双语化学辞典Chem Lexicon
本科Undergraduate 配位化学与晶体场 Coordination chemistry & ligand fields

配合物逐级与累积稳定常数Stepwise and overall stability constants

\[K_i = \frac{[\mathrm{ML}_i]}{[\mathrm{ML}_{i-1}][\mathrm{L}]},\qquad \beta_n = \prod_{i=1}^n K_i = \frac{[\mathrm{ML}_n]}{[\mathrm{M}][\mathrm{L}]^n}\]
各配合物物种分布分数species distribution fractions
\[\alpha_{\mathrm{ML}_i} = \frac{\beta_i[\mathrm{L}]^i}{1 + \sum_{j=1}^n \beta_j[\mathrm{L}]^j}\]

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 form1

推导Derivation

  1. 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.

  2. 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.

  3. 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.