含义Meaning
配体逐个取代水分子的平衡常数。通常 \(K_1 > K_2 > \cdots\)(统计因素与静电、位阻),lg β 越大配合物越稳定。
Equilibrium constants for successive ligand binding; usually \(K_1 > K_2 > \cdots\) (statistics, electrostatics, sterics). Larger lg β means a more stable complex.
符号说明Symbols
| 符号Symbol | 含义 Meaning | 单位 Unit |
|---|---|---|
| \(K_i\) | 第 i 级稳定常数i-th stepwise constant | (mol·L⁻¹)⁻¹ |
| \(\beta_n\) | n 级累积稳定常数overall constant | (mol·L⁻¹)⁻ⁿ |
| \(\alpha\) | 分布分数fraction of metal in each form | 1 |
推导Derivation
每一步写出平衡常数,相乘时中间物种浓度抵消得 \(\beta_n\)。
Multiply stepwise constants; intermediate concentrations cancel.
金属总浓度 \(c_\mathrm{M} = [\mathrm{M}](1 + \sum\beta_j[\mathrm{L}]^j)\),除得分布分数。
Total metal \(c_\mathrm{M} = [\mathrm{M}](1 + \sum\beta_j[\mathrm{L}]^j)\) gives the fractions.
统计因素:若各位点等价,\(K_i/K_{i+1} = \frac{(N-i+1)(i+1)}{i(N-i)}\)(N 为最大配位数)。
Statistical factor for equivalent sites: \(K_i/K_{i+1} = (N-i+1)(i+1)/[i(N-i)]\).
适用条件与局限Assumptions & limitations
实测常数依赖离子强度和温度;用浓度表示的常数为“条件”常数。
Measured constants depend on ionic strength and temperature.
热力学稳定 ≠ 动力学惰性(如 [Co(NH₃)₆]³⁺ 在酸中热力学不稳定但交换极慢)。
Thermodynamic stability is not kinetic inertness.
例题Worked example
[Cu(NH₃)₄]²⁺:lg K₁…K₄ = 4.1, 3.5, 2.9, 2.1,lg β₄ = 12.6。
[Cu(NH₃)₄]²⁺: lg K₁–K₄ = 4.1, 3.5, 2.9, 2.1; lg β₄ = 12.6.