Experiment No: 5
Experiment Name:
Study of pH metric Titration
Introduction
In pH metric titration the end point of the titration is determined by the sharp change of the
pH of the solution. Often it is found very difficult to determine the end point of a titration
using only indicators. In those cases pH metric titration gives higher accuracy. For acid-base
neutralization titration this process is very effective. The objective of this experiment was to
know about pH metric titration, the use of pH meter and to find out the first and second
dissociation constants for Na2CO3.
Instruments
A pH meter is an electronic instrument used to measure the pH (acidity or alkalinity) of a
liquid (though special probes are sometimes used to measure the pH of semi-solid
substances). A typical pH meter consists of a special measuring probe (a glass electrode)
connected to an electronic meter that measures and displays the pH reading.
The pH probe measures pH as the activity of hydrogen ions surrounding a thin-walled glass
bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is
measured and displayed as pH units by the meter.
The meter circuit is fundamentally no more than a voltmeter that displays measurements in
pH units instead of volts. The input impedance of the meter must be very high because of the
high resistance approximately 20 to 1000 MΩ of the glass electrode probes typically used
with pH meters. The circuit of a simple pH meter usually consists of operational amplifiers in
an inverting configuration, with a total voltage gain of about -17. The inverting amplifier
converts the small voltage produced by the probe (-0.059 volt/pH in basic solutions, +0.059
volt/pH in acid solutions) into pH units, which are then offset by seven volts to give a reading
on the pH scale.
A glass electrode is used in the probe of the pH meter. A glass electrode is a type of ion-
selective electrode made of a doped glass membrane that is sensitive to a specific ion.
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Figure 2.1 - Glass Electrode
Almost all commercial electrodes respond to single charged ions, like H +, Na+, and Ag+. The
most common glass electrode is the pH-electrode. Only a few chalcogenide glass
electrodesare sensitive to double-charged ions, like Pb 2+, Cd2+ and some other. There are
different types of pH glass electrode; some of them have improved characteristics for working
in alkaline or vice versa, acidic medium. But almost all electrodes have sufficient properties
for working in the most popular pH range from pH =1 till pH =12. Special electrodes should
be used only for working in aggressive conditions.
The construction of a general pH meter electrode can be shown by the following figure.
Figure 2.2 – pH meter elctrode
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1. A sensing part of electrode, a bulb made from a specific glass.
2. Sometimes the electrode contains a small amount of AgCl precipitate inside the glass
electrode
3. Internal solution, usually 0.1M HCl for pH electrodes or 0.1M MeCl for pMe electrodes
4. Internal electrode, usually silver chloride electrode or calomel electrode
5. Body of electrode, made from non-conductive glass or plastics.
6. Reference electrode, usually the same type as 4.
7. Junction with studied solution usually made from ceramics or capillary with asbestos or
quartz fiber.
A typical modern pH probe is a combination electrode, which combines both the glass and
reference electrodes into one body. The bottom of a pH electrode balloons out into a round
thin glass bulb. The pH electrode is best thought of as a tube within a tube. The inside most
tube (the inner tube) contains an unchanging saturated KCl and a 0.1M HCl solution. Also
inside the inner tube is the cathode terminus of the reference probe. The anodic terminus
wraps itself around the outside of the inner tube and ends with the same sort of reference
probe as was on the inside of the inner tube. Both the inner tube and the outer tube contain a
reference solution but only the outer tube has contact with the solution on the outside of the
pH probe by way of a porous plug that serves as a salt bridge.
This device is essentially a galvanic cell. The reference end is essentially the inner tube of the
pH meter, which for obvious reasons cannot lose ions to the surrounding environment (as a
reference is good only so long as it stays static through the duration of the measurement). The
outer tube contains the medium, which is allowed to mix with the outside environment (and as
a consequence this tube must be replenished with a solution of KCl due to ion loss and
evaporation).
The measuring part of the electrode, the glass bulb on the bottom, is coated both inside and
out with a ~10nm layer of a hydrated gel. These two layers are separated by a layer of dry
glass. The silica glass structure (that is, the conformation of its atomic structure) is shaped in
such a way that it allows Na+ ions some mobility. The metal cations (Na+) in the hydrated gel
diffuse out of the glass and into solution while H+ from solution can diffuse into the hydrated
gel. It is the hydrated gel, which makes the pH electrode an ion selective electrode.
H+ does not cross through the glass membrane of the pH electrode, it is the Na+ which
crosses and allows for a change in free energy. When an ion diffuses from a region of activity
to another region of activity, there is a free energy change and this is what the pH meter
actually measures. The hydrated gel membrane is connected by Na+ transport and thus the
concentration of H+ on the outside of the membrane is 'relayed' to the inside of the membrane
by Na+.
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All glass pH electrodes have extremely high electric resistance from 50 to 500 Ohm.
Therefore, the glass electrode can be used only with a high input-impedance measuring device
like a pH meter, or, more generically, a high input-impedance voltmeter which is called an
electrometer.
