Unit 8 Neutralization Titration & Acid Value
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Transcript of Unit 8 Neutralization Titration & Acid Value
51
Neutralization
Titration-I
UNIT 8 NEUTRALIZATION TITRATION-I
Structure
8.1 Introduction Objectives
8.2 Basic Concepts of Titrimetry, Primary and Secondary Standards
8.3 Titration Curves Titration of A Strong Acid Versus Strong Base
Titration of Weak Acid Versus Strong Base
Titration of a Weak Base Versus Strong Acid
Titration of Weak Acid Versus Weak Base
Titration of Sodium Carbonate Versus Strong Acid
Titration of Polyprotic Acid Versus Strong Base
8.4 Theory of Indicators Ostwald’s Theory
Modern Quinoid Theory
8.5 Colour Change Range of an Indicator
8.6 Selection of Indicator and Indicator Error 8.7 Summary
8.8 Terminal Questions
8.9 Answers
8.1 INTRODUCTION
The term titrimetric analysis refers to quantitative chemical analysis carried out by
determining the volume of a solution of accurately known concentration, which is
required to react quantitatively with the solution of the substance to be determined.
The solution of accurately known strength is called the standard solution. The weight
of the substance to be determined is calculated from the volume of the standard
solution used and the known laws of stoichiometry. The standard solution is usually
added from a burette. The process of adding the standard solution until the reaction is
just complete is known as titration, and the substance to be determined is titrated.
The point at which this occurs is called the equivalence point or the theoretical (or
stoichiometric) end-point. The end point is judged usually, by the addition of an
auxiliary reagent, known as indicator.
The neutralization titrations include the titration of free bases, or those formed from
the salts of weak acids by hydrolysis with standard acids (acidimetry), and the
titration of acids or those formed by the hydrolysis of salts of weak bases, with
standard base (alkalimetry). These reactions involve the combination of hydrogen and
hydroxide ions to form water. This chapter describes the various types of acid–base
neutralization titrations, including the titration of strong acids or bases and weak acids
or bases. Through a description of the theory of indicators, the selection of a suitable
indicator for detecting the completion of a particular titration has been discussed.
Objectives
After studying the unit, you should be able to:
• State and explain the concept of titrimetry
• explain the nature of neutralization titration curves
• understand primary and secondary standards
• describe the theory of indicators
• select the appropriate indicator for a particular titration
• calculate the pH of acid, base and buffer solution.
52
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
8.2 BASIC CONCEPT OF TITRIMETRY, PRIMARY AND
SECONDARY STANDARDS
The acid – base titration involves a neutralization reaction in which an acid is reacted
with an equivalent amount of base. The titrant is always a strong acid or a strong base.
The object of neutralization, say, an alkaline solution with a standard solution of an
acid in the determination of the amount of acid which is exactly equivalent chemically
to the amount of base present. The point at which this is reached is equivalence point
or theoretical end point; an aqueous solution of the corresponding salt results. If both
the acid and base are strong electrolytes, the resultant solution will be neutral and have
a pH of 7; but if either the acid or base is a weak electrolyte, the salt will be
hydrolyzed to a certain degree, and the solution at the equivalence point will be either
slightly alkaline or slightly acidic. The exact pH of the solution at the end point can
readily be calculated from the ionization constant of the weak acid or the weak base
and the concentration of the solution. For any actual titration the correct end point will
be characterized by a definite value of the hydrogen – ion concentration of the
solution, the value depending upon the nature of the acid and the base and the
concentration of the solution.
Primary Standard
A primary standard is a substance which satisfies the following requirements:
1. It must be easy to obtain, to purify, to dry (preferably at 110-120oC) and to
preserve in pure state.
2. The substance should remain unaltered during weighing i.e., it should not be
hygroscopic, or oxidized by the air, or affected by carbon dioxide.
3. The substance should be capable of being tested for impurities by qualitative
and other tests of known sensitivity.
4. It should have a high equivalent so that the weighing errors may be negligible.
5. The substance should be readily soluble under the experimental conditions.
6. The reaction with the standard solution should be stoichiometric and practically instantaneous.
In practice, it is difficult to obtain a primary standard, and a compromise between the
above ideal requirements is necessary. The commonly employed primary standards
include sodium carbonate, sodium tetraborate, potassium hydrogen phthalate,
constant-boiling-point hydrochloric acid, potassium hydrogen iodate, and benzoic
acid.
Secondary Standard
A substance, which fulfills the requirement that it can be weighed accurately to
provide a known amount of reactant but which is not a pure substance, is called
secondary standard. It may be used for standardizations, and whose content of the
active substance has been found by the comparison against a primary standard.
SAQ 1
a) Mention any two requirements of a primary standard.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
b) How can secondary standards be used for standardizations?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
53
Neutralization
Titration-I
8.3 TITRATION CURVES
A titration curve is constructed by plotting pH of the solution during titration as
ordinates and the amount of acid or base added as abscissa. These curves are useful to
indicate equivalence point graphically. The change in pH in the neighborhood of the
equivalence is of greatest importance, as it enables us to select an indicator, which will give the smallest error. The nature of titration curve depends on the ionization
constants of acid and base employed in titration i.e., their strength. The principles of
acid–base equilibria are important for the construction and interpretation of titration
curves in neutralization titrations.
