BUFFER (2014-2015)

DETERMINATION OF BUFFER CAPACITY

A buffer is a solution characterized by the ability to resist changes in pH when limited
amounts of acid or base are added to it. Buffer solutions contain either a weak acid and its
conjugate base or a weak base and its conjugate acid. Thus, a buffer contains an acid and a
base species in equilibrium. This equilibrium can lighten the effect in pH change in case of
adding strong acid or strong base. When adding a limited amount of a strong acid or base to a
buffer solution, the pH change is much smaller than in case of adding the same amount of
acid or base to distilled water. The reason is the following. The limited amount of the strong
acid, added to the buffer, reacts with the weak base in the solution. (In case of adding a strong
base, the weak acid reacts.) This reaction shifts the equilibrium and changes the ratio of the
weak acid and its conjugate base, but the change is much smaller than in case of adding a
strong acid (or base) to distilled water. Therefore, the change in the pH of the buffer is very
small.

Buffers can be characterized by their pH and buffer capacity.

Calculation of the pH of a buffer solution:
pH = pK
a
+ log ([A
-
]/[HA]) or: [H
+
] = K
a
([HA]/[A
-
])
{in case of base + conjugated acid: pH = pK
a
+ log ([B]/[BH
+
]), because
[OH
-
]=K
base
([B]/[BH
+
]), pK
a
= 14-pK
base
and pOH = 14 pH}
As the difference between dissociation of the weak acid and its conjugated base in the
buffer solution is negligible, the inital concentrations can be used for the calculations
instead of the equilibrium concentrations: [HA] = c
HA
, s [A
-
] = c
A
-

Therefore the followings can be used directly for pH calculations:
[H
+
] = K
a
(c
HA
/c
A
-) or : pH = pK
a
+ log (c
A
-/c
HA
)

Buffer capacity: the number of moles of a strong monoprotic acid or base added to 1L of
a buffer solution causing 1 unit change in the pH.

Theoretical calculation of buffer capacity:

o in case of adding a strong acid: x is the buffer capacity when x mol strong acid
was added, and the pH has changed by 1 unit (decreased), [H
+
] increased 10-fold
The reaction: A
-
+ H
+
= HA
Before acid was added: [H
+
]
1
= K
a
(c
HA
/c
A
-)
After acid was added: [H
+
]
2
=[H
+
]
1
10, and also [H
+
]
2
=K
a
((c
HA
+x)/(c
A
-x)),
Using the equations above: K
a
(c
HA
/c
A
-)10 = K
a
((c
HA
+x)/(c
A
-x))
After arrangement the buffer capacity for acid addition is the following:

o in case of adding a strong base: x is the buffer capacity when x mol strong base
was added, and the pH has changed by 1 unit (increased), [H
+
] decreased 10-fold.
The reaction: HA + OH
-
= A
-
+ H
2
O
Before base was added: [H
+
]
1
= K
a
(c
HA
/c
A
-)
After base was added: [H
+
]
2
=[H
+
]
1
/10, and also [H
+
]
2
=K
a
((c
HA
x)/(c
A
-+x)),
Using the equations above: K
a
(c
HA
/c
A
-)=K
a
((c
HA
x)/(c
A
-+x))
9 c
HA
c
A
-
10 c
HA
+c
A
-
x =
BUFFER (2014-2015)
After arrangement the buffer capacity for base addition is the following:


Preparation of a dihydrogenphosphate/hydrogenphosphate buffer solution and
determination of its buffer capacity by acid-base titration


