双语化学辞典Chem Lexicon
本科Undergraduate 酸碱平衡与 pH 计算 Acid–base equilibria & pH

两性物质溶液的 pHpH of an amphiprotic species

\[[\mathrm H^+] = \sqrt{\frac{K_{a1}(K_{a2}c + K_w)}{K_{a1} + c}} \approx \sqrt{K_{a1}K_{a2}},\qquad \mathrm{pH} \approx \tfrac12(\mathrm pK_{a1} + \mathrm pK_{a2})\]

含义Meaning

既能给出又能接受质子的物质(如 NaHCO₃、NaH₂PO₄、氨基酸两性离子),浓度不太稀时 pH 近似与浓度无关。

For species that can both donate and accept a proton (NaHCO₃, NaH₂PO₄, amino-acid zwitterions), pH is nearly concentration-independent when not too dilute.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(K_{a1}, K_{a2}\)两性物质两侧的两级解离常数dissociation constants flanking the amphiprotic species1

推导Derivation

  1. 以 HA⁻ 为参考的质子条件:\([\mathrm H^+] + [\mathrm H_2\mathrm A] = [\mathrm A^{2-}] + [\mathrm{OH^-}]\)。

    Proton condition referenced to HA⁻.

  2. 代入 \([\mathrm H_2\mathrm A] = [\mathrm H^+]c/K_{a1}\)、\([\mathrm A^{2-}] = K_{a2}c/[\mathrm H^+]\)([HA⁻] ≈ c),解出 [H⁺]。

    Substitute with [HA⁻] ≈ c and solve.

  3. 当 \(c \gg K_{a1}\) 且 \(K_{a2}c \gg K_w\) 时化简为几何平均。

    For c ≫ Ka1 and Ka2c ≫ Kw it reduces to the geometric mean.

适用条件与局限Assumptions & limitations

  • 稀溶液中必须用完整式。

    Use the full expression for dilute solutions.

例题Worked example

NaHCO₃:pH ≈ (6.35 + 10.33)/2 = 8.34;NaH₂PO₄:(2.15 + 7.20)/2 = 4.68。

NaHCO₃: pH ≈ 8.34; NaH₂PO₄: 4.68.