Titrimetric analysis

B. R. Thorat
Govt of Maharashtra

Ismail Yusuf Arts,

Science and
Commerce
College, Mumbai
Monday, June 24, 2024 B.R.THORAT 1
 Introduction

Titrimetric analysis is a quantitative method of

analysis based on measurement of volume &
finally concentration of component of sample
present in solution.
 Term used in titrimetric analysis
Titrant: From burette

Titrand: Being titrated

Titration: The process of addition (mixing) of the titrant to the titrand leading
reaction between them.

Indicator: substance added externally, shows color change when reaction between
titrant and titrand is complete

Equivalence Point: point during the titration where the reaction between titrant and
titrand is complete. volume of titrant corresponding to the equivalence point is Veq.

End point of the titration: point of titration at which completion of reaction

between titrant and titrand is judged with the help of the change in color of indicator

Titration error: Ideally the end point and equivalence point of the titration should
coincide. The difference between these two points is known as titration error.
 Requirement of the reaction is to be used in titrimetric analysis

Titrimetric analysis is based on the reaction between titrant and

titrand.
1. The reaction should be quantitative. The reaction should be
represent with the help of balance chemical equation.

2. The reaction should be rapid and complete under given

reaction conditions. It should have high equilibrium
constant.

3. A suitable indicator should be available which indicate the

completion of reaction by color change. If suitable indicator
is not available then completion of reaction should be
confirm by measuring change of some physical property
which based on change of concentration.
 Classification of titrimetric analysis

Depending on the type of the reaction involve between titrant

and titrand, titrimetric analysis has been classified in two major
groups:
1. Reaction involving transfer of electrons.
2. Reaction between ions/molecules with ions/molecules.

1. Reaction involving transfer of electrons.

During the titration, reaction between titrant and titrand
involving transfer of electrons is known as redox reaction or
oxidation-reduction reaction and the titration as redox titration.
e.g. 1. Fe(II) with potassium dichromate
2. Iodine with sodium thiosulphate.
 Classification of titrimetric analysis
2. Reaction between ions/molecules with ions/molecules.

A. Reaction between ions: (Precipitation titration)

During the titration, reaction between ions (titrant and titrand) leads to the formation
of a sparingly soluble salts is known as precipitation reaction & titration as
precipitation titration. E.g. KCl vs AgNO3; BaCl2 vs K2SO4, etc.
A solution of potassium chloride can be titrated against silver nitrate solution using
suitable indicator such as K2CrO4, adsorption indicator, by potentiometry, etc.

B. Reaction between ions & molecules: (Complexometric titrations)

During titration, a reaction between metal ion and neutral complexing agent leads
the formation of stable complex. E.g. Estimation of Ca/Mg ions by EDTA.

C. Reaction between molecules: (Acid-Base titration)

The reaction between acid and base leads the formation of salt and water. It can may
be come in category of reaction between ion & molecule or between two ions. e.g.
HCl vs NaOH; HCl vs NH4OH; CH3COOH vs NaOH; CH3COOH vs NH4OH, etc.
 Acid Base Titration

All acid-base titration involve neutralization reaction i.e. reaction

of proton of acid reacts with hydroxide ion of base forming water.
E.g. The titration of free acid or salt of weak base with the
standard base or titration of free base or salt of weak acid with
standard acid.
The equivalence point of the titration was measured by using
indicator which is also called as end point where indicator shows
color change.
The end point detection in an acid base titration is based on sharp
change in pH that occur in the vicinity of the equivalent point.
 Theory of acid base indicator
Number of synthetic and naturally occurring compounds shows different color
depending on the pH of the solution in which they are dissolved.

Indicator is weak organic acid or weak organic base. The dissociation of indicators are
accompanied by internal structural arrangement that are responsible for color changes.

Weak acid:
HIn + H2O ↔ H3O+ + In- (1)
(acid color) (base color)
In acidic medium, HIn will be major constituent and therefore show acid color. In basic
medium, HIn undergoes deprotonation to In - which will be the major constituent &
therefore same indicator shows basic color.

