1、 A strong electrolyte is a substance that completely (or almost completely) dissociates into ions in solution.All strong acids, strong bases and all soluble salts are strong electrolytes. Strong Electrolytic Solution A weak electrolyte is a substance that only partially ionizes into ions in solution
2、. Weak acids, weak bases and a handful of salt are weak electrolytes. (degree of ionization )2022-4-293 Number of ionized molecules (已解离分子数已解离分子数) = - - 100% 100% total number of solute molecules (原有分子总数原有分子总数) Definition: concentration of ionized electrolyte = - -100%100% initial concentration of e
3、lectrolyte (degree of ionization ) The degree of ionization can be calculated from the observed colligative properties. 电解质解离度的大小,除决定于电解质的本性外,电解质解离度的大小,除决定于电解质的本性外,还与溶剂、温度、溶液的浓度等条件有关。还与溶剂、温度、溶液的浓度等条件有关。 在相同温度、浓度下,在相同温度、浓度下,不同电解质的解离度大小不同电解质的解离度大小反映电解质的相对强弱,反映电解质的相对强弱,电解质愈弱,其解离度就越电解质愈弱,其解离度就越小,反之亦然。小,
4、反之亦然。通常通常0.1 molkg0.1 molkg-1-1溶液中,溶液中,30% 30% strong electrolyte5% 5% weak electrolyte=5%-30%=5%-30% middle strong electrolyte二、二、DEbye-Huckel 的离子互吸理论的离子互吸理论(Ion Interaction Theory) 由于离子氛存在,致使离由于离子氛存在,致使离子间相互作用而互相牵制,表子间相互作用而互相牵制,表观解离度(观解离度( degree of apparent dissociation )不是)不是100%100%。离子对模型离子对模型
5、ion pair 强电解质与弱电解质的解离度的意义完全不同:强电解质与弱电解质的解离度的意义完全不同: 弱电解质的解离度表示解离了的百分率;而强电弱电解质的解离度表示解离了的百分率;而强电解质的解离度只是反映离子间相互牵制作用的强弱程解质的解离度只是反映离子间相互牵制作用的强弱程度,其解离度被称为表观解离度。度,其解离度被称为表观解离度。 表观的解离度表观的解离度 实际解离度(实际解离度(1)对于强电解质溶液:对于强电解质溶液:= 原有浓度原有浓度 表观的解离度表观的解离度表观解离的浓度表观解离的浓度BbBB表观的解离度表观的解离度 =表观解离的浓度表观解离的浓度原有浓度原有浓度表观的解离度表
6、观的解离度 =表观解离的分子数表观解离的分子数原有分子总数原有分子总数三、离子的活度和离子强度三、离子的活度和离子强度B = BbB/b活活 度:度:可以看作是能完全离解成独立自由的离子的那部分可以看作是能完全离解成独立自由的离子的那部分溶质的浓度。溶质的浓度。该定义仅针对于强电解质溶液。该定义仅针对于强电解质溶液。离子强度离子强度I=def1/2ibiZi2表征强电解质溶液中离子间作用力的物理量。表征强电解质溶液中离子间作用力的物理量。 Theory of Acid-base Any substance that can donate a proton, H+ ion to a base,
7、e.g. HCl, NH4+i.e: hydrogen-ion donor or proton donor Any substance that can accept a proton, H+ ion from an acid, e.g. OH-, NH3i.e: hydrogen-ion acceptor or proton acceptor (一)定义(一)定义2022-4-2912baseacidConjugate acid-base pair(共轭酸碱对共轭酸碱对)lH2CO3H+ + HCO3-lHCO3-H+ + CO32-lNH4+H+ + NH3lH3O+H+ + H2OlH2
8、OH+ + OH-Amphoteric substance(两性物质两性物质)2022-4-2913RAcid or base may be a molecule, or ion(酸碱可酸碱可以是分子、也可以是离子以是分子、也可以是离子).RSome molecules or ions are capable of donating a proton, and also accepting a proton, which named amphoteric substance(两性物质两性物质).RThere are no concepts of salt(无盐的概念无盐的概念) in acid
9、-base proton theory.R酸越强,其共轭碱酸越强,其共轭碱(conjugate base)越弱;碱越越弱;碱越强,其共轭酸强,其共轭酸(conjugate acid)越弱越弱Essence of Acid and Base Reaction2022-4-2917三、三、Proton self-transfer equilibrium of water 水的质子自递平衡水的质子自递平衡H2O(l) + H2O(l)H3O+ (aq) + OH-(aq) Water is capable of acting as a proton donor and proton acceptor
10、 toward itself. The process by which this occurs is called proton self-transfer reaction of water.Kw = H3O+OH-2022-4-2918The pH Scale of solution(水溶液的pH) pH = -log H3O+ pOH = -logOH- At 25, H3O+OH- = Kw= 110-14 So, pH + pOH =pKw= 14.00 In neutral solutions, pH7pOH, In acid solutions, pH 7 pOH In bas
