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關(guān)于雙水解反應(yīng)

2022-02-01 08:47 作者:匆匆-cc  | 我要投稿

????????雙水解反應(yīng)(The double hydrolysis reaction)是指弱酸陰離子和弱堿陽離子相互促進(jìn)水解的反應(yīng)。

????????事實上,并不是所有的雙水解反應(yīng)進(jìn)行得都很徹底。

????????比如說,醋酸銨%5Cce%7BCH3COONH4%7D的水解。

%5Cce%7BCH3COONH4%7D%2B%5Cce%7BH2O%7D%5Cce%7B%3C%3D%3E%7D%5Cce%7BCH3COOH%7D%2B%5Cce%7BNH3%5Ccdot%20H2O%7D

????????根據(jù)K%20的定義,我們得到

%5Cbegin%7Balign%7D%0AK%20%26%3D%20%5Cfrac%7Bc_%7B(%5Cce%7BCH3COOH%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BNH3%5Ccdot%20H2O%7D)%7D%7D%7Bc_%7B(%5Cce%7BCH3COO-%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BNH4%2B%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BCH3COOH%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc_%7B(%5Cce%7BNH3%5Ccdot%20H2O%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bgreen%7D%7Bc_%7B(%5Cce%7BH%2B%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BCH3COO-%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BH%2B%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc_%7B(%5Cce%7BNH4%2B%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bgreen%7D%7BK_w%7D%7D%7B%5Ccolor%7Bred%7D%7BK_%7Ba%5Cce%7B(CH3COOH)%7D%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7BK_%7Bb%5Cce%7B(NH3%5Ccdot%20H2O)%7D%7D%7D%7D%0A%5Cend%7Balign%7D

????????查表

%5Cbegin%7Barray%7D%7B%7Cc%7Cc%7C%7D%0A%5Chline%0A%5Ctextbf%7B%E5%BC%B1%E7%94%B5%E8%A7%A3%E8%B4%A8%7D%20%26%20%5Ctextbf%7B%E7%94%B5%E7%A6%BB%E5%B9%B3%E8%A1%A1%E5%B8%B8%E6%95%B0%7D%5C%5C%0A%5Chline%0A%5Cce%7BCH3COOH%7D%20%26%201.76%5Ctimes10%5E%7B-5%7D%5C%5C%0A%5Chline%0A%5Cce%7BNH3%5Ccdot%20H2O%7D%20%26%201.78%5Ctimes%2010%5E%7B-5%7D%5C%5C%0A%5Chline%0A%5Cend%7Barray%7D

????????易得

%5Cbegin%7Balign%7D%0AK%26%3D%5Cfrac%7BK_w%7D%7BK_%7Ba%5Cce%7B(CH3COOH)%7D%7D%5Ccdot%20K_%7Bb%5Cce%7B(NH3%5Ccdot%20H2O)%7D%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B1%5Ctimes%2010%5E%7B-14%7D%7D%7B1.76%5Ctimes%2010%5E%7B-5%7D%5Ctimes1.78%5Ctimes%2010%5E%7B-5%7D%7D%0A%5C%5C%26%5Capprox%203.19%5Ctimes%2010%5E%7B-5%7D%0A%5Cend%7Balign%7D

????????水解程度很小。

????????來看%5Cce%7BAlO2-%7D%5Cce%7BHCO3-%7D的情況。

%5Cce%7BAlO2-%7D%2B%5Cce%7BHCO3-%7D%2B%5Cce%7BH2O%7D%5Cce%7B%3C%3D%3E%7D%5Cce%7BAl(OH)3%7D%2B%5Cce%7BCO3%5E2-%7D