Weak base:
In + H2O ↔ InH+ + HO- (2)
(base color) (acid color)
In basic medium, In will be the major constituent and will shows basic color whereas in
an acidic medium, HIn+ is the major constituent and will show the acid color.
 Theory of acid base indicator
According to law of mass action-
KIn(a) = [H3O+][In-]/[HIn] (3)
KIn(b) = [HIn ][HO ]/[In]
+ -
(4)
Rearrange the equation (3) –
KIn(a) x [HIn] = [H3O+] x [In-]
[H3O+] = KIn(a) x [HIn]/[In-] (5)
For the indicator HIn, concentration [HIn] is in acidic form & [In ] is in basic form, therefore
-

[H3O+] = KIn(a) x [Acid form]/[Basic form] (6)

Since pH = - log[H ] = - log[H3O ]
+ +

Taking –log of both side of equation (6) as –

-log[H3O+] = - logKIn(a) + log[Basic form]/[Acidic form]
i.e. pH = pKIn(a) + log[Basic form]/[Acidic form] (7)
Similarly from equation (4), we can obtain-
pH = pKw - pKIn(b) - log[Acidic form]/[Basic form] (8)
For any given indicator, at constant pH the color of solution depends on the ratio [Acidic form]/[Basic form].

For solution containing indicator, with variation of pH, there will be continuous change in color.
The human eye is not enough sensitive to detect these color changes. Generally ten fold excess of one form over the other is required before the color of
that form appear to the observer. Thus the color of HIn acidic form detect by the eye only when –
[HIn]/[In-] ≥ 10 (9)
And only the color In basic form when –
-

[HIn]/[In-] ≥ 1/10 (10)

Substitute equation (9) and (10) in equation (7), we have –
pH = pKIn(a) + log 10 = pKIn(a) + 1
and pH = pKIn(a) + log (1/10) = pKIn(a) - 1
The indicator changes color over a two pH range and is given as
pH = pKIn(a) ± 1 (11)
e.g. For the indicator having KIn(a) = 10 will shows complete color change when pH of the solution (in which indicator is present) changes from 5 to 7.
-6
 Theory of acid base indicator
The same conclusion can also be drawn for indicator of the basic type.

For the selection of the indicator for acid-base titration, following two aspects must be consider as-
(1) An indicator whose pKIn is same or close to the pH of equivalence point of titration. (2) The two
contrasting colors should be clearly distinguishable.
e.g. Following indicators may be used for the acid-base titration.
Sr. Common Name Type pKIn pH range Color
No. Acid form Base form

01 Methyl Orange Base 3.46 3.1 – 4.4 Red Orange Yellow

02 Bromocresol green Acid 4.90 3.8 – 5.4 Yellow Blue

03 Methyl red Base 5.00 4.4 – 6.2 Red Yellow

04 Phenol red Acid 8.00 6.4 – 8.2 Yellow Red

05 Phenolphthalein Acid 9.60 8.3 – 10 Colorless Red (pink red)

06 Thymolphthalein Acid 9.70 9.3 – 10.3 Colorless Blue

 Chose of the indicators for acid base titration:
The magnitude of pH change will primarily depends on the acid and base used for the
titration.
The indicator selected for the titration should therefore shows color change in this region.

e.g. 1. For the titration between strong acid HCl and strong base NaOH, the pH change at
the equivalence point is from about 4 to 10. The indicator selected should have the pH
range in between 4 to 10. Methyl orange (3.1-4.4); Methyl red (4.4-6.2); Phenol red (6.4-
8.2); Phenolphthalein (8.3-10) could be used as indicator. The indicator shows acid color
up to equivalence point and after that it shows basic color.

2. For the titration between weak acid CH 3COOH and strong base NaOH, the pH change at
the equivalence point is from about 7.7 to 10. The suitable indicator for such titration will
be Phenol red (6.4-8.2) or Phenolphthalein (8.3-10). The indicator shows acid color up to
equivalence point and after that it shows basic color.

