Title : Potentiometric titration of an acid mixture

Objective : 1) In this experiment, the quantitative composition of a solution, which is a mixture of

monoprotic strong acids and a weaker triprotic acid will be determined by potentiometric methods.

2) To be able to construct a potentiometric titration and construct a titration curve.

Introduction :

In this experiment, we will be performing a potentiometric titration to determine the

unknown concentrations of two acids. There is two types of acids such as the strong acids and the
weak acids. The strong acid, like hydrochloric acid, are completely dissociated in the water. But for
the weak acids, like acetic acid, are only partially dissociated. The extent of dissociation can be
calculated from the value of the equilibrium constant and the amounts of weak acid and strong base
added to the solution. In order to perform this titration, we use pH meter as an electrode which
monitors the pH change. It does not need a chemical indicator to observe the endpoint. Since the
hydrogen ion inside the electrode responds to the activity of the hydrogen ion in the analyte
solution, after sometime, sudden change of pH will signal the endpoint of the titration.

The relative acidities of acids are commonly expressed on terms of pKa = -log 10 Ka, where
Ka is the dissociation constant for the reaction:
+
HA → H + A-
In the following derivation, a ,
A- [A-] , and ƳA- represent the activity , the molar concentration and the
activity coefficient of the conjugate base, - respectively.
A
+ - + -
Ka = ( (aH+) (aA-) ) / ( (aHA) ) = ( [H ] [A ] ) / ( [HA] ) * ( (ƳH ) (ƳA ) ) / ( (ƳHA) )

Since pKa ≡ - log Ka

+ -
Then pKa ≡ -[log (aH ) + log(aA ) - log (aHA)]
+
Since pH ≡ -log (aH )

Then pKa = pH + log (aHA) – log (aA-)

pKa= pH –log ( (aA- ) / (aHA ) )

pKa= pH – log{ ([A-]) / ([HA]) x ([ƳA-]) / ([ƳHA]) }

Making approximation that ([ƳA-])/([ƳHA])≡1

Yields an apparent pH = pKa + log ([A-]/[HA]).

The equation is referred to as the Henderson-Hasselbalch equation. It is very useful in the

buffering region of the titration of a weak acid. The pKa is –logKa at the ionic strength of the
solution. Accordingly , the value of Ka obtained will deviate slightly from values listed in standard
references since they report the thermodynamic value at zero ionic strength.

For a triprotic acid the successive dissociation constants are defined by:
 - +
H3A = H2A + H K1 = [H2A-] [H+] / [H3A]
- 2- +
H2A = HA + H K2 = [HA2-] [H+] / [H2A-]
2- 3- +
HA = A +H K3 = [A 3-] [H+] / [HA2-]
The normality of an acid solution is the number of equivalents per liter ( moles per liter) of
protons that it can dissociate. The normality of a solution of a base is equal to the number of
equivalents of acid it can neutralize. The normality of a solution of a triprotic acid is three times its
molarity. In discussing titrations of acid and base solutions, it is often convenient to think in terms of
milliequivalents.

Chemicals / Reagents : 0.05 M sodium hydroxide, potassium acid phthalate (KHP), phenolphthalein
indicator, calcium chloride, mixture of acid ( HCl and phosphoric acid ), distilled water

Apparatus: pH meter

Procedure:

A) Standardization of Approximately 0.05M Sodium Hydroxide

First and foremost, difference three samples of KHP were weighed into 50-mL Erlenmeyer
flasks. Sample weights should be 30 mg for the primary standard. All weights was estimated
to ±0.1mg (0.0001 g) and all data was recorded immediately in the notebook. After that, the
KHP samples was dissolved by swirling in 7mL of distilled water. Warming may be necessary.
It is essential that the samples dissolve completely; even a few small particles remaining can
cause a serious titration error. Besides, 1 drop of phenolphthalein was added and was
titrated with the sodium hydroxide solution from a 50 mL buret. Finally, the titration was
repeated twice and the results was recorded in a table.
B) Titration of a Mixture of Hydrochloric Acid and Phosphoric acid
Firstly, 1.00 mL of the acid mixture was pipeted by using a volumetric pipet into a 50 mL
beaker. Then , 19.0 mL of distilled water was added by using a pipet. The pH electrode was
rinsed with distilled water into an empty beaker and the electrode and buret filled with
sodium hydroxide was positioned as shown in figure 3. With continuous gentle stirring, small
increments (about 0.1ml-0.5ml ) of the approximately 0.05M standard solution of NaOH
from buret was added. Be sure that the pH electrode is not in a position to be damaged by
the magnetic stir bar. Besides, the solutions was given and the pH meter is time to
equilibrate. The pH of the solution after addition of each portion of the NaOH solution was
read an recorded in the notebook. Apart from this, do not take pH reading above pH 11.5
because high pH damages the glass electrode. After the first potentiometric titration was
completed, the electrode was removed from the solution, washed it with distilled water and
the electrode was allowed to stand in a beaker of distilled water for at least 10 minutes
before proceeding with the econd titration.
 Results:
Part A