8.3.1 Titration of A Strong Acid Versus Strong Base
In the case of a strong acid versus strong base, both the titrant and analyte are
completely ionized. An example is the titration of hydrochloric acid with sodium
hydroxide.
H+
+ Cl − + Na+ + OH − → H2O + Na
+ + Cl −
The H+ and OH − combine to form H2O, and the other ions (Na+ and Cl − ) remain
unchanged, so the net result of neutralization is conversion of the HCl to a neutral
solution of NaCl.
The calculation of the titration curves involves computation of the pH for the
concentration of the particular species at the various stages of the titration. The pH during neutralization processes will be calculated as follows:
1. Up to the equivalence point the pH of the solution is determined by the amount
of the strong acid remaining present.
2. At the equivalence point pH is 7.
3. After passing the equivalence point the pH value is defined by the excess of the
base.
Before any NaOH is added to 1.0 M HCl solution, its pH is zero. As the titration
proceeds, part of H+ is removed from the solution as water. So the concentration of H
+
gradually decreases but this decrease is not significant, probably, due to the reason that the strong acids are good buffers at low pH. The results of calculation of pH during the
titration of 100 cm3 of HCl with NaOH of equal concentration are presented in Table
8.1. Fig. 8.1 is the graphical representation of these data.
Fig. 8.1: Neutralisation curves of 100 cm
3 of HCl with NaOH of same concentration
(calculated)
54
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
After 50 cm3 addition of NaOH solution, 50 cm
3 of un-neutralized acid will be present
in a total volume of 150 cm3.
[H+] = 50 x 1/150 M = 0.33 M , or pH = 0.48
After 75 cm3 addition of NaOH, [H
+] = 25 × 1/175 M = 0.143 M, or pH = 0.84
After 90 cm3addition of NaOH, [H+] = 10 × 1/190 M = 0.0526 M, or pH = 1.3
After 99 cm3addition of NaOH, [H
+] = 1 × 1/199 M = 0.00503 M, or pH = 2.3
After 99.9 cm3 addition of NaOH, [H+] = 0.1 × 1/199.9 M = 0.0005 M, or pH = 3.3
After 100 cm3 addition of base, the pH will change sharply to 7, i.e., the theoretical
end point provided carbon dioxide is absent; the resulting solution is simply one of
sodium chloride.
Where the pH for the over titrations of 0.10 and 1.0 cm3 corresponding to pH 10.7 and
11.7, respectively can be calculated as given below:
After 100.1 cm3 addition of NaOH, [OH─] = 0.1/200.1 M = 0.0005 M,
pOH = 3.3, and pH = 10.7
With 101 cm3 of base, [OH
─] = 1/201 = 0.005 M, pOH = 2.3, and pH = 11.7
These results show that as the titration proceeds, initially the pH rises slowly, but
between the addition of 99.9 and 100.1 cm3 of alkali, the pH of the solution rises from
3.3 to 10.7, 4.3 to 9.7 and 5.3 to 8.7 in case of 1 M, 0.1 M and 0.001 M solutions
respectively. Further addition of base does not cause a significant change in pH. The
results of titration are presented in Table 8.1 for 1M, 0.1 M and 0.01 M solutions of
acid and base, respectively.
Table 8.1: pH during Titration of 100 cm3 of HCl with NaOH of Equal
Concentration
NaOH added
cm3
1.0 M solution
pH
0.1 M solution
pH
0.01 M solution
pH
0.0 0.0 1.0 2.0
50.0 0.5 1.5 2.5
75.0 0.8 1.8 2.8
90.0 1.3 2.3 3.3
98.0 2.0 3.0 4.0
99.0 2.3 3.3 4.3
99.5 2.6 3.6 4.6
99.8 3.0 4.0 5.0
99.9 3.3 4.3 5.3
100.0 7.0 7.0 7.0
100.1 10.7 9.7 8.7
100.2 11.0 10.0 9.0
100.5 11.4 10.4 9.4
101.0 11.7 10.7 9.7
102.0 12.0 11.0 10.0
110.0 12.7 11.7 10.7
125.0 13.0 12.0 11.0
150.0 13.3 12.3 11.3
55
Neutralization
Titration-I
In the quantitative analysis we are especially interested in the change of pH near the
equivalence point. This part is accordingly shown on a large scale in Fig. 8.2, on
which are also indicated the colour change intervals of some of the common
indicators. The magnitude of the break will depend on both the concentration of the
acid and the concentration of the base. The reverse titration will be the mirror image of
these titrations.
