TITRATION

 is a method of quantitative chemical analysis

 is used to determine an unknown concentration of an identified solution
 is a method by volume measurements (volumetric analysis)

Concepts
 stock solution: is made from the sample of material for determination
 standard solution of the reagent: is made from a compound that can react the unknown
material, its concentration is known accurately (pre-determined)
 endpoint of titration (equivalence point): is measured by volume of the standard reagent
solution needed for the small quantities of stock solution in the stoichiometric ratio

Procedure
 making a stock solution (if needed) by dissolving or diluting of the material to be determined
or using the solution as a stock solution to be determined (depending on its concentration)
– used equipment: measuring flask (calibrated to a single volume, eg. 100 mL, 250 mL)
 pulling out small units of stock solution into a flask (flat bottom flask or Erlenmeyer flask with
wide neck)
– used equipment: bulb pipette (calibrated to a single volume, eg. 10.00 mL, 20.00 mL)
rubber pipette ball
 giving extra utility solutions, indicator into the wide neck flask if needed (depending of the
determination)
– used equipments: measuring cylinders, pipettes etc.
 adding of standard reagent solution to the small unit of stock solution (with extras) until the
endpoint of titration that indicate a change of color or something other
– used equipments: burette (a graduated tube with a tap)

Calculation
 known data:
– mass or volume of sample of material to be determined
– volume of stock solution made for titration (Vs)
– volume of small units of stock solutions (“analyte”) measured into the wide neck flask (Va)
– balanced equation of the reaction occurs
– accurate concentration of standard solution (“titrant”) (ct)
 measured data:
– accurate volume of standard solution (“titrant”) needed when reaching the endpoint (Vt)
 from Vt and ct  nt na
from na and Va  ca or from na and Vs/Va ratio  n of the total sample
further calculations for getting result

Back titration
 used if:
– the material to be determined is too volatile
– the material to be determined isn’t soluble in the solvent (mostly water)
– the material to be determined would decompose during titration
– the reaction used is too slow for finding the endpoint of the titration
 principle:
– the material to be determined is reacted with a reagent using it in excess
– the excess of the reagent will be determined by another reagent (titration)
 calculation:
– known data: the mass or volume of the material to be determined (mx or Vx)
the volume of the reagent using it in excess (Ve)
the accurate concentration of the reagent using it in excess (ce)
the balanced equation(1) between the material do be determined and reagent
the balanced equation(2) between the reagent and the another reagent
the accurate concentration of the another reagent (“titrant”) (ct)
– measured data:
accurate volume of standard solution (“titrant”) needed when reaching the endpoint (Vt)
– from Vt and ct → nt excess of the first reagent (nex)
– from Ve and ce → ne
– ne and nex the amount of reagent needed for the material to be determined (n? = ne – nex)
– from n? tha amount of the material to be determined (nx)
– further calculation for getting result

Equipments

Erlenmeyer flask measuring flasks flat bottom flask

bulb pipettes rubber pipette balls burettes with stand

 ACID-BASE TITRATION

Acidimetric titration: the titrant is a strong acid (eg. HCl, H2SO4)

The material to be determined is basic: eg. NH3, NaOH, carbonates, hydrogen carbonates,
amines etc
Alkalimetric titration: the titrant is a strong base (eg. NaOH)
The material to be determined: eg. HCl, H2SO4, hydrogen sulphate, oxalic acide, other organic,
weak acids etc.

Standardization of the titrant: with material to be measured accurately, eg. oxalic acide for base or
KHCO3 for acids.

Choosing appropriate indicator: depending on range of color change and weakness of analyte.

Indicator Color on Acidic Side Range of Color Change Color on Basic Side

Methyl Violet Yellow 0.0 - 1.6 Violet

Bromophenol Blue Yellow 3.0 - 4.6 Blue

Methyl Orange Red 3.1 - 4.4 Yellow

Methyl Red Red 4.4 - 6.3 Yellow

Litmus Red 5.0 - 8.0 Blue

Bromothymol Blue Yellow 6.0 - 7.6 Blue

Phenolphthalein Colorless 8.3 - 10.0 Pink

Alizarin Yellow Yellow 10.1 - 12.0 Red

For choosing appropriate indicator we can draw titration curve:

Titration of a strong acid by strong base and vs.

The range of color change of indicator should be between pH of 4.00 and 10.00.
Titration of a strong and a weak acid by strong base

The range of color change of the indicator is around 8.00 for acetic acid.
Generally the range of change of the indicator is around the pH of the salt solution formed (over pH
of 7.00).

Titration of a strong and a weak acid by strong base

Generally the range of change of the indicator is around the pH of the salt solution formed (under
pH of 7.00).

Detecting the end-point

Generally it is at the color transition. For an accurate result we need to boil the solution for driving
out the CO2 dissolved. If the analyte is alkaline we need to boil the solution when we reached the
end-point. After cooling it we can finish the titration with 1-2 drops of titrant.

Back titration

Most of the carbonates (eg. CaCO3, BaCO3): they don’t dissolve in water.
Ammonia: it is volatile.
 REDOX TITRATION

Oxidimetry

The titrant an oxidizing agent. Eg. permanganometry. The reaction:

MnO4– + 5e– + 8 H+ = Mn2+ + 4 H2O ° = 1,52 V

It is commonly used in acidic solution (H2SO4).

