Joanna Liao

Phil Cox
1/22/2013

BUFFERS
Introduction
Buffers prevent a drastic change in a solution upon small additions of an acid or a
base. This application is especially important for humans, because the carbonate and
phosphate buffers in the blood keep the pH at a healthy level. Buffers are comprised of a
weak acid and its conjugate base or weak base and its conjugate acid in a solution. For
this introduction I will be talking in terms of a weak acid HA (conjugate base A-), but the
following applies to weak bases as well.
What makes an effective buffer is when the concentration of HA and A- are
relatively large in solution, and the ratio of their concentrations is close to 1. The reason
for large concentrations of HA and A- is because when a small amount of acid or base is
added to the solution only a small percentage of HA or A- will be affected compared to
the large amount of HA and A- that is still free in the solution. This small effect on the pH
of the buffer solution is also due to the acid dissociation constant (Ka) of the acid. Ka is
essentially the measure of the strength of the acid in a particular solvent, or in other
words, its tendency to dissociate in that solvent. The larger the Ka, the stronger the acid
since it will be more likely to dissociate and create H3O+ and A- instead of staying in HA
form. However, for an effective buffer we look for a smaller Ka value because this means
in solution that the acid will not dissociate as much, meaning the acid and its conjugate
base will remain in the solution. Polyprotic acids acids that have more than one
Hydrogen will often have several Ka values, one for each H+ removed. A deprotonated
form of a polyprotic acid often makes a good buffer, because it has a smaller Ka value.
With this knowledge, the question presented was to determine the effectiveness of
a phosphate buffer. In this case we prepared separate solutions containing dissolved
K2HPO4 and KH2PO4, and then mixed various ratios of these two stock solutions. The
goal was to determine the buffer capacities of the various solutions. Buffer capacity, as
defined by Van Slyke, is:
[]
[]
=
=

where is the buffer capacity. Essentially it measures the effect of added base or acid on
the pH. If this ratio is large then this means the solution is an effective buffer and can
withstand a larger addition of strong base or strong acid without as large a change in the
pH. If the ratio is small, then the opposite is true.
To determine the buffer capacity of the various phosphate solutions we had to
determine the pH upon additions of OH- (NaOH) and upon additions of H+ (HCl), and
then use the Van Slyke equation.
Determining the buffer capacity of a phosphate solution is a laboratory
application, but what of the real world? What is the buffer capacity of, for example,
common medications that we take? To gain insight to this question, we tested the buffer
capacities of Aspirin and Bufferin (Bayer Aspirin).

Experimental Methods
PART ONE: Buffer capacities of phosphate solutions
Begin by creating 0.10 molar solutions of KH2PO4 and K2HPO4 in separate beakers.
Make 100 mL of each solution and label them. Now create solution 1 by measuring and
pouring 40 mL of your K2HPO4 stock solution into a new beaker. Add 60 mL of
deionized water. Mix the solution and record the pH. Now take 20 mL of solution 1 and
dispense 0.25 mL of 0.5 molar Hydrochloric acid (HCl) into the solution. Mix, and record
the pH. Dispose of the solution in the waste container. Now in order to dilute the HCl
dispense 0.25 milliliters of 0.5 molar HCl into a larger amount of stock solution. For
example, take 40 milliliters of solution 1 and add in the HCl. Mix the solution and record
the pH. After 1-2 dilutions, use the remaining solution 1 to do the same measurements
with Sodium Hydroxide (NaOH). Repeat this procedure of adding HCl and NaOH with
solutions 2-5 (see Table 1 for solution composition).
Be sure to measure the pH of 100 mL of deionized water as a baseline measure. The pH
should be pH 7.
Solution No.

Volume 0.1 M
Volume 0.1 M
Volume DI water
K2HPO4 (mL)
KH2PO4 (mL)
(mL)
1
40.00
0.00
60.00
2
30.00
10.00
60.00
3
20.00
20.00
60.00
4
10.00
30.00
60.00
5
0.00
40.00
60.00
Table 1: The solution composition of the different phosphate solutions that are to be
tested.
PART TWO: Buffer capacity of Bufferin and Aspirin
Weigh 0.2 gram of aspirin and mix with 25 mL of water, then weigh 0.2 gram of bufferin
and mix with 25 mL of water in a separate beaker. Proceed to stir both solutions, and
make note of solubility; please note that not all of the solid will dissolve. Once you have
mixed the solutions record the pH of each sample. Now add 0.25 mL of 0.5 molar HCl to
each solution. Mix the solution, and record the pH. Dispose of the solution in the waste
container and make two new solutions of bufferin and aspirin as per the instructions
above. Instead of adding HCl, add 0.25 mL of 0.5 molar NaOH, mix well, and record the
pH. Discard of these solutions in the waste container as well.

