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
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.
加热颜色变深,冷却颜色变浅
Heating deepens the colour; cooling pales it
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
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.
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.
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.