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Puzzler in pH calculations

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Hey!

 

I just wanted to pose a question that I hope someone can find the time to answer.

 

It's regarding part of my homework - don't worry, I already have the answer. I was just confused about some of the methods.

The question is part of a larger one:

 

"Calculate the pOH of a 0.0500 mol dm-3 aqueous solution of methylamine. State any assumptions made in your calculation."

We are given the Kb value at 4.37*10-4 mol dm-3

The assumption is referring to the fact that I can disregard the concentration value in the denominator of this equation [H+]2/C-[H+]=Ka

I could see two ways of calculating the answer. The first one gave me the right answer.

If [H+]2/C=Ka then [OH-]2/C=K

We can isolate for the [OH-] value (0.004674), and take the negative logarithm in base 10 of it, producing a pOH of 2.33

 

I wanted to be thorough and double check my answer, so I ran through the next method too:

 

pOH = 14 - pH

pH = -log[H+]

[H+] = sqrt(Ka*C)

Ka = 10-pKa

pKa = 14 - pKb

pKb = -log(Kb)

Putting in values and collecting equations I get: pOH = 14 - (-log(sqrt(10-(14-(-log0.000437))*0.05)))

This gives me a pOH value of 8.03 which is ridiculous, since methylamine is a weak base.

 

My question: what am I doing wrong in the second method? I know it's an unnecessary way around it, but from what I've read all the constants are mathematically connected to their conjugates. In theory, shouldn't it work?

 

Thank you!

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