Titrimetric methods

(03/09 – 03/09 2021)

 Titrimetric methods

It includes group of analytical methods that are based on

determining the amount of a reagent of known
concentration that is required to react completely with the
analyte.
 Types of Titration

Precipitation Complexometric
Acid Redox
Base

Mohr's method
Volhard’s Back titration
Iodometry or method
Iodimetry, Fagan’s Replacement
Strong acid-strong base
Bromatometry method. titration,
Weak acid-strong base
Permanganometry Direct
Strong acid-weak base and titration,
Weak acid-weak base Dichrometry
Indirect
titration
 Principle of Titrimetric Analytical Method

 Sample solution (in flask) + Titrant (from a burette) + indicator

→ product is formed at Equivalence point
 Concentration of analyte in the original sample solution is
calculated from the volume of standard titrant required to reach
equivalence point
 The balanced chemical equation for the reaction between the
analyte and titrant must be known e.g HCl + NaOH → NaCl +
H2O or 2HCl + Na2CO3 → 2NaCl + CO2 + H2O
 H2Hh
 Principle of Titrimetric Analytical Method
Volumetric titrimetry is used to measure the volume of a
solution of known concentration that is needed to react completely
with the analyte.
 Gravimetric titrimetry is like volumetric titrimetry, but the
mass of the reagent is measured instead of the volume.
 Coulometric titrimetry is where the reagent is a constant
direct electrical current of known magnitude that consumes the
analyte; the time required (and thus the total charge in coulombs)
to complete the electrochemical reaction is measured.
The current is known to the unknown solution until all the
unknown species are oxidized or reduced to a new state, this will
indicate an end point
 The benefits of these methods are that they are rapid,
accurate, convenient, and readily available
 Terms

 Titration: is performed by adding a standard solution from

a buret or other liquid-dispensing device to a solution of the
analyte until the reaction between the analyte and reagent is
judged to be complete.
Standard solution (titrant): A reagent of exactly known
concentration which is used in a titrimetric analysis.
 Primary standard is an ultrapure compound that serves as
the reference material for a titration or for another type of
quantitative analysis. For example, NaC2O4 (sodium oxalate),
K2Cr2O7 (potassium dichromate),
A secondary standard: less pure compound used in place
of a primary standard as the reference material after its purity
has been established by chemical analysis. For example,
 Primary Standards

The accuracy of a method depends on the properties of

primary standard.
 Important requirements for a primary standard are:
1. High purity;
2. Atmospheric stability;
3. Absence of hydrate water so that the composition of the
solid does not change with variations in humidity.
 Primary Standards

4. Readily available at a modest cost;

5. Reasonable solubility in the titration medium;
6. Reasonably large molar mass so that the relative error
associated with weighing the standard is minimized.
 Compounds that meet or even approach these criteria are
few, and only a few primary standards are available
commercially.
 Standard Solutions

Standard solutions play a key role in titrimetric methods

Desirable properties of standard solutions:
1. Be sufficiently stable so that it is necessary to determine its
concentration only once;
2. React rapidly with the analyte so that the time required
between additions of reagent is minimized;
3. React more or less completely with the analyte so that
satisfactory end points are realized; and
4. Undergo a selective reaction with the analyte that can be
described by a balanced equation.
 Establishment of the concentration of
standard solutions

 Direct method
Weighed quantity of the primary standard is dissolved in the
suitable solvent and diluted to an exactly known volume in a
volumetric flask.
 Standardization
The concentration of a volumetric solution is determined by
titrating it against a carefully measured quantity of a primary
or secondary standard or an exactly known volume of another
standard solution.
 Terms

 Equivalence point in a titration is a theoretical point at

which the amount of added titrant is chemically equivalent to
the amount of analyte in the sample.

 End point: the point in titration at which an observable

physical change occurs that is associated with the condition
of chemical equivalence.