3. For the titration between weak base NH 4OH and Strong acid HCl, the pH change at the
equivalence point is from about 6.6 to 4.0. The suitable indicator for such titration will be
methyl orange (4.4-3.1) or methyl red (6.2-4.4). The indicator shows basic color up to
equivalence point and after that it shows acidic color.
The improper selection of indicator shows appropriate error in titration.
 Instrumental methods used in titrimetric analysis

Some cases such as solution may be colored or very

dilute, suitable indicator is not available or end point
obtained is differ from equivalence point. Such titration
has been carried out by detection suitable property of
solution by using instrument i.e. instrumental titrations.
There are two common instrumental methods usually
used for such titrations as-
Electronic methods: Electronic property is measured.
Conductometric titrations, potentiometric titrations, etc.
Optical methods: Absorption, emission, scattering of
light is measured. Photometric titrations.
 CONDUCTOMETRIC TITRATIONS

Conductance is the one of important property of solution

of electrolytes.
1. number of ions present in the solution,
2. velocity of ions,
3. the current carrying property of ions, etc.
When solution containing single electrolyte, the measured
conductance was related to concentration of the
electrolyte.
The end point of titration has been detected by measuring
conductance of total solution.
This titration become less accurate with increasing the
total electrolyte concentration of the solution
(electrophoretic and asymmetric effect).
 PRINCIPLES OF CONDUCTOMETRIC TITRATIONS
When solution of one electrolyte is added to the solution of another electrolyte without
appropriate change in volume, the conductance of the solution will alter, if ionic reactions
occur. If there is no ionic reaction, ionic conductance of the solution is simply increases.
But when ionic reaction occurs, the ion added may be replaced another ion of solution and hence
conductance of solution changes.
e.g. 1) Due to addition of strong base NaOH to strong acid HCl, conductance of the solution
decreases due to replacement of high moving H+ (higher conductance) by slow moving (lower
conductance) Na+ ions. Hence conductance of the overall solution decreases along with addition
up to equivalence point and then increases.
2) Addition of strong base to a weak acid, conductance of the solution increases due to
production of more ions with addition (formation of ionized salt).
e.g. Electrolyte A+B- will be titrated against C+D-. The ionic reaction occur during the titration &
forming unionized or weakly ionized product AD.
A+B- + C+D- = AD + C+B-
As titration proceeds, A+ ions of the solution are replaced by the C + ions. The conductance of the
solution increases or decreases depending on, whether conductance of C + is greater than or less
than that of A+. After equivalence point, conductance of the solution increases continuously due
to excess addition of the titrant CD.
“The conductance of solution changes in conductometric titrations is due the difference in
conductance of ions or due to production of more number of ions in the solution”
 EXPERIMENTAL SET UP FOR CONDUCTOMETRIC TITRATIONS

A definite volume (Vml) of the solution is pipette out in beaker which is going to be
titrated. A dip type conductivity cell is placed into solution, if cell does not
completely dip into solution then adds distilled water. Put the beaker on magnetic
stirrer and connect the cell to conductometer & measure the conductance (say G).
Fill the micro-burette with titrant. Add titrant in small portions, generally 0.5 or 0.2
ml at time, stir the solution for minute and measure the conductance of the solution
after each addition. Continue the addition till about seven to eight reading beyond
the equivalence point.
Plot the graph of conductance against volume of the titrant added which is used
to locate the equivalence point.
If titrant is ten to twenty times more concentrated, then volume required for
equivalence point is less and effect of dilution is insignificant (less). If this is not the
case then it may be necessary to apply volume correction and calculate the
corrected conductance (say G’) as follow-
Vcorrected = (V + v)/V G’ = G x Vcorrected
Where ‘v’ ml is volume of titrant added. Plot the graph of corrected conductance
(G’) against titrant volume to get equivalence point.
 TITRATION CURVES IN CONDUCTOMETRIC TITRATIONS

Titration of strong acid against strong base:

e.g. NaOH vs HCl. Add NaOH solution from burette
to the HCl solution. The reaction occurs as-
H+ Cl- + Na+ OH- → H 2O Conductance due to H+ & Na+

+ Na+ Cl-
During the titration, H+ was replaced by Na+ ion.
The ionic conductance of the H+ ions is higher than
that of Na+ ions. During the titration, amount of H+ Conductance
ions decreases with increase the amount of Na+ ions,
Conductance due to Na+ & HO-
therefore conductance of the solution decreases
gradually with the addition of NaOH solution. Conductance due to Na+

When neutralization complete, conductance of the Equivalence point

solution increases further with addition of titrant due Volume of strong base added

to increases the number of ions (Na+ and HO- both).