Fig. 8.2: Neutralisation curves of 100 cm3 of HCl with NaOH of same concentration in
vicinity of equivalence point (calculated)
8.3.2 Titration of Weak Acid Versus Strong Base
We illustrate this case by the titration curve of 0.1 M acetic acid with 0.1 M sodium
hydroxide as shown in Fig. 8.3. The neutralization reaction is:
CH3COOH + Na+ + OH − →
H2O + Na+ + CH3COO–
The acetic acid, which is only few percent ionized, depending on the concentration, is
neutralized to water and an equivalent amount of the salt, sodium acetate. Before the
titration is started, we have 0.1 M CH3COOH. As soon as the titration is started some
of the CH3COOH is converted to CH3COONa, and a buffer system is set up. As the
titration proceeds, the pH slowly increases as the ratio [CH3COO–] / [CH3COOH]
changes. At the mid point of titration, [CH3COO–] = [CH3COOH], and the pH is equal
to pKa. At the equivalence point we have a solution of CH3COONa. Since this is
Bronsted base (it hydrolyzes), the pH at the equivalence point will be alkaline. The
pH will depend on the concentration of CH3COONa. The greater the concentration,
the higher the pH. As excess of NaOH is added beyond the equivalence point, the
ionization of base CH3COO– is suppressed to a negligible amount, and the pH is
determined only by the concentration of excess OH − . Therefore, the titration curve
beyond the equivalence point follows that for the titration of a strong acid.
56
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
Fig. 8.3: The pH titration curve of weak acid (CH3COOH) and strong base (NaOH)
The slowly rising region before the equivalence point is called the buffer region. It is
flattest at the midpoint, and so the buffer capacity is greatest at a pH corresponding
to pKa. The buffering capacity also depends on the concentrations of CH3COOH and
CH3COO–, and the total buffering capacity increases as the concentration increases. In
other words, the distance of the flat portion on either side of pKa will increase as
[CH3COOH] and [CH3COO–] increase.
For plotting the titration curve the pH values can be calculated as:
1. pH of weak acid can be calculated from the following equation:
pH = ½ pKa – ½ log [acid] … (8.1)
Strictly, [H+] = 0.5 ( (Ka2
+ 4Ka [acid]0.5) – Ka )
2. Up to equivalence point pH of the solution is determined by the dissociation
exponent of the weak acid and by the ratio of the concentration of free acid
(HA) and titrated acid (A − = salt) (buffer solution):
[ ][ ]acid
saltlogpKpH a += … (8.2)
3. The pH at the equivalence point is greater than 7 due to the alkaline hydrolysis
of the resulting salt:
pH = ½ pKw + ½ pKa + ½ log [salt]
or, pH = 7 + ½ pKa – ½ pc … (8.3)
Concentration of the salt is c mol dm − 3 to be consistent we use here pc = -log c.
4. After passing the equivalence point the excess of the base determines the pH of
the solution as if the hydrolyzing salts were not present at all.
The initial pH of 0.1 M acetic acid solution is computed from Eq. (8.1); the
57
Neutralization
Titration-I
dissociation of acid is relatively so small that it may be neglected in expressing the
concentration of acetic acid.
pH = ½ (-log 1.82 × 10 − 5) – ½ log 0.1
or, pH = 2.87 when 50 cm3 of 0.1 M alkali has been added,
[salt] = 50 × 0.1/150 = 3.33 × 10 − 2
and [acid] = 50 × 0.1/150 = 3.33 × 10 − 2
pH can be computed from Eq. (8.2)
pH = –log 1.82 x 10 − 5 + log 2
2
1033.3
1033.3−
−
×
×
or, pH = 4.74
The pH of solution at the equivalence point can be calculated using Eq. (8.3).
pH = 7 –1/2 log 1.82 × 10 − 5 + 1/2 log 5 × 10 − 2
= 7 + 2.37 – 1/2 (1.3) = 8.72
The pH values at other points on the titration curve can be similarly calculated. After
the equivalence point has been passed, the solution contains excess of OH − ions
which will repress the hydrolysis of the salt; the pH may be assumed, with sufficient
accuracy for our purpose, to be that due to the excess of base present, so that in this
region the titration curve will almost coincide with that for 0.1 M hydrochloric acid.
The results of titration are presented in Table 8.2. The results for the titration of 100
cm3 of a weaker acid (Ka = 1 × 10 − 7
) with 0.1 M sodium hydroxide at the laboratory
temperature are also included.
Table 8.2: Neutralization of 100 cm3 of 0.1 M acetic acid (Ka = 1.82 ×××× 10
− 5) and
of 100 cm3 of 0.1 M – HA (Ka = 1 ×××× 10
− 7) with 0.1 M sodium hydroxide.