Results

Solution Initial
pH w/
pH w/
pH w/
pH w/ OH- pH with
pH
H3 O+
diluted HCl diluted
addition
Diluted OHaddition
(1)
HCl (2)
(1)
1
2
1
9.43
7.83 7.90
7.81
11.43
2
7.56
7.20
8.13
7.803
3
7.07
6.69
7.36

4
6.46
5.53
6.164
6.785
5
4.47
3.53
5.47
DI Water
8.22
2.83
11.17
Aspirin
2.65
2.14
3.31
Bufferin
3.79
3.28
4.47
Table 2: Data collected during procedure using a LabPro pH probe.
1
Dilution: 0.5 mL of 0.5 Molar HCl
2
Dilution: 2.0 mL of 0.5 Molar HCl
3
Dilution: Doubled the stock solution (from 20 mL to 40 mL)
4
Dilution: Doubled the stock solution (from 20 mL to 40 mL)
5
Dilution: Had to make more of stock solution #4. The solution was also 9:27:54 ratio
instead of 10:30:60 (H2HPO4: KH2PO4: DI Water). Initial pH was 6.62.
Solution
No.

Theoretical buffer
Experimental buffer
Experimental buffer
capacity
capacity (w/ H+)
capacity (w/ OH-)
-4
1 1.86x10
0.00797
0.00305
2
0.017
0.01715
0.01294
3
0.023
0.0162
0.0213
4
0.0173
0.01035
0.0194
-4
5 1.14x10
0.00657
0.00617
DI Water
0
0.00115
0.002
Aspirin
X
0.009706
0.0075
Bufferin
X
0.009706
0.0073
Table 3: Theoretical and experimentally determined buffer capacities.

Comparison of Experimental Buffer Capacity Values to Theoretical
Buffer Capacity curve

0.025
Theoretical
Buffer
Capacity

Buffer Capacity

0.02

0.015

Buffer
Capacity
(with [H+]
addition)

0.01

Buffer
Capacity
(with [OH-]
addition)

0.005

0
5

5.5

6.5

7
pH

7.5

8.5

Graph A: The graph is a comparison of the measured buffer capacity values to how well
it fits to the theoretical buffer capacity curve on the pH range of 5-9.

Discussion
The numerical values of measured and theoretical buffer capacities did not match
when compared to one another, but the general trend did. Solution 1 was a relatively
weak buffer, compared to solution 2, which was weak compared to solution 3. After
solution 3 the buffer capacities decrease, solution 4 being weaker than 3, and solution 5
being a weaker buffer than 4.
Solution 3 had the largest calculated numerical value for buffer capacity (0.0162
when HCl was added, and 0.0213 when NaOH was added). This is not a surprise.
Solution 3 contained equal moles of the acid and its conjugate base. As stated in the
introduction the more effective buffers have equal, large concentrations in large amounts
close to a ratio of 1. Only a small percent of the H2PO4- species and HPO4-2 species were
converted into the other, so the composition of solution was kept mostly the same,
thereby keeping the pH change small.
However, note that the buffer capacity of solution 3 when HCl was added was
0.0162, which is a lower capacity than solution 2 when HCl was added (0.01715). This
higher-than-expected value may have been due to a measurement error. However, the
reasoning I used to put solution 3 at a higher buffer capacity than solution 2 is because
the average of solution 3s capacities is larger than solution 2s, 0.01875 versus 0.015045
respectively.
The two solutions that had the smallest buffer capacities were 1 and 2, both with
capacities measured in the 1x10-3 range. Solution 1 had a buffer capacity of 0.00797
when HCl was added, and a capacity of 0.00305 when NaOH was added. In solution 5
the buffer capacity when HCl was added was 0.00657 and when NaOH was added the
capacity of was 0.00617. This means that the change in pH was large compared to the
amount of HCl or NaOH added, which is not ideal for a buffer.
The experimental values of my measured buffer capacities do not agree with each
other. For instance in solution 4 my buffer capacity with added HCl was 0.01035 whereas
the buffer capacity with added NaOH was 0.0194 which is much higher than 0.01035.
These discrepancies may be due to the preference of reaction direction. For example, take
solution 2. The experimental buffer capacity when HCl is added is 0.01715, which is
higher than when NaOH is added (a capacity of 0.01294). This may be due to the
composition of the solution. Solution 2 is predominantly HPO4-2 ions and a few H2PO4ions. When HCl is added it dissociates to form H3O+. This will bond with the HPO4-2 and
create H2PO4-, with a product of neutral H2O. In this sense the H3O+ is reacting out the
solution, and will not affect pH drastically. The buffer capacity will therefore be larger.
However, when NaOH is added, the OH- will try to react with H2PO4- to create HPO4-2;
but the Ka of this reaction (6.23x10-8) is small, meaning it is less likely for this reaction to
occur. Thus the OH- remains in the solution, and pH will be affected more so than when
H3O+ was in solution.
Looking at Graph A the pH range that produces the best buffer is around the
range of 7.07 to 7.56 pH. In this range there are four measured buffer capacities that are
rather close to the theoretical buffer capacity curve at its peak. Some other pHs that an

