Wednesday, April 25, 2018

acid base - How much can the pH change through dilution?


Consider an acidic solution with Hydrogen ion concentration, [HX+] of 105M. Since pH=log[HX+] the pH of solution is 5. Suppose we dilute solution 10 times with water. Now, [HX+] is 106M and pH is 6. Further dilution should increase pH from 6 to 7 and then from 7 to 8 and so on. Can this go in for ever? Does this not imply that an acidic solution can be made basic/alkaline simply by adding water? But that doesn't happen? What prevents it?


Is there anyone already found answer for this problem or it is just an unsolved basic problem of chemistry?



Answer



Water undergoes autoionization, i.e., it reacts as follows:


HX2O+HX2OHX3OX++OHX


The equilibrium constant for this reaction at standard conditions is Kw=[HX3OX+][OHX]1.01014. In pure water, [HX3OX+]=[OHX], hence [HX3OX+]=Kw1.0107 M.


Suppose we dilute a solution with some initial concentration of [HX3OX+]i=niVi, where ni is the initial number of moles of HX3OX+ and Vi is the initial volume. If I now add a volume ΔV of pure water (which would contain (1.0107)ΔV moles of HX3OX+) the resulting final concentration can be crudely approximated as:



[HX3OX+]fni+(1.0107)ΔVVi+ΔV


We can see what value this expression approaches as we make the solution more and more dilute by taking the limit as ΔV:


limΔVni+(1.0107)ΔVVi+ΔV=1.0107


Therefore, [HX3OX+] tends towards 1.0107 with further dilution, so pH will approach a value of 7.0.


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