0.1M-HA(Ka = 1 ×××× 10− 7
) 0.1 M NaOH used
cm3
0.1 M acetic acid
pH pH
0.0 2.9 4.0
10.0 3.8 6.0
25.0 4.3 6.5
50.0 4.7 7.0
90.0 5.7 8.0
99.0 6.7 9.0
99.5 7.0 9.3
99.8 7.4 9.7
99.9 7.7 9.8
100.0 8.7 9.9
100.2 10.0 10.0
100.5 10.4 10.4
101.0 10.7 10.7
110.0 11.7 11.7
125.0 12.0 12.0
150.0 12.3 12.3
200.0 12.5 12.5
58
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
For 0.1 M acetic acid and 0.1 M sodium hydroxide, it is evident from the titration
curve that neither methyl orange nor methyl red can be used as indicators. The
equivalence point is at pH 8.7, and it is necessary to use an indicator with a pH range
of slightly alkaline side, such as phenolpthalein, thymolpthalein, or thymol blue (pH
range, as base, 8.0-9.6). For the acid with Ka = 1 × 10 − 7 the equivalence point is at pH
= 10.0, but here the rate of change of pH in the neighborhood of the stoichiometric
point is very less pronounced, owing to considerable hydrolysis. Phenolphthalein will
commence to change colour after 92 cm3 of alkali have been added, and this change
will occur to the equivalence point; thus the end point will not be sharp and the
titration error will be appreciable. With thymolphthalein, however, the colour change
covers the pH range 9.3-10.5; this indicator may be used, the end-point will be more
sharp than for phenolphthalein, but nevertheless somewhat gradual, and the titration
error will be about 0.2 per cent. Acids having Ka < 1 × 10 − 7 cannot be satisfactorily
titrated in 0.1 M solution with simple indicator. In general it may be stated that weak
acids (Ka > 5 ×10 − 6) should be titrated with phenolphthalein, thymolphthalein, or
thymol blue as indicators.
Fig. 8.4: Titration of 50 cm3 of 0.1 M-H3PO4 with 0.1 M-KOH
Fig. 8.4 shows the titration curves for 50 cm3 of 0.1 M solutions of weak acids of
different Ka values titrated with 0.1 M KOH. The sharpness of the end point decreases
as Ka decreases. As in Fig. 8.4 sharpness will also decrease as the concentration
decreases. Generally for macro titrations (ca. 0.1 M), acids with Ka values of 10 − 6 can
be titrated accurately with a visual indicator; and with suitable colour comparisons,
those with Ka values approaching 10 − 8 can be titrated with reasonable accuracy. A pH
meter can be used to obtain better precision for the very weak acids by plotting the
titration curve. Weaker acids can be titrated in nonaqueous solvents that do not
possess the acidity or basicity of water.
59
Neutralization
Titration-I
8.3.3 Titration of a Weak Base Versus Strong Acid
The titration of a weak base with a strong acid is similar to the above case, but the
titration curves are reverse of those for a weak acid versus strong base. This
neutralization titration can be illustrated by the titration curve for 100 cm3 of 0.1 M
ammonia with 0.1 M hydrochloric acid as shown in Fig. 8.5. The neutralization
reaction is,
NH3 + H+ + Cl − → NH4+ + Cl −
Fig. 8.5: The pH titration curve of 100 cm3 0.1M ammonia (NH4OH) with 0.1M
hydrochloric acid (HCl)
At the beginning of the titration, we have 0.1 M NH3 and the pH is calculated for a
weak base. As soon as some acid is added, some of the NH3 is converted into NH4+
and the buffer region is formed. End point is judged by inflection point of the titration
curve but the jump in pH is smaller than in case of strong base - strong acid titration.
The pH values obtained in the course of titration can be calculated as given below:
1. The pH of the solution of a weak base:
pH = pKw – ½ pKb + 1/2 log [base] … (8.4)
Strictly, [H+] = Kw / (0.5 ( (
2
bK + 4Kb [base])0.5
– Kb )
2. The pH upto the equivalence point:
[ ][ ]salt
baselogpK pKpH bw +−= … (8.5)
3. The pH of the equivalence point is lower than 7, due to the hydrolysis of
resulting salt:
pH = 1/2 pKw – 1/2 pKb –1/2 log [salt]
or, pH = 7 – 1/2 pKb + 1/2 pc … (8.6)
C and pc have the same meaning as used in Eq. (8.3).
4. After the attainment of equivalence point, the solution contains the excess of H+
ions, hydrolysis of the salt will be repressed, and the subsequent pH change may
be assumed with sufficient accuracy for our purpose, to those due to the excess
of acid present.
60
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
Example
Titration of 100 cm3 of 0.1 M aqueous ammonia (Kb = 1.8 × 10 − 5) with 0.1 M HCl at
the ambient temperature. The pH of the solution at the equivalence point is given by
the Eq. (8.6):
pH = 7 – 1/2 pKb + 1/2 pc
= 7 – 2.37 + ½ (1.3)
= 5.28
For the titration of weak base and strong acid, those indicators are generally used
which change their colour in the acidic pH range. It is clear from the Fig. 8.4 that
neither thymolphthalein nor phenolpthalein can be employed in the titration of 0.1M
aqueous ammonia. The equivalence point is at pH 5.3, and it is necessary to use an
indicator with a pH range on the slightly acid side (3 – 6.5), such as methyl orange,
methyl red, bromophenol blue, or bromocresol green. The last named indicators are
applicable for the titration of all weak bases (Kb > 5 × 10 − 6) with strong acids
For the weak base (Kb = 1 × 10 − 7), bromophenol blue or methyl orange may be used;
no sharp colour change will be obtained with bromo-cresol green or with methyl red,
and the titration error will be considerable.
