PROF. R.C.

SHARMA
PHONE: 9911322574
E-mail: [email protected]
Titration Reaction types Classification of titration by end-point techniques
1.Acid-Base Titrations 10.1) Conductometric titration
10.2) Potentiometric titration
2.Redox titrations 10.3) Spectrophotometric titration
3.Complexometric Titrations 10.4) Amperometric titration
10.5) Thermometric or enthalpimetric titration
4.Zeta- potential Tittrations 10.6) Nonaqueous titration
10.7) Automatic titration
5.Miscellaneous titration 10.8) Electrochemical titration
6.Iodimetry titration 11. Back titrations
7.Precipitation titration 12. Virus titration
8.KjeldahlTitration  Titrimatery types:
9.Argentometric Titrations • Volumetric titrimetry
9.1) The Mohr titration: • Gravimetric or weight titrimetry
9.2) Volhard titration • Coulometric titrimetry
9.3) Fajans titration • Standardization
 Types of Titrations
1.Acid-Base Titrations
2.Redox titrations
3.Complexometric titration
4.Precipitation titration
Acid BaseTitration 1. Strong acid – strong base 2. Strong acid- weak base,
3. Weak acid- strong base 4. Weak acid- weak base.

Titration Curve: A titration curve is a plot of

pH vs. the amount of titrant added.
Typically the titrant is a strong (completely)
dissociated acid or base. Such curves are
useful for determining endpoints and
dissociation constants of weak acids or
bases.
Features of the Strong Acid-Strong Base
Titration Curve

1. The pH starts out low, reflecting the high [H3O+] of the

strong acid and increases gradually as acid is neutralized
by the added base.
2. Suddenly the pH rises steeply. This occurs in the
immediate vicinity of the equivalence point. For this type
of titration the pH is 7.0 at the equivalence point.
3. Beyond this steep portion, the pH increases slowly as more
base is added.
 Sample Calculation: Strong Acid-Strong
Base Titration Curve
Problem 24-1. Consider the titration of 40.0 mL of 0.100 M
HCl with 0.100 M NaOH.
Region 1. Before the equivalence point, after adding 20.0 mL of
0.100 M NaOH. (Half way to the equivalence point.)
Initial moles of H3O+ =
- Moles of OH- added =

 amount (mol) of H O remaining
[H 3O ]  3

original volume of acid  volume of added base

 Sample Calculation: Strong Acid-Strong
Base Titration Curve (Cont. I)
Region 2. At the equivalence point, after adding 40.0 mL of 0.100
M NaOH.
Initial moles of H3O+ = 0.0400 L x 0.100 M = 0.00400 M H3O+
- Moles of OH- added = 0.0400 L x 0.100 M =0.00400 mol OH-


 amount (mol) of H O remaining
[H 3O ]  3

original volume of acid  volume of added base

 Sample Calculation: Strong Acid-Strong
Base Titration Curve (cont. II)
Region 3. After the equivalence point, after adding 50.0 mL of 0.100
M NaOH. (Now calculate excess OH-)
Total moles of OH- = 0.0500 L x 0.100 M = 0.00500 mol OH-
-Moles of H3O+ consumed = 0.0400 L x 0.100 M =0.00400 mol

 amount (mol) of OH remaining
[OH ] 
original volume of acid  volume of added base
HPr = Propionic Acid
The four Major Differences Between a Strong
Acid-Strong Base Titration Curve and a Weak
Acid-Strong Base Titration Curve

1. The initial pH is higher.

2. A gradually rising portion of the curve,
called the buffer region, appears before
the steep rise to the equivalence point.
3. The pH at the equivalence point is greater
than 7.00.
4. The steep rise interval is less pronounced.
 Sample Calculation: Weak Acid-Strong
Base Titration Curve
Problem 24-2. Consider the titration of 40.0 mL of 0.100 M
HPr (Ka = 1.3 x 10-5) with 0.100 M NaOH.
Region 1. The solution of weak acid to be titrated, before any base
is added.
Solution:

Ans:
 Sample Calculation: Weak Acid-Strong
Base Titration Curve (Cont.I)
Problem 24-2. Consider the titration of 40.0 mL of 0.100 M
HPr (Ka = 1.3 x 10-5) with 0.100 M NaOH.
Region 2. After 30. mL of base (total) has been added. This is
clearly in the buffer region of the titration curve.
Solution: Refer to Lecture 23.
Can use the calculator program, ‘Buf’ developed in lecture 23. But
first must calculate the nominal amounts of acid and base forms of
the weak acid created by addition of the strong base. These are:
[HA]0 =
[A-]0 =
Ans: From buffer program: pH =
 Sample Calculation: Weak Acid-Strong
Base Titration Curve (Cont.ll)
Problem 24-2. Consider the titration of 40.0 mL of 0.100 M
HPr (Ka = 1.3 x 10-5) with 0.100 M NaOH.
Region 3. After 40. mL of base (total) has been added. This is
clearly at the equivalence point of the titration curve.
Solution: Refer to Lecture 23.
Can use the calculator program developed in lecture 23. But first
must calculate the nominal amounts of acid and base forms of the
weak acid created by addition of the strong base. These are:
[HA]0 =
[A-]0 =
Ans: From buffer program: pH =
 Sample Calculation: Strong Acid-Strong
Base Titration Curve (cont. IIl)
Region 4. After the equivalence point, after adding 50.0 mL of 0.100
M NaOH. (Now calculate excess OH-)
Total moles of OH- =
-Moles of weak acid consumed =
Moles of OH- remaining =


 amount (mol) of OH remaining after neutraliza tin
[OH ] 
original volume of acid  volume of added base
The four Major Differences Between a Weak
Acid-Strong Base Titration Curve and a Weak
Base-Strong Acid Titration Curve
1. The initial pH is above 7.00.
2. A gradually decreasing portion of the curve,
called the buffer region, appears before a
steep fall to the equivalence point.
3. The pH at the equivalence point is less than
7.00.
4. Thereafter, the pH decreases slowly as
excess strong acid is added.
 Features of the Titration of a
Polyprotic Acid with a Strong Base
1. The loss of each mole of H+ shows up as
separate equivalence point (but only if the
two pKas are separated by more than 3 pK
units).
2. The pH at the midpoint of the buffer region
is equal to the pKa of that acid species.
3. The same volume of added base is required
to remove each mole of H+.
• A salt formed between a strong acid
and a weak base is an acid salt, for
example NH4Cl.
• A salt formed between a weak acid
and a strong base is a basic salt, for
example CH3COONa.
• These salts are acidic or basic due to
their acidic or basic ions as shown in
the tables here.
Ions of Neutral Salts: pH = 7
Cations Anions

Na+ Mg2+ Cl- ClO4-

K+ Ca2+ Br- BrO4-

Rb+ Sr2+ I- ClO3-

Cs+ Ba2+ NO3-

Acidic salts: pH < 7

Acidic Ions Transition

metal ions
NH4+ Fe2+
Al3+ Cu2+
HSO4- Pb2+
H2PO4- Sn2+
Basic Salts: pH > 7
Basic
Ions

F- C2H3O2- NO2- HCO3-

CN- CO32- S2- HSO4-

HPO42- PO43- CN-

A redox titration is a titration of a reducing agent by an
oxidizing agent or titration of an oxidizing agent by a
reducing agent.
This type of titration involves a redox indicator
Redox titrations are named according to the titrant that is used:
• Permanganatometry uses potassium permanganate (KMnO4)
• Dichrometry uses potassium dichromate (K2CrO4 and K2Cr2O7 )
• Iodometry uses iodine (I2) in vivo or in situ
• Cerimetry employs cerium(IV) salts (Ce SO4
• Bromometry uses a bromine (Br2) titrant
 Redox Titrations
Shape of a Redox Titration Curve

• Voltage Change as a Function of Added Titrant

 Consider the Titration Reaction (essentially goes to completion):

K ≈ 1016

 Ce4+ is added with a buret to a solution of Fe 2+

 Pt electrode responds to relative concentration

of Fe3+/Fe2+ & Ce4+/Ce3+

 Calomel electrode used as reference

Indicator half-reactions at Pt electrode:
Eo = 0.767 V

Eo = 1.70 V
 Redox Titrations
Shape of a Redox Titration Curve

• Titration Curve has Three Regions

 Before the Equivalence Point
 At the Equivalence Point
 After the Equivalence Point

Region 1: Before the Equivalence Point

 Each aliquot of Ce4+ creates an equal
number of moles of Ce3+ and Fe3+

 Excess unreacted Fe2+ remains in solution

 Amounts of Fe2+ and Fe3+ are known, use

to determine cell voltage.

