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

酸碱滴定曲线Acid–base titration curves

\[[\mathrm H^+] - [\mathrm{OH^-}] = \frac{c_aV_a - c_bV_b}{V_a + V_b}\ (\text{强酸–强碱}),\qquad \mathrm{pH}_{V_b = V_e/2} = \mathrm pK_a\ (\text{弱酸})\]\[[\mathrm H^+] - [\mathrm{OH^-}] = \frac{c_aV_a - c_bV_b}{V_a + V_b}\ (\text{strong acid – strong base}),\qquad \mathrm{pH}_{V_b = V_e/2} = \mathrm pK_a\ (\text{weak acid})\]
弱酸能被准确滴定(误差 ≤ 0.2%)的判据criterion for accurate titration of a weak acid
\[K_ac \ge 10^{-8}\]

含义Meaning

滴定过程中 pH 随滴定剂体积的变化。计量点附近出现 pH 突跃,指示剂的变色范围必须落在突跃内。弱酸半中和点 pH = pKa。

pH versus titrant volume. A pH jump appears at equivalence, and the indicator’s range must fall inside it. For a weak acid, pH = pKa at half-neutralisation.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(c_a, V_a\)被滴酸的浓度与体积acid concentration and volumemol·L⁻¹, mL
\(c_b, V_b\)滴定剂(碱)浓度与已加体积titrant concentration and volume addedmol·L⁻¹, mL
\(V_e\)计量点体积equivalence volumemL

推导Derivation

  1. 强酸–强碱:电荷平衡 \([\mathrm H^+] + [\mathrm{Na^+}] = [\mathrm{Cl^-}] + [\mathrm{OH^-}]\),代入浓度并与 Kw 联立解出 [H⁺](本图即按此精确计算)。

    Strong–strong: charge balance with Kw gives [H⁺] exactly (as plotted).

  2. 弱酸:计量点前为 HA/A⁻ 缓冲(亨德森方程),计量点为 A⁻ 的水解(pH > 7),计量点后由过量 OH⁻ 决定。

    Weak acid: buffer region, then hydrolysis of A⁻ at equivalence (pH > 7), then excess OH⁻.

  3. 突跃大小随浓度增大而增大(强酸)或随 Ka 增大而增大(弱酸)。

    The jump grows with concentration and with Ka.

适用条件与局限Assumptions & limitations

  • 指示剂选择:强酸–强碱可用甲基橙、酚酞;弱酸–强碱用酚酞(变色 8.2–10);弱酸–弱碱无明显突跃,不宜直接滴定。

    Indicators: any for strong–strong; phenolphthalein for weak acid–strong base; weak–weak titrations lack a usable jump.