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(Volumetric analysis)
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Theoretical volumetric analysis
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Changing the Concentration
Adding water to a titrant or analyte will change the concentration of that solution. Each
solution has a molarity, which is equal to the number of moles of a solvent per liter of
solution. When you add water to a solution, the number of moles of the solvent stays the same
while the volume increases. Therefore, the molarity decreases; the solution is diluted.
Consider an indicator which is a weak acid, with the formula HIn. At equilibrium, the
following equilibrium equation is established with its conjugate base:
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The acid and its conjugate base have different colors. At low pH values the concentration of
H3O+ is high and so the equilibrium position lies to the left. The equilibrium solution has the
color A. At high pH values, the concentration of H3O+ is low - the equilibrium position thus
lies to the right and the equilibrium solution has color B.
Phenolphthalein is an example of an indicator which establishes this type of equilibrium in
aqueous solution:
Phenolphthalein is a colourless, weak acid which dissociates in water forming pink anions.
Under acidic conditions, the equilibrium is to the left, and the concentration of the anions is
too low for the pink color to be observed. However, under alkaline conditions, the equilibrium
is to the right, and the concentration of the anion becomes sufficient for the pink color to be
observed.
We can apply equilibrium law to indicator equilibria - in general for a weak acid indicator:
Kln is known as the indicator dissociation constant. The color of the indicator turns from
color A to color B or vice versa at its turning point. At this point:
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So, from equation:
The pH of the solution at its turning point is called the pKln and is the pH at which half of the
indicator is in its acid form and the other half in the form of its conjugate base.
Indicator Range
At a low pH, a weak acid indicator is almost entirely in the HIn form, the color of which
predominates. As the pH increases - the intensity of the color of HIn decreases and the
equilibrium is pushed to the right. Therefore, the intensity of the color of In- increases. An
indicator is most effective if the color change is distinct and over a low pH range. For most
indicators the range is within ±1 of the pKln value: - please see the table below for examples,
to the right is a model of the acid form of each indicator - with the color of the solution at the
turning point.
A Universal Indicator is a mixture of indicators which give a gradual change in color over a
wide pH range - the pH of a solution can be approximately identified when a few drops of
universal indicator are mixed with the solution.
Indicators are used in titration solutions to signal the completion of the acid-base reaction.
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5- Theories of indicator behavior
There are two theories which explain the change of color indicators with change in pH.
A- Ostwald's Theory
According to Ostwald’s theory the color change of any indicator is due to its ionization. The
unionized form of indicator has different color than its ionized form.
An indicator is either a weak acid or base, so its ionization is highly affected in acids and
bases. If an indicator is a weak acid, its ionization would be very much low in acids due to
common H+ ions while it is fairly ionized in alkalies. In the same way, if the indicator is a
weak base, its ionization is large in acids and low in alkalies due to common OH- ions.
B- Quinonoid theory
According to quinonoid theory, an acid-base indicator exists in two tautomeric forms having
different structures which are in equilibrium. One form is termed benzenoid form and the
other quinonoid form.
The two forms have different colors. The color change is due to the interconversion of one
tautomeric form into other. One form mainly exists in acidic medium and the other in alkaline
medium.
Thus, during titration the medium changes from acidic to alkaline or vice-versa. The change
in pH converts one tautomeric form into other and thus, the color change occurs.
Phenolphthalein has benzoic form in acidic medium and thus, it is colourless while it has
quinonoid form in alkaline medium which has pink color.
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Methyl orange has quinonoid form in acidic solution and benzenoid form in alkaline solution.
The color of benzenoid form is yellow while that of quinonoid form is red.
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3. Replacement Titration: When direct or back titrations do not give sharp endpoints or
when there is no suitable indicator for the analyte the metal may be determined by this
method. The metal to be analyzed is added to a metal-EDTA complex. The analyte ion (with
higher Kf') displaces EDTA from the metal and the metal is subsequently titrated with
standard EDTA. For example, in the determination of Mn an excess of Mg EDTA chelate is
added to Mn solution. The Mn ions quantitatively displace Mg from Mg-EDTA solution
because Mn forms a more stable complex with EDTA. The freed Mg metal is then directly
titrated with a standard solution of EDTA using Eriochrome black T indicator. Ca, Pb and Hg
may also be determined by this method.