At the equivalence point, conductance of the
solution is minimum which can be determined by
plotting the graph G vs V ml of base (NaOH) added.
The point of intersection of two lines is the
equivalence point as shown in following fig.
 Titration curves in conductometric titrations

CH3COOH + Na+ OH- → H 2O + Na+ CH3COOH + NH4OH → H2O + NH4+

CH3COO- CH3COO-

Conductance due
to Na+ & HO-
Conductance
Conductance

Conductance due
Conductance due
to acetate anion to acetate anion
& Na+ Equivalence & NH4+ Equivalence
point point
Volume of strong base added Volume of weak base added
 Titration curves in conductometric titrations
H+ Cl- + Na+ OH- → H2O + Na+ Cl- H+ Cl- + NH4OH → H 2O + NH4+ Cl-

CH3COOH + Na+ OH- → H2O + Na+ CH3COO- CH3COOH + NH4OH → H 2O + NH4+ CH3COO-

V1 is the volume equivalence of

V1 is the volume equivalence of strong acid in mixture

Conductance
Conductance

strong acid in mixture

(V2-V1) is the volume equivalence

of weak acid in mixture (V2-V1) is the volume equivalence
of weak acid in mixture
Equivalence Equivalence
V1 points V2 V1 points V2
Volume of strong base added Volume of weak base added
 Titration curves in conductometric titrations
H+ Cl- + Na + OH - → H2O + Na+ Cl - CH3COOH + Na + OH - → H2O + Na+ CH3COO-

H+ Cl- + NH4OH → H2O + NH4+ Cl- CH3COOH + NH4OH → H2 O + NH4+ CH3COO-

V1 is the volume equivalence of

V1 is the volume equivalence of
strong base in mixture
strong base in mixture
Conductance

Conductance
(V2-V1) is the volume equivalence
of weak base in mixture
(V2-V1) is the volume equivalence
Equivalence of weak base in mixture
V1 points V2 Equivalence
V1 points V2
Volume of strong acid added
Volume of weak acid added
 Titration curves in conductometric titrations
Na+ Cl- + Ag+NO3- → AgCl↓ + Ba2+ + 2OH- + MgSO4 →
Na+ NO3- Mg(OH)2↓ + BaSO4↓

Conductance
Conductance

Equivalence
Equivalence
Veq points
Veq points
Volume of MgSO4 added
Volume of AgNO3 added
 Conductometric titrations
Advantageous Limitations

1. Colored solutions can be titrated. 1. In dilute solutions, obtuse curves are

obtain in which it is difficult to
2. This method is equally well for dilute determine the equivalence point.
solution also, as it is based on the change
in conductance rather than the absolute 2. The overall accuracy of the
value of conductance. conductometric titration is limited as
technique does not permit the addition
3. In conductometric titrations, it is not of small increments of the titrant.
necessary to make the observations
around the equivalence point. 3. The precipitation titrations can not
perform very accurately due to-
4. An extremely weak acids and bases are (a) Slow separation of precipitate during
titrated conductometrically which is not titration and
possible by normal titrimetry. (b) Adsorption of the ions in solution on the
precipitate.
5. Simulataneous determination of
mixture of strong and weak acids or bases
are possible by conductance measurement.
 POTENTIOMETRIC TITRATIONS

Potentiometric titrations are based on the measurement of potential.

