Titrimetric Methods of Analysis

based upon measuring the amount of reagent of known concentration (SR) that is consumed by the analyte (A) a A + b SR -- In c P widely used for routine analyses because they are rapid, convenient, accurate and readily automated

Titrimetric Methods of Analysis

1.

Volumetric Titrimetry Gravimetric Titrimetry Coulometric Titrimetry

involves measuring the volume of a solution of known concentration that is needed to react essentially completely with the analyte differs only in that mass of the reagent is measured instead of its volume the reagent is a constant direct electrical current of known magnitude that directly or indirectly reacts with the analyte; the time required to complete the electrochemical reaction is measured

2.

3.

Advantages of Weight Titrations

1. Calibration of glassware and tedious

cleaning to ensure proper drainage is avoided. 2. Temperature corrections are unnecessary. 3. Weight measurement can be made with considerably greater precision and accuracy. 4. Weight titrations are more easily automated.

Volumetric Titrimetry

Titration
performed by slowly adding a standard solution from a buret to a solution of the analyte until the reaction between the two is judged complete volume of reagent needed to complete the titration is determined from the difference between the initial and final volume readings

Equivalence Point
amount T = amount A

End Point - a physical

change associated with the condition of chemical equivalence occurs during titration

Et = Veq - Vep

Volumetric Titrimetry
Indicator
often added to the analyte solution in order to give an observable physical change (the end point) at or near the equivalence point typical indicator changes: appearance/disappearance of color, a change in color, appearance/disappearance of turbidity
instruments to detect end

points: voltmeters, ammeters, ohmmeters, colorimeters, temperature recorders and refractometers kept at a minimum amount, intensely colored and react last with the titrant

weaker than the analyte,

Volumetric Titrimetry
Primary Standard
a highly purified compound that serves as a reference material in all volumetric methods accuracy of a method is critically dependent on the properties of this compound
Characteristics:
high purity stability toward air absence of hydrate water ready availability at

modest cost reasonable solubility in the titration medium reasonably large molar mass

Volumetric Titrimetry
Secondary Standard
standard solution / standard titrant a reagent of known concentration that is used to carry out a titrimetric analysis expressed in terms of molarity and normality
Characteristics:
be sufficiently stable react rapidly with the

analyte react more or less completely with the analyte undergo a selective reaction with the analyte

Methods for Establishing Concentration of Standard Titrants A. Direct Method

carefully weighed quantity of a primary standard is dissolved in a suitable solvent and diluted to an exactly known volume in a volumetric flask

B. Standardization
1. weighed quantity of a primary standard 2. measured volume of another standard solution/secondary standard

Types of Titration Methods

1. Direct Titration Method
titrant reacts directly with analyte a simple relationship exist between the titrant used and the analyte present

2. Indirect Titration Method

Replacement 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

Types of Titration Methods

3. Back-Titration Method
Residual Titration Method a known excess of the titrant is added to the analyte solution amount of analyte is found by difference
Chemical Equations:
Direct Titration:
aA aA

+ bT

In

cP

Indirect Titration:

+ b R c NS d NS + e T In f P
Back-Titration:
aA d T1

+ b T1 c P
excess

excess

+ e T2

In

fP

Classification of Volumetric Methods

1. Acid-Base
many compounds, both inorganic and organic, are either acids or bases and can be titrated with a standard solution of a strong base or a strong acid end points of these titrations are easy to detect, either by means of an indicator or by following he change in pH with a pH meter

2. Precipitation
the titrant forms an insoluble product with the analyte indicators can be used to detect the end point or the potential of the solution can be monitored electrically

Classification of Volumetric Methods

3. Complexometric
the titrant is a reagent that forms a water-soluble complex with the analyte, a metal ion the titrant is often a chelating agent ; EDTA reverse titration may be carried out also indicators can be used to form a highly colored complex with metal ion

4. REDOX
involves the titration of an oxidizing agent with a reducing agent or vice-versa there must be a sufficiently large difference between the oxidizing and reducing capabilities end points detected by appropriate indicators or by various electrometric means

Exercise 6
Analysis of Table Wine A 25.00-mL sample of white table wine was diluted to about 100-mL and titrated with 28.40mL of 0.05412-N NaOH with phenolphthalein as indicator. Express the acidity of the wine in terms of grams of tartaric acid (H2C4H4O6) per 100 mL.
Molar Masses: H2C4H4O6 = 150.09 NaOH = 40.00
Sample Analyte Indicator Titrant Method Reaction Titration Method

White Table Wine H2C4H4O6 Phenolphthalein NaOH Volumetric Titrimetry Acid-Base Reaction Direct Titration Method

Given: 25.00-mL sample 28.40-mL of 0.05412-N NaOH

Answer:

0.4614 g /100 mL

Exercise 6
Standardization of HCl Exactly 50.00-g of HCl required 29.71-g of 0.01963-Mw Ba(OH)2 to reach an end point with bromocresol green indicator. Calculate the weight molarity of the HCl solution.
Molar Masses: HCl = 36.46 Ba(OH)2 = 171.36
Analyte Standard Indicator Method Reaction

HCl Ba(OH)2 Bromocresol Green Weight Titrimetry Acid-Base Reaction

Type of Standardization & Titration Method

Secondary Standardization Direct Titration Method Given: 50.00-g HCl 29.71-g 0.01963-MW Ba(OH)2
Answer:

0.02333-MW

Exercise 6
A sample of copper ore weighing 2.132-g is dissolved in acid and the copper is electrolyzed:
Cu 2+ + 2 e- Cu

Analysis of Copper Ore

Sample Analyte Method Reaction Given:

Copper Ore Copper Coulometric Titrimetry Redox Reaction

If 8.04-min is required for the electrolysis using a constant current of 2.00-A, calculate the percentage of copper in the ore.
Molar Mass: Cu = 63.54

2.132-g sample 8.04-min - 2.00A

Answer:

14.9%