2.3 Theory
In passing from acid to alkaline solutions the concentration of hydrogen ions can vary within
very wide limits to permit a convenient means of expressing the concentration of hydrogen
ions without involving negative exponents; on the pH of any solution is given by,
pH = -log10 aH+
Where, aH+ = Hydrogen activity
Fritz, Haber and Z Klemensiewiez first showed that when a glass membrane separates two
solutions of different pH a potential established across the membrane whose magnitude
depends on the difference in the pH of the two solutions. If the pH of one of these solutions is
held constant and while that of the second is varied, the emf of the electrode follows the
equation:
RT
E=Eo - ln aH+
F
2.303 RT
E=Eo - pH
F
E o−E
pH= 2.303 RT
F
Hence it is seen that pH is the function of emf a pH meter employed which using potential
differences gives pH directly. When known solution of acid or base added to unknown base or
acid, pH changes with the addition of known solution and measuring pH against volume
added plot could be constructed this has a sharp break at the end point of each reaction.
Chemical Reactions
The combination electrode was dipped in the Na2CO3 solution taken in a beaker. Since the
solution inside the glass tube was maintained at a constant pH potential of the calomel
electrode inserted into it was constant and so was the potential between the HCl solution and
inner surface of the glass tubes and test solution varied with the change of hydrogen ion
concentration of the solution.
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With every addition of HCl from the burette into the solution of Na2CO3, pH varied and
consequently emf of the combination electrode changed. This emf was recorded by an in built
potentiometer of the pH meter. This potentiometer reading was automatically converted
electrically to a direct reading of pH of the solution.
Reactions involve in the process are
H+ (solution) + Na+ (glass) = Na+ (solution) + H+ (glass)
HA= H+ + A-
K=¿ ¿
A−¿
Log K= Log [H+] + log [ ¿]
HA
When 50% acid is neutralized then the concentration of acid and salt will be equal. In that
case,
pKa = pH
The reaction involved here is completed by two steps. They are as follows:
Na2CO3 + HCl =NaHCO3 + NaCl
NaHCO3 + HCl =NaCl + H2CO3
Determination of End Point
pH metric process to determine the end point of titration is an important method. By this
method, for an acid-base titration pH changes gradually as titrant is added. Around the
equivalence point, however the pH changed abruptly. The rate of change is greatest at the
equivalence point. This can be seen with the plot pH VS volume of HCl plot. A plot dpH/dV
vs. volume also shows a sharp peak at the equivalence point.
Experimental Setup
Chemicals
Buffer solution
Sodium Carbonate (Na2CO3)
Hydrochloric Acid (HCl)
Distilled water
Apparatus
Beaker
Pipette
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Burette
Stirrer
pH meter
Working Procedure
First the pH meter was standardized by a buffer solution.20 ml of Na 2CO3 was taken in a
beaker. HCl was added to the beaker in a very low amount using a burette. After every
addition of HCl the pH of the solution was taken by the pH meter. The HCl was added
repeatedly until the pH reached almost 3. The pH values were plotted against the
corresponding volume of HCl. Also, the graphs of ΔpH/ΔV and Δ2pH/ΔV2 were plotted,
which gave the actual end point of the titration. The volume used for titrating Na 2CO3 and
NaHCO3 completely were used later to find out the first dissociation constant and the second
dissociation constant respectively.
Observed Data & Calculated Data:
Table 5.1 - Table for volume of HCl, corresponding pH and calculated data
Volume of
HCl ∆ pH ∆2 pH
Obs no. pH ∆V ∆ pH
(V) ∆V ∆V2
(ml)
1 0.0 9.74 0.5 0.22 0.44 -0.12
2 0.5 9.52 0.5 0.19 0.38 0.20
3 1.0 9.33 0.5 0.24 0.48 0.28
4 1.5 9.09 0.5 0.31 0.62 0.86
5 2.0 8.78 0.2 0.21 1.05 2.00
6 2.2 8.57 0.2 0.29 1.45 6.25
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7 2.4 8.28 0.2 0.54 2.70 4.00
8 2.6 7.74 0.2 0.70 3.50 -10.50
9 2.8 7.04 0.2 0.28 1.40 -3.75
10 3.0 6.76 0.2 0.13 0.65 0.25
11 3.2 6.63 0.2 0.14 0.70 -0.50
12 3.4 6.49 0.2 0.12 0.60 -0.50
13 3.6 6.37 0.2 0.10 0.50 0.50
14 3.8 6.27 0.2 0.12 0.60 -1.25
15 4.0 6.15 0.2 0.07 0.35 0.75
16 4.2 6.08 0.3 0.15 0.50 -0.20
17 4.5 5.93 0.5 0.22 0.44 0.48
18 5.0 5.71 0.5 0.34 0.68 0.34
19 5.5 5.37 0.2 0.17 0.85 5.42
20 5.7 5.20 0.3 0.58 1.93 14.22
21 6.0 4.62 0.2 1.24 6.20 -19.50
22 6.2 3.38 0.1 0.23 2.30 -7.00
23 6.3 3.15 0.1 0.16 1.60 -7.50
24 6.4 2.99 0.2 0.17 0.85 -1.25
25 6.6 2.82 0.3 0.18 0.60 -0.87
26 6.9 2.64 0.5 0.17 0.34 -0.16
27 7.4 2.47 0.5 0.13 0.26 -0.20
28 7.9 2.34 0.5 0.08 0.16 -0.04
29 8.4 2.26 0.5 0.07 0.14 -0.08
30 8.9 2.19 1 0.10 0.10 -0.02
31 9.9 2.09 1 0.08 0.08 -0.26
32 10.9 2.01 -10.9 2.01 -0.18 -0.02
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Calculation:
From the graph,
The first end point of the reaction was found at 2.6 mL of HCl
The second end point of the reaction was found at 6 mL of HCl
Volume of Na2CO3, V1= 20 mL
Strength of Na2CO3, S1 = 0.1 M = 0.05 N
V1 S1 = V2 S2
S2 = (V1 × S1) / V2
= {(20 × 0.05) / 6}N
= 0.167 N
HCl present in the solution is 0.167 N.