 In any titration, the end point is signaled by indicator colour

change or a change in an instrumental response.
End point
 Terms

 The difference between the end point and equivalence

point should be very small and this difference is referred to as
titration error.
 In volumetric methods, the titration error: Et = Vep – Veq

Et is the titration error

Vep is the actual volume used to get to the end point
Veq is the theoretical volume of reagent required to reach the
equivalence point.
 Indicators are used to give an observable physical change
(end point) at or near the equivalence point by adding them
to the analyte solution
 Terms

 Back-titration: It is a process in which an excess of the

standard solution used to consume the analyte is determined by
titration with a second standard solution. In this instance the
equivalence point corresponds with the amount of initial titrant
is chemically equivalent to the amount of analyte plus the
amount of back- titrant.
 Back titration is required when the rate of reaction between
the analyte and reagent is slow or when the standard solution
lacks stability or one of the reactants is volatile (e.g. Ammonia)
as an insoluble salt (e.g. calcium carbonate)
 Key concept of back-titration
This is normally a two stage analytical process
1. Reactant A of unknown concentration (analyte) is reacted
with excess reactant B of known concentration (titrant 1).

2. A direct titration is then performed to determine the

amount of reactant B in excess by using a second known
standard solution (titrant 2)
 Example of back-titration
 The amount of phosphate in a sample can be determined
by adding a measured excess of standard AgNO3 (titrant 1)
to a solution of the sample, which leads to the formation of
insoluble Ag3PO4

3Ag+ + PO43 → Ag3PO4

 Excess AgNO3 is back-titrated with a standard solution of

potassium thiocyanate (titrant 2):
Ag+ + SCN → AgSCN(s)

 The amount of AgNO3 is chemically equivalent to the

amount of phosphate ion plus the amount of thiocyanate used
for the back titration.
Example of Titration and Setup
 Volumetric calculations
Example 1: Describe the preparation of a 5.0 L of 0.10 M
Na2CO3 (105.99 g/mol) solution.
Number of moles= Concentration x Volume

n=CxV

mol
mol Na 2CO3  5 L  0.1  0.5 mol
L
g
mass Na 2CO3  0.5 mol 105.99  53.0 g
mol
The solution is prepared by dissolving 53.0 g of Na2CO3 in
water and diluting to 5 L.
 Volumetric calculations
Example 2: A 0.0100 M standard solution of Na+ is required to
calibrate a flame photometric method to determine the element.
Describe how 500 mL of this solution can be prepared from the
primary standard Na2CO3 (105.99 g/mol).

amount of Na2CO3 = 0.5 L x 0.0100 mol Na+ x 1 molNa2CO3

L 2 mol Na+
= 0.00250 mol

mass of Na2CO3 = 0.00250 mol X 105.99 g/mol = 0.265 g

To prepare 0.0100 M Na+ solution, dissolve 0.265 g of Na2CO3

in water and dilute to 500 mL.
Volumetric calculations

Example 3: How would you prepare 50 mL portions of standard

solutions that are 0.00500 M, 0.00200 M, and 0.00100 M from a
standard solution of 0.0100 M Na+?
Applying dilution law:
amount of Na+ from conc. solution = amount of Na+ in dil.
solution
CconcVconc  CdilVdil
1
CdilVdil 50 mL  0.005 mol L
Vconc   1
 25.0 mL
Cconc 0.01 mol L
Volumetric calculations

To prepare 50.00 mL of 0.00500 M Na+, 25.00 mL of 0.0100

M Na+ solution should be diluted to 50.0 mL.

Similar calculations for the preparation of the other two

standards result in diluting 10.0 and 5.00 mL of the
concentrated solution to 50.0 mL.
 How to deal with titration data…

Example 4: A 50.00 mL HCl solution required 29.71 mL of

0.01963 M Ba(OH)2 to reach an end point with bromocresol
green indicator. Calculate the molarity of the HCl.
2HCl + Ba(OH)2 → BaCl2 + H2O

2 mol HCl ≡ 1 mol Ba(OH)2

mol Ba(OH)2 = 0.02971 L x 0.01963 M = 5.83 x 104mol

mol HCl = 5.83 x 104mol x 2 mol HCl = 1.1664 x 103mol

1 mol Ba(OH)2

CHCl = 1.1664 x 103mol

0.050 L
= 0.02333M
How to deal with titration data…
Example 5: Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)
required 43.31 mL of KMnO4. What is the molarity of the KMnO4
solution?
2MnO4 + 5C2O42- + 16H+ → 2Mn2+ + 10CO2 + 8H2O