Indicator and end-point

There isn’t need any indicator for detecting of end-point. Adding to the analyte the titrant will be
colorless time to time. At the end-point the pale pink color is formed from the last drop of titrant.
Important notice! Titrate slowly, don’t pour the titrant at once. If you are too quick, permanganate
can be turn to MnO2 and this brown precipitation dissolves slowly and the end-point can’t be
detected accurately.

Standardization
Potassium permanganate can be reduced easily so we can’t prepare a solution of an accurate
concentration. Permanganate can be determined by oxalic acide (/COOH/ 2 ∙ 2 H2O) which can be
weighed out very accurately.

2 MnO4– + (COOH)2 + 6 H+ = 2 Mn2+ + 10 CO2 + 8 H2O

The titration is done at 60 °C (because of the reaction rate).

What for?
It can be determined the following materials: Fe2+, SO2, NO2–, oxalates, chemical oxygen demand,
biological oxygen demand etc.

Back titration
Nitrites: they can decompose in acidic solution (3 NO2– + 3 H+ = 2 NO + NO3–).
Formic acid: it can be oxidized in alkaline solution, when permanganate turns into MnO2. The
MnO2 and the excess of MnO4– can be titrated back in a back soured solution by oxalic acid.

Reductometry

The titrant a reducing agent. Eg. iodometry. The titrant is thiosulphate that can reduce iodine. The
reaction:

I2 + 2 S2O32– = 2 I– + S4O62–

Iodine can be formed in a reaction between the analyte and potassium iodide (KI). For example:

2 I– + Cl2 = I2 + 2 Cl–
Cu2+ + 2 I– = CuI + ½ I2
5I– + IO3– + 6 H+ = 3 I2 + 3 H2O

Sometimes 5–10 minutes of waiting is needed for forming all of iodine.

Indicator and end-point
The indicator is starch solution. Iodine forms dark blue complex with starch. The end-point of the
titration is the discoloration of the solution. The blue color of the solution should not come back
before 30 sec.
The indicator should be added to the analyte near to the endpoint (pale yellow solution showing the
presence of a small amount of iodine). The starch would form too strong complex with iodine at
start of the titration so at the end-point the coming out of iodine from the complex wouldn’t be
quick enough.

Standardization
Sodium thiosulphate can be oxidized easily so we can’t prepare a solution of an accurate
concentration. Thiosulphate can be determined by potassium hydrogen iodate (KH(IO 3)2) which can
be weighed out very accurately. The stock solution made from reaction between potassium
hydrogen iodate and potassium iodide (given in excess) and iodine will be titrated by sodium
thiosulphate solution.
Sodium thiosulphate solution decomposes on standing:
S2O32– = SO32– + S
Sulphite ion is formed that can react with iodine too:
SO32– + I2 + H2O = SO42– + 2 I– + 2 H+
Specialty! The partially decomposed thiosulphate titrant shows a virtually greater concentration at
standardization because of the 1 : 1 stoichiometric rate of reaction between SO 32– and iodine.

Back titration
Some organic reagent needs an excess of iodine and some time for finishing the reaction. Other
possibility is to combine iodometry with bromatometry.
Bromine is made from reaction between iodate (accurate volume and known concentration) and
iodide (given in excess) in acidic solution:
5Br– + BrO3– + 6 H+ = 3 Br2 + 3 H2O
Eg. phenol react with bromine in a time-consuming reaction:
C6H5–OH + 3 Br2  C6H2Br3–OH + 3 HBr
The rest of bromine can react with potassium iodide (given in excess) and the iodine formed can be
titrated by thiosulphate.
 PRECIPITATION TITRATION

The most common titration is argentometric titration. The silver ions form precipitate with
chloride, bromide, iodide and rodanide (thiocyanate) ions:
Ag+(aq) + Cl–(aq) = AgCl(s)
Ag+(aq) + Br–(aq) = AgBr(s)
Ag+(aq) + I–(aq) = AgI(s)
Ag+(aq) + SCN–(aq) = AgSCN(s)
The titrant is silver nitrate solution (don’t need to standardize; it can be weighed out accurately).

Detecting the end-point

Mohr method
Potassium or sodium dichromate solution is used as an indicator. During titration, as long as
chlorides are present, concentration of Ag + is too low for silver chromate formation. Near
equivalence point concentration of silver cations rapidly grows, allowing precipitation of
intensively red (fulvous) silver chromate precipitation which signals end point.
It is good for chloride and bromide, the end-point is very hardly detectable for determination I – or
SCN–.

Fajans method
Fluorescein or eosin is used as an indicator. During titration the excess of chloride ion is adsorbed
on the surface of the silver chloride particles. At the end-point chloride ions are run out and the
fluorescein or eosin will be adsorbed on the surface of the particles. The color of the precipitation
will turn to pink or red raspberries. Nitric acid needs to be added to the analyt on occur of pH
dependence of the adsorpcion. Titration must be done protected from light because silver chloride
can turn to gray in sunlight.

Volhard method
This is a back titration using iron(III) nitrate solution as an indicator. Silver nitrate solution in
excess is given to the halide ions to be determined. The excess of silver ions will be determined by
KSCN solution. When silver ions run off iron(III) ions form red [Fe(SCN) 2]+ complex ions with
rodanide ions at the end-points.