effective phosphate buffer could exist at depend on the Ka values. To create a buffer at a
particular pH you should choose a species with a pKa that is closest to the desired pH. In
this case we can use this rule in reverse, and determine the approximate pH that the
buffer would have. For instance, a buffer containing H3PO4 and H2PO4- will have a pKa
of 2.12, which is roughly equivalent to the buffer pH. For a buffer with H2PO4- and HPO42
the pH will be around 7.21. For a buffer with HPO4-2 and PO4-3 the pH will be around
12.67. In order to obtain correct ratios of these acids and their conjugate bases the
solutions containing phosphate species need to be titrated solutions with the correct
amount of HCl or NaOH.
Now looking at the real world application of buffer capacities, I calculated the
experimental buffer capacity of aspirin with added HCl to be 0.009706 and with NaOH to
be 0.0075. For bufferin (Bayer Aspirin) I calculated an experimental buffer capacity with
HCl to be 0.009706 and with NaOH to be 0.0073. Between the 2 medications these are
extremely similar values. But the numbers are rather small, suggesting that the two
medications are not effective buffers. However, based on the active ingredients in
bufferin and aspirin, bufferin should theoretically be the better buffer since it contains
acetylsalicylic acid (which is the only active ingredient in aspirin) but also calcium
carbonate. Calcium carbonate is not very soluble, but it can dissociate and bond with
H3O+ ions to form HCO3-2, keeping the change in pH to more of a minimum than aspirin.
This function of calcium carbonate in addition to acetylsalicylic acid means that bufferin
should have a higher buffer capacity than aspirin. A possible reason for this error may be
due to not spending enough time stirring the solution and allowing the calcium carbonate
more time to dissolve in water.
There were some errors in the carrying out of the procedure. The most prominent
is when adding HCl to solution 1. There was a lapse in communication and understanding
of the lab, and instead of adding HCl to more of the stock solution (so the HCl would
essentially be diluted) my lab partner and I added more HCl, increasing the concentration
and thus getting a larger change in pH and more inaccurate measurement of buffer
capacity. The resulting calculated buffer capacity is likely smaller than in actuality.
In addition, there was a deviation in our procedure. For solution 4 we ran out of
solution in testing pH changes with HCl, so I had to create a new stock solution.
However, this new stock solution had an initial pH of 6.62, which differed from the initial
pH of 6.46 measured before HCl was added. To account for this, I simply included the
new initial pH in my calculation of buffer capacity with OH- (see calculations).

Conclusion
By determining the buffer capacity when a small amount of acid or base was
added various phosphate solutions we essentially also tested the idea of whether a more
effective buffer has an acid/conjugate base ratio of 1.
From the experiment the calculated buffer capacities of the phosphate solutions
increased as the ratio of HPO4-2 and H2PO4- moved closer to 1. This supports the concept
of buffers, that they are more effective as their concentrations near a ratio of 1. The buffer
capacities of a solution with just one ion species (ie: solutions 1 and 5) made the least
effective buffers, since there was very little conjugate acid or base to prevent a large
change in pH.

As for the buffer capacity of bufferin and aspirin, I received the same calculated
capacity for both medications dissolved in solution. However, this is likely incorrect due
to the short amount of time that was given to the Bufferin to dissolve in water. The buffer
capacity may have increased given more time in water, since the active ingredient
calcium carbonate is not very soluble, but contributes to a higher buffer capacity of the
solution. While these values may be incorrect, the calculated buffer capacities of bufferin
and aspirin are both very small being in the range of 10-3. This suggests they are not
effective buffers.
Calculations
Grams of and KH2PO4
!
0.01 ! ! 174.18 !"# = 1.74 ! !
Theoretical Initial pH for solutions 1-5
Using Kb: Solution 1
HPO! !! +
I 0.04
N/A
C -X
E 0.04-X

H2 O

0
+X
X

!
110!!"
=
= !
! 6.2310!!
!
1.60510 =
0.04
= 8.01210!! = ! !
!!

log 8.01210!! = 9.90

Using Henderson-Hasselbalch: Solution 3
[! ]
= +
[]
[0.002]
= 7.21 +
[0.002]
= 7.21

Theoretical Buffer capacity

Solution 1
(! )[! ]
= ln (10)
( + ! )
(! + [! ])!

H! PO! !

OH !

+
0
+X
X

(6.2310!! )[10!!.!" ]
= ln (10)
(0.04)
(6.2310!! + [10!!.!" ])!
= 1.8610!!
Measured Buffer capacity (For H+ and OH-)
Solution 1
[]

!"# =

!"#

= []

0.00050 0.5
0.02025
=
= 0.00797
7.90 9.43

Buffer capacity for solution 4 with OH- (Please see 5 in table 2)

0.00025 0.5
0.04025
!"#$ =
= 0.0194
6.62 6.78
Buffer capacity of a solution with diluted HCl/NaOH
Solution 2: NaOH
[]

!"#$ =

!"#$

= []

0.00025 0.5
0.04025
=
= 0.01294
7.56 7.80