4. Indirect Titration: Certain anions that form precipitate with metal cations and do not
react with EDTA can be analyzed indirectly. The anion is first precipitated with a metal cation
and the precipitate is washed and boiled with an excess of disodium EDTA solution to form
the metal complex. The protons from disodium EDTA are displaced by a heavy metal and
titrated with sodium alkali. Therefore, this method is also called alkalimetric titration. For
example, barbiturates can be determined by this method.
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There are three factors that are important in determining the magnitude of break in titration
curve at end point.
The stability of complex formed: The greater the stability constant for complex
formed, larger the charge in free metal concentration (pM) at equivalent point and clearer
would be the end point.
The number of steps involved in complex formation: Fewer the number of steps
required in the formation of the complex, greater would be the break in titration curve at
equivalent point and clearer would be the end point.
Effect of pH: During a complexometric titration, the pH must be constant by use of a
buffer solution. Control of pH is important since the H + ion plays an important role in
chelation. Most ligands are basic and bind to H + ions throughout a wide range of pH. Some of
these H+ ions are frequently displaced from the ligands (chelating agents) by the metal during
chelate formation.
Equation below shows complexation between metal ion and H+ ion for ligand:
M2+ + H2-EDTA → M-EDTA + 2H+
Thus, stability of metal complex is pH dependent. Lower the pH of the solution, lesser would
be the stability of complex (because more H+ ions are available to compete with the metal ions
for ligand). Only metals that form very stable complexes can be titrated in acidic solution, and
metals forming weak complexes can only be effectively titrated in alkaline solution.
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Mechanism of action of indicator:
During an EDTA titration 2 complexes are formed: i) M-EDTA complex and ii) M-indicator
complex. The metal-indicator complex must be less stable than the metal-indicator complex.
M-In + EDTA → M-EDTA + In
Erichrome black T is a metal ion indicator. In the pH range 7-11 the dye itself has a blue
color. In this pH range addition of metallic salts produces a brilliant change in color from blue
to red.
M2+ + HIn2- → MIn- + H+
(Blue) (Red)
This color change can be obtained with the metal ions. As the EDTA solution is added, the
concentration of the metal ion in the solution decreases due to the formation of metal-EDTA
complex. At the end point no more free metal ions are present in the solution. At this stage,
the free indicator is liberated and hence the color changes from red to blue.
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9- Auxiliary reducing reagents
A number of metals are good reducing agents and have been used for the prereduction of
analytes. Included among these reductants are zinc, aluminum, cadmium, lead, nickel, copper,
and silver (in the presence of chloride ion). Sticks or coils of the metal can be immersed
directly in the analyte solution. After reduction is judged complete, the solid is removed
manually and rinsed with water. The analyte solution must be filtered to remove granular or
powdered forms of the metal. An alternative to filtration is the use of a redactor, such as that
shown in Figure 20-1.3 In the redactor, the finely divided metal is held in a vertical glass tube
through which the solution is drawn under a mild vacuum. The metal in a redactor is normally
sufficient for hundreds of reductions.
A typical Jones redactor has a diameter of about 2 cm and holds a 40- to 50-cm column of
amalgamated zinc. Amalgamation is accomplished by allowing zinc granules to stand briefly
in a solution of mercury (II) chloride, where the following reaction occurs:
Zinc amalgam is nearly as effective for reductions as the pure metal and has the important
virtue of inhibiting the reduction of hydrogen ions by zinc. This side reaction needlessly uses
up the reducing agent and also contaminates the sample solution with a large amount of zinc
(II) ions. Solutions that are quite acidic can be passed through a Jones redactor without
significant hydrogen formation.
Silver is not a good reducing agent unless chloride or some other ion that forms a silver salt of
low solubility is present. For this reason, prereductions with a Walden redactor are generally
carried out from hydrochloric acid solutions of the analyte. The coating of silver chloride
produced on the metal is removed periodically by dipping a zinc rod into the solution that
covers the packing. Table 20-1 suggests that the Walden redactor is somewhat more selective
in its action than is the Jones redactor.
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10- A/ Calculate the pAg and pCl for the solution containing 25
ml of 0.2 F NaCl and 5 ml of 0.9 F AgNO3?
Ksp AgCl = 1.82 x10-10
B/ What is the normality of HCl solution if 95 ml are required
to titrate 1.5 gm of pure Na2CO3 to H2CO3?