8.3.4 Titration of Weak Acid Versus Weak Base
This can be illustrated by titration of 100 cm3 of 0.1 M acetic acid (Ka = 1.8 × 10 − 5
)
with 0.1 M aqueous ammonia (Kb = 1.8 × 10 − 5). The pH at the equivalence point is
given by:
pH = 1/2 pKw + ½ pKa – ½ pKb … (8.7)
= 7.0 + 2.37 – 2.37 = 7.0
The neutralization curve upto the equivalence point is almost identical with that using
0.1 M sodium hydroxide as the base; beyond this point the titration is virtually the
addition of 0.1 M aqueous ammonia solution to 0.1 M ammonium acetate solution and
Eq. (8.5) is applicable to the calculation of the pH. The titration curve for the
neutralization of 100 cm3 0.1 M acetic acid with 0.1 M aqueous ammonia at the
laboratory temperature is shown in Fig. 8.6. The main feature of the curve is that the
change of pH near equivalence point and, indeed, during the whole of the
neutralization curve is very gradual.
Fig. 8.6: Titration curve of weak base and weak acid
61
Neutralization
Titration-I
In this sort of titration, no sudden change in pH, and hence no sharp end point can be
found with any simple indicator. A mixed indicator which exhibits a sharp colour
change over a very limited pH range, may sometimes be found which is suitable. Thus
for acetic acid – ammonia solution titrations, neutral red methylene blue indicator may
be used, but on the whole, it is best to avoid the use of indicators in titrations involving
both a weak acid and a weak base.
8.3.5 Titration of Sodium Carbonate Versus Strong Acid
Sodium carbonate is a Bronsted base that is as a primary standard for the standardization of
strong acids. It hydrolyses in two steps:
CO32 − + H2O � HCO3
¯ + OH¯ 2w1 10x1.2KH −
===2
1a
b K
KK .. (8.8)
HCO3¯ + H2O � CO2 + H2O + OH − 8w
2 10x3.2KH −===
1
2a
b K
KK ... (8.9)
where 1a
K and 2a
K refer to the Ka values of H2CO3.
HCO3¯ is the conjugate acid of CO3
2 − and H2CO3 is the conjugate acid of HCO3¯ and
Kb values are calculated for salts of weak acids and bases (i.e., from KaKb = Kw).
A titration curve for Na2CO3 with HCl is shown in Fig. 8.7 (solid line). Even though
1bK is considerably larger than the 10 − 6 required for a sharp end point, the pH break
is decreased by the formation of CO2 beyond the first equivalence point. The second
end point is not very sharp either, because 2bK is smaller than 10 − 6. Fortunately, this
end point can be sharpened because the CO2 produced from the neutralization of
HCO3− is volatile and can be boiled out of the solution. This is described below.
Fig. 8.7: Titration of 100 cm3 of 0.1 M-Na2CO3 with 0.1 M-HCl
62
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
At the start of the titration, the pH is determined by the hydrolysis of the Bronsted
base −2
3CO . After the titration is begun, part of the −2
3CO is converted to HCO3¯ ; and
−
3
-2
3 /HCOCO buffer region is established. At the first equivalence point, there remains
a solution of HCO3¯, and
21 aa ][H KK≈+ . Beyond the first equivalence point, the
HCO3¯ is partially converted to H2CO3 (CO2) and a partial buffer region is established,
the pH being established by [HCO3¯]/[CO2]. The pH at the second equivalence point is
determined by the concentration of the weak acid CO2.
Phenolphthalein is used to detect the first equivalence point, and methyl orange is used
to detect the second one. Neither the point, however, is very sharp. In actual practice,
the phenolphthalein end point is used only to get an approximation of where the
second end point will occur; phenolphthalein is colourless beyond the first end point
and does not interfere. The second equivalence point, which is used for accurate
titrations, is normally not very accurate with methyl orange indicator because the
gradual changes in colour of the methyl orange. This is caused by the gradual decrease
in pH due to the HCO3¯ /CO2 buffer system beyond the first end point.
If beyond the first end point the solution is boiled after each addition of HCl to remove
the CO2 from the solution, the buffer system of −
3HCO /CO2 would be removed,
leaving only HCO3¯ in the solution. This is both a weak acid and a weak base whose
pH (≈ 8.3) is independent of concentration (21 aa ][H KK=
+ or21 bb ][OH KK=
− .
Then the pH would remain essentially constant until the equivalence point when we
are left with a neutral solution of water and NaCl (pH = 7.0).
8.3.6 Titration of Polyprotic Acid Versus Strong Base
Diprotic acids can be titrated stepwise, if 1aK ≥ 10
4 x
2aK , the solution behaves like a
mixture of two acids with constants 1aK and
2aK respectively. Thus for sulphurous
acid (H2SO3), 1aK = 1.7 × 10 − 2
and 2aK = 1.0 × 10 − 7
, it is evident that there will be a
sharp change of pH near the first equivalence point, but for the second stage the
change will be less pronounced, yet first sufficient for the use of , say thymolphthalein
as indicator. For carbonic acid (H2CO3), 1aK = 4.3 × 10 − 7
and 2aK = 5.6 × 10 − 11
,
only the first stage will be just discernible in the neutralization curve, the second stage
is far too weak to exhibit any point of inflexion and there is no suitable indicator for
direct titration.