????? ? 易得

%5Cbegin%7Balign%7D%0AK%20%26%3D%20%5Cfrac%7B%5C%23%20c_%7B(%5Cce%7BAl(OH)3%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BCO3%5E2-%7D)%7D%7D%7Bc_%7B(%5Cce%7BAlO2-%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BHCO3-%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BAl(OH)3%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc_%7B(%5Cce%7BCO3%5E2-%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BH%2B%7D)%7D%7D%7D%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BAlO2-%7D)%7D%5Ccdot%20c_%7B(%5Cce%7BH%2B%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc_%7B(%5Cce%7BHCO3-%7D)%7D%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bblue%7D%7BK_%7Ba(%5Cce%7BHCO3-%7D)%7D%7D%7D%7B%5Ccolor%7Bred%7D%7BK_%7Ba(%5Cce%7BAl(OH)3%7D)%7D%7D%7D%0A%5Cend%7Balign%7D

????## 這里本來不應(yīng)該把%5Ccolor%7Bgray%7D%7B%5Cce%7BAl(OH)3%7D%7D寫進(jìn)表達(dá)式的,很遺憾的是筆者沒有找到相應(yīng)的%5Ccolor%7Bgray%7D%7BK_%7Bsp_a%7D%7D值,只好湊了一個酸式電離常數(shù)進(jìn)去。

????????查表

%5Cbegin%7Barray%7D%7B%7Cc%7Cc%7C%7D%0A%5Chline%0A%5Ctextbf%7B%E5%BC%B1%E7%94%B5%E8%A7%A3%E8%B4%A8%7D%20%26%20%5Ctextbf%7B%E5%B9%B3%E8%A1%A1%E5%B8%B8%E6%95%B0%7D%5C%5C%0A%5Chline%0A%5Cce%7BHCO3-%7D%20%26%205.6%5Ctimes10%5E%7B-11%7D%5C%5C%0A%5Chline%0A%5Cce%7BAl(OH)3%7D%20%26%206.3%5Ctimes%2010%5E%7B-13%7D%5C%5C%0A%5Chline%0A%5Cend%7Barray%7D

????????容易計算出

%5Cbegin%7Balign%7D%0AK%20%26%3D%5Cfrac%7BK_%7Ba(%5Cce%7BHCO3-%7D)%7D%7D%7BK_%7Ba(%5Cce%7BAl(OH)3%7D)%7D%7D%0A%5C%5C%26%3D%20%5Cfrac%7B5.6%5Ctimes10%5E%7B-11%7D%7D%7B6.3%5Ctimes%2010%5E%7B-13%7D%7D%0A%5C%5C%26%5Capprox%2088.9%0A%5Cend%7Balign%7D

??????? 常數(shù)不大,說明反應(yīng)可以發(fā)生,可認(rèn)為不大量共存。

? ? ? ? 再來看%5Cce%7BAl%5E3%2B%7D%5Cce%7BHCO3-%7D的情況。

%5Cce%7BAl%5E3%2B%7D%2B3%5Cce%7BHCO3-%7D%5Cce%7B%3C%3D%3E%7D%5Cce%7BAl(OH)3%7D%2B3%5Cce%7BCO2%20%5E%7D

????????易得

%5Cbegin%7Balign%7D%0AK%20%26%3D%20%5Cfrac%7Bc%5E3_%7B(%5Cce%7BH2CO3%7D)%7D%7D%7Bc_%7B(%5Cce%7BAl%5E3%2B%7D)%7D%5Ccdot%20c%5E3_%7B(%5Cce%7BHCO3-%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bblue%7D%7Bc%5E3_%7B(%5Cce%7BH2CO3%7D)%7D%5Ccdot%20%5Ccolor%7Bgreen%7D%7Bc%5E3_%7B(%5Cce%7BH%2B%7D)%7D%5Ccdot%20%7Bc%5E3_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%7D%7D%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BAl%5E3%2B%7D)%7D%5Ccdot%7Bc%5E3_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%20%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc%5E3_%7B(%5Cce%7BH%2B%7D)%7D%5Ccdot%20c%5E3_%7B(%5Cce%7BHCO3-%7D)%7D%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bgreen%7D%7BK%5E3_w%7D%7D%7B%5Ccolor%7Bred%7D%7BK_%7Bsp_b(%5Cce%7BAl(OH)3%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7BK%5E3_%7Ba(%5Cce%7BH2CO3%7D)%7D%7D%7D%0A%5Cend%7Balign%7D