 Residual amount of Ce4+ is unknown

 Redox Titrations
Shape of a Redox Titration Curve

Region 2: At the Equivalence Point

 Enough Ce4+ has been added to react with all Fe2+
- Primarily only Ce3+ and Fe3+ present
- Tiny amounts of Ce4+ and Fe2+ from equilibrium

 From Reaction:

- [Ce3+] = [Fe3+]
- [Ce4+] = [Fe2+]

 Both Reactions are in Equilibrium at the

Pt electrode
 [ Fe 2  ] 
E   0.767  0.05916 log  
 [ Fe 3  ] 
 

 [Ce 3  ] 
E   1.70  0.05916 log  
 [Ce 4  ] 
 
 Redox Titrations
Shape of a Redox Titration Curve

Region 3: After the Equivalence Point

 Opposite Situation Compared to Before the Equivalence Point

 Equal number of moles of Ce3+ and Fe3+

 Excess unreacted Ce4+ remains in solution

 Amounts of Ce3+ and Ce4+ are known, use

to determine cell voltage.

 Residual amount of Fe2+ is unknown

1) Permanganate Titrations
• KMnO4 is the oxidizing agent in redox titration.
• The solution(unknown oxalic acid/ Mohr salt etc) is titrated in
presence of excess H+ ions which is maintained with addition of
dilute sulphuric acid.
• the permanganate ion MnO4– acts as a self-indicator in this method.
The solution remains colourless prior to the endpoint. The equation
of redox reaction
MnO4- + 8H+ + 5e → Mn2+ + 4H2O
Fe2+ → Fe3+ + e x5
MnO4- + 8H+ + 5 Fe2+ → Mn2+ + 5Fe3+ + 4H2O
• The end point is noticeable when oxidation of the
last of the reductant such as Fe2+ or C2O42– occurs. At
this point, the solution turns pink.
• The equivalence point is where reductant and
oxidant are equal with respect to the mole
stoichiometry.
• The KMnO4 titration helps in the estimation of
oxalic acid, hydrogen peroxide, ferrous salts,
oxalates and more.
• Important : Always standardize the KMnO4 solution
prior to use.
2) Dichromate Titrations
• K2Cr2O7 acts as the oxidant in the acidic medium.
• It is necessary to maintain the acidity of the
medium by addition of dilute sulphuric acid.
• The equation of the reaction is
Cr2O72- + 14H+ + 6e → 2Cr3+ + 7H2O
Fe2+ → Fe3+ + e x6
Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O
• In this situation, there is no substantial auto
colour change as seen in the MnO4– titration.
• Cr2O72– is not a self-indicator.
• However, Cr2O72– oxidizes the indicator
substance diphenylamine soon after
achieving the equivalence point thereby
producing an intense blue colour.
• Ferric chloride solution can be used as
external indicator.
• This method helps in the estimation of
ferrous salts and iodides.
3) Iodometric Titrations
• When KI solution is added, I- ions are first oxidized to free I2 .
The liberated iodine is then titrated against standard hypo
(Na2S2O3) solution.
2I- - 2e → I2
• On reaction with hypo, free I2 is reduced to I- ions.
• The oxidation and reduction reactions are
I2 + 2e → 2I-
Indicator used is Freshly prepared starch solution.
End point- blue colour to colourless.
The medium is kept free from mineral acids. This method is used
to estimate Cu(II) salts in neutral/ mineral acid free medium.
• The ability of iodine to produce intense blue colour with starch
as the substance and its capacity to react with thiosulphate
ions (S2O32– ) forms the basis of this method. The specific
reaction with (S2O32–) is also a redox reaction
2Cu2+ + 4I- → 2Cu+ + 2I2
I2 + 2S2O32- → 2I- + S4O62-
• In this case, I2 is insoluble in water but it remains in the solution
in the form of KI3 that contains KI. After the addition of starch
near the end point or the intensity of yellow colour is very low,
then iodine in the reaction produce intense blue colour.
However, the colour disappears on the completion of reaction
between iodine and the thiosulphate ions. At the endpoint,
blue colour changes to colourless/ white.
• Iodometric titration is used to determine Copper in the ore.
• Complexometric titration is a form of volumetric
analysis in which the formation of a colored
complex is used to indicate the end point of a
titration.
• Complexometric titrations are particularly useful
for the determination of a mixture of different
metal ions in solution.
• An indicator capable of producing an
unambiguous color change is usually used to
detect the end point of the titration.
• Types of complexing agents
• Unidentate (Monodentate) Ligand or "Simple Ligand"
• The ligand attached to metal at one site e.g. H2O , NH3 , CN - ,
Cl - , I - , Br - , (i.e. forming one coordinate bond, or capable of
donating one unshared pair of electrons)

Bidentate, tridentate, tetradentate, hexadentate ligands are

used used in complexometric titrations.
• Bidentate Ligand
The ligand attached to metal at two sites.