Now the titration curve for diprotic acid (H2A) versus Na2CO3 is to be discussed.
During titration upto first equivalance point, a solution of HA − / H2A buffer region is
established. At the first equivalance point, a solution of HA¯ exists, and
21 aa ][H KK≈+ or
21 aa Kp2
1Kp
2
1pH += . Beyond this, a A2 − / HA − buffer exists;
and finally the second equivalance point, the pH is determined from the hydrolysis of
A2 − .
For triprotic acid (H3PO4), the ionization is given below:
H3PO4 � H+ + H2PO4
− 1aK = 7.5 × 10 − 3
= ]PO[H
]PO[H ][H
43
-
42
+
... (8.10)
H2PO4− � H
+ +
−2
4HPO 2aK = 6.2 × 10 − 8
= ]PO[H
][HPO ][H
42
-2
4
−
+
… (8.11)
63
Neutralization
Titration-I
−2
4HPO � H+ + −3
4PO 3aK = 5 × 10 − 13 =
]PO[H
][PO ][H2
4
-3
4
−
+
… (8.12)
The overall ionization constant is the product of the individual ionization constants:
H3PO4 � 3H+ + −3
4PO
]PO[H
][PO ][H 10x32.2
43
-3
4
322
aaaa 321
+
−=== KKKK … (8.13)
Orthophosphoric acid will behave like a mixture of three monoprotic acids. The pH of
the first equivalance point for 0.1 M H3PO4 with 0.1 M NaOH is given approximately
by:
4.6pKpK21 a2
1a2
1 =+ … (8.14)
and that of the second equivalance point by:
7.9pKpK32 a2
1a2
1 =+ … (8.15)
In the very weak third stage, the curve is flat and no indicator is available, the third
equivalance point may be computed approximately from the following equation:
pcpKpKpH 21
a21
w21
3−+= … (8.16)
= 7 + 6.15 – ½ (1.6) = 12.35
(Here the terms have their usual meaning)
The experimental neutralization curve of 50 cm3 of 0.1 M H3PO4 with KOH and
suitable indicators are shown in Fig. 8.4.
SAQ 2
a) Calculate the pH at 0, 10, 90, 100 and 110 % of the titration for the titration of
50 cm3 of 0.5 M HCl with 0.5 M NaOH.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
b) Calculate the pH at 0, 25 and 50 cm3 titrant in the titration of 50 cm
3 of 1 M
acetic acid with 1 M NaOH.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
c) Calculate the concentration of OH − and the pH of a solution that is 0.2 M in
aqueous NH3 and 0.1 M in NH4Cl.
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
64
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
d) What is the buffer region?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
8.4 THEORY OF INDICATORS
Indicators are the organic substances, the presence of very small amount of which
indicates the termination of a chemical reaction by a change of colour. Indicators are
of various types, e.g., acid-base indicators, redox indicators, adsorption indicator, etc.
Acid-base indicators are the organic substances, which have one colour in acid
solution while different colour in alkaline solution. The following theories have been
put forward to explain the colour change of the acid base indicator.
8.4.1 Ostwald’s Theory
According to the Ostwald theory indicators are such weak acids ( HIn) or bases
(InOH) whose colours are different from that of the indicator-ion formed by their
dissociation. The equilibria in the aqueous solution may be written as:
HIn � H+ + In
¯
InOH � OH¯
+ In+
Unionized ionized
colour colour
If the indicator is a free amine or substituted amine the equilibrium is:
In + H2O � OH¯ + HIn+
Indicator-acids HIn dissociate in aqueous solution as follows:
HIn � H+
+ In¯
Applying the law of mass action to this dissociation
a
-
[HIn]
][In ][HK=
+
… (8.17)
from which
]In[
]HIn[]H[ a −
+= K … (8.18)
The actual colour of the indicator, which depends upon the ratio of the concentration
of the ionized and unionized forms, is thus directly related to the hydrogen–ion
concentration. Eq. (8.18) may be written as
apK]HIn[
]In[logpH +=
−
... (8.19)
In this equation [HIn] represents the concentration of the undissociated indicator-
molecule whose colour is called ‘acid colour’ while [In − ] denotes the concentration of
the indicator-anions, the colour of which is called ‘alkaline colour’. Ka is the
dissociation constant of the indicator- acid.
The indicator base may be characterized similarly to the indicator acid
InOH � In+ + OH −
65
Neutralization
Titration-I
b
]InOH[
]OH[]In[K=
−+
… (8.20)
taking the ionic product of water into consideration
bw
]InOH[]H[
]In[K
K=
+
+
… (8.21)
[ ][ ]InOH
In]H[
b
w
+
+=
K
K … (8.22)
]In[
]InOH[logpKpKpH bw +
+−= … (8.23)
where Kw represents the ionic product of water, Kb denotes the dissociation constant of
the indicator base, the colour of which is the alkaline colour ; the acid colour is due to
the In+
ions.
