charpter4 配合物的稳定性(双语)

The formation of complex is that coordinated water molecules of metal ions are substituted by ligands,
取代反应是分步进行的，在溶液中有各级配离子存在。
substitute reaction is proceeding step by step, there are stepwise coordinated ions in solution.
In the discuss about balance constant: concentration used instead of activity
金属离子在水中都进行水合，
Metal ions are all hydrated in water,
配合物的生成反应是 水和金属离子的配位水分子被配体取代的反应，
Stability in aqueous
[Be(NH3)4]Cl2 ＜ [Ni(NH3)6]Cl2
在溶液中的稳定性不仅是只决定于__________和____________， _____________________也是一个重要因素。
In solution, stability is not only decided by the bond in strong or weak between central atom and ligand, but hydration of metal ion is also an important factor.
the numerical value of concentration and activity are equality.
In experiment, C常用溶液=0.01≈5M， fA ＜1，activity＜ concentration Cavailability(有效）↓。
平衡常数的讨论中常用浓度代替活度。
[Be(NH3)4]Cl2 ＞ [Ni(NH3)6]Cl2 In aqueous solution of NH3 , Be2+ doesn’t form Be2+-NH3 complex, but alkyl complex(烃基配合物). K([Ni(NH3)6]2+ formation) = 6.3×107（very large）
For example：
在含Zn2+的溶液中加入氨水，[ Zn(NH3)4]2+按4个步骤生成：
Enter ammonia into solution containing Zn2+, [ Zn(NH3)4]2+ formation is shows as following four step: [Zn(H2O)4]2+ + NH3 [ZnNH3(H2O)3]2+ + NH3 [Zn(NH3)2 (H2O)2]2++NH3 [Zn(NH3)3 (H2O)]2++ NH3 [ZnNH3(H2O)3]2+ + H2 O （ 1 ） （ 2）
Charpter 4
配离子的稳定性 Stability of coordinate ions

讨论和稳定性有关的热力学函数 discuss the thermodynamics function related with stability 中心原子对稳定性的影响 the effect of central atom to stability 配体性质对稳定性的影响 the effect of ligand character to stability 螯合配体和冠醚配体 Chelate ligand and crown ether ligand 配合物稳定性的差别的若干应用 the several applications of the complex stability different
用累积稳定常数来表示配合物的平衡： Equilibrium of complex is expressed by over-all stability constant: [Zn(H2O)4]2+ + NH3 [ZnNH3(H2O)3]2+ + H2O （1）
β1=[[ZnNH3(H2O)3]2+]/([ [Zn(H2O)4]2+][ NH3])=102.37 [ZnNH3(H2O)3]2+ + NH3 [Zn(NH3)2(H2O)2]2+ + H2O （2） β2=[[ Zn(NH3)2(H2O)2]2+]/([ [Zn (H2O)4]2+ [ NH3]2)=104.81 [Zn(NH3)3 (H2O)]2+ + H2O [Zn(NH3)4]2+ + H2O （3）
100
55.5
55.5 4
54
[H2O]
[Cu(NH3)x(H2O)6-x]2+ 的量%
5 3 50 1 2
0 10-6 10-5 10-4 10-3 10-2 10-1 [NH3] 10-0
In the solution:
一种金属离子的性质决定于在其周围的基团（配体）的性质。
The character of one kind metal ion is decided by the character of surrounding group (ligand).
K1=[[ZnNH3(H2O)3]2+]/([Zn(H2O)4]2+][NH3])=102.37 [Zn(NH3)2(H2O)2]2+ + H2O [Zn(NH3)3 (H2O)]2+ + H2O [Zn(NH3)4]2+ + H2O K2=[[Zn(NH3)2(H2O)2]2+]/([ZnNH3(H2O)3]2+[NH3])=102.44 （ 3） （ 4）
§4-1 稳定常数 stability constant 在一定温度下处于平衡状态的反应混合物中，
At certain temperature, in reaction mixture at equilibrium state, c d a C aD aA + bB + … K a b 常数 cC + dD + … a A aB
The relationship betweenβand K：
Kn = βn/βn-1 βn = K1•K2•K3•K4 ┅ Kn=
so， Kn↑andβn↑， 配离子越难离解，配合物也愈稳定， coordinate ion is more difficult to dissociate, and complex is more stable. 因此由K值可以算出溶液中各级配离子的平衡浓度。 Equilibrium concentration of stepwise coordinate ions can be calculated by the value of K in solution.
物种A的活度是它的浓度与活度系数fA的乘积。
activity of A is the product of its concentration and activity coefficient fA. In very thin solution(极稀溶液)，suppose(假设): fA = 1，
浓度和活度在数值上相等。




配合物在溶液中的稳定性 complex stability in solution
配离子在溶液中离解成金属离子和配体，当离解达平衡时，离解程度的大小。 Coordinate ions is dissociated to metal ions and ligands in solution, the dissociation extent is when dissociation reach balance. KAl(SO4)2•12H2O(铝钒) and CsRh((SO4)2•12H2O (铑矾) ， are completely dissociated to K+，Al3+，SO42and Cs+，Rh3+，SO42- in solution. Partly dehydrated 溶解dissolved (部分脱水) CsRh((SO4)2•12H2O CsRh(SO4)2•4H2O [Rh(H2O)4 (SO4)2][Rh(H2O)4 (SO4)2]Rh(H2O)43+ + 2SO42溶液中的稳定性为配合物特有的一个重要性质。 Stability in solution is an important own character of complex. 不同于配合物的其它稳定性，如氧化还原稳定性和热稳定性等。 Different from other stabilities of complexes, for example, redox stability and thermo-stability and so on.
Cu(II)+NH3
[Cu(NH3)x(H2O)6-x]2+
生成多种产物，每一物种的相对量决定于[Cu 2+]和[NH3] ： Form multi-products, the relatively quantity of every species is decided by [Cu 2+] and [NH3] ：
HF H F
K电离
[ H ][ F ] [ HF ]
Broad sense definition of complex(配合物广义的定义)：
一种由两个或多个能够独立存在的简单物种相结合而形成的物种。