NH2 NH2 H 2N
H2C H2C CH2
2 + Cu2+ Cu
H2C H2C CH2
NH2 NH2 H 2N

Ethylene diamine
• Tridentate Ligand:
The Ligand attached to metal at 3 sites

Diethylene triamine

• Tetradentate Ligand:
The Ligand attached to metal at 4 sites

Triethylene tetramine
• Hexadentate Ligand (EDTA-disodium salt)

EDTA disodium salt of EDTA

•Classification of Complexometric
Titration
1.Direct
2.Back
3.Replacement
4.Alkalimetric titration of metals
Precipitation Titration
• It is a titrimetric method which involves the formation of precipitates
during the experiment of titration.
• The titrant reacts with the analyte and forms an insoluble substance.
• The titration is continued till the last drop of the analyte is consumed.
• When the titrant is excess it reacts with the indicator and signals to
terminate the titration process.
• Examples: determination of halide ions with silver nitrate
There are three common types of precipitation
titrations -
1. Mohr Method - CrO42- indicator

(yellow to red)
2. Volhard Method - back titration of excess
Ag+ with SCN-, Fe3+ indicator

(clear to red)
3. Fajans Method - adsorption indicator =
dichlorofluorescein anion (pink at
endpoint)
Volhard’s method – This method involves the titration
of bromides, iodides, and chlorides, in an acidic
medium. The chloride in the solution is converted to
silver chloride when reacted with excess silver nitrate
solution. The leftover silver nitrate is estimated against
potassium thiocyanate solution. When all thiocyanate
consumes all the silver, the excess of thiocyanate is
made to react with an indicator. It gives a red color on
reacting with ferric ammonium sulfate indicator and a
ferrous thiocyanate complex is formed.
 Mohr
MohrMethod
Method
Titration of a halide (Cl-, Br-, I-) with AgNO3 to form a precipitate
using K2CrO4 as the indicator.

e.g. Ag+ + Cl- → AgCl

eq. pt. color change to red
The indicator combines with excess Ag+ at the eq. pt. Before the eq. pt., the
solubility of the Ag-halide precipitate must be less than the Ag-indicator,
otherwise the latter would precipitate out during the titration!
2 Ag+ + CrO42- → Ag2CrO4(s) red
Ag+ + Cl- → AgCl(s) white

1
 Ksp  11
S AgCl   1 1   Ksp  1.8x10 10  1.3x10 5
 1 1 
1 1

 Ksp  21  2.0x10 -12

3
S Ag2CrO4   1 1      7.9x10 5

 2 1   4 
Fajan’s method – This method uses the reaction
between the precipitate formed and indicator. The
indicator used is dichlorofluorescein which acts as an
anion in solution. In chloride solution, due to excess
of chloride ions, they form the primary layer of the
precipitate. The second layer is formed by the
cations of sodium. The reaction ends with the silver
ion in excess. Therefore the positively charged silver
ion becomes the primary layer and attracts indicator
to form a secondary layer. The color of the indicator
 Volhard
VolhardMethod
Method
1. Excess AgNO3 is added to precipitate out all of
the halide.
2. The excess Ag+ is back-titrated with KSCN using
Fe3+ as the indicator
e.g. Ag+ + Cl- → AgCl(s)
added in excess
then Ag+ + SCN- → AgSCN(s)
excess titrant
after the endpoint -
Fe3+ + SCN- → FeSCN2+

[Cl-] = total Ag+ - amount backtitrated

Fajan’s method

1. In a flask, carefully pipet 20.00 mL of your chloride sample. Use a graduated cylinder
to add about 10 mL of 1% dextrin solution and about 20 mL of distilled water to the
flask.
2. Rinse and fill a 50 mL buret with 0.04M AgNO3 solution. Tap to remove bubbles and
make certain that the buret tip is filled with solution. Record the initial reading.
3. Add 3 - 4 drops of dichlorofluorescein indicator solution. Titrate to the first
appearance of a persistent faint pink color. Read the buret to the nearest 0.01 mL and
record the value on your data sheet.
4. Repeat the procedure till you get concordant readings.
 Fajans
FajansMethod
Method

The indicator adsorbs onto the colloid particles after the eq. pt.
and changes color to pink.