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Practical volumetric chemistry
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4- storing the solution of AgNO3 in an amber colored glass bottle
The silver nitrate reacts with atmospheric energy provided by sunlight if kept in a transparent
bottle and get decomposed to silver oxide Ag2O so, the silver nitrate is kept in colored bottle.
A primary standard is some substance such as oxalic acid which can be precisely weighed out
in pure form, so that the number of moles present can be accurately determined from the
measured weight and the known molar mass.
The standard solution used in an acid-base titration need not always be primary standard, the
different between primary and secondary standard is primary standard are typically used in
titration to determine an unknown concentration and secondary standard is a chemical that has
been standardized against a primary standard for use is a specific analysis.
Standardization and titration are two related chemical terms. Although they use the same
technique to get a measurement, their applications are different from each other.
Standardization is used to determine the exact concentration of a prepared solution. Titrations
are used to determine the unknown concentrations of samples. Most often, standardization is
also done as a titration. The main difference between standardization and titration is
that standardization processes essentially uses primary standard solutions whereas titrations
do not essentially use primary standard solutions.
Since you know how much standard you have used and its concentration you can work out the
concentration of the unknown sample. Remember you should always repeat whole process at
least 3 times to ensure you have an accurate result, as there is the potential for both random
and systematic errors to affect your results.
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Q3 / Explain types of titration with example?
There are many types of titration when considering goals and procedures. However, the most
common types of titration in quantitative chemical analysis are redox titration and acid-base
titration.
Titrations can be classified as:
1. Acid-Base Titration
The strength of an acid can be determined using a standard solution of a base. This process is
called acidimetry. In the same way, the strength of a base can be found with the help of a
standard solution of an acid, which is known as alkalimetry. Both titrations involve in
the neutralization reaction of alkali.
2. Redox Titrations
The redox titration is also known as an oxidation-reduction reaction. In this type of titration,
the chemical reaction takes place with a transfer of electrons in the reacting ions of aqueous
solutions. The titrations are named after the reagent that is used in are as follows;
Permanganate Titrations
Dichromate Titrations
Iodometric and Iodometric Titrations
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Permanganate Titrations
In this titration, the potassium permanganate is used as an oxidizing agent. It is maintained
with the use of dilute sulphuric acid. Here is the equation.
2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2 + 5O
Or MnO4– + 8H + 5e → Mn2++ 4H2O
Further, the solution remains colorless before the endpoint. The potassium permanganate is
used to estimate oxalic acid, ferrous salts, hydrogen peroxide, oxalates and more. While the
solution of potassium permanganate is always standardized before it is used.
Dichromate Titrations
These are titrations in which, potassium dichromate is used as an oxidizing agent in acidic
medium. The medium is maintained acidic by the use of dilute sulphuric acid. The potential
equation is:
K2Cr2O7 + 4H2SO4 → K2Cr2(SO4) + 4H2O + 3[O]
Or Cr2O27- + 14H + 6e → 2 Cr3+ + 7H2O
The solution of potassium dichromate can be directly used for titrations. It is mainly used for
the estimation of ferrous salts and iodides.
3. Precipitation Titrations
The titration is based on the insoluble precipitate formation when the two reacting substances
are brought into contact are called precipitation titration. For instance, when the solution of
silver nitrate is used to a solution of ammonium thiocyanate or sodium chloride, it reacts and
forms a white precipitate of silver thiocyanate or silver chloride.
AgNO3 + NaCl → AgCl + NaNO3
AgNO3 + NH4CNS → AgCNS + NH4NO3
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4. Complexometric Titrations
The complexometric titration is where an undissociated complex is formed at an equivalence
point. It is greater than the precipitation titrations, and there will be no error due to co-
precipitations.
Hg2+ + 2SCN– → Hg (SCN)2
Ag+ + 2CN– → [Ag (CN)2]–
Ethylenediaminetetraacetic acid (EDTA) is an important reagent that forms complexes with
metals.
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Q4 / Calculate the weight required to prepare 500 ml, 0.01 M
K2SO4?
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Q5/ What is the volume required to prepare 1000 ml, 0.5 N
CH3COOH (if you know sp.gr = 1.048, 37%)?
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References:
[1] Clackamas Community College: Dilution Calculations
[2] Titration of a Weak Acid with a Strong Base
[3] Mountain Empire Community College: Lesson 7: Acids and Bases
[4] https://www.ajlobby.com/2018/01/fundamentals-of-analytical-chemistry.html
[5] https://byjus.com/chemistry/complexometric-titration/
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