Analytical Chemistry

Reference: Analytical Chemistry by Larry G. Harris

TITRIMETRY - Continuation
Relative Merits of Methods for Determining End Points
 End-point methods relying on data near the equivalence point are
potentially suitable only for reactions that “go to completion” readily
(have a large equilibrium constant).

 There are some otherwise suitable reactions for which this is not true.

 Clearly the great advantages of visual indicators lie in their simplicity

and speed.

 The titrant can be added more or less continuously without the need for
periodic volume measurements and the human eye can serve as an
instantaneous detector.

 There are chemical reactions, however, for which no suitable indicators

are readily available.

 Furthermore, visual indicators cannot be used with highly colored

samples of titrants, or when diverse substances are present that can
destroy their indicating properties.

 Graphic methods using data away from the equivalence point have the
advantage of being applicable to chemical reactions with smaller
equilibrium constants that are present that are required for indicator
methods, but they take considerably more time and require some sort of
instrumental measurement device.

 All such methods require the collection of data at periodic intervals and
subsequent preparation of a graph to determine the end point.
CALCULATING AMOUNT AND CONCENTRATIONS
Three different ways in which titrations are used to determine the
amount of an analyte:

Direct Titration Method

 The titrant reacts directly with the analyte and a simple relationship
exists between the amount of titrant used and the amount of analyte
present:

Amount analyte = amount titrant x reacting ratio

where the amount of titrant used is expressed in units of moles or

millimoles

 In the titration of phosphoric acid with sodium hydroxide according to

the reaction
H3PO4 + 2NaOH  Na2HPO4 + 2H2O (Reaction 1)
Analyte Titrant
H3PO4 is the analyte and NaOH is the titrant

2 molecules or moles of sodium hydroxide are needed to react with each

molecule or mole of phosphoric acid, and

Amount H3PO4 (mmol) = amount NaOH (mmol) x H3PO4 / 2NaOH

Once the amount of phosphoric acid has been calculated it can be

converted to a weight and a percentage

wt H3PO4 = amount of H3PO4 x MW H3PO4

% H3PO4 = (wt H3PO4/wt sample ) x 100

Examples:

1. A 300.0 mg sample containing phosphoric acid and inert material was

diluted with water and titrated with 0.05000M NaOH according to
Reaction 1. The end point was reached after 29.00 mL of titrant was
added. Calculate the % H3PO4 in the sample.

Solution

The percent of H3PO4 is given by

% H3PO4 = (wt H3PO4/wt sample) x 100

The amount of H3PO4 is found from the amount of titrant:

Amount H3PO4 = amount NaOH x H3PO4 / 2NaOH

= (29.00 mL x 0.05000 M) x H3PO4 / 2NaOH = 0.7250 mmol

= 0.7250 mmol x 98.00 mg/mmol = 71.05 mg

Finally,
% H3PO4 = (71.05 mg H3PO4/300.0 mg sample) x 100 = 23.68 %

Many titrants are not available as primary standards, and their

concentrations must be determined by titration with some other primary
standard. The problem is somewhat the opposite of example 1, that is,
the amount of analyte (standard) is known and the concentration of
titrant is the unknown.
2. Exactly 600.0 mg of pure sodium oxalate , Na2C2O4, was dissolved in acid
and titrated with a potassium permanganate solution according to the
reaction
2MnO4- + 5C2O4- + 16H+ 2Mn2+ + 10CO2 (g) + 8H2O

The end point was reached after adding 34.00 mL of titrant. Calculate
the molarity of the KMnO4.

Solution

The molar concentration is given by

CKMnO4 = amount KMnO4 (mmol) / volume solution (mL)

The amount of KMnO4 can be found from the amount of Na2C2O4 with
which it reacted:

amount KMnO4 = amount Na2C2O4 x 2 KMnO4 / 5 Na2C2O4

= 600.0 mg Na2C2O4 / (134 .0 mg Na2C2O4 / mmol Na2C2O4) x 2/5 = 1.791 mmol

= 600.0 mg Na2C2O4 x (1 mmol Na2C2O4 x 134 .0 mg Na2C2O4) x 2/5 = 1.791 mmol

Then CKMnO4 = 1.791 mmol / 34.00 mL = 0.05268 M

Replacement or Indirect Titration Method

This titration method employs a preliminary reaction in which the

analyte is replaced by an equivalent amount of another substance which
is then determined by titration. For example, iron can be determined this
way by treating a solution of ferric ions with excess potassium iodide and
titrating the liberated iodine with a sodium thiosulfate titrant. The
reactions are

2Fe3+ + 2I-  2Fe2+ + I2 (Reaction 2)

2Fe3+ is the analyte

I2 + 2S2O32-  2I- + S4O62- (Reaction 3)

2S2O32- is the titrant

 Note that the titrant and analyte do not react with each other, but they are
related through the iodine. To develop the quantitative relationship between
titrant and analyte, the stoichiometries of both reactions 2 & 3 must be
taken into account,

3. A 750.0 mg sample of iron ore was dissolved in acid and treated to oxidize
all of the iron to ferric ion. After destroying any remaining oxidizing agent,
excess KI was added. The liberated I2 required 28.50 mL of 0.07500 M
Na2S2O3 for titration. What is the % Fe in the sample?
Solution
Using the stoichiometries of Reactions 2 & 3

2Fe3+ + 2I-  2Fe2+ + I2 (Reaction 2)

2Fe2+ is the analyte

I2 + 2S2O32-  2I- + S4O62- (Reaction 3)

2S2O32- is the titrant

we can work backward to find the amount of Fe3+

amount I2 = amount S2O32- x 1I2/2S2O32-

amount Fe3+ = amount I2 x 2Fe3+/ 1I2

where amount is in millimoles or moles. Combining these gives

amount Fe3+ = amount S2O32- x 1I2/2S2O32- x 2Fe3+/ 1I2

= (18.50mL)(0.07500M)(1/2)(2/1) = 1.388 mmol

Wt Fe = amount Fe X at.wt. Fe

= 1.388 mmol x 55.85 mg/mmol = 77.52 mg

%Fe = (wt Fe/wt sample) x 100

= (77.52 mg/750.0 mg) x 10 = 10.34

Homework:
A sodium thiosulfate solution is standardized by weighing & dissolving 250.0
mg of pure copper metal. The copper solution is treated with excess KI and the
liberated Iodine requires 44.90 mL of the thiosulfate titrant to reach the end
point. What is the molarity of the sodium thiosulfate?