The primary prerequisite is to set up the suitable galvanic cell and
measure it potential as the titrant is added. The galvanic cell consist of
two half cells as reference half cell or electrode and an indicator
electrode.
 INDICATOR ELECTRODE

Potentiometric titrations involve the measurement of potential for each addition of the
cell formed by two electrodes as indicator electrode and reference electrode.
The indicator electrode is reversible to the ions which will be titrated and its choice is
depends on the type of titration.
There are major four types of titrations depending on the type of reaction involved are
observed.
a. Acid base titrations, b. Precipitation titration, c. Complexmetric titration, d. Redox
titration.
a. Acid-Base titration:
The change in concentration of hydrogen ion during the titration is detected. The
indicator electrode used should be reversible with hydrogen ions. E.g. Hydrogen
electrode, quinhydron electrode, glass electrode, etc are used as indicator electrodes.
Glass electrode. Combined glass reference electrode consists of indicator and
reference electrodes in the same body.
Buffer solutions of known pH are used for the pH calibration. The pH values of some
buffers are temperature dependent. For high accuracy, calibration and measurements
are to be performed at the same temperature.
 INDICATOR ELECTRODE

Potentiometric pH measurement.mp4

a. Acid-Base titration:
Glass electrode:
 INDICATOR ELECTRODE
Precipitation titration:
Precipitation titration involves the reaction between a cation and
anion to form sparingly soluble salt.
M+(aq) + A-(aq) → MA(s)
The indicator electrode used is reversible to the cation M + or A-. e.g.
Titration between NaCl with aq. AgNO3, the reaction takes place is-
Ag+(aq) + Cl-(aq) → AgCl(s)
The indicator electrode used can be Ag(s)│Ag+ electrode or Ag(s)-
AgCl(s)│Cl- electrode or Pt, Cl2│Cl- electrode.

e.g. Ion-selective electrodes are used for detection of specific ion in

a mixture of ions. The sensor element, ion-selective membrane, has a
construction similar to that of glass electrode. For calibration of ion-
selective electrodes a standard addition method is often employed.
 INDICATOR ELECTRODE

Complexometric titrations:
Compleximetric titration involves titration between metal
ion and complexing agent hence the metal ion electrode is
used as indicator electrode.
In case of EDTA titration, such type of metal ion
electrode is not used because of use of buffer solution
(constancy of pH). In such titrations, mercury electrode
with mercury EDTA complex is used as indicator
electrode.
 INDICATOR ELECTRODE
Redox electrode:
Redox titration involve two redox couple (oxidizing and reducing
agent). As both oxidized and reduced forms are present in same phase,
no special electrode is needed, a platinum wire inserted act as
indicator electrode. E.g. Fe(II) with Ce(IV) involves Fe(II) and
Fe(III) as one redox couple & Ce(IV) and Ce(III) is another.

Gold redox electrodes are seldom used in potentiometric titrations.

The gold electrodes are better behaved than platinum electrodes in
view of rate of response and stability toward formation of oxides.
These features are of high importance in continuous mode of titration.
e.g. A good example is the use of gold electrodes in the titration of
ascorbic acid with bromine in continuous mode, where the response of
the platinum electrode is unsatisfactory.
 REFERENCE ELECTRODE

It is an electrode used having constant known potential.

Either primary or secondary reference electrode can be
combined with indicator electrode to set up the cell. E.g.
Wiston electrode, saturated calomel electrode is most
commonly used in number of cases.
 Basic principles of Potentiometric titration
The potential of a suitable cell which is the function of the volume of titrant added is
measured.
As titration proceed, the concentration of
the ion being titrated changes and therefore
potential of the indicator electrode will also
change which change the overall potential
of cell.
Around equivalence point for any titration,
the ion being titrated shows large changes
in concentration, this will produce large
change in potential of indicator electrode
and therefore potential of cell with small
addition of titrant.
During the overall titration, initially the
variation of potential is smaller with
addition of titrant near to equivalent point,
around the equivalent point is large or
considerable and after equivalent point is
smaller with addition of titrant.
 Potentiometric titrations
The initial concentration of an ion such as Fe 2+ can be found by titrating with a strong oxidizing
agent such as Ce4+. The titration is carried out by constructing cell as -
Pt(s) | Fe2+, Fe3+ || reference electrode
Reaction of titration: Fe2+ + Ce4+ → Fe3+ + Ce3+

Once the first drop of ceric ion titrant has been added, the
potential of the left electrode is controlled by the ratio of
oxidized and reduced iron according to the Nernst equation
which causes the potential to rise as more iron becomes
oxidized.