11、ic solutions pH 7 pOH一、弱酸、弱碱的解离平衡及其平衡常数一、弱酸、弱碱的解离平衡及其平衡常数aaKDissociation Equilibrium of Weak electrolyte Dissociation Equilibrium and equilibrium constant 类似地类似地,碱碱A A- -在水溶液中有下列平衡在水溶液中有下列平衡A-(aq) + H2O(l) HA (aq) + OH-(aq) Kb为碱解离平衡常数为碱解离平衡常数Base-Ionization Constant or base constant。Kb的大小表示碱接受质子能力的的
12、大小表示碱接受质子能力的大小,大小,Kb值愈大,碱性愈强。值愈大,碱性愈强。 pKb是碱解离常数的负对数。是碱解离常数的负对数。bHAOH A K for polyprotic acid(多元酸多元酸) or polyprotic base (多元多元碱碱),there are Ka, Ka 2, Ka3, (or Kb, Kb2, Kb3, ). 类似地类似地,碱碱A A- -在水溶液中有下列平衡在水溶液中有下列平衡A-(aq) + H2O(l) HA (aq) + OH-(aq) Kb为碱解离平衡常数为碱解离平衡常数Base-Ionization Constant or base cons
13、tant。Kb的大小表示碱接受质子能力的的大小表示碱接受质子能力的大小,大小,Kb值愈大,碱性愈强。值愈大,碱性愈强。 pKb是碱解离常数的负对数。是碱解离常数的负对数。bHAOH A K for polyprotic acid(多元酸多元酸) or polyprotic base (多元多元碱碱),there are Ka, Ka 2, Ka3, (or Kb, Kb2, Kb3, ). 3. Only a change in temperature will change the value of the equilibrium constant . 1. Ka stands for “a
14、cid constant” Kb stands for “base constant” 2. Do not confuse a weak acid(弱酸弱酸) with a dilute acid (稀酸稀酸). A weak acid has a small Ka , and a dilute acid has a low concentration.Emphasis:The relationship between conjugate acid-base pair三、酸碱平衡的移动三、酸碱平衡的移动Shifting an Acid-Base EquilibriumFor a weak ac
15、id:HA + H2OH3O+ + AEq: c c c cIf 102且远大于水的且远大于水的离子积,所以,溶液中的离子积,所以,溶液中的H3O+ 与第一步解离产生的与第一步解离产生的H3O+近似相等。近似相等。2、多元弱酸第二步及以后各步的质子传递平衡所得的、多元弱酸第二步及以后各步的质子传递平衡所得的相应共轭碱的浓度都很低。相应共轭碱的浓度都很低。由以上两条件带入可求得:由以上两条件带入可求得: 第二步解离平衡所产生的共轭碱的浓度近似等于第二步解离平衡所产生的共轭碱的浓度近似等于Ka2。3aa1HO c K 三、多元弱酸弱碱三、多元弱酸弱碱pH值的计算值的计算 polyprotic ac
16、id and polyprotic base例例 已知已知H2CO3的的Ka1=4.510-7, Ka2=4.710-11, 计算计算0.020molL-1 H2CO3溶液中溶液中H3O+、 H2CO3 、HCO3-、CO32-及及 OH- 。 Ka1 Ka2, 求求H3O+只需考虑一级解离只需考虑一级解离. 又又 Ca Ka1 20 Kw,Ca/ Ka1500 ,+-7-1-5-13a1H O =c = 4.5 100.020 mol L =9.5 10 mol LKHCO3-=H3O+=9.510-5 molL-1H2CO3=0.02molL-1 2022-4-2943H2CO3(aq)+
17、H2O(l) H3O+(aq) + HCO3-(aq) 解解HCO3-(aq)+H2O(l) H3O+(aq) + CO32-(aq) Ka1=4.510-7Ka2=4.710-11K 323a23H O CO,HCO K 3211-13a23HCO CO4.710mol LH O K 101w3OH 1.010mol LH O 多元弱酸第二步解离平衡所得的共轭碱的浓度多元弱酸第二步解离平衡所得的共轭碱的浓度近似等于近似等于K Ka2a2,与酸的浓度关系不大。,与酸的浓度关系不大。 多元弱酸第二步及以后各步质子传递平衡所得的多元弱酸第二步及以后各步质子传递平衡所得的共轭碱的浓度都很低。共轭碱的
18、浓度都很低。2022-4-2944polyprotic base(Kb 1 / Kb2 10 2 , cb Kb1 20 Kw, c b/ Kb1500)c K bb1OH 2022-4-2945两性物质作为酸时的解离平衡常数。两性物质作为酸时的解离平衡常数。 两性物质作为碱时,其共轭酸的解离平衡常数。两性物质作为碱时,其共轭酸的解离平衡常数。The pH scale of amphoteric substancesCACDDAAD2022-4-2950 2. Does a precipitate form if 0.100 L of 3.0 10 -3 molL-1 Pb(NO3)2 is
19、added to 0.400 L of 5.0 10 -3 molL-1 Na2SO4? possible precipitate form is PbSO4 ( Ksp = 1.6 10-8 ) Solution: 1043. 000.2000.5000.2010. 000.5010. 0LmolHA1029. 000.2000.5000.2010. 0LmolA1558. 43106 . 210LmolOH531075. 1HAAOHKa105. 01005010. 0LmolCA105141071. 51075. 1100 . 1awbKKK73. 827. 51034. 51071.
20、505. 0500,20610pHpOHCKOHKCKCKbbwb2022-4-2953 c(Pb2+)= 6.0 10-4 molL-1 c(SO42-) =4.0 10-3 molL-1 Ip = c(Pb2+) c(SO42-) = (6.0 10 - 4)(4.0 10-3) = 2.4 10 - 6 Because Ip Ksp, PbSO4 will precipitate! IpDoes a precipitate form if 0.100 L of 3.0 10 -3 molL-1 Pb(NO3)2 is added to 0.400 L of 5.0 10 -3 molL-1 Na2SO4? possible precipitate form is PbSO4 ( Ksp = 1.6 10-8 ) Solution: