COMMON ION EFFECT AND BUFFERS

M. DE LEON1
1National Institute of Molecular Biology and Biotechnology, College of Science
University of the Philippines Diliman, Quezon City 1101, Philippines
Date Submitted: 26 February 2019
Date Performed: 19 February 2019

ANSWERS TO QUESTIONS

1. Account for the differences in color of Solutions 1, 2, 3, and 4, after adding the
appropriate virtual indicators. Explain in terms of the pKa’s of phenolphthalein and
methyl orange.

Table 1. pH using Visual Indicators and pH meter.

Color of Solution
Solution pH Reading
+ Methyl Orange + Phenolphthalein

1 Red - 2.71
2 Yellow - 4.51
3 - Dark Violet 10.69
4 - Light Violet 9.25

For the first part of the experiment, methyl orange indicator was added to Solutions 1 and 2.
Methyl orange is an acid-base indicator that changes between colors red to yellow depending on
the pH value [1]. The transition range for this indicator is around 3.1 to 4.4 (acceptable up to 4.5),
wherein leaning towards the former (more acidic) would result to a change of color to red while if
the pH value is closer to the latter (more basic), then it would result to a change of color to yellow
[2]. According to the results of the actual experiment, there were no significant differences up to this

point.

In solution 1, the hydrolysis of the weak Acetic acid (HOAc) is given by this equation,

CH3COOH + H2O ↔ CH3COO- + H3O+ (1)

As seen on the chemical equation, CH3COOH partially dissociates to produce H3O+ (hydronium)
ions. These hydronium ions would account for a certain pH. Due to the production of H 3O ions
being undisturbed, a reaction with methyl orange would be shifted to the left, according to this
equation,

HInd + H2O ↔ H3O+ + Ind- (2)

The reaction with the indicator is shifted to the left because when the solution exhibits a color (i.e.
red), the HInd form predominates (the Ind- predominates if the color is yellow). And since HInd is in
the reactants’ side of the equation, the reaction would be shifted to the left. The pH reading justifies
this, having a pH of 2.71 which is in the range of the indicator.
Upon calculation for the ideal pH of this solution, a pH of 2.87 is obtained by the usage of the ICE
(Initial-Change-Equilibrium) table and the acid dissociation constant of HOAc (Ka = 1.8 x 10-5).
Theoretically, the solution should have had a deeper red color than a plain red color (near to
salmon pink).

On the other hand, Solution 2 is a buffer solution, comprised of a weak acid and its soluble ionic
salt. Solutions with weak acids and their soluble ionic salts are always less acidic than a solution
containing the weak acid alone [3]. This indicates that solution 2 is expected to have a much higher
pH than solution 1.

Compared to solution 1, there is an additional source of CH3COO- ions from NaCH3COO in solution
2. Due to the excess number of ions, the equilibrium is shifted to the left since there was a need to
overcome stress and re-establish equilibrium as stated by the common-ion effect. When a solution
of a weak electrolyte is altered by adding one of its ions from another source, the ionization of the
weak electrolyte is inhibited; that behavior is the common-ion effect [3]. To reverse the given
reaction, H3O+ ions are used up. By this, the dissociation of CH3COOH is suppressed or inhibited.

Upon calculation for the ideal pH of this buffer solution, it is appropriate that the Henderson-
Hasselbalch equation, which is used to calculate the pH of buffer solutions, (3) be used [4], given by
the equation,
𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑏𝑎𝑠𝑒
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ( ) (3)
𝑎𝑐𝑖𝑑

By using the given equation, it yields an ideal pH of 4.75. Because H3O+ ions were used up, there
was a lack of it and causes a rightward shift in equation (2). Having a rightward shift makes the
Ind- form to predominate, thus, resulting to a yellow color (in this specific part of the experiment).
In the actual experiment, the pH was less than the ideal (4.51) but was still in the range wherein
yellow color is exhibited.

Phenolphthalein is known to be the most common acid-base indicator used [4]. It has a range of
transition between 8.3 and 10.0, wherein a pH value closer to the former value would yield a
colorless solution while a pH value nearing the latter would exhibit a fuchsia/ violet color of the
solution.

The chemical equation for Solution 3 is as follows,

NH3 + H2O ↔ NH4+ + OH- (4)

The hydrolysis of NH3, which is a weak base, produces OH- ions, which correspond to a specific pH
value given by this equation,

pH = 14 – pOH (5)

The calculated pH value (considered as ideal pH), through the manipulation of the ICE table, the
base dissociation constant for NH3 (1.8 x 10 -5), and equation (5), is found to be 11.13. Since this
value is near 10.0, the color of the solution should have a fuchsia or dark violet color. This is
supported by the actual experiment, which had a dark violet colored solution.

Solution 4, like Solution 2, is a buffer solution comprised of a weak base and its soluble ionic salt.
Solutions containing weak bases and their ionic soluble salts are always less basic than solutions
with weak bases alone. By that fact, a pH value lower than that of solution 3 is expected.

A modified version of the Henderson-Hasselbalch equation (3) suitable for a solution comprised of
a weak base is to be used to find the pH of this solution,
 𝑐𝑜𝑗𝑢𝑔𝑎𝑡𝑒 𝑎𝑐𝑖𝑑
𝑝𝑂𝐻 = 𝑝𝐾𝑏 + 𝑙𝑜𝑔 ( 𝑏𝑎𝑠𝑒
) (6)

Using both equation (6) and equation (5), the calculated ideal pH value of the solution is 9.25. The
solution is expected to have a light violet color. Experimentally, the solution also had a light violet
color which verifies with theoretical expectations.

2. Describe and Rationalize the observed effect of additional acid or base on Solutions 1,
2, 3, and 4

Table 2. Effect of Strong Acid and Strong Base on Buffers.

Estimated pH range pH Reading

Solution + Methyl Orange + Phenolphthalein pH meter Calculated

a pH < 3.1 - 1.95 1.82

1 b 3.1 < pH < 4.5 - 3.23 4.00
c 3.1 < pH < 4.5 - 3.15 2.87
diluted 3.02
a pH > 4.5 - 4.40 4.60
2 b pH > 4.5 - 4.69 4.87
c pH > 4.5 - 4.37 4.75
diluted 4.75
a - 8.3 < pH < 10.00 9.35 10.02
3 b - pH > 10.00 11.25 11.71
c - pH > 10.00 10.45 11.13
diluted 10.99
a - 8.3 < pH < 10.00 8.46 9.14
4 b - 8.3 < pH < 10.00 9.12 9.39
c - 8.3 < pH < 10.00 8.80 9.25
diluted 9.27

In the second part of the experiment, for solutions 1 and 3, it is expected that the pH would
drastically change (rise or fall) from the addition of drops of strong acids and bases since they are
not buffer solutions. They are pure solutions of weak acids and bases without much capacity to
counteract additional stresses, unlike solutions 2 and 4 which are buffer solutions that are
expected to negate or minimize pH changes.

In solution 1a, the addition of HCl follows a special case of Le Chatelier’s principle, the Common-ion
effect. This is when a weak electrolyte’s dissociation is suppressed by the addition of one of its ions
from another source [2]. In this solution, the common ion is H3O+. Suppression would cause the
formation of hydronium ions from the acid source, CH3COOH, to be negligible. Because of this,
majority of the hydronium ions would come from the addition of 1.0 M HCl,

CH3COOH + HCl → CH3COO- + H3O+ (7)

For solution 1b, a neutralization reaction occurred given by the following chemical equation,

CH3COOH + NaOH → NaCH3COO + H2O (8)

The neutralization would cause some CH3COOH to be consumed in the production of a salt,
NaCH3COO. Ideally, this would cause a lowered hydronium ion concentration due to the presence of
the common ion, CH3COO-, from NaCH3COO, causing a leftward shift in the equilibrium. Equation
(3) can then be used to calculate for the new pH.

Solutions 2a and 2b follow a similar course as that of the divisions of solution 1. But because this is
a buffer solution, the change in pH level is different, or lowered to some extent. NaCH3COO
completely dissociates into Na+ and CH3COO- but CH3COOH undergoes partial ionization only.
Because of the common ion CH3COO-, there will be minimal change of pH in the solution compared
to solutions 1a and 1b. CH3COO- will react with HCl, a strong acid, for solution 2a while CH 3COOH
will react with NaOH, a strong base, for solution 2b.

For solution 3a, it is a neutralization reaction with the following expression,

NH3 + HCl → NH4Cl (9)

The formation of NH4Cl, a salt of the neutralization reaction, would add a source for common ions
in the hydrolysis reaction given by equation (4). This would lead to a decrease in OH - ions due to
the leftward shift of the reaction.

Solution 3b is another case of the common-ion effect, this time with OH- as the common ion. Its
addition would increase the pH due to the reformation of the base by the leftward shift. The change
in pH solutions 3a and 3b are -0.60 and +0.57 respectively. Solutions 4a and 4b follow a similar
course as that of the divisions for solution 3. Again, change in pH level is minimal compared to
solutions 3a and 3b because solution 4 is a buffer solution. For solution 4a, the H + ions from adding
HCl reacts with NH3 producing more NH4+. And for solution 4b, the OH- ions from adding NaOH
reacts with NH4+ to form NH3.

From the results in table 2, pH meter results and calculated pH results are slightly different. This is
due to experimental errors and the accuracy of the used pH meter. Even so, when adding an acid, it
should lower the pH level and when adding a base, it should increase the pH level. For the results in
the experiment, there were no abnormalities in the trend and the said trend was followed.

3. Compare the different methods of determining pH: visual indicators, pH meter, and
calculations. Compare the accuracy of the three methods.
Calculations are generally the most reliable out of the three methods. The values used and the
equations are widely accepted by the scientific community. The results of these equations should,
therefore, yield the ideal pH values. Even so, experimental results are still encouraged to be done as
to verify the calculations.

A pH meter is more dependable than a visual indicator in terms of finding the definite quantitative
value of the pH. The pH meter is calibrated enough to find an accurate pH value for a solution of
substance [5]. Visual indicators are unreliable because color interpretation is subjective and differs
from person to person. pH cannot be accurately determined under a subjective basis [6]. Even so,
the pH meter could also have deviating pH values. These deviant values or extremes could be
brought about by contamination by the atmosphere that surrounds the device.

4. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.

Due to experimental errors in solution preparation, there might have been slight inconsistencies
with pH level change, but it is not at all extreme. The experimental pH values might have been
deviated due to the inconsistency in molarity produced and volume added of the solutions.
Depending on molarity and volume change, this would have led to an increase or decrease in pH
level.
Aside from that, the pH level could be also altered when the pH meter was used. The pH meter, a
sensing mechanism, may have been contaminated. By contaminated, it may not have been
thoroughly washed or cleansed with distilled water thus, leading to slight inaccuracy. If
contaminated with an acid, it might have led to a lower reading and if it was with a base, a higher
reading.

REFERENCES

[1] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole,
Cengage Learning. 757.
[2] Harris, D. Quantitative Chemical Analysis 8th ed. 2010. Madison Avenue, NY: W.H. Freeman
and Company. 221.
[3] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole,
Cengage Learning. 743.
[4] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole,
Cengage Learning. 755.
[5] Barnes, K. Determining pH: Methods & Classification.
https://study.com/academy/lesson/determining-ph-methods-classification.html (accessed Feb
25, 2019).
[6] Gillespie, C. https://sciencing.com/methods-testing-ph-liquids-5809509.html (accessed Feb
25, 2019).
APPENDIX A
Sample calculations:
pH for Solution 4 : 0.20 M NH3 – 0.20 M
pH of Solution 1 : 0.10 M HOAc NH4Cl

CH3COOH CH3COO- H+ 𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑏𝑎𝑠𝑒

𝑝𝑂𝐻 = 𝑝𝐾𝑏 + log ( )
↔ + 𝑎𝑐𝑖𝑑
Initial 0.10 0 0 𝑝𝑂𝐻
Change -x +x +x = − log(1.8 × 10−5 )
Equilibrium 0.10 - x x x 0.2 − 1.332670973 × 10−3
+ log ( )
0.2 + 1.332670973 × 10−3
H+ is from H3O+ = H2O + H+ (MH2O is pOH = 4.744727495
negligible) pH = 14 – 4.744727495
[𝐶𝐻3 𝐶𝑂𝑂− ][𝐻 + ] pH = 9.25
𝐾𝑎 = 1.8 × 10−5 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻]
(𝑥)(𝑥)
1.8 × 10−5 =
(0.10 − 𝑥)
𝑥 = [𝐻 + ] = 1.332670973 × 10−3
𝑝𝐻 = − log[𝐻 + ]
𝑝𝐻 = − log(1.332670973 × 10−3 ) = 2.87

pH of Solution 2 : 0.20 M HOAc – 0.20 M

NaOAc

𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑏𝑎𝑠𝑒
𝑝𝐻 = 𝑝𝐾𝑎 + log ( )
𝑎𝑐𝑖𝑑
𝑝𝐻
= − log(1.8 × 10−5 )
0.2 + 1.332670973 × 10−3
+ log ( )
0.2 − 1.332670973 × 10−3
pH = 4.75

pH of Solution 3 : 0.10 M NH3

NH3 ↔ NH4+ OH-

+
Initial 0.10 0 0
Change -x +x +x
Equilibrium 0.10 - x x x

−5
[𝑁𝐻4 + ][𝑂𝐻− ]
𝐾𝑏 = 1.8 × 10 =
[𝑁𝐻3 ]
(𝑥)(𝑥)
1.8 × 10−5 =
(0.10 − 𝑥)
𝑥 = [𝑂𝐻 ] = 1.332670973 × 10−3
−

𝑝𝑂𝐻 = − log[𝑂𝐻 − ]
𝑝𝑂𝐻 = − log(1.332670973 × 10−3 )
𝑝𝑂𝐻 = 2.875277062
𝑝𝐻 = 14 − 𝑝𝑂𝐻 = 14 − 2.87
𝑝𝐻 = 11.13
Other calculations:
Solution 1
+3 drops 0.1M HCl (Soln. 1a)

HOAc ⇌ OAc- + H+ Solution 2

I 0.099 0.015 +3 drops 0.1M HCl (Soln. 2a)

C -x +x +x HOAc ⇌ OAc- + H+
E 0.099-x x 0.015+x I 0.099 0.099
K 𝑥(0.15 + 𝑥) C +0.015-x -0.015+x +x
= 1.85 × 10−5 =
a 0.099 − 𝑥
E 0.114-x 0.084+x x
p = − 𝑙𝑜𝑔 (0.015 + 𝑥) = 1.82
H K 𝑥(0.084 + 𝑥)
= 1.85 × 10−5 =
a 0.114 − 𝑥

p = − 𝑙𝑜𝑔 𝑥 = 4.600
H

+3 drops 0.1M NaOH (Soln. 1b) +3 drops 0.1M NaOH (Soln. 2b)

HOAc ⇌ Oac- + H+ HOAc ⇌ Oac- + H+

I 0.099 I 0.099 0.099

C -0.015-x +0.015+x +x C -0.015-x +0.015+x +x

E 0.084-x 0.015+x x E 0.084-x 0.114+x x

K 𝑥(0.015 + 𝑥) K 𝑥(0.114 + 𝑥)
= 1.85 × 10−5 = = 1.85 × 10−5 =
a 0.084 − 𝑥 a 0.084 − 𝑥

p = − 𝑙𝑜𝑔 𝑥 = 3.997 p = − 𝑙𝑜𝑔 𝑥 = 4.865

H H

Diluted (Soln. 2c)

HOAc ⇌ Oac- + H+

Diluted (Soln. 1c) I 0.050 0.050

HOAc ⇌ Oac- + H+ C -x +x +x

E 0.050-x 0.050+x +x
I 0.050
K 𝑥(0.05 + 𝑥)
C -x +x +x = 1.85 × 10−5 =
a 0.05 − 𝑥
E 0.050-x x x
p = − 𝑙𝑜𝑔 𝑥 = 4.745
K 𝑥2 H
a = 1.85 × 10−5 =
0.050 − 𝑥
p = − 𝑙𝑜𝑔 𝑥 = 3.023
H
Solution 3

+3 drops 1.0M HCl (Soln. 3a)

NH3(+H2O) ⇌ NH4+ + OH- Solution 4

I 0.099 +3 drops 1.0M HCl (Soln. 4a)

C -0.015 0.015 NH3(+H2O) ⇌ NH4+ + OH-

E 0.084-x 0.015+x x I 0.099 0.099
K 𝑥(0.015 + 𝑥) C -0.015-x +0.015+x +x
= 1.85 × 10−5 =
b 0.084 − 𝑥
E 0.084-x 0.114+x x
p = 14 +𝑙𝑜𝑔 𝑥 = 10.015
H K 𝑥(0.114 + 𝑥)
= 1.85 × 10−5 =
b 0.084 − 𝑥

p = 14 +𝑙𝑜𝑔 𝑥 = 9.135
H

+3 drops 1.0M NaOH (Soln. 3b) +3 drops 1.0M NaOH (Soln. 4b)

NH3(+H2O) ⇌ NH4+ + OH- NH3(+H2O) ⇌ NH4+ + OH-

I 0.099 0.015 I 0.099 0.099

C -x +x +x C +0.015+x -0.015-x +x

E 0.099-x +x 0.015+x E 0.114-x 0.084+x x

K 𝑥(0.015 + 𝑥) K 𝑥(0.084 + 𝑥)
= 1.85 × 10−5 = = 1.85 × 10−5 =
b 0.099 − 𝑥 b 0.114 − 𝑥

p = 14 +𝑙𝑜𝑔 (0.005 + 𝑥) = 11.709 p = 14 +𝑙𝑜𝑔 𝑥 = 9.388

H H

Diluted (Soln. 4c)

NH3(+H2O) ⇌ NH4+ + OH-

Diluted (Soln. 3c) I 0.050 0.050

NH3(+H2O) ⇌ C -x +x +x
NH4+ + OH-
E 0.050-x 0.050+x x
I 0.050
K 𝑥(0.050 + 𝑥)
C -x +x +x = 1.85 × 10−5 =
b 0.050 − 𝑥
E 0.050-x +x +x
p = 14 +𝑙𝑜𝑔 𝑥 = 9.267
K 𝑥2 H
b = 1.85 × 10−5 =
0.050 − 𝑥
p = 14 +𝑙𝑜𝑔 𝑥 = 10.987
H