Adsorption Indicator - Dichlorofluorescein

before the eq. pt. the lattice ion in excess is after the eq. pt. the lattice ion in excess is
the halide (Cl- etc) so the colloid is the titrant Ag+ so the colloid is positively
negatively charged charged and then the negative adsorption
indicator will bind and change color.
Mohr’sMethod:
• This method utilizes chromate as an indicator.
• Chromate forms a precipilate with Ag+ but this precipitate has a greater solubility than
that of AgCl. Therefore, AgCl is formed first and after all Cl-is consumed, the first drop
of Ag+ in excess will react with the chromate indicator giving a reddish precipitate.
2Ag+ + CrO42- = Ag2CrO4
In this method, neutral medium should be used. In alkaline solutions pH>10, silver will
react with the hydroxide ions forming AgOH.
In acidic solutions, chromate will be converted to HCrO4- and the end point is delayed.
In other words silver chromate solubility grows due to the protonation of chromate
anions. Therefore, the pH of solution should be kept at about 7.
There is always some error in this method because a dilute chromate solution is used
due to the intense color of the indicator. This will require additional amount of Ag+ for
the Ag2CrO4 to form. This leads to a late equivalent point. To correct for this error we
can determine a blank
Volhard’sMethod:
• This is an indirect method used for determining the anions that precipitate with
silver e.g Cl-,Br-and I. For example an excess amount of standard Ag+ is added to
the chloride unknown solution containing Fe3+ as anindicator. Ag+ + Cl- ↔
white precipitate of AgCl The excess Ag+ is then titrated with standard SCN-
solution Ag+ + SCN-↔ white precipitate of AgSCN until are d dishcolordue to
Fe(SCN)2+ complex formation is obtained which results from the reaction: Fe3+
+ SCN- = reddish complex Fe(SCN)2+ The indicator system is very sensitive and
usually good results are obtained
• The medium should be acidic to avoid the formation of Fe(OH)3. If AgX is less
soluble than AgSCN as in the case of I- and Br-,the excess Ag+ can be titrated in the
presence of AgX precipitate. But in the case of AgCl when SCN-is added just after
the equivalent point the following reaction will take place: AgCl + SCN-↔ AgSCN+
Cl-
• This means that , SCN-instead of reacting with the indicator it will react with the
AgCl precipitate .
We have two ways to overcome this problem
• The first includes addition of some organic solvent which is heavier and immiscible with water
such as nitrobenzene or chloroform, which covers the AgCl precipitate in the bottom of conical
flask and shields it from the aqueous medium which contains the excess Ag+ that can be titrated
with SCN-.
• The second procedure involves filtration of the precipitate directly after precipitation, which
protects the precipitate from coming in contact with the added SCN- solution and titrating the
excess Ag+ in the filtrate
Advantages of Volhard’smethod:
1. The acidic environment give advantage for halide analysis because anions such as carbonate,
oxalate and arsenate that do not form precipitate with silver in acidic medium (but they do in
basic medium) will not interfere with halides.
2. 2-Give accurate results due to back titration
Limitations of Volhard’s method:
• 1-Can not be used in neutral or basic medium.
• 2-Timeconsuming
• Fajan’sMethod :Fluorescein and its derivatives are adsorbed to the surface of
colloidal AgCl. After all chloride is used, the first drop of Ag+ will react with
fluorescein(FI-) forming. Ag+ + F- = AgF
• Since fluorescein and its derivatives are weak acids, the pH of the solution should
be slightly alkaline to keep the indicator in the anion form but, at the same time,
is not alkaline enough to convert Ag+ into AgOH. Fluorescein derivatives that are
stronger acids than fluorescien(like eosin) can be used at acidic pH without
problems. This method is simple and results obtained are reproducible.
How do adsorption indicators work?
• In the Fajans method for Cl–using Ag+ as a titrant,for example, the an ionic dye
dichlorofluoroscein is added to the analyt’s solution. Before the end point, the
precipitate of AgCl has a negative surface charge due to the adsorption of excess
Cl–. Because dichlorofluoroscein also carries a negative charge, it is repelled by
the precipitate and remains in solution where it has a greenish-yellow color