- + Ni + 3 H+ HPO32- + SO42- + H+ = PO43- + SO2 + H2O154制备 P4O6 + 6 H2O(冷) 4 H3PO3 P4 + OH(浓) PH3+ H2PO2 H2PO2 + Ba(OH) 2 = Ba(H2PO2) 2 Ba(H2PO2) 2+ H2SO4 =BaSO4 +H3PO2浓缩) （273K） ( 403 K, H3PO32(晶体)H3PO32(晶体)H3PO32(晶体)H3

55、PO32(晶体)H3PO32(晶体)H3PO2(晶体)H3PO2(晶体) P + H3PO4 H3PO2H3PO2 (晶体) 亚 次 155PO43、P2O72、PO3的鉴定 PO43 P2O72 PO3Ag+ 黄 白 白HNO3 溶 不溶 不溶HAc/蛋白液 无 白1564-4 As、Sb、Bi 4-4-1 Elements 4-4-2 M2O3 / hydrate、M2O5 / hydrate 4-4-3 Sulfide/硫代酸盐 4-4-4 MX3 4-4-5 MH31574-4-1 Elements 自然界中As、Sb、Bi 主要以硫化物矿存在：雌黄 As2S3、雄黄As4S4、辉锑矿

56、Sb2S3、辉铋Bi2S3，另有 少量广泛存在 于MS中（制M或H2SO4时，含杂质 As），少量以游离态存在。158PreparationM2S3 + 3 O2 M2O3 + 3 SO2 （ calcine 煅烧）M2O3 + C ( active carbon) = 2 M + 3 COM2S3 + 3 Fe (powder) = 3 FeS + 2 M （high temperature ） 159Property低熔点，易挥发,As4 (g) 同P4，Sb、Bi固体的导电、导热等性质比液态时的差M + X2 MX3M + O2 / S M2O3 / M2S3M + H2SO4 (con

57、c. ) As2O3 / Sb2(SO4) 3 / Bi2(SO4) 3 + SO2 （heat）M + HNO3 H3AsO4 / Sb2O3Xh2O 或HSb(OH) 6 / Bi(NO3) 3 + NO （heat ）M + HCl + HNO3 SbCl6As + NaOH Na3AsO3 + AsH3 M + A A3M (A 金属) （heat ） 160Summary of non-metals reacting with NaOH2F2 +2 OH = 4 F + 2H+ O2Cl2 + 2OH = Cl + ClO + H2O3Cl2 + 6OH = 5Cl + ClO3 +

58、 3H2O （heat ）Br2 / I2 + OH = Br + BrO3 + H2O 3 S + 6 NaOH(conc.) = 2 Na2S + Na2SO3 + 3 H2O(heat)4P + 3H2O+3OH = 3H2PO2 + PH32As +3 NaOH = Na3AsO3 + AsH3Si + 2 OH+ H2O = SiO32 + 2 H2 161Usages semiconductor materials：GaAs, InAs, AlGaAs, GaSb, AlSbGaCl3 + Sb(SiMe3) 3 GaSb 1624-4-2 M2O3 / hydrate、M2O5

59、/ hydrate 4-4-2-1 Properties 酸碱性 固体 水合物As4O6 白色s. 两性偏酸 微溶 H3AsO3 H2AsO3- HAsO32- As(OH) 3 As3+Sb4O6 白色s. 两性偏碱 难溶 Sb(OH) 3 Sb3+ SbO+ Sb(OH) 3 SbO33-Bi2O3 白色s. 弱碱 极难溶 Bi(OH) 3 Bi3+ BiO+163As2O5 白色s. H3AsO4 As2O5Sb2O5 酸性 HSb(OH) 6 Sb2O5Bi2O5 无纯品 HBiO3 固体 水合物164H3AsO4 / H3AsO3 = 0.56 VSb2O5 / SbO+ = 0.5

60、8 VBi2O5 / BiO+ = 1.6 VAsO43 + 2I + 2H+ = AsO33 + I2 + H2O（ pH 8)H3SbO4 + 2 HCl = H3SbO3 + Cl2 + H2O5NaBiO3 + 2Mn2+ + 14H+ = 2MnO4 + 5Bi3+ + 7H2O + 5Na+ （heat ）NaBiO3 + 6 H+ + 2 Cl(conc.) = Bi3+ + Cl2 + 3 H2O + Na+ （heat ）Bi (OH) 3 + Cl2 + 3 NaOH = NaBiO3 + 2 NaCl + 3 H2OCl2 /Cl= 1.36 V BiO3/Bi(OH)3