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Buffer
Buffer
HA + A- + H2O HA + A- + H2O
Adding NaOH or HCl to this buffer would shift the reaction toward the right, but with different
results. This is because of Rule 2 (click 1). Both components in the buffer must change
any time acid or base is added to the buffer. This is because of Rule 3 (click 1). Finally, we
take into account the HA and A- components, expecting to see a decline in the overall buffer.
Such is not found because of Rule 4 (click 1). Hence, Rule 5 summarizes an important
principle that we must know (click 1).
Rules
1. Buffer reactions never go to completion.
2. H+ can only react with A-, OH- can only react with HA.
3. The conjugate acid and conjugate base must change proportionately and in opposite
directions.
4. The sum of the concentrations of base and acid components stays constant, i.e, HA + A-
before = HA + A- after.
5. Only the ratio, never the total, of HA to A- changes as a result of buffer action.
Putting the Rules to Work
Let’s now see how the 5 rules apply to a buffer reaction. Lets start with the buffer
(click 1). Suppose we add OH- to the buffer (click 1). Rule 2 tells us the following would occur
(click 1) 10 moles, ratio A-/HA = 2.43/1.0
2 moles
HA + A- + H2O HA + A- + H2O
3 moles 7 moles
Finally, if we calculate HA and A- before and after the addition of OH-, we see that both
add up to 10 moles in either case (click 1). This verifies Rule 4. Thus, we started with a
ratio of A- to HA = 5/5 = 1.0 before the reaction and after the reaction the ratio of A to HA-
= 7/3= 2.3 to 1.0, but the total did not change. Click to go on.
Principle Behind Buffer Action
Buffers are composed of weak acids and their salts. A salt is the acid minus its
proton. Weak acids and their salts have two properties that are important for buffering
action. First, weak acids are a reserve of the protons that neutralize OH- and prevent the
solution from becoming alkaline. Salts of weak acids are strong bases and prevent the
solution from becoming acidic. Both components are needed and both are
interchangeable through the loss (or gain) of a single proton.
A buffer’s power lies in its reserves (click 1). A buffer is at optimal strength
when there is an equal amount of HA and A- in solution as shown. This will only occur
when the pH of the solution equals the pKa of the acid’s group. Adding OH- causes the
buffer to respond by calling on the reserve pool of HA. A- is formed at the expense of HA
(click 1). This continues until all the excess OH- is neutralized. At the end the salt pool
has increased (and the acid pool has decreased) by the same number of moles of base
that were added. Click to go on.
HA A- A-
OH-
HA OH- A -
A- A- Neutralized
HA HA A A- A-
-
HA A-
HA HA HA A A-
-
- A
-
HA A - A
HA HA A- A-
In the previous illustration you saw the importance of knowing the ratio of HA and
A-. Now you will see that it is the ratio that determines the pH of the solution, and vice
versa, the pH allows you to determine the ratio. It all begins with an equilibrium expression
(click 1). If we take the log of all components we derive a logarimic expression of the same
equation (click 1),
[HA]
–Log [H+] = –Log Keq – Log
[A-]
Substituting pH and pK for the appropriate terms in the equation and making the log of HA/A-
positive by reversing numerator and denominator gives (click 1)
Knowing the ratio of [A-]/[HA] allows you to calculate pH. Always treat the ratio as a
whole number, i.e., do not separate numerator from denominator. As an example, assume 2
moles of NaOH are added to 10 moles of a pH 5.2, pK = 4.8 buffer (HA + A-). You want to
know the moles of HA after neutralization and the new pH. Follow these steps to the solution
(click 1)
First determine the moles of HA at the start (click 1)
[A-] Solving for Log [A-]
pH = pK + Log
[HA] [HA]
[A-]
Log = pH – pK
[HA]
= 5.2 – 4.8 The ratio of A- to HA is 2.5 parts to 1 part. This means the 10
moles are represented by 3.5 parts. If 2.5 parts of the 10 are
= 0.4 moles of A- and 1.0 part is HA, then before OH- was added
[A-] there were 7.1 moles of A- and 2.9 moles of HA. Together the
= 2.5 / 1.0 two add up to 10 and their ratio is 2.5:1.0 (click 1).
[HA]
When OH- is added, 2.0 moles of NaOH react with 2.9 moles
of HA. As a consequence, HA goes from 2.9 to 0.9 and A-
goes up from 7.1 to 9.1 moles. The new pH is determined
from the ratio 9.1 to 0.9 or 10.1. This computes to pH = 5.8
Test and Enhance your Understanding
Q: Why must buffers always have two components?
A: Several reasons. First, Rule 2 say that a base will only react with an acid and an acid with a base.
The two components assure the buffer protects against both. Second, it is the ratio of conjugate base to
conjugate acid that determines pH. Neither one alone would suffice.
Q: Is there a way of telling when a buffer will be most effective at a given pH?
A: Yes. The pK of the buffer (sometimes referred to as pKa for an acid) immediately tells you the
pH that will result in equal amounts of conjugate acid and base in solution, which is the optimal
condition for any buffer.
Q: Suppose you added 2 moles of acid to 10 moles of buffer in a solution where pH and
the pK have the same value. What would be the result?
A: Since the pH = pK, you know that there are equal moles of conjugate acid and conjugate base, 5
moles of each. The 2 moles of acid would convert 2 moles of the base component to the acid changing
the ratio of A-/HA from 1.0 to 0.43, which would lower the pH of the solution by 0.37 units.