? ? ? ? 查表

%5Cbegin%7Barray%7D%7B%7Cc%7Cc%7C%7D%0A%5Chline%0A%5Ctextbf%7B%E5%BC%B1%E7%94%B5%E8%A7%A3%E8%B4%A8%7D%20%26%20%5Ctextbf%7B%E5%B9%B3%E8%A1%A1%E5%B8%B8%E6%95%B0%7D%5C%5C%0A%5Chline%0A%5Cce%7BH2CO3%7D%20%26%204.5%5Ctimes10%5E%7B-7%7D%5C%5C%0A%5Chline%0A%5Cce%7BAl(OH)3%7D%20%26%201.1%5Ctimes%2010%5E%7B-33%7D%5C%5C%0A%5Chline%0A%5Cend%7Barray%7D

????????容易計算出

%5Cbegin%7Balign%7D%0AK%26%3D%5Cfrac%7BK%5E3_w%7D%7BK_%7Bsp_b(%5Cce%7BAl(OH)3%7D)%7D%5Ccdot%20K%5E3_%7Ba(%5Cce%7BH2CO3%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B(1%5Ctimes%2010%5E%7B-14%7D)%5E3%7D%7B1.1%5Ctimes%2010%5E%7B-33%7D%5Ctimes%20(4.5%5Ctimes%2010%5E%7B-7%7D)%5E3%7D%0A%5C%5C%26%5Capprox%201.0%5Ctimes10%5E8%20%0A%5Cend%7Balign%7D

????????常數(shù)較大,可認(rèn)為不共存。

????????再來看%5Cce%7BAl%5E3%2B%7D%5Cce%7BAlO2-%7D的情況。

%5Cce%7BAl%5E3%2B%7D%2B3%5Cce%7BAlO2-%7D%2B6%5Cce%7BH2O%7D%5Cce%7B%3C%3D%3E%7D4%5Cce%7BAl(OH)3%7D

????????易得

%5Cbegin%7Balign%7D%0AK%20%26%3D%20%5Cfrac%7B%5C%23%20c%5E3_%7B(%5Cce%7BAl(OH)3%7D)%7D%7D%7Bc_%7B(%5Cce%7BAl%5E3%2B%7D)%7D%5Ccdot%20c%5E3_%7B(%5Cce%7BAlO2-%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bblue%7D%7Bc%5E3_%7B(%5Cce%7BAl(OH)3%7D)%7D%5Ccdot%20%5Ccolor%7Bgreen%7D%7Bc%5E3_%7B(%5Cce%7BH%2B%7D)%7D%5Ccdot%20%7Bc%5E3_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%7D%7D%7B%5Ccolor%7Bred%7D%7Bc_%7B(%5Cce%7BAl%5E3%2B%7D)%7D%5Ccdot%7Bc%5E3_%7B(%5Cce%7BOH-%7D)%7D%7D%7D%20%5Ccdot%20%5Ccolor%7Bblue%7D%7Bc%5E3_%7B(%5Cce%7BH%2B%7D)%7D%5Ccdot%20c%5E3_%7B(%5Cce%7BAlO2-%7D)%7D%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B%5Ccolor%7Bgreen%7D%7BK%5E3_w%7D%7D%7B%5Ccolor%7Bred%7D%7BK_%7Bsp_b(%5Cce%7BAl(OH)3%7D)%7D%7D%5Ccdot%20%5Ccolor%7Bblue%7D%7BK%5E3_%7Ba(%5Cce%7BAl(OH)3%7D)%7D%7D%7D%0A%5Cend%7Balign%7D