When the equivalence point is reached, the Fe 2+ will have been

totally consumed, the potential will then be controlled by the
concentration ratio of Ce3+/Ce4+. The end point is found not
by measuring a particular cell voltage, but by finding what
volume of titrant gives the steepest part of the curve i.e. E
vs V ml added or ∆E/∆V vs mean V or ∆2E/∆V2 vs mean V.
 POTENTIOMETRIC TITRATIONS
Advantageous:
1. Any ion or molecule can be determined potentiometrically if its indicator
electrode is available.
2. All four catagories of titrations can be carried out.
3. All catagories of acid-base titrations has been carried out i.e. titration of
strong, weak, monobasic, dibasic, mixture of acids can be carried out. Acid-base
titration in non-aqueous medium can also be carried.
4. The precipitation titration has been carried out by using metal-metal ion or
metal-isoluble salt type indicator electrode.
5. Compleximetric titration can be carried out by using mercury as indicator
electrode.
6. Many redox system can be titrated potentiometrically. A mixture of two
reductant can be also being analysed with the help of same oxidant.
7. The titration error is minimum.

Limitations:
It is time consuming and laborious method. It required large number of
 PHOTOMETRIC TITRATIONS
A photometric titration involves the measurement of
absorbance values during the titration. The absorbance of the
solution is given by the Beer’s-Lambert’s law as-
Absorbance = A = logI0/It = ε x C x l
Where, I0 is the intensity on incident light; It is the intensity of
transmitted light; C is the concentration of absorbing species
in mol/lit; l is pathlength in cm and ε is the molar absorptivity.
The absorbance of the solution is the function of
concentration of absorbing species and is change with
changing the concentration.
 PHOTOMETRIC TITRATIONS

Principle of Photometric titration:

The titration can be represented as-
Reactant + Titrant → product.
The end point can be obtained by plotting the graph of absorbance
against volume of reagent added by using burette. The solvent used
does not absorbs any light during the course of titration.
Photometric titration curves:
There are four types of photometric titration curves-
1. Reactant is the absorber.
2. Titrant is the absorber.
3. Product of the titration is absorber.
4. Both reactant & product absorb light but in different extend.
 PHOTOMETRIC TITRATIONS

1. The reactant is absorber while titrant

Absorbance
and product do not absorb at all. E.g.
Photometric titration of p-toluidine in
Equivalence
butanol against perchloric acid. Veq points

Volume of titrant added

2. The titrant is absorber while reactant

Absorbance
and product does not absorb at all.
E.g. Titration AsCl3 against Br2 (or
Equivalence
mixture of KBr + KBrO3). Veq points

Volume of titrant added

3. The product is absorber while

Absorbance
reactant and titrant does not absorb
at all. E.g. Titration of Cu(II) or Ni(II) Equivalence
Veq points

with EDTA. Volume of titrant added

 PHOTOMETRIC TITRATIONS
4. Both the reactant and titrant absorb
but to different extents. In this case, a
colored reactant is converted into

Absorbance
colorless product by using colored
titrant. E.g. Bromination of red dye. Equivalence
Veq points

Volume of titrant added

5. Photometric titration can also be used to
analyse the mixture of metal like Cu and Bi by
using EDTA at 745 nm. At 745nm, Cu(II),
Bi(III), EDTA and Bi-EDTA complex does not

Absorbance
shows any absorbance but Cu-EDTA shows
strong absorbance. The Bi(III) forming complex Equivalence
first with EDTA than Cu(II). As titration points
V1
V2
proceeds, absorbance of the solution remains
conctant upto first end point (all Bi3+ is reacted) Volume of EDTA added
V1 and then start increase steadly upto second
end point (all Cu2+ is reacted) V2 and finally
after second end point, it remains constant.
 PHOTOMETRIC TITRATIONS
Advantageous:
1. Photometric titrations are resorted to when end point is not sharp
enough to be detected.

2. Photometric titration can be carried out in the case of dilute

solutions in the concentration range 10 -6 to 10-2 M.

Limitations:
3. It is not carried out if there is change in the molecular condition of
the absorbing species in the solution i.e. dissociation or association.

4. It is not preferred for high concentrating solutions i.e. above 10 -2 M.

5. It required strictly monochromatic beam which is not absorb by the

solvent.
 OOPSSSSS
……

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