mol Na2C2O4 = 0.2121 g = 1.583 x 103 mol

134.00 g/mol

mol KMnO4 = 1.583 x 103 mol x 2 mol KMnO4 = 6.33 x 104 mol
5 mol Na2C2O4

CKMnO4 = 6.33 x 104 mol = 0.01462 M

0.04331 L
How to deal with titration data…
Example 6: A 0.8040-g sample of an iron ore is dissolved in
acid. The iron is then reduced to Fe2+ and titrated with 47.22 mL
of 0.02242 M KMnO4 solution. Calculate the results of this
analysis in terms of (a) % Fe (55.847 g/mol) and (b) % Fe3O4
(231.54 g/mol).
MnO4 + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
mol MnO4 = 0.04722 L x 0.02242 M (mol/L) = 1.06 x 103 mol

mol Fe2+ = 1.06 x 103 mol MnO4 x 5 mol Fe2+ = 5.29 x 103 mol
1 mol MnO4
mass of Fe2+ = 5.29 x 103 mol x 55.847 g/mol
= 0.2956 g
% Fe = 0.2956 g x 100 = 36.77 %
0.8040 g

(b) Work at your own time

 How to deal with titration data…

Example 7: Determine the concentration of a volatile

substance:
First the student pipetted 25.00 ml of a cloudy ammonia
solution into a 250 ml conical flask

Then 50 ml of 0.1 M HCl standard solution was added to the

conical flask which reacted with the ammonia in solution

The excess (unreacted) HCl was then titrated with 0.05

mol/L Na2CO3

21.50 ml of Na2CO3 was required to calculate the

concentration of ammonia in the cloudy ammonia solution
 How to deal with titration data

Step 1: Determine the amount of HCl in excess from the

titration results
1.Write the equation of the titration
2HCl + Na2CO3 2NaCl + CO2 + H2O

2. Calculate the number of moles of Na2CO3 that reacted in

the titration
n=CxV
0.05 mol/L x (21.50 ml x 1L/1000 ml)
1.075 x 10-3 mol

3. From the balanced chemical equation 1 mole of Na2C03

reacts with 2 moles of HCl
n (HCl excess) = 2 x 1.075X10-3 mol
= 0.00215 mol
 How to deal with titration data
Step 2: Determine the amount of ammonia in the cloudy
solution
1. Calculate the total moles of HCl originally added to the
diluted cloudy ammonia solution
n (HCl total added) = C x V
=0.1 mol/L x (50.00 ml x 1 L/1000 ml)
= 5 x 10-3 mol

2. Calculate the number of moles that reacted with the

ammonia in the diluted cloudy ammonia solution
n (HCl titrated) + n (HCl reacted with ammonia) = n (HCl total added)
n (HCl total added) = 5 x 10-3 mol
n (HCl titrated)= 2.15x10-3 (calculated in step 1)
n (HCl reacted with ammonia)= 5 x 10-3 mol - 2.15x10-3
= 2.85 x 10-3 mol
 How to deal with titration data
Step 2: Determine the amount of ammonia in the cloudy
solution

3. Write the balanced chemical Equation

NH3 + HCl NH4Cl
From the reaction above 1 mol of NH3 reacts with 1 mol of HCl
Therefore, = 2.85 x 10-3 mol HCl reacted with 2.85 x 10-3 mol
NH3 in the cloudy ammonia solution

4. Calculate the concentration of ammonia in the cloudy

solution
C = n/v
2.85 x 10-3 /( 25.00 ml x 1L/1000 ml)
0.114 mol L-1
 How to deal with titration data
Example 8: Determine the amount of an insoluble salt
Scenario: A student was asked to determine the mass in
grams of calcium carbonate present in a 0.125 g of chalk

The student placed the chalk sample in a 250 ml conical flask

and added 50.00 ml of 0.2 mol L-1 of HCl using a pippet.