So, the concentration of
From the graph,
pK1=9.25, pK2= 6.45
The equivalence point for the primary stage of reaction is at
pK 1 + pK 2
pH =
2
9.25+6.45
=
2
= 7.85
So, pH at first nutralization point = 7.85
From first graph, pH at first nutralization point = 7.50
The equilibrium constant for the primary stage of reaction is at
pK1= 9.25
K1=10-9.25 = 5.62 ×10−10
The equilibrium constant for the secondary stage of reaction is at
pK2=6.45
K2= 10-6.45 = 3.55 ×10−7
Oveall volume at secondary equivalence point =Volume of Na2CO3 +Volume of required HCl
= (20+6) mL
= 26 mL
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0.05× 20
Concentration of H2CO3 = N = 0.0385 N = 0.01925 M
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So, [H+] = (3.55 ×10−7× 0.01925)1/2 M = 8.27× 10-5 M
The equivalence point for the second stage of reaction is at pH=-log(8.27 × 10-5)= 4.08
So, the pH at second neutralization point = 4.08
From graph, pH at second neutralization point = 4.4
Results
The pH for the 1st end point(from calculation) 7.85.
The pH for the 2nd end point(from calculation 4.08.
Discussions
In this experiment, rather than using a base, Na 2CO3 salt solution has used to study the pH behavior.
Before adding any HCl acid the pH of the solution was high. pH gradually decreases with the addition
of HCl acid as Na+ of Na2CO3 is replaced by the H+ . The pH value changes very slowly at the
beginning of the reaction but in the region of the neutral point a very sharp change in pH value occurs
on the addition of a very small quantity of base.
To determine the neutralization point accurately three curves are plotted. The plots showed the
naturalization reaction between HC1 acid and Na2CO3 in the two steps by the two peaks. In the first
step, Na2CO3 is converted to NaHCO3 and in the second step NaHCO3 is further neutralized to H2CO3.
The experimental plots conducted in this experiment are agreed with the theoretical one. The plots
showed the naturalization reaction between HCl acid and Na2CO3 in the two steps by the two peaks.
The first peak is not as sharp as the second peak.
There may be four main reasons for the first peak’s not being as sharp as the second one. They are:
Impurities might be present in the Na2CO3 solution and distilled water used in this
experiment
To make the pH of the solution stable sometime should be given between two
successive observations, but sufficient time was not spent here
The solution was not stirred properly
From the plots, two information have found. First, the concentration of the solution
can be calculated by determining the end point. Second, the dissociation constant can
be known that gives the strength of the solution. The more the dissociation constant,
the more easily the solution will dissociate. From the plot it has found that Na 2CO3 has
large dissociation constant (pK1 = 8.9) than NaHCO3 (pK2 = 6.6)
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Advantages
pH metric titration has some unique advantages. Some of them are given below:
1. In colored solutions, Indicators cannot detect endpoints where as pH metric titration is
not subjected to this limitation
2. Indicators for any acid-base titration must be chosen so that the pH at which the
indicator changes color corresponds more or less to the pH of the solution at the
equivalence point. Hence some information is required concerning the relative
strength of the acid base involved. pH metric titration always yield the equivalence
point whether this point comes exactly at the neutral point or on the acid or basic acid
3. With indicators it is some-times impossible or difficult to titrate a polybasic acid or a
mixture of a strong acid and weak acid with a base. In such cases pH metric titration
gives accurate result
4. Oxidation titration can be carried out by this method
5. In precipitation reaction, pH metric titration can be employed without any difficulty
6. Titration of weak acid-weak base, strong acid-weak base, weak acid strong base, when
indicator choosing is difficult or indicator does not show distinct color change, then by
pH metric titration end point of the titration can be detected easily
Limitations
The main limitation of pH metric titration arises when strong, alkaline solution is used. In this
case the glass electrode is affected by the alkaline solution. The glass electrode shows very
little response to divalent actions. Special care should be taken in handling this glass
electrode, as it is very expensive otherwise it can be damaged or broken.
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