Saturday, April 14, 2018

acid base - Does dilution of a buffer affect pH?


The Henderson-Hasselbalch equation for the pH of a buffer solution of the monoprotic acid HA is given by pH=pKa+log[AX][HA] Since concentration appears in both the numerator and denominator of the fraction [AX][HA] and pKa is constant (at a fixed temperature), it appears that dilution of the solution with pure HX2O would not change the pH. However, since pH=log[HX+] the amount of substance of HX+ must increase in order for pH to stay constant upon dilution.


Where is this additional HX+ coming from? I know that diluting an acid causes it to dissociate to a greater extent. But at the same time, you would be diluting its conjugate base and causing it to associate more, cancelling the dissociation of the acid.



Answer



In the Henderson-Hasselbalch equation, Ka is a product of concentrations and considered a constant.


In reality, Ka, when defined as a product of concentrations, is not a constant:


https://commons.wikimedia.org/wiki/File:PK_acetic_acid.png


Upon dilution (decrease in ionic strength) the pKa will change, and therefore the pH of the solution will change.


In addition to the above reason, pH will always approach 7 at extreme dilution as it approaches being pure water.



No comments:

Post a Comment

periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, MgX2+ is closest in radius to LiX+. Is this true, and if so, why would a whole larger shell ($\ce{...