Titrimetric Methods; Precipitation Titrimetry

Lecture 5

Titration
Based on a reaction between the analyte and a standard reagent known as the titrant. The end point is signaled by an indicator color change or a change in an instrumental response. Widely used to determine acids, bases, oxidants, reductants, metal ions, protein, and many other species.

Titrimetric Methods
Volumetric titrimetry
the volume of a standard reagent is the measured quantity

Gravimetric titrimetry
the mass of the reagent is measured quantity

Coulometric titrimetry
the quantity of charge in coulombs required to complete a reaction with the analyte is the measured quantity The reagent is a constant direct electrical current of known magnitude that consumes analyte. The time required (and thus the total charge) to complete the electrochemical reaction is measured When the analytical reactions involve electron transfer. These methods are often called redox titrations.

Terms used in Volumetric Titrimetry

Standard solution (or standard titrant)
a reagent of exactly known concentration that is used in a titrimetric analysis.

Titration
a process in which a standard reagent is added to a solution of an analyte until the reaction between the analyte and reagent is judged to be complete.

Back-titration
a process in which the excess of a standard solution used to consume an analyte is determined by titration with a second standard solution. Required when the rate of reaction between the analyte and reagent is slow or when the standard solution lacks stability.

Equivalence Points and End Points

Equivalence point:
When the amount of added standard reagent is chemically equivalent to the amount of analyte. Cannot be determined experimentally. Can be estimated by observing some physical change associated with the condition of equivalence (i.e., the end point).

End point:
When a physical change occurs that is associated with the condition of chemical equivalence. Indicators are often added to the analyte solution to produce an observable physical change (the end point) at or near the equivalence point.

Titration error:
The difference in volume or mass between the equivalence point and the end point.

Primary & Secondary Standards

Primary Standards
Highly purified compound that serves as a reference material in volumetric and mass titrimetric methods. Requirements:
High purity Atmospheric stability Absence of hydrate water so that the composition of the solid does not change with variations in humidity Modest cost Reasonable solubility Reasonably large molar mass so that the relative error associated with weighing the standard is minimized

Secondary standards
A compound whose purity has been established by chemical analysis and that serves as the reference material for a titrimetric method of analysis.

Standard Solutions
Desirable properties:
be sufficiently stable so that it is necessary to determine its concentration only once; react rapidly with the analyte so that the time required between additions of reagent is minimized; react more or less completely with the analyte so that satisfactory end points are realized; undergo a selective reaction with the analyte that can be described by a balanced equation.

Volumetric Calculations
Concentration of standard solutions:
Molarity, c
gives the number of moles of reagent contained in one liter of solution

Normality, cN
gives the number of equivalents of reagent in the same volume

EXAMPLE 13-1

EXAMPLE 13-2

EXAMPLE 13-3
How would you prepare 50.0-mL portions of standard solutions that are 0.00500 M, 0.00200 M, and 0.00100 M in Na from the solution in Example 13-2 The number of millimoles of Na: Since,
where Vconcd and Vdil are the volumes in milliliters of the concentrated and diluted solutions, respectively, and cconcd and cdil are their molar Na+ concentrations.

For the 0.00500-M solution, this equation rearranges to

To produce 50.0 mL of 0.00500 M Na, 25.0 mL of the concentrated solution should be diluted to exactly 50.0 mL.

Treating Titration Data EXAMPLE 13-4

A 50.00-mL portion of an HCl solution required 29.71 mL of 0.01963 M Ba(OH)2 to reach an end point with bromocresol green indicator. Calculate the molarity of the HCl. 1 mmol of Ba(OH)2 reacts with 2 mmol of HCl:

The number of millimoles of the standard Ba(OH)2 :

The number of millimoles of HCl:

The concentration:

EXAMPLE 13-5

EXAMPLE 13-6
A 0.8040-g sample of an iron ore is dissolved in acid. The iron is then reduced to Fe2+ and titrated with 47.22 mL of 0.02242 M KMnO4 solution. Calculate the results of this analysis in terms of (a) % Fe (55.847 g/mol) and (b) % Fe3O4 (231.54 g/mol). The reaction is:

EXAMPLE 13-7

EXAMPLE 13-8 (back-titration)

EXAMPLE 13-9 (back-titration)

The CO in a 20.3-L sample of gas was converted to CO2 by passing the gas over iodine pentoxide heated to 150C: The iodine was distilled at this temperature and was collected in an absorber containing 8.25 mL of 0.01101 M Na2S2O3.

