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Buffers
• Buffers are aqueous systems that tend to resist changes in pH
when small amounts of acid (H+) or base (OH-) are added.
• A buffer system consists of a weak acid (the proton donor) and its
conjugate base (the proton acceptor).
• As an example, a mixture of equal concentrations of acetic acid
and acetate ion, found at the midpoint of the titration is a buffer
system.
• At buffering region/system in a titration curve, the pH is equal to
the pKa.
• The pH of acetate buffer system resist changes on the addition of
H+ or OH- , compared to pure water or strong acid, strong base or
solution of salt of the same amount of H+ or OH- is added.
• Buffering results from two reversible reaction equilibria
occurring in a solution of nearly equal concentrations of a
proton donor and its conjugate proton acceptor.
• Whenever H+ or OH- is added to a buffer, the result is a small
change in the ratio of the relative concentrations of the weak
acid and its anion and thus a small change in pH.
• The decrease in concentration of one component of the system
is balanced exactly by an increase in the other.
• The sum of the buffer components does not change, only their
ratio.
• Each conjugate acid-base pair has a characteristic pH zone in
which it is an effective buffer.
The H2PO4
-/HPO4
2-
pair has a pKa of 6.86
and thus can serve as
an effective buffer
system between
approximately pH 5.9
and pH 7.9; the NH4
-
/NH3 pair, with a pKa of
9.25, can act as a
buffer between
approximately pH 8.3
and pH 10.3
• The shape of the titration curve of any weak acid is described by
the Henderson-Hasselbalch equation, which is important for
understanding buffer action and acid-base balance in the blood
and tissues of vertebrates.
• This equation is simply a useful way of restating the expression
for the dissociation constant of an acid
• Consider the dissociation of a weak acid HA into H⁺ and A⁻ , the
Henderson-Hasselbalch equation can be derived as follows:
• First solve for [H⁺]
Ka =
H⁺ [A⁻]
[HA]
H⁺ = Ka
[HA]
[A⁻]
• Taking negative logarithm of both sides
• Substitute pH for –log [H⁺] and pKa for –logKa
• Inverting – log
[HA]
[A⁻]
, will change its sign, and this will give us the
Henderson-Hasselbalch equation:
• This equation is generally more written as
-log H⁺ = -log Ka – log
[HA]
[A⁻]
pH = pKa + log
[A⁻]
[HA]
pH = pKa – log
[HA]
[A⁻]
pH = pKa + log
[proton acceptor]
[proton donor]
Exercises
1. Calculate the pKa of lactic acid, given that when the concentration
of lactic acid is 0.010 M and the concentration of lactate is 0.087
M, the pH is 4.80.
2. Calculate the pH of a mixture of 0.10 M acetic acid and 0.20 M
sodium acetate. The pKa of acetic acid is 4.76.
3. Calculate the ratio of the concentrations of acetate and acetic
acid required in a buffer system of pH 5.30

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Buffers.pptx

  • 2. • Buffers are aqueous systems that tend to resist changes in pH when small amounts of acid (H+) or base (OH-) are added. • A buffer system consists of a weak acid (the proton donor) and its conjugate base (the proton acceptor). • As an example, a mixture of equal concentrations of acetic acid and acetate ion, found at the midpoint of the titration is a buffer system. • At buffering region/system in a titration curve, the pH is equal to the pKa. • The pH of acetate buffer system resist changes on the addition of H+ or OH- , compared to pure water or strong acid, strong base or solution of salt of the same amount of H+ or OH- is added.
  • 3. • Buffering results from two reversible reaction equilibria occurring in a solution of nearly equal concentrations of a proton donor and its conjugate proton acceptor. • Whenever H+ or OH- is added to a buffer, the result is a small change in the ratio of the relative concentrations of the weak acid and its anion and thus a small change in pH. • The decrease in concentration of one component of the system is balanced exactly by an increase in the other. • The sum of the buffer components does not change, only their ratio. • Each conjugate acid-base pair has a characteristic pH zone in which it is an effective buffer.
  • 4. The H2PO4 -/HPO4 2- pair has a pKa of 6.86 and thus can serve as an effective buffer system between approximately pH 5.9 and pH 7.9; the NH4 - /NH3 pair, with a pKa of 9.25, can act as a buffer between approximately pH 8.3 and pH 10.3
  • 5. • The shape of the titration curve of any weak acid is described by the Henderson-Hasselbalch equation, which is important for understanding buffer action and acid-base balance in the blood and tissues of vertebrates. • This equation is simply a useful way of restating the expression for the dissociation constant of an acid • Consider the dissociation of a weak acid HA into H⁺ and A⁻ , the Henderson-Hasselbalch equation can be derived as follows: • First solve for [H⁺] Ka = H⁺ [A⁻] [HA] H⁺ = Ka [HA] [A⁻]
  • 6. • Taking negative logarithm of both sides • Substitute pH for –log [H⁺] and pKa for –logKa • Inverting – log [HA] [A⁻] , will change its sign, and this will give us the Henderson-Hasselbalch equation: • This equation is generally more written as -log H⁺ = -log Ka – log [HA] [A⁻] pH = pKa + log [A⁻] [HA] pH = pKa – log [HA] [A⁻] pH = pKa + log [proton acceptor] [proton donor]
  • 7. Exercises 1. Calculate the pKa of lactic acid, given that when the concentration of lactic acid is 0.010 M and the concentration of lactate is 0.087 M, the pH is 4.80. 2. Calculate the pH of a mixture of 0.10 M acetic acid and 0.20 M sodium acetate. The pKa of acetic acid is 4.76. 3. Calculate the ratio of the concentrations of acetate and acetic acid required in a buffer system of pH 5.30