Titration number 1 2 3
Initial volume of 0.00 3.50 7.00
burette(cm3 )
Final volume of 3.50 7.00 10.2
burette(cm3)
Total volume of sodium 3.50 3.50 3.20
hydroxide solution(cm3)

Average volume of the sodium hydroxide used in the titration= (3.50+3.50+3.20)/3= 3.4cm 3
Part B

Volume of 0.05M standard pH value (titration 1) pH value(titration 2)

solution of NaOH
0.00 1.77 1.76
0.50 1.83 1.86
1.00 1.92 1.90
1.50 2.01 1.91
2.00 2.14 2.06
2.50 2.26 2.43
2.75 - 2.58
3.00 2.52 2.74
3.25 - 3.01
3.50 2.90 3.15
3.75 - 4.32
4.00 5.13 5.87
4.50 6.46 6.65
5.00 6.97 7.06
5.25 - 7.40
5.50 7.53 7.55
5.75 - 7.76
6.00 9.5 8.43
6.25 - 10.75
6.50 10.83 11.01
7.00 11.20 -

Calculations:

3) Based on the graph for the titration 1,

The volume of NaOH added to reach the first endpoint = 3.75cm 3

The volume of NaOH added to reach the second endpoint = 5.75cm 3

Then , the average volume of NaOH added to reach the endpoint
= [(3.75+5.75)cm3] / 2
= 4.75cm3
 So the pka2 = pH = 6.75

a) The literature value of pKa2 is 6.3. The value of the pKa2 that we calculated is quite close
to the literature value.
b) From my own experimental data, the pKa value is small when there is a clear and
sharp turning point. As a result, the value of the pKa1 must be smaller than the value
of the pKa3 since there is the clear and sharp turning point.
c) Based on the titration curve, we can observe that the turning point of pK a3 is not sharp
compare to the turning point of the pKa1.Therefore, we can estimate that the value of the
pKa3 is bigger. This is due to if there is a sharp turning point, then it must have a
small pH value.
4)Average volume of the sodium hydroxide used in the titration = 3.4 cm 3

Average mass of KHP used to conduct the experiment =(0.0295+0.0297+0.0304)/3= 0.0299g

The molar mass of KHP= 204.22g/mol
Mole of KHP = 0.0299g/(204.22g/mol)
= 1.4641×10 -4 mol

Molarity of KHP= 1.4641×10-4mol/ 0.007L

=0.021M
M1V1=M2V2
(0.021)(0.007)=M2(0.0034)
So, the molarity of NaOH= 0.043M
Based on the graph that we plotted, the volume of NaOH between the 2nd equivalence point
and the 1st equivalence point:
5.75cm3 – 3.75cm3 =2.00cm3
Mole of NaOH= (0.002L)(0.05mol/L)
= 1.00×10-4mol

Hence , the mole of H2PO4- and H3PO4 is similar to the mole of NaOH.

So, the molarity of H3PO4= 1.00×10-4mol/ 0.001L

= 0.1M
The volume of NaOH that require to reach the 1st equivalence point is 3.75cm3
Mole of NaOH= mole of H2PO4
= 0.05mol/L(0.00375L)
=1.875×10-4 mole
The mole of the HCL = (1.875×10-4) – (1.00×10-4)
= 8.75×10-5mol
The molarity of HCl = 8.75×10-5mol/(0.001)
= 0.0875M
Discussion :

Potentiometric titration is a titration in which the end-point is indicated by a change in

potential at an electrode immersed in the solution. This change in potential occurs as the solution
changes from having excess substance to be determined to having excess titrant. In this experiment,
we will titrate both of the strong monoprotic acid and the weaker triprotic acid with a standardized
strong base. After that, the standardized base will be added to the acid mixture. The aim that the
standardized base is added to the acid mixture is to measure the resulting pH value. When the
volume of the base added is plotted on the graph as a function of pH , the titration curve is
produced. Based on the curve, it is possible to determine the amount of base is needed to neutralize
the amount of acid present in the solution of unknown concentration. In addition , the shape of the
titration curve is dependent on the type of acid being titrated. After conducting this experiment,
there is two type of the titration curve that we obtained.

When a strong monoprotic acid, such as HCl , is dissolved in water, it will totally ionizes into
hydrogen ions and chloride ions . In addition , when the sodium hydroxide which act as the strong
base is added to the acid solution, then the available hydroxide ions will combine with some of the
available hydrogen ions to form the water. If the sodium hydroxide is continue to be added to the
acid solution and we record the resulting pH , then we will obtain a titration curve that quite similar
to the first graph that we plotted.

