定义Definition
朗伯-比尔定律指出:当一束平行单色光通过均匀的吸光物质溶液时,吸光度 A 与吸光物质的浓度 c 和光程长度 b 成正比:A = εbc。它是分光光度法定量分析的理论基础。
The Beer–Lambert law states that when a parallel beam of monochromatic light passes through a homogeneous absorbing solution, the absorbance A is proportional to the concentration c and the path length b: A = εbc. It is the basis of quantitative spectrophotometry.
原理与公式Principle and formula
透光率 T = I/I₀,吸光度 A = −lg T = lg(I₀/I)。光每通过一薄层,强度按比例减弱,积分后得到指数衰减 I = I₀·10^(−εbc)。ε 为摩尔吸光系数(L·mol⁻¹·cm⁻¹),是物质在特定波长下的特征常数,ε 越大测定越灵敏:ε > 10⁴ 为强吸收(如共轭体系 π→π* 跃迁),ε < 10² 为弱吸收(如 n→π*、d-d 跃迁)。吸光度具有加和性:多组分体系总吸光度等于各组分吸光度之和。
Transmittance T = I/I₀ and absorbance A = −log T = log(I₀/I). Each thin layer removes a fixed fraction of the light, so integration gives exponential decay, I = I₀·10^(−εbc). The molar absorptivity ε, in L·mol⁻¹·cm⁻¹, is characteristic of the substance at that wavelength; the larger ε, the more sensitive the measurement: above 10⁴ is strong absorption (such as π→π* in conjugated systems) and below 10² weak (n→π*, d–d transitions). Absorbances are additive, so a mixture's total absorbance is the sum of its components'.
由来Origin
1729 年法国的布格尔发现光强随吸收层厚度呈指数衰减;1760 年德国的朗伯用数学形式表述了这一关系;1852 年德国的奥古斯特·比尔发现吸光度与溶液浓度成正比。三者结合即为现在的朗伯-比尔定律(也称布格尔-朗伯-比尔定律)。
In 1729 Bouguer in France found that light intensity decays exponentially with the thickness of an absorbing layer; Lambert in Germany put this in mathematical form in 1760; and in 1852 August Beer in Germany found absorbance proportional to concentration. Together these give the Beer–Lambert (or Beer–Lambert–Bouguer) law.
偏离与适用条件Deviations and conditions
定律只在以下条件下严格成立:单色光、稀溶液(通常 < 0.01 mol/L,浓溶液中分子相互作用改变 ε)、吸光物质不发生解离、缔合或化学反应、溶液均匀无散射。仪器方面的杂散光和多色光会使高浓度时标准曲线向下弯曲。实际测定时吸光度控制在 0.2–0.8 范围内相对误差最小。
The law holds strictly only for monochromatic light, dilute solutions (usually below 0.01 mol/L, since interactions change ε at higher concentration), absorbers that do not dissociate, associate or react, and homogeneous, non-scattering solutions. Stray light and polychromatic light make calibration curves bend downward at high concentration. Relative error is smallest with absorbances between about 0.2 and 0.8.
反应Reactions
b 通常为 1 cm 比色皿光程。
b is usually the 1 cm cell path.
由吸光度计算浓度
Concentration from absorbance
年表Timeline
- 1729
布格尔发现光吸收与厚度关系
Bouguer relates absorption to thickness
- 1760
朗伯数学表述
Lambert's mathematical statement
- 1852
比尔发现吸光度与浓度成正比
Beer finds absorbance proportional to concentration
相关公式Formulas
例题Worked example
KMnO₄ 在 525 nm ε = 2.4×10³ L/(mol·cm),1 cm 比色皿测得 A = 0.48:c = 0.48/2400 = 2.0×10⁻⁴ mol/L。
KMnO₄ at 525 nm (ε = 2400): A = 0.48 in 1 cm gives c = 2.0×10⁻⁴ M.