Introduction:

Determination of sulphate in a salt solution is done by complexometric titration.

Complexometric titration is a type of titration based on complex formation between the
analyte and titrant. EDTA, ethylenediamminetetraacetic acid, is used as a complex
making reagent here.
Anions do not complex directly with EDTA, but methods can be devised for the
determination of the appropriate anions which involve either (i) adding an excess of a
solution containing a cation which reacts with the anion to be determined, and then using
EDTA to measure the excess of cation added; or (ii) the anion is precipitated with a
suitable cation, the precipitate is collected, dissolved in excess EDTA solution and then
the excess EDTA is titrated with a standard solution of an appropriate cation. Here fpr the
determination of sulphate we will follow the second way.
EDTA has four carboxyl groups and two amine groups that can act as electron
pair donors, or Lewis bases. The ability of EDTA to potentially donate its six lone pairs
of electrons for the formation of coordinate covalent bonds to metal cations makes EDTA
a hexadentate ligand. However, in practice EDTA is usually only partially ionized, and
thus forms fewer than six coordinate covalent bonds with metal cations.EDTA,
commonly used in the standardization of aqueous solutions of transition metal cations,
only forms four coordinate covalent bonds to metal cations at pH values less than or
equal to 12 as in this range of pH values the amine groups remain protonated and thus
unable to donate electrons to the formation of coordinate covalent bonds.

HOOCH2C

CH2COOH
:N-CH2-CH2-N:

HOOCH2C

CH2COOH

In analytical chemistry the shorthand "H4Y" is typically used to designate

disodium EDTA. This shorthand can be used to designate any species of EDTA. The "Y"
stands for the EDTA molecule, and the "Hn" designates the number of acidic protons
bonded to the EDTA molecule.
EDTA forms an octahedral complex with most 2+ metal cations, M2+, in aqueous
solution. The main reason that EDTA is used so extensively in the standardization of

metal cation solutions is that the formation constant for most metal cation-EDTA
complexes is very high, meaning that the equilibrium for the reaction:
M2+ + H4Y MH2Y + 2H+
lies far to the right. Carrying out the reaction in a basic buffer solution removes H+ as it is
formed, which also drives the reaction to the right. For most purposes it can be
considered that the formation of the metal cation-EDTA complex goes to completion, and
this is chiefly why EDTA is used in titrations / standardizations of this type.
To carry out metal cation titrations using EDTA it is almost always necessary to
use a complexometric indicator, usually an organic dye such as Fast Sulphon Black,
Eriochrome Black T, Eriochrome Red B or Murexide, to determine when the end point
has been reached. These dyes bind to the metal cations in solution to form colored
complexes. However, since EDTA binds to metal cations much more strongly than does
the dye used as an indicator the EDTA will displace the dye from the metal cations as it is
added to the solution of analyte. A color change in the solution being titrated indicates
that all of the dye has been displaced from the metal cations in solution, and that the
endpoint has been reached.
Eriochrome Black T (EBT) is a complexometric indicator which is used in this
titration. Its chemical formula is HOC10H6N=NC10H4(OH)(NO2)SO3Na. In its
protonated form, Eriochrome Black T is blue and it turns red when it forms complex with
calcium, magnesium, or other metal ions. When used as an indicator in an EDTA titration
the characteristic blue end-point is reached when sufficient EDTA is added and metal ions
form complexes with the EDTA instead of the eriochrome.

In the determination of sulphate, first, sulphate is being precipitated as barium

sulphate ( BaSO4). For this, barium chloride (BaCl) is added after checking the solution
to acidic with pH paper. This process must be done carefully as the sulphate solution is to
be heated near to boiling and the warm BaCl is to be added drop by drop.The whole
system is then heated on a steam bath. After a certain time precipitate is filtered through
Whatman No 42 filter paper. The precipitate is washed thoroughly with cold water and
drained. Now EDTA and ammonia (NH3) is added with the precipitate and boiled gently.
After boiling some more concentrated NH3 is added to facilitate the dissolution of
precipitation. Now the resulting clear solution is cooled and a buffer solution of pH 10 is
added along with 3-4 drops of EBT indicator. Now the excess EDTA is titrated by
manganous sulphate solution to violet color.

Chemicals:
Sulphate salt solution, BaCl, NH3, MnSO4, EDTA and EBT

Calculation:
Amount of EDTA given, x = 35 ml
Determination of excess EDTA
No. of
Burette reading
Obs.
Initial
Final
1
2

19.7
26.4

26.4
33.0

Volume of
MnSO4
ml
6.7
6.6

33.0

39.7

6.7

Here, Volume of MnSO4, V1 = 10 ml

Normality of MnSO4, N1 = 0.1 N
Normality of EDTA, N2 = 0.1 N
V1

Volume of EDTA, V2 =

N1

N2
10

=
9.86

0.1

Average Volume of
MnSO4
ml
6.67

= 0.1014 N
So, the amount of excess EDTA, y =
amount of reacted