The conjugated acid-base pair and the equilibrium in the solution

H
2
PO
4
-
H
+
+ HPO
4
2-


Preparation of the buffer solution

Using NaH
2
PO
4
and Na
2
HPO
4
solutions, having the concentrations of 500 mmol/dm
3
,
prepare a 100-mL NaH
2
PO
4
and a 100-mL Na
2
HPO
4
stock solution according to the table
below. (The practical teacher assigns which buffer you should prepare.) To do so, pipette the
appropriate amounts of 500 mmol/dm
3
NaH
2
PO
4
and 500 mmol/dm
3
Na
2
HPO
4
solutions into
100 mL-volumetric flasks. Use 10 mL-volumetric pipette for this purpose. Fill up the flasks
with distilled water to the marks and homogenize the solutions by shaking. Calculate the
concentrations of the stock solutions you prepared and put these values (c
HA
and c
A
-) to the
table. Using a 10 mL volumetric pipette, transfer 20-20 mL of the stock solutions into two
100 mL-beakers. (Measure 20 mL from both solutions to both beakers in order to have two
times 40 mL of buffer solutions.)

You should prepare only one of these buffers. Ask your practice teacher which one.
Buffer
Volume of 500 mmol/dm
3

NaH
2
PO
4
solution to be used
(mL)
Volume of 500 mmol/dm
3

Na
2
HPO
4
solution to be used
(mL)
1. 10 10
2. 10 20
3. 10 30
4. 20 10
5. 20 20
6. 20 30
7. 30 10
8. 30 20
9. 30 30
Calculate the concentration of both the weak acid (NaH
2
PO
4
) and its conjugate base
(Na
2
HPO
4
) in the buffer. These values will be used in the formulas given in the introduction
of this syllabus as c
HA
and c
A
-, respectively. (Please note that mixing 20-20 mL of the stock
solutions decreases the concentration of both NaH
2
PO
4
and Na
2
HPO
4
to one-half of the stock
solution concentrations.)

9 c
HA
c
A
-
10 c
A
-+c
HA
x =
BUFFER (2014-2015)
Determination of buffer capacity of the prepared buffer solution

Measure the pH of the prepared buffer using pH-meter. After that, titrate the solution
in the first beaker with a 0.1 mol/dm
3
HCl solution, and with a 0.1 mol/dm
3
NaOH solution in
the second beaker. (Continuous magnetic stirring is very important during the titration!)
The titration procedure is the following. Add the acid or base solution from the burette
in 1 mL portions to the beaker. Record the pH of the solution after each 1 mL of acid or base
added. Continue this process until the change in the pH is higher than 1 unit compared to the
initial pH. (You will get a pH vs. volume of HCl or NaOH solution graph that helps you to
determine the buffer capacity more accurately.)


Buffer capacity of the ion-exchanged water

Put 40-40 mL of ion-exchanged water into two 100 mL-beakers and measure the pH.
Using continuous magnetic stirring, add one drop of 0.1 mol/dm
3
HCl from the burette into
the first beaker and one drop of 0.1 mol/dm
3
NaOH from the other burette into the second
beaker and measure the pH again.


Results and calculations

Draw the two titration curves (an acidic and a basic) applying the measured pH
values connected to the used volume of acid and base. (Use the x-axis for the volume in mL
and the y axis for the pH.) Determine the precise volumes connected to the 1.0 unit change
in the pH compared to the initial one.
Calculate the buffer capacity of the prepared buffer solution both for acidic and basic
directions using the determined volume of 0.1 mol/dm
3
HCl and NaOH solutions. (Use 40 mL
as a constant volume of the buffer during the titration, so neglect the change in the volume of
the buffer to simplify the calculations.)
Calculate the theoretical pH value and the buffer capacities of the prepared buffer
solution and compare them with the measured values. (H
3
PO
4
: K
a2
= 6.210
-8
)
Calculate the buffer capacity of the distilled water for acidic and basic directions and
compare with your experiences.


Check your lab report whether it contains all of the following results:

1. theoretical pH of the buffer (calculated from the formula)
2. measured pH of the buffer
3. & 4. theoretical buffer capacity for both acid and base addition (calculated from the
formula)
5. & 6. measured buffer capacity for both acid and base addition (calculated from the
results of the titrations)
7. change in the pH of ion-exchanged water by adding 1 drop of acid or base to it
8. buffer capacity of ion-exchanged water for both acid and base addition