8.4.2 Modern Quinoid Theory
According to the modern quinoid theory an acid-base indicator is a dynamic
equilibrium mixture of two alternative tautomeric forms; ordinarily one form is
benzenoid while the other is quinoid. Out of these one form exists in the acidic
solution, while the other in alkaline solution. Change in pH causes the transition of
benzenoid form to quinoid form and vise versa and consequently a change in colour.
The colour changes in case of methyl orange and phenolphthalein are given below:
Methyl Orange
Na O3S N=N N(CH
3)
2+
+
Yellow Benzenoid form (in bases)
Na O3S N N=
H H
H
N (CH3)
2+
+
+
+
Red Quinoid form (in acids)
Phenolphthalein
C O HO C
O
COO
H
HOH
OH
C=O
+
++
Colourless, benzenoid form
(in acid)
Red, Quinoidform
(in alkali)
66
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
SAQ 3
Why the quinoid form of the indicator is coloured or darker than benzenoid form?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
8.5 COLOUR CHANGE RANGE OF AN INDICATOR
A large number of acid-base indicators are available, which possess different colour
according to the hydrogen-ion concentration in the solution. The important
characteristics of these indicators is that the change from a predominantly acid colour
to predominantly alkaline colour is not sudden and abrupt, but takes place within a
small interval of pH (generally about two pH units) termed the colour-change
interval of the indicator . In this pH interval the indicator shows mixed colours of
different shades of the acid and alkaline colours, i.e. the colour intensity of one colour
indicators increases gradually. The acidic red colour of methyl orange and methyl red
is more sensitively perceivable beside the alkaline yellow colour, since the colour
intensity of red form is greater. The position of the colour-change interval in the pH
scale varies widely with different indicators. For most acid-base titrations we can
therefore select an indicator, which exhibits a distinct colour change at a pH close to
that obtained at the equivalence point. Table 8.3 summarizes a selected list of
indicators suitable for neutralization titration.
Table 8.3: The pH Transition Ranges and Colours of Some Indicators
Indicator pH range Colour in
acid solution
Colour in
alkaline solution pK����In
Brilliant cresylblue (acid) 0.0-1.0 Red-orange Blue -
Cresol red (acid) 0.2-1.8 Red Yellow -
Thymol blue (acid) 1.8-2.8 Red Yellow 1.7
m-Cresol purple 1.2-2.8 Red Yellow -
Bromo-phenol blue 3.0-4.6 Yellow Blue 4.1
Methyl Yellow 2.9-4.0 Red Yellow 3.3
Ethyl Orange 3.0-4.5 Red Orange -
Methyl orange 3.1-4.4 Red Orange 3.7
Congo red 3.0-5.0 Blue Red -
Bromo-cresol green 3.8-5.4 Yellow Blue 4.7
Methyl red 4.2-6.3 Red Yellow 5.0
Ethyl red 4.5-6.5 Red Orange -
Propyl red 4.6-6.6 Red Yellow -
Chlorophenol red 4.8-6.4 Yellow Red 6.1
4-Nitrophenol 5.6-7.6 Colourless Yellow 7.1
Bromo-cresol purple 5.2-6.8 Yellow Purple 6.1
Bromo-phenol red 5.2-6.8 Yellow Red -
Bromo-thymol blue 6.0-7.6 Yellow Blue 7.1
Neutral red 6.8-8.0 Red Orange -
Phenol red 6.8-8.4 Yellow Red 7.8
Cresol-red (base) 7.2-8.8 Yellow Red 8.2
m-Cresol purple 7.6-9.2 Yellow Purple -
Thymol blue (base) 8.0-9.6 Yellow Blue 8.9
o-Cresol-phthalein 8.2-9.8 Colourless Red -
Phenol-phthalein 8.3-10.0 Colourless Red 9.6
Thymolphthalein 8.3-10.5 Colourless Blue 9.3
Alizarin yellow R 10.1-12.0 Yellow Orange red -
Brilliant crystal blue (base) 10.8-12.0 Blue Yellow -
Tropaeolin O 11.1-12.7 Yellow Orange -
67
Neutralization
Titration-I
SAQ 4
What is the usual pH range for the colour change of an indicator at the end point?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
8.6 SELECTION OF INDICATOR AND INDICATOR
ERROR
The primary consideration in choosing an indicator for a given titration is that the
indicator should change, that is the end point should occur, within the required
increment, ∆v of the equivalence point. As a general rule it may be stated that for a
titration to be feasible there should be change of approximately two units of pH at or
near the stochiometric point produced by the addition of small volume of the reagent.
The pH range at either side of the equivalence point (0.1-1 cm3) may be calculated,
and the difference will indicate whether the change is large enough to permit a sharp
end point to be observed. Alternatively, the pH change on the both sides of the
equivalence point is noted from the neutralization curve determined by potentiometric
titration. If the pH change is satisfactory an indicator should be selected that changes
its colour at or near the equivalence point. Next, the molar absorptivity of the indicator
in its two forms should be known in order that the amount of indicator required to give
a readily observable change can be determined, and this amount should be small to
avoid consumption of titrant. Finally the personal preference to the operator can be
consulted as a selection of colours, etc., most studied to his vision. Yet, again it should
be added that the indicator reaction should be fast.
