双语化学辞典Chem Lexicon
本科Undergraduate 误差统计、校准与色谱 Statistics, calibration & chromatography

范第姆特方程van Deemter equation

\[H = A + \frac{B}{u} + C\,u,\qquad u_\text{opt} = \sqrt{\frac BC},\quad H_\text{min} = A + 2\sqrt{BC}\]

含义Meaning

塔板高度与流动相线速度的关系(1956):A 涡流扩散、B/u 纵向分子扩散、Cu 传质阻力。存在使 H 最小的最佳流速。

Plate height versus linear velocity (1956): A for eddy diffusion, B/u for longitudinal diffusion, Cu for mass-transfer resistance; an optimum velocity minimises H.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(u\)流动相线速度linear velocitycm·s⁻¹
\(A\)涡流扩散项(∝ 填料粒径 d_p)eddy diffusion (∝ particle size)cm
\(B\)纵向扩散项(∝ 扩散系数 D_M)longitudinal diffusion (∝ D_M)cm²·s⁻¹
\(C\)传质阻力项(∝ d_p²/D_M)mass transfer (∝ d_p²/D_M)s

推导Derivation

  1. 峰展宽的各独立来源的方差相加:\(\sigma^2 = \sigma_A^2 + \sigma_B^2 + \sigma_C^2\),\(H = \sigma^2/L\)。

    Independent broadening variances add, with \(H = \sigma^2/L\).

  2. 填充颗粒造成多条流路长度不同 → 与流速无关的 A 项。

    Different flow paths through packing → velocity-independent A.

  3. 沿柱方向的分子扩散在柱中停留时间 ∝ 1/u → B/u。

    Axial diffusion during residence time ∝ 1/u → B/u.

  4. 两相间传质有限速度使溶质分布滞后,∝ u → Cu。对 H(u) 求极小得 \(u_\text{opt}\)。

    Finite mass-transfer rates → Cu; minimise H(u) for the optimum.

适用条件与局限Assumptions & limitations

  • 经验模型;Knox、Giddings 方程更精细。开管毛细柱 A = 0(戈雷方程)。

    Empirical; Knox and Giddings refinements exist; open tubes have A = 0 (Golay).