Back to chapter

15.9:

酸の混合物

JoVE Core
Kimya
Bu içeriği görüntülemek için JoVE aboneliği gereklidir.  Oturum açın veya ücretsiz deneme sürümünü başlatın.
JoVE Core Kimya
Mixtures of Acids

Diller

Paylaş

In a mixture of a strong acid and a weak acid, the strong acid dissociates completely and significantly increases the concentration of hydronium ions, whereas the weak acid only partially dissociates. Similarly, in a mixture of two weak acids, the acid that is relatively stronger produces more hydronium ions than the weaker acid. In both cases, the dissociation of the weaker acid is suppressed when it is in the presence of a stronger acid. Le Châtelier’s principle explains that the formation of hydronium ions by the stronger acid shifts the equilibrium towards the reactants, thereby reducing the dissociation of the weak acid. Thus, the pH of a mixture of acids is mainly determined by the concentration of the stronger acid. For example, in a mixture that contains 0.15 molar hydrochloric acid and 0.30 molar hydrocyanic acid, hydrochloric acid–a strong acid–produces a hydronium ion concentration of 0.15 molar. In contrast, hydrocyanic acid–a weak acid–only partially dissociates. The concentration of hydronium ions produced by hydrocyanic acid can be calculated from its acid dissociation constant, Ka, and an ICE table. The initial concentration of hydronium ions is equal to the initial concentration of hydrochloric acid, 0.15 molar, and the initial concentration of cyanide ions is zero. The change in concentration of hydronium ions and cyanide ions is denoted by x. As x is a relatively small number, 0.30 minus x can be approximated to 0.30, and 0.15 plus x can be approximated to 0.15 using the 5% rule. The Ka for hydrocyanic acid is 4.9 × 10−10, and it is equal to the concentration of hydronium ions times the concentration of cyanide ions divided by the concentration of hydrocyanic acid. Substituting the values from the ICE table into the Ka expression gives the concentration of hydronium ions produced by hydrocyanic acid, which is negligible compared to the concentration of hydronium ions produced by hydrochloric acid. The pH can be calculated by taking the negative log of the concentration of hydronium ions: 0.15 molar. Therefore, the pH of the mixture is solely determined by the concentration of hydrochloric acid, the strong acid. Similarly, the pH of a mixture of two weak acids present in equal amounts will be primarily determined by the concentration of the relatively stronger acid. For example, in a mixture of hydrofluoric acid and hydrocyanic acid, hydrofluoric acid will be the major determinant of the mixture’s pH, as it has a Ka of 3.5 × 10−4, which is almost a million times higher than the Ka of hydrocyanic acid. 

15.9:

酸の混合物

酸を含む溶液のpHは、その酸の解離定数と初期濃度を用いて決定することができます。ある溶液に2種類の酸が含まれている場合は、酸の相対的な強さと解離定数に応じて、いくつかの方法でpHを決定することができます。

強酸と弱酸の混合物

強酸と弱酸の混合溶液では、強酸は完全に解離し、溶液中に存在するほとんどすべてのヒドロニウムイオンの供給源となります。一方、弱酸は部分的に解離し、ごくわずかな濃度のヒドロニウムイオンしか生成しません。強酸が生成する高濃度のヒドロニウムイオンは、弱酸の解離をさらに低下させます。これは、ル・シャトリエの原理により、平衡状態にある化学系が乱されると、その乱れを最小にする方向に系が移動するために起こる現象です。その結果、弱酸の解離量が減少します。このため、強酸と弱酸の混合物のpHは、強酸の濃度のみから算出することができます。例えば、強酸である塩酸と弱酸であるギ酸を同じ濃度で混合した場合のpHは、塩酸の濃度のみから求めることができます。混合物中のHClの濃度が0.0020 Mであれば、そのpHは次のように計算できます。

Eq1

ここでは、HCHO2や水の自己イオン化によって生成されるヒドロニウムイオンの濃度は無視できます。

解離定数の異なる2つの弱酸の混合物

2つの弱酸の混合物において、強酸の解離定数が弱酸よりも著しく大きい場合、混合物のpHは強酸によって決定されます。例えば、同濃度の亜硝酸(HNO2)と次亜塩素酸(HClO)の混合物では、HNO2が主にpHを決定します。亜硝酸のKa(4.6 × 10−4)は次亜塩素酸のKa (2.9 × 10−8)の約1万倍であり、ル・シャトリエの原理によれば、HClOはHNO2の存在下で解離量が減少します。