Indicator Error
The indicator error follows from the fact, that the indicator itself will consume a
certain amount of the standard solution. The amount of this consumption of standard
solution depends first of all upon the nature of indicator and its concentration; whether
it is alkaline for instance, etc. If ct. vt >> cind. vind where ct and cind are the
concentrations of titrant and the indicator solution; vt and vind are the volumes used of
titrant and indicator, respectively, then the indicator error will be negligible.
SAQ 5
What is the indicator error?
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
8.7 SUMMARY
In this unit we have described the basic concept of titrimetry. The neutralization
curves for strong acid with strong base, weak acid with strong base, weak base with
strong acid, weak acid with weak base, sodium carbonate with strong acid, and
polyprotic acid with strong base have been illustrated. The nature of titration curves
68
Estimations Based On
Kinetic and Acid-Base
Equilibria Studies
has been explained. The calculations of pH of the solution before titration, at the
equivalence point, and after the equivalence point have been illustrated. The theory of
indicators and the selection of the appropriate indicator for a particular titration have
been discussed.
8.8 TERMINAL QUESTIONS
1. Only strong acid or base is used as the titrant, why?
2. Calculate the [OH−
], pOH, pH and percent ionization for 0.2 M aqueous NH3.
3. Calculate the concentration of the species in a 0.1 M H2SO4. K2 = 1.2 × 10− 2
.
4. When the mixtures of acids (or bases) can be titrated stepwise?
5. Calculate the pH of a solution prepared by adding 25 cm3 of 0.10 M NaOH to
30 cm3 of 0.20 M acetic acid.
6. Write the criteria for choosing an indicator.
8.9 ANSWERS
Self Assessment Questions
1. a) A primary standard is a substance which satisfies the following
requirements:
• It must be easy to obtain, to purify, to dry ( preferably at 110-
120oC) and to preserve in pure state.
• The substance should remain unaltered during weighing i.e., it
should not be hygroscopic, or oxidized by the air, or affected by
carbon dioxide.
• The substance should be capable of being tested for impurities by
qualitative and other tests of known sensitivity.
b) Secondary standards may be used for standardizations by finding the
content of the active substance comparing against a primary standard.
2. a) 0.30, 0.39, 1.58, 7.00, and 12.48
b) 2.37, 4.74, and 9.07
c) [OH¯] = 3.6 x 10
− 5 M and pOH = 9.56
d) The slowly rising region before the equivalence point is called the buffer
region. It is flattest at the midpoint, and so the buffer capacity is greatest
at a pH corresponding to pKa.
3. The increased per cent conjugation in the quinoid form of the indicator results
the shifting of the λmax from a shorter to a greater wave length (i.e., from the
ultra violet region to the visible region).
4. The point at which the colour change for the indicator occurs in a titration is
called end point. Typically, colour changes occur over a range of 1.5 to 2.0.
5. Section 8.6, 2nd Para.
69
Neutralization
Titration-I
Terminal Questions
1. The magnitude of the break at the equivalance point is significant and the end
point can be obtained with greater accuracy.
2. [OH−
] = 1.9 x 10− 3
M, pOH = 2.72, pH = 11.28 and % ionization = 0.95%
ionized.
3. In first step, complete ionization of H2SO4 is complete.
−++→+ 43242 HSOOHOHSOH
0.10 M 0.10 M 0.10 M
In second step, ionization is not complete.
OHHSO 24 +−
� −+
+2
43 SOOH and ]HSO[
]SO[]OH[
4
2
432 −
−+
=K =1.2 × 10 − 2
Let x = ]HSO[ 4
−that ionizes. Therefore at equlibrium
OHHSO 24 +−
� −+
+2
43 SOOH
(0.1-x) M (0.10 + x )M xM
↓ ↓
I step II step
2
4
2
432 102.1
)10.0(
)()10.0(
]HSO[
]SO[]OH[ −
−
−+
×=−
+==
x
xxK
x cannot be ignored because K is too large
[H3O+] = [
−2
4SO ] = 0.01M. The concentrations of species in 0.1 M H2SO4 are:
[H2SO4] ≈ 0.0 M ; −
4HSO = (0.10-x) M = 0.09 M; [−2
4SO ] = 0.01 M
[H3O+] = (0.10 + x) M =0.11M
[OH−
] = Kw/ [H3O+] =1.0 × 10
− 14/0.11 = 9.1 × 10
− 14
4. There should be an appreciable difference in their strength and one acid or base
should be at least 104 times weaker than the other to titrate separately.
5. CH3COOH + NaOH � CH3COONa + H2O
m mol of CH3COOH formed = m mol of NaOH added =2.5 m mol
Unneutralized CH3COOH = 6.0 –2.5 = 3.5 m mol
pH= 4.76 + log 2.5/3.5 = 4.61
6. Choose an indicator with a pKa near the equivalence.