The excess HCl was then titrated with 0.25 mol L-1 of NaOH

The average NaOH titre was 32.12 ml . Calculate the mass of

calcium carbonate in grams, present in the chalk sample
 How to deal with titration data
Example 8: Solution:
Step 1: Determine the amount of HCl in excess from the titration results
1.Write the equation of the titration
HCl + NaOH NaCl + H20

2. Calculate the number of moles of NaOH tat reacted in the titration

n=CxV
0.25 mol/L x (32.12 ml x 1L/1000 ml)
8.03 x 10-3 mol

3. From the balanced chemical equation 1 mole of NaOH reacts with 1 moles of
HCl
n (HCl excess) = 1 x 8.03 x 10-3 mol
= 8.03 x 10-3 mol

4. Therefore the amount of HCl that was added to the chalk in excess was
8.03 x 10-3 mol
 How to deal with titration data

Step 2: Determine the amount of calcium carbonate in the

chalk

Calculate the total moles of HCl originally added to the chalk

n (HCl total added)= CxV
=0.2 mol/L x (50ml x1 L/1000 ml)
=0.01mol

2. Calculate the number of moles that reacted with the calcium

carbonate in the chalk
n (HCl titrated) + n (HCl reacted with calcium carbonate) = n (HCl total added)
n (HCl total added) = 0.01mol
n (HCl titrated)= 8.03X10-3 mol (calculated in step 1)
n (HCl reacted with calcium carbonate)= 0.01 mol – 8.03x10-3
= 1.97 X10-3 mol
 How to deal with titration data

Step 2: Determine the amount of calcium carbonate in the chalk

3. Write the balanced chemical Equation
CaCO3 + 2HCl CaCl2 + CO2 + H2O

From the reaction above 1mol of CaCO3 reacts with 2 mol of

HCl, therefore 1mol HCl reacts with ½ mol of CaCO3

Therefore, = 1.97 x 10-3 mol HCl reacted with ½ (1.97X10-3 )

mol CaCO3 in the cloudy ammonia solution
= 9.85 x 10-4 mol CaCO3 in the chalk

4. Calculate the mass of CaCO3 in the chalk solution

m = n x Mr
m= 9.85 x 10-4 X 100.09
0.09 g
How to deal with titration data…

Example 9: The phosphorus in a 4.258 g sample of a plant

food was converted to PO43- precipitated as Ag3PO4 through
the addition of 50.00 mL of 0.0820 M AgNO3. The excess
AgNO3 was back-titrated with 4.06 mL of 0.0625 M KSCN.
Express the results of this analysis in terms of % P2O5. The
chemical reactions are:

P2O5 + 9H2O → 2PO43- + 6H3O+

2PO43- + 6Ag+ → 2Ag3PO4(s)
Ag+ + SCN- → AgSCN(s)
The stoichiometric ratios are:
1 mol P2O5 and 1 mol KSCN
6 mol AgNO3 1 mol AgNO3
total amount of AgNO3 added = 0.0500 L x 0.0820 mol/L
= 0.00410 mol
amount of AgNO3 consumed by KSCN is:
= 0.00406 L x 0.0625 mol KSCN x 1 mol AgNO3
L 1 mol KSCN
= 2.5375 x 10-4 mol
amount of P2O5 = (0.00410 – 0.000254) mol AgNO3x 1mol P2O5
6 mol AgNO3
= 6.41 x 10-4 mol P2O5
mass of P2O5 = 6.41 x 10-4 mol x 141.9 g/mol = 0.09096 g
% P2O5 = 0.09096 g X 100% = 2.14%
4.258 g sample
How to deal with titration data…

Problem: A 100.0-mL sample of brackish water was made

ammoniacal, and the sulfide it contained was titrated with
16.47 mL of 0.02310 M AgNO3. The analytical chemical
reaction is as follows 2Ag+ + S2- → Ag2S(s)
Calculate the concentration of H2S in the water in parts per
million, cppm
 Gravimetric titrimetry

 Mass of the titrant is measured rather than volume.

Balance and weighable solution dispenser are substituted for
a buret and its markings.
The unit of concentration for weight titrations is weight
molarity.

no. mol A no. mmol A

Weight molarity  
no. Kg solution no. g solution
Advantages of weight titrations

Weight titrations offer certain advantages over their volume counterparts:

 Calibration of glassware and tedious cleaning to ensure proper drainage

are completely eliminated.

 Temperature corrections are unnecessary because weight molarity does

not change with temperature.

 Weight measurements can be made with considerably greater precision

and accuracy.

