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Exercise 13 Prelab:
Preparation and Standardization of Postlab:
Sodium Thiosulfate Solution Accuracy:
Precision:

I. Objectives
At the end of the exercise, the student should be able to:
1. Properly prepare and standardize 0.05N NA2S2O3 solution; and
2. Apply the proper techniques or iodometric titrations.

II. Principles
Iodine (I2) existing in its solid elemental form has a solubility that is enhanced by the help of
sodium or potassium iodide, since I2 alone is only slightly soluble in water. The ionic compound
helps through the formation of the triiodide ion as shown below:

Equation 13.1

Analytical methods about the iodine iodide ion equilibrium have been developed with the
standard potential for the half-reaction value equal to +0.535 V (Equation 13.2). Iodine dissolved
in water is simply written as I2 when balancing chemical equations for simplification.

Equation 13.2

A good indicator used for titrations involving iodine is starch. Colloidally dispersed starch is a
sensitive indicator. It forms a hydrated colloidal particle with iodine adsorbed upon it. This
complex have an intense blue color that is reversible and can be used to detect traces of iodine in
the solution being titrated (Equation 13.3). This blue color however, is destroyed when done in
solutions with pH 8 and above. Heat, alcohol, and concentrated solution of strong electrolytes
also have the same effect for they either coagulate colloids of hinder the adsorption of iodine
(Harris, 2010). This decreases the sensitivity of the indicator and should therefore be avoided.

Equation 13.3

Iodine is used in titration in two major classifications: (a)Iodimetric or direct method and
(b)Iodometric or indirect method. Iodimetry employs the use of a solution of Iodine as a standard
oxidizing agent, while iodometry involves the formation of free iodine (I2) through the use of an
oxidizing agent that is allowed to react to excess iodide ions.

Iodimetry can only be done on a number of substances. This is because iodine is a weak
oxidizing agent and is therefore limited for use as a titrant. The most common titration reactions
for iodimetry are:

Equation 13.4
Equation 13.5
Equation 13.6
Equation 13.7

Iodometric methods, on the other hand, are useful when it comes to determining the oxidizing
properties of substances. It usually follows a general scheme:

Equation 13.8
Equation 13.9

The amount of Aox in the sample in Equation 13.8 is stoichiometrically equivalent to the iodine
formed since the iodine added (from potassium or sodium iodide) is in excess which is not a
standard solution. The iodine formed is then titrated with the Na2S2O3 standard to form iodide
and tetrathionate ions as seen in equation 13.9. The starch indicator is only added when the tinge
of yellow color due to the excess iodine has disappeared (which happens near the equivalence
point), this is because if the starch is added when the iodine concentration is still high, it may
decompose irreversibly (Fajardo, 2009). The endpoint is marked by the disappearance of the blue
color color.

Some of the reactions of substances that can be determined by iodometry are given below:

Equation 13.10
Equation 13.11
Equation 13.12
Equation 13.13

A standard sodium thiosulfate solution reacts as shown in Equation 13.9 and proceed smoothly
around pH of 5-9. Sodium thiosulfate pentahydrate (Na2S2O3*5H2O) has a tendency lose some
of its water of hydration which is a reason why it is not usually regarded as a primary standard. A
prepared solution of Na2S2O3*5H2O can be standardized with the use of a primary standard
like potassium dichromate or potassium iodate or a previously standardized iodine solution
(Skoog, 2013).

Na2S2O3*5H2O crystals are soluble in water which makes its solution preparation easy from its
salt. However, factors that influence the stability of the thiosulfate ion are considered: (a) the pH
of the solution; (b) the presence of heavy metal impurities; and © the presence of bacteria that
can metabolize the thiosulfate ion.

The standardization of the sodium thiosulfate solution is done by using a primary standard
dissolved in a highly acidic solution and addition of potassium iodide follows. This is to liberate
a significant amount of iodine according to the reaction in equation 13.14. The reaction occurs
slowly, thus, it is left for a few minutes to allow completion before titration with the sodium
thiosulfate solution with starch as the indicator one again according to the reaction in equation
13.9.
 Equation 13.14.

Sources:

Fajardo, N. N.,et. al. (2009) CHEM 32.1: Quantitative Inorganic Analysis Laboratory. 4th
Revision. University of the Philippine Los Baños: Institute of Chemistry. (pp. 39-41; 47-
49)

Harris, D. C. (2010) Quantitative Chemical Analysis. 8th Edition. New York: W. H. Freeman and
Company. (pp. 351)

Skoog, D. A. , et.al, (2013) Fundamentals of Analytical Chemistry. 9th Edition. Cengage Learning.
(pp. 442-445)

III. Prelab Calculations and Formulas

Mass of Reagent-grade 𝑲𝑴𝒏𝑶𝟒

𝑔
𝐹𝑊𝐾𝑀𝑛𝑂4 158.034 𝑚𝑜𝑙 𝑔
𝐸𝑊𝐾𝑀𝑛𝑂4 = = 𝑒𝑞 = 31.067
𝑛 5 𝑒𝑞
𝑚𝑜𝑙
𝑔𝐾𝑀𝑛𝑂4 𝑐𝑟𝑦𝑠𝑡𝑎𝑙 = 𝐸𝑊𝐾𝑀𝑛𝑂4 𝑥 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑥 𝑉𝑜𝑙𝑢𝑚𝑒𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (Eq. 11.4.)
𝑔 𝑒𝑞
= 31.607 𝑥 0.1 𝑥 0.250 𝐿 = 0.7902 𝑔 𝐾𝑀𝑛𝑂4
𝑒𝑞 𝐿

Standardization of 𝑲𝑴𝒏𝑶𝟒 solution

𝑔
𝐹𝑊𝐻2 𝐶2 𝑂4 •2𝐻20 126.066 𝑔
𝑚𝑜𝑙
𝐸𝑊𝐾𝑀𝑛𝑂4 = = = 63. 033 𝑒𝑞
𝑛 2
𝑔
(𝑁𝑉)𝐾𝑀𝑛𝑂4 = (𝑒𝑞 𝑥 𝑉)𝐻2 𝐶2𝑂4 (Eq. 11.5)

IV. Answers to the Prelab Questions

1. Enumerate and explain how each of the precautions taken in the preparation of
Na2S2O3 solution ensures the stability of the solution.
2. When must the indicator be added to the analyte and why?
3. What is the product formed that is responsible for the green color of the solution?