双语化学辞典Chem Lexicon
本科Undergraduate 溶液与依数性 Solutions & colligative properties

渗透压(范特霍夫公式)Osmotic pressure (van 't Hoff equation)

\[\Pi = i\,c_\mathrm{B}RT\]
严格形式(不可压缩溶剂)exact form for an incompressible solvent
\[\Pi V_{m,\mathrm{A}} = -RT\ln x_\mathrm{A}\]
高分子溶液的维里展开virial form for polymer solutions
\[\frac{\Pi}{c} = RT\left(\frac{1}{M_n} + A_2 c + \cdots\right)\]

含义Meaning

阻止溶剂通过半透膜进入溶液所需施加的额外压强。形式与理想气体方程相同(1887)。

The extra pressure needed to stop solvent flowing through a semipermeable membrane into the solution — formally like the ideal-gas law (1887).

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(\Pi\)渗透压osmotic pressurePa
\(c_\mathrm{B}\)溶质物质的量浓度molar concentration of solutemol·m⁻³
\(A_2\)第二维里系数second virial coefficientmol·m³·kg⁻²
\(M_n\)数均摩尔质量number-average molar masskg·mol⁻¹

推导Derivation

  1. 平衡时膜两侧溶剂化学势相等:\(\mu_\mathrm{A}^*(p) = \mu_\mathrm{A}(x_\mathrm{A}, p + \Pi)\)。

    At equilibrium the solvent chemical potential is equal on both sides: \(\mu_\mathrm{A}^*(p) = \mu_\mathrm{A}(x_\mathrm{A}, p + \Pi)\).

  2. 右边 \(= \mu_\mathrm{A}^*(p) + RT\ln x_\mathrm{A} + \int_p^{p+\Pi} V_{m,\mathrm{A}}\,dp\),得 \(\Pi V_{m,\mathrm{A}} = -RT\ln x_\mathrm{A}\)。

    The right side equals \(\mu_\mathrm{A}^*(p) + RT\ln x_\mathrm{A} + \int V_{m,\mathrm{A}}\,dp\), giving \(\Pi V_{m,\mathrm{A}} = -RT\ln x_\mathrm{A}\).

  3. 稀溶液 \(-\ln x_\mathrm{A} \approx x_\mathrm{B} \approx n_\mathrm{B}/n_\mathrm{A}\),且 \(n_\mathrm{A}V_{m,\mathrm{A}} \approx V\),故 \(\Pi = n_\mathrm{B}RT/V = cRT\)。

    Dilute: \(-\ln x_\mathrm{A} \approx n_\mathrm{B}/n_\mathrm{A}\) and \(n_\mathrm{A}V_{m,\mathrm{A}} \approx V\), so \(\Pi = cRT\).

适用条件与局限Assumptions & limitations

  • 稀溶液、理想半透膜(只透过溶剂)。

    Dilute solution and an ideal semipermeable membrane.

  • 高分子溶液偏差大,需用维里形式外推 \(c \to 0\) 求 \(M_n\)。

    Polymer solutions need the virial form extrapolated to \(c \to 0\) to obtain \(M_n\).

例题Worked example

人体血浆约 0.30 mol/L 溶质粒子,37 °C 时 Π = 0.30×1000×8.314×310 ≈ 7.7×10⁵ Pa(7.6 atm);生理盐水 0.9% NaCl 与之等渗。

Blood plasma (~0.30 mol/L particles) at 37 °C: Π ≈ 7.7×10⁵ Pa (7.6 atm); 0.9 % saline is isotonic.