????## 同樣,這里本來不應(yīng)該把%5Ccolor%7Bgray%7D%7B%5Cce%7BAl(OH)3%7D%7D寫進(jìn)表達(dá)式的,很遺憾的是筆者沒有找到相應(yīng)的%5Ccolor%7Bgray%7D%7BK_%7Bsp_a%7D%7D值,只好湊了一個酸式電離常數(shù)進(jìn)去。

????????查表

%5Cbegin%7Barray%7D%7B%7Cc%7Cc%7Cc%7C%7D%0A%5Chline%0A%5Ctextbf%7B%E5%BC%B1%E7%94%B5%E8%A7%A3%E8%B4%A8%7D%20%26%20%5Ctextbf%7B%E5%B9%B3%E8%A1%A1%E5%B8%B8%E6%95%B0%7D%20%26%20%5Ctextbf%7B%E5%A4%87%E6%B3%A8%7D%5C%5C%0A%5Chline%0A%5Cce%7BAl(OH)3%7D%20%26%206.3%5Ctimes10%5E%7B-13%7D%20%26%20K_a%5C%5C%0A%5Chline%0A%5Cce%7BAl(OH)3%7D%20%26%201.1%5Ctimes%2010%5E%7B-33%7D%20%26%20K_%7Bsp_b%7D%5C%5C%0A%5Chline%0A%5Cend%7Barray%7D

????????容易計算出

%5Cbegin%7Balign%7D%0AK%20%26%3D%5Cfrac%7BK%5E3_w%7D%7BK_%7Bsp_b(%5Cce%7BAl(OH)3%7D)%7D%5Ccdot%20K%5E3_%7Ba(%5Cce%7BAl(OH)3%7D)%7D%7D%0A%5C%5C%26%3D%5Cfrac%7B(1%5Ctimes%2010%5E%7B-14%7D)%5E3%7D%7B1.1%5Ctimes%2010%5E%7B-33%7D%5Ctimes%20(6.3%5Ctimes%2010%5E%7B-13%7D)%5E3%7D%0A%5C%5C%26%5Capprox%203.6%5Ctimes%2010%5E%7B27%7D%0A%5Cend%7Balign%7D

????????反應(yīng)幾乎完全進(jìn)行,應(yīng)認(rèn)為不共存。

????????除了以上提及的部分,下列雙水解也應(yīng)引起注意。

%5Cbegin%7Barray%7D%7B%7Cc%7Cc%7C%7D%0A%5Chline%0A%5Cce%7BAl%5E3%2B%7D%20%26%20%5Cce%7BS%5E2-%7D%2C%5Cce%7BHS-%7D%2C%5Cce%7BCO3%5E2-%7D%2C%5Cce%7BSiO3%5E2-%7D%2C%5Cce%7BClO-%7D%5C%5C%0A%5Chline%0A%5Cce%7BAlO2-%7D%20%26%20%5Cce%7BFe%5E3%2B%7D%2C%5Cce%7BNH4%2B%7D%5C%5C%0A%5Chline%0A%5Cce%7BFe%5E3%2B%7D%20%26%20%5Cce%7BCO3%5E2-%7D%2C%5Cce%7BHCO3-%7D%2C%5Cce%7BSiO3%5E2-%7D%2C%5Cce%7BClO-%7D%5C%5C%0A%5Chline%0A%5Cend%7Barray%7D

????????本文中的K來自各方資料,如有差錯請自行糾正。

????????網(wǎng)上很多推導(dǎo)過程中%5Cce%7BAl(OH)3%7D的酸式電離常數(shù)均取了1.6%5Ctimes%2010%5E%7B-13%7D,而標(biāo)準(zhǔn)一些的書籍中均取了6.3%5Ctimes%2010%5E%7B-13%7D,筆者遵循后者,對前者持有懷疑態(tài)度。



關(guān)于雙水解反應(yīng)的評論 (共 條)

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