Based on the titration curve that we plotted on the first graph, we will observe that when
the end point has reached, the pH of the solution will start to stay nearly constant. We know that pH
is a measure of the hydrogen ion concentration. Since the strong acid is totally ionized, then it will
have the large amount of the hydrogen ions available in the solution. The hydrogen ions that
available in the solution will react with any base added immediately. However, there is only have a
small change in the total hydrogen ion concentration. This is due to there is a such large amount of
the hydrogen ions react with the few millilitres of the base. Other than that, we also know that pH +
pOH=14. The pH will remain relatively unchanged since any hydroxide ion that is added is
immediately neutralized.

When the neutralization point has reached, then the concentration of the hydrogen and the
hydroxide ions will start to change. The concentration of the hydrogen ions will drops while the
concentration of the hydroxide ions will increases. Since the concentration of the hydroxide ions
increases, then the pH value will also be increased. The pH value will continue to increase until the
pH of the base being added is reached. After that, the further addition of the base will also lead to
little effect only and the pH become relatively constant again.

Apart from this, the weak triprotic acid which is phosphoric acid do not totally ionize in the
solution. In fact, most of the phosphoric acid will remain as unionized phosphoric acid molecules in
the solution. On the other hand , the small amount of those can ionize in the solution will exist as a
series of the equilibrium equations. Each of them will produce some hydrogen ions.
 + - - +
Reaction 1 : H3PO4 H + H2PO4
󠆶 Ka1=[H2PO4 ][H ] / [H3PO4 ] = 7.5×10-3
- +
Reaction 2: H2PO4 H+ + HPO4-2 Ka2=[HPO4-2][H ] / [H2PO4- ] = 6.2×10-8

Reaction 3: HPO4
-2
H+ + PO4-3 Ka3=[PO4-3][H
+
] / [HPO4-2] = 3.6×10-13
Based on the titration curve that we plotted on the second graph, we will observe that the pH
value increases slowly. Furthermore , the pH transitions through the end point of the acid are not
abrupt but instead are gradual. When there is no large readily available amount of the hydrogen ions
, there are still have three sources where the hydrogen ions can be obtained as needed. We have
shown that the weak triprotic acid exist as a series of equilibrium equations. Hence , if we shift the
equilibrium out of balance, then the systems will adjust to reestablish the equilibrium. When the
available hydrogen ion is used to neutralize the added base, then some unionized acid from each of
the three equilibrium equations must ionize to reestablish the equilibrium of the hydrogen ion to
near the original value. Once the concentration of the hydrogen ion is changing very little , this
means that the pH will also changes very little. Apart from this, the mixture of the weak acids and
their salts will shift the various equilibrium equations . The reason of shifting the equilibrium
equations is to stabilize the hydrogen ion concentration upon addition of small amount of base. This
is also known as buffering the solution.

On the other hand, the size of the equilibrium constant is to measure the degree of the
ionization. The larger the value then the greater the ionization. Based on this explanation, K1 is going
to supply more the hydrogen ions compared to the K2 and K3. As a result, when the sodium
hydroxide is added, the reaction 1 will provide more equilibrium concentration of hydrogen ion than
the reaction 3. Therefore, the reaction 1 will then be used up first. This situation also means that the
endpoint of the reaction 1 will be reached first. After the hydrogen ion from the reaction 1 is used,
the pH will be increased slowly. The pH value will be increased to the hydrogen ion value that can be
supplied by the equilibrium reactions 2 and 3.

Last but not least, after the hydrogen ion from the reaction 2 is used, then we will follow to
observe the third rise in pH . As the size of the K3 is very small in size , so it is difficult to obtain an
accurate measurement for the titration of reaction 3.

Conclusion :

In a conclusion, the average volume of sodium hydroxide solution to be used in the titration
is 3.4 cm3. In addition, the volume of NaOH between the second equivalence point and the
first equivalence point is 2.00cm3. The molarity of the phosphoric acid used in this
experiment is 0.1 M. Beside that, the molarity of the hydrochloric acid that used in this
experiment is 0.0875 M. Furthermore, the value of the pKa2 that obtain based on the graph
is 6.75. Last but not least, we must make sure that all the solution is to be measured
accurately when conducting the experiment.
Reference:

1) Mark Bishop(2013)Weak Acid Equilibrium. Available at

http://preparatorychemistry.com/Bishop_weak_acid_Equilibrium.htm
2) Science Dictionary(2013)What is POTENTIOMETRIC TITRATION? Definition of
POTENTIOMETRIC TITRATION. Available at
http://thesciencedictionary.org/potentiometrictitration
3) Science, D.o.c.,(2017). Potentiometric Titration of an Acid Mixture. In : UDEC 1224
CHEMISTRY LABORATORY II. Kampar: s.n., pp.3-7.