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SISON REVIEW CENTER: Chemistry Boards Review

Analytical Chemistry: Titration

Outline:
Concentration
Dilution Exercises
Titration Overview
Titration Techniques
General Types of Titration

CONCENTRATION


Recall: = = = log( )


Routine calculations: = = = =

h = # H+
= # OH-
= e- lost
= e- gained
= charge

Examples: H2SO4 + 2 NaOH Na2SO4 + 2 H2O FeCl2 + K2Cr2O7 products (Fe3+, Cr3+)
FW:
EW:

mass:
mol:
eq:

DILUTION EXERCISES


= = 1 1 = 2 2 = 3 3 = =

Example 1: What volume of 0.30 M Sr(OH)2 must be added to 100 mL 0.20 M NaOH to give a 0.45 M OH- solution?

Example 2: A stock standard solution of 1x10-3 M Fe2+ was prepared from ferrous sulfate. Standard A was prepared
by adding 3.00 mL of the stock solution in a 100-mL volumetric flask and diluting up to the mark. Standard B was
prepared by adding 15.00 mL of Standard A in another 100-mL volumetric flask and diluting to mark. Find the Fe2+
concentrations in standards A and B.

Example 3: A 100.00 mL water sample was diluted with deionized water in a 500-mL volumetric flask. A 20.0 mL
aliquot of the solution was titrated with EDTA and was found to contain 50.0 mg CaCO 3. How much CaCO3 is
present in the water sample? a.) mg CaCO3 b.) mg CaCO3/L

Example 4: A 5.00 mL of a milk sample containing 120 mg Ca/L was diluted to 100.0 mL. A 25.0 mL aliquot of the
resulting solution was then diluted to 150.0 mL. How much Ca is present in a 4.00 mL aliquot of the final solution?

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SISON REVIEW CENTER: Chemistry Boards Review
Analytical Chemistry: Titration

TITRATION OVERVIEW

Standard all solids or solutions with accurately known concentration


Primary standard solution solution prepared from a primary standard (solid)
Secondary standard solution solution whose concentration is calculated based on a primary standard solution
Standardization determination of the concentration of a secondary standard solution
Titrant reactant with known concentration (a standard); incrementally added in most cases

Primary Standard Requirements:


1. Very high purity
2. High molecular mass
3. Stable at drying temperatures

Analyte solution with unknown concentration; reacted with titrant or a standard


Equivalence point the amount of titrant or standard added is stoichiometrically equal to the amount of analyte
Indicator a substance or a device that produces a visible change near or very near the equivalence point
End point point where the visible change of the indicator occurs; ideally equal to equivalence point
Titration error difference between end point (actual) and equivalence point (theoretical)

Titration Requirements:
1. Stoichiometric reaction
2. Complete reaction
3. No side reaction
4. Rapid reaction

TITRATION TECHNIQUES

1.) DIRECT TITRATION

General reaction: a A + t T pdts


General equation: = or VT nT nA DF A (M, %, mass, etc.)

Example 5: Acid-Base Titration


What is the molarity of a 1 L Na2CO3 solution if a 25.0 mL aliquot required 20.1 mL 0.110 M HCl to reach the
titration end point?

Example 6: Acid-Base Titration


An HCl solution was standardized using 0.2510 g Na 2CO3 (106 g/mol). 37.2 mL HCl solution was required to reach
the end point. The HCl was then used as titrant in the analysis of a soda ash sample. 0.2077 g sample was
dissolved in 50 mL distilled water and the resulting solution required 35.10 mL of the HCl to reach the end point.
a.) What is the concentration of the HCl solution?
b.) What is the % Na2CO3 in the soda ash sample?

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SISON REVIEW CENTER: Chemistry Boards Review
Analytical Chemistry: Titration

Example 7: Complexometric Titration


A 25.0-mL water sample to be analysed for its hardness was diluted to 250mL. A 10.00mL aliquot required
24.50mL 0.0200 M EDTA solution to reach the EBT endpoint. Calculate the water hardness of the water sample
expressed as ppm CaCO3.

2.) INDIRECT TITRATION

General reaction: a A + exc. B cC


cC + tT pdts


General equation: = or VT nT nC nA DF A (M, %, mass, etc.)

Example 8: Redox Titration


A piece of brass weighing 220 mg was dissolved for iodometric titration. Excess KI was added and the liberated
iodine required 26.9 mL of 0.0847 N Na2S2O3 to reach the starch endpoint. Calculate the % Cu in the brass.

Example 9: Redox Titration


The dissolved oxygen in a 250.0 mL water sample from Laguna Lake was analyzed using the Winkler Method and
the procedure performed is outlined below. 7.00 mL 0.10 M Na 2S2O3 was required to reach the starch end-point.
a.) Calculate the dissolved oxygen content of the water sample expressed as mg/L or ppm O2.
b.) Calculate the dissolved oxygen titer for the analysis (using 0.10 M Na2S2O3).
c.) Calculate the dissolved oxygen in a 100.0 mL water sample from Taal Lake which required 5.0 mL Na2S2O3.

1. Excess MnCl2, NaI, and NaOH were added to the sample.


2. The resulting mixture was acidified with conc. H2SO4.
3. The liberated I2 was titrated with Na2S2O3.

Important: Review balancing redox reactions! Winkler method summary:

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SISON REVIEW CENTER: Chemistry Boards Review
Analytical Chemistry: Titration

3.) BACK-TITRATION

General reaction: a A + b1 B pdts , = , ,


b2 B + t T pdts

2
General equation: = (, ) ; , = ; , =
1

VT nT nB remaining nB reacted nA DF A (M, %, mass, etc.)

Example 10: Precipitation Titration


25.0 mL 0.20 M NaCl was added to a 100.0 mL AgNO3 solution. The precipitate was filtered and the excess Cl- was
analyzed using the Mohr method. The titration required 12.0 mL of standard 0.05 M AgNO3 to reach the formation
of a brick-red precipitate (end-point). What is the concentration of the AgNO3 solution?

Example 11: Acid-Base Titration


A 2.00 g cat feed sample was analyzed using the Kjeldahl Method to determine the nitrogen and protein content.
The sample was digested in concentrated H2SO4 and was treated to liberate ammonia which was then distilled in
100 mL 0.1N H2SO4. 42.7 mL 0.09N NaOH was required for back-titration. Find the % N and % protein in the feed.
(% protein factors: 6.25 feeds / 6.25 meats / 6.38 dairy / 5.70 cereal x %N )

GENERAL TYPES OF TITRATION Effect of Keq


Titration CurveI on Titration CurvesII

1.) Acid-Base Titration pH / pOH vs. Vtitrant

2.) Complexometric Titration pM vs. Vtitrant

3.) Precipitation Titration pAg / pX vs. Vtitrant

4.) Redox Titration Ehalf cell vs. Vtitrant

I. Titration curves are used to evaluate the end-point and identify suitable indicators.
The choice of indicator in an acid-base titration is determined by the pH at the equivalence point.

II. As the reaction completeness or Keq of the titration reaction increases, the sharpness of the curve also increases.
- Titration of a weak acid with higher Ka will give a sharper curve. Strong acids have the sharpest curves.
- A higher Ksp or Kf precipitation or complexometric will give a sharper titration curve.
The titration curve also becomes sharper as the concentration of the reactants increases.
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