 Weight titrations are more easily automated than are volumetric titrations.
Precipitation titrimetry

Argentometric methods:
 Precipitation titrimetry based on AgNO3 as a precipitating
agent

 AgNO3 is used for the determination of

halides, Cl, Br, I
halides like anions, SCN, CN, CNO
Precipitation titration curves

It is constructed from 3 distinct stages

 pre-equivalence point
 equivalence point
 post-equivalence point
 Precipitation titration curves

Example 10: Generate titration points based on the titration of

50.00 mL of 0.0500 M NaCl with 0.1000 M AgNO3 based on
10.00 mL (added before equivalence point is reached), at
equivalence point and 26.00 mL (added post-equivalence point)
AgNO3, Ksp for AgCl = 1.82 x 1010.

Ag+(aq) + Cl-(aq) = AgCl(s)

Precipitation titration curves
1. Pre-equivalence point
10.00 mL AgNO3 was added

original mol analyte  mol added

Canalyte 
total volume solution
n  Canalyte  Vanalyte
original mol NaCl  mol AgNO3 added
C NaCl 
total volume added
Precipitation titration curves
Original nNaCl  C NaCl  VNaCl  0.05 M  0.05 L  2.5 10 3 mol
mol AgNO3 added  0.1 M  0.01 L  1.0 10 3 mol
2.5 10 3 mol  1.0 10 3 mol
C NaCl   0.025 M
0.05 L  0.01 L
[Cl  ]  0.025 M
10
Ksp 1.82  10
[ Ag  ]  
  7. 28  10 9
M
[Cl ] 0.025
pAg   log( 7.28 10 9 )  8.14

Additional pre-equivalence points can be obtained in the

same way.
Precipitation titration curves
2. At equivalence point

Ag   Cl 
 

Ag Cl   1.82 10

  10

Ag   1.82 10

 2 10

Ag   1.349 10 M

 5

pAg   log 1.349 10   4.87

5
Precipitation titration curves
3. Post- equivalent point data
26 mL AgNO3 was added, Ag+ is in excess

C 26 .000.1000 50 .000.0500

AgNO3  1.316 10 3 M
50 .00  26 .00

pAg  2.88

Additional post-equivalence points can be obtained in the

same way.
Indicators for argentometric titrations
Requirements for an indicator for a precipitation titration:

1) Color change should occur over a limited range in p-function

of the reagent or the analyte and

2) Color change should take place within the steep portion of

the titration curve for the analyte.
Mohr method

Mohr method for chloride:

Titration reaction: Ag+ + Cl- = AgCl(s) (white)
Indicator reaction: 2Ag+ + CrO42- = Ag2CrO4(s) (red)
Na2CrO4 is the indicator used during argentometric
determination of Cl, Br and CN
Na2CrO4 will react with Ag+ to form brick-red Ag2CrO4
precipitate in the equivalence point region.
Concentration of Ag+ at equivalent point with Cl is

Ag  

ksp  1.82 10 10  1.35 10 5 M
 Mohr method
Chromate ion concentration required to initiate formation of
Ag2CrO4 is:

CrO  
12
2 Ksp 1.2 10 3
  6.6 10 M
4
Ag  1.3510 
 2 5 2

 Mohr titration must be carried out at a pH of 7 to 10

because chromate ion is the conjugate base of the weak
chromic acid. Consequently, in more acidic solutions, the
chromate ion concentration is too low to produce the
precipitate near the equivalence point.
A suitable pH is achieved by saturating the analyte solution
with sodium hydrogen carbonate.
Fajans method

Adsorption indicator is applied.

An adsorption indicator is an organic compound that tends to
be adsorbed onto the surface of the solid in precipitation
titration.

Fluorescein is used for the titration of Cl- with AgNO3

In aqueous solution, fluorescein partially dissociates into

hydronium ions and negatively charged fluoresceinate ions
that are yellow-green. The fluoresceinate ion forms an
intensely red silver salt.
Volhard method

Ag+ ions are titrated with a standard solution of thiocyanate

ion
Ag+ + SCN  AgSCN(s)
Fe(III) serves as the indicator.
Fe3+ + SCN  FeSCN2+
K f  1.05 103 
Fe ( SCN ) 
2

red Fe SCN 

3 

Titration must be carried out in acidic solution to prevent

precipitation of Fe3+ as the hydrated oxide.
Application of Volhard titration

 Excess AgNO3 is added

 Excess Ag+ is determined by back-titration with
standard thiocyanate solution