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You can calculate the pH of a buffer solution or the concentration of the acid and base using the

Henderson Hasselbalch equation. Here's a look at the Henderson Hasselbalch equation and a
worked example that explains how to apply the equation.

Henderson-Hasselbalch Equation
pH = pKa + log ([A-]/[HA])
[A-] = molar concentration of a conjugate base
[HA] = molar concentration of a undissociated weak acid (M)
The equation can be rewritten to solve for pOH:
pOH = pKb + log ([HB+]/[ B ])
[HB+] = molar concentration of the conjugate base (M)
[ B ] = molar concentration of a weak base (M)

Example Problem Applying the Henderson-Hasselbalch Equation


Calculate the pH of a buffer solution made from 0.20 M HC2H3O2 and 0.50 M C2H3O2- that has
an acid dissociation constant for HC2H3O2 of 1.8 x 10-5.
Solve this problem by plugging the values into the Henderson-Hasselbalch equation for a weak
acid and its conjugate base.
pH = pKa + log ([A-]/[HA])
pH = pKa + log ([C2H3O2-] / [HC2H3O2])
pH = -log (1.8 x 10-5) + log (0.50 M / 0.20 M)
pH = -log (1.8 x 10-5) + log (2.5)
pH = 4.7 + 0.40
pH = 5.1

pH vs pKa
pH is a measure of the concentration of hydrogen ions in an aqueous solution. pKa (acid
dissociation constant) is related, but more specific, in that it helps you predict what a molecule
will do at a specific pH. Essentially, pKa tells you what the pH needs to be in order for a
chemical species to donate or accept a proton.

The lower the pH, the higher the concentration of hydrogen ions, [H+]. The lower the
pKa, the stronger the acid and the greater its ability to donate protons.

pH depends on the concentration of the solution. This is important because it means a


weak acid could actually have a lower pH than a diluted strong acid. For example,
concentrated vinegar (acetic acid, which is a weak acid) could have a lower pH than a
dilute solution of hydrochloric acid (a strong acid). On the other hand, the pKa value is a
constant for each type of molecule. It is unaffected by concentration.

Even a chemical ordinarily considered a base can have a pKa value because the terms
"acids" and "bases" simply refer to whether a species will give up protons (acid) or
remove them (base). For example, if you have a base Y with a pKa of 13, it will accept
protons and form YH, but when the pH exceeds 13, YH will be deprotonated and become
Y. Because Y removes protons at a pH greater than the pH of neutral water (7), it is
considered a base.

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PH

How Do You Measure PH

Chemistry

Buffer

Acids and Bases

Relating pH and pKa With the Henderson-Hasselbalch Equation


If you know either pH or pKa you can solve for the other value using an approximation called
the Henderson-Hasselbalch equation:
pH = pKa + log ([conjugate base]/[weak acid])
pH = pka+log ([A-]/[HA])
pH is the sum of the pKa value and the log of the concentration of the conjugate base divided by
the concentration of the weak acid.
At half the equivalence point:
pH = pKa
It's worth noting sometimes this equation is written for the Ka value rather than pKa, so you
should know the relationship:
pKa = -logKa

Assumptions That Are Made for the Henderson-Hasselbalch Equation


The reason the Henderson-Hasselbalch equation is an approximation is because it takes water
chemistry out of the equation. This works when water is the solvent and is present in a very large
proportion to the [H+] and acid/conjugate base. You shouldn't try to apply the approximation for
concentrated solutions. Use the approximation only when the following conditions are met:

1 < log ([A]/[HA]) < 1

Molarity of buffers should be 100x greater than that of the acid ionization constant Ka.

Only use strong acids or strong bases if the pKa values fall between 5 and 9.

Example pKa and pH Problem


Find [H+] for a solution of 0.225 M NaNO2 and 1.0 M HNO2. The Ka value (from a table) of
HNO2 is 5.6 x 10-4.
pKa = log Ka = log(7.4104) = 3.14
pH = pka + log ([A-]/[HA])
pH = pKa + log([NO2-]/[HNO2])
pH = 3.14 + log(1/0.225)

pH = 3.14 + 0.648 = 3.788


[H+] = 10pH = 103.788 = 1.6104

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