双语化学辞典Chem Lexicon
定律 · 物理化学 · 化学平衡 Physical chemistry · Chemical equilibrium

勒夏特列原理Le Chatelier's principle

拼音Pinyin lè xià tè liè yuán lǐ 别名Also 平衡移动原理;the equilibrium law;Chatelier&# x27;s principle

定义Definition

勒夏特列原理指出:处于平衡的体系,若改变影响平衡的一个条件(浓度、压强或温度),平衡将向减弱这种改变的方向移动。它是判断平衡移动方向的定性规则。

Le Chatelier's principle states that when a condition affecting a system at equilibrium (concentration, pressure or temperature) is changed, the equilibrium shifts in the direction that partly counteracts the change. It is a qualitative rule for predicting which way an equilibrium moves.

原理Principle

增大反应物浓度,平衡向生成物方向移动;增大压强,平衡向气体分子数减少的方向移动;升高温度,平衡向吸热方向移动。浓度和压强的改变只改变反应商 Q,平衡常数 K 不变;只有温度会改变 K 本身。催化剂同等加快正逆反应,不使平衡移动。

Adding reactant shifts the equilibrium toward products; raising the pressure shifts it toward fewer moles of gas; raising the temperature shifts it in the endothermic direction. Changes in concentration and pressure alter only the reaction quotient Q, not the equilibrium constant K; only temperature changes K itself. A catalyst speeds forward and reverse reactions equally and does not shift the equilibrium.

由来Origin

法国化学家亨利·勒夏特列在 1884 年提出这一规律,并于 1888 年给出更一般的表述。荷兰化学家范特霍夫在 1884 年也独立给出了温度对平衡影响的规律,德国物理学家布劳恩于 1887 年提出类似的物理表述,因此又称勒夏特列-布劳恩原理。

French chemist Henry Le Chatelier stated the rule in 1884 and gave a more general form in 1888. Van 't Hoff independently described the effect of temperature on equilibrium in 1884, and the German physicist Braun proposed a similar physical statement in 1887, which is why it is also called the Le Chatelier–Braun principle.

热力学基础与局限Thermodynamic basis and limits

原理的严格依据是 ΔG° = −RT ln K 和范特霍夫方程 d ln K/dT = ΔH°/RT²。它是定性规则,存在反例:恒温恒压下向 N₂ + 3H₂ ⇌ 2NH₃ 体系加入 N₂,在某些组成下平衡反而向生成 N₂ 的方向移动;恒容加入惰性气体则平衡不移动。定量判断应比较 Q 与 K。

Its rigorous basis is ΔG° = −RT ln K together with the van 't Hoff equation d ln K/dT = ΔH°/RT². It is qualitative and has exceptions: adding N₂ at constant temperature and pressure to N₂ + 3H₂ ⇌ 2NH₃ can, at some compositions, shift the equilibrium toward forming more N₂, and adding an inert gas at constant volume does not shift it at all. For quantitative work compare Q with K.

应用Applications

哈伯法合成氨采用高压、及时分离氨来提高转化率,同时在约 450 °C 下兼顾速率与平衡。接触法制硫酸、酯化反应中用过量醇或除水,都是利用该原理提高产率。生理上,血液中 CO₂、H₂CO₃ 与 HCO₃⁻ 的平衡调节也可用它解释。

The Haber process uses high pressure and removes ammonia as it forms to raise conversion, while running near 450 °C to balance rate against equilibrium. The contact process and esterifications driven by excess alcohol or water removal use the same principle to raise yield. In physiology it explains how the CO₂ / H₂CO₃ / HCO₃⁻ equilibrium in blood responds to change.

反应Reactions

N2(g) + 3 H2(g) ⇌ 2 NH3(g) ΔH° = −92 kJ/mol

加压、降温、移走 NH₃ 都使平衡右移。

Raising pressure, lowering temperature and removing NH₃ all shift the equilibrium to the right.

2 NO2(g, 红棕色) ⇌ N2O4(g, 无色) ΔH° < 02 NO2(g, ) ⇌ N2O4(g, colourless) ΔH° < 0

加热颜色变深,冷却颜色变浅

Heating deepens the colour; cooling pales it

Fe3+ + SCN− ⇌ [Fe(SCN)]2+血红色Fe3+ + SCN− ⇌ [Fe(SCN)]2+

加入 Fe³⁺ 或 SCN⁻ 溶液颜色加深

Adding Fe³⁺ or SCN⁻ deepens the red colour

年表Timeline

  • 1884

    勒夏特列首次提出平衡移动规律;范特霍夫发表温度对平衡影响的研究

    Le Chatelier first states the rule; van 't Hoff publishes on temperature and equilibrium

  • 1887

    布劳恩提出类似的物理表述

    Braun gives a similar physical statement

  • 1888

    勒夏特列发表更一般的表述

    Le Chatelier publishes a more general statement

  • 1913

    哈伯-博施法实现工业合成氨,成为该原理的经典应用

    The Haber–Bosch process enters industry, the textbook application

相关公式Formulas

范特霍夫方程 van 't Hoff equation→
\[\frac{d\ln K}{dT} = \frac{\Delta_rH^\circ}{RT^2},\qquad \ln\frac{K_2}{K_1} = -\frac{\Delta_rH^\circ}{R}\left(\frac{1}{T_2} - \frac{1}{T_1}\right)\]
例题Worked example

N₂ + 3H₂ ⇌ 2NH₃(ΔH° = −92 kJ/mol):K(298 K) ≈ 6×10⁵,K(700 K) ≈ 10⁻⁴ ——高温不利于平衡产率,所以哈伯法需权衡速率与平衡。

Ammonia synthesis: K falls from ~6×10⁵ at 298 K to ~10⁻⁴ at 700 K — the Haber trade-off between rate and yield.

同离子效应 Common-ion effect→
\[\mathrm{AgCl\ 在\ } c\ \mathrm{mol/L\ Cl^-\ 中}:\quad s = \frac{K_{sp}}{c + s} \approx \frac{K_{sp}}{c}\]\[\mathrm{AgCl\ \text{ in }\ } c\ \mathrm{mol/L\ Cl^-\ \text{ in }}:\quad s = \frac{K_{sp}}{c + s} \approx \frac{K_{sp}}{c}\]
例题Worked example

AgCl 在 0.10 mol/L NaCl 中:s ≈ 1.8×10⁻⁹ mol/L,比纯水中小 7000 倍。

AgCl in 0.10 M NaCl: s ≈ 1.8×10⁻⁹ M, 7000× lower than in water.

勒夏特列原理的定量形式 Le Chatelier's principle, quantitatively→
\[\left(\frac{\partial\ln K_x}{\partial p}\right)_T = -\frac{\Delta n_g}{p},\qquad \left(\frac{\partial\ln K}{\partial T}\right)_p = \frac{\Delta_rH^\circ}{RT^2}\]
例题Worked example

N₂O₄ ⇌ 2NO₂(298 K,Kp = 0.148):1 bar 时解离度 18.9%,10 bar 时 6.1%。

N₂O₄ ⇌ 2NO₂: dissociation 18.9 % at 1 bar, 6.1 % at 10 bar.