The excess Na2S2O3 was back-titrated with 2.16 mL of 0.00947 M I2 solution. Calculate the concentration in milligrams of CO (28.01 g/mol) per liter of sample.

 The stoichiometric ratios for the two reactions

The total amount of Na2S2O3:

The amount of Na2S2O3 consumed in the back-titration:

The number of millimoles of CO:

Advantages of Weight Titrations

Calibration of glassware and tedious cleaning to ensure proper drainage are completely eliminated. Temperature corrections are unnecessary. Weight measurements can be made with considerably greater precision and accuracy than can volume measurements. Weight titrations are more easily automated than are volumetric titrations.

Titration Curves in Titrimetric Methods

An end point is an observable physical change that occurs near the equivalence point of a titration. The two most widely used end points
changes in color due to the reagent, the analyte, or an indicator a change in potential of an electrode that responds to the concentration of the reagent or the analyte.

Titration Curves
Sigmoidal curve:
important observations are confined to a small region (typically 0.1 to 0.5 mL) surrounding the equivalence point.

Linear segment curve:

measurements are made on both sides of, but well away from, the equivalence point.

The sigmoidal type offers the advantages of speed and convenience. The linear segment type is advantageous for reactions that are complete only in the presence of a considerable excess of the reagent or analyte.

Concentration Changes during Titrations

The equivalence point in a titration is characterized by major changes in the relative concentrations of reagent and analyte Titration curves for reactions involving complex formation, precipitation, and oxidation/reduction all exhibit the same sharp increase or decrease in p-function in the equivalence-point region.

Titration curve for the titration of 50.00 mL of 0.1000 M AgNO3 with 0.1000 M KSCN. Any end-point signal that occurs at a pAg between about 4.0 and 8.0 will yield a titration error of about 0.01 mL or less, which corresponds to a relative error of about 0.02% for an analysis based on this reaction

Precipitation Titrimetry
Based on reactions that yield ionic compounds of limited solubility. Because of the slow rate of formation of most precipitates, there are only a few precipitating agents that can be used in titrimetry.
The most widely used precipitating reagent is silver nitrate, which used for the determination of the halide, the halide-like ions (SCN-, CN-, CNO-), and etc. Titrimetric methods based on silver nitrate are sometimes called argentometric methods. The most common method of determining the halide ion concentration of aqueous solutions is titration with a standard solution of silver nitrate.

Precipitation Titration Curves Involving Silver Ion

A titration curve for this method usually consists of a plot of pAg versus the volume of silver nitrate added. To construct titration curves, three type of calculations are required, each of which corresponds to a distinct stage in the reaction: (1) preequivalence, (2) quivalence, and (3) postequivalence.

EXAMPLE 13-10
Perform calculations needed to generate a titration curve for 50.00 mL of 0.0500 M NaCl with 0.1000 M AgNO3 (for AgCl, Ksp = 1.82 10-10). (1) Preequivalence-Point Data
Molar analytical concentration cNaCl is readily computed. For example, when 10.00 mL of AgNO3 has been added,

(2) Equivalence Point pAg

(3) Postequivalence-Point Data

At 26.00 mL AgNO3 added, Ag+ is in excess, so

Additional data points calculations:

Fig 13-4

With the 0.01 M reagent, the change is markedly less but still pronounced. For the more dilute chloride solution, the change in pAg in the equivalence-point region would be too small to be detected precisely with a visual indicator.

The Effect of Reaction Completeness on Titration

The change in pAg at the equivalence point becomes greater as the solubility products become smaller
By careful choice of indicator: one that changes color in the region of pAg from 4-6 in previous Figure.

Ions forming precipitates with solubility products much larger than about 10-10 do not yield satisfactory end points.

Titration Curves for Mixtures of Anions

Consider the titration of 50.00 mL of a solution that is 0.0500 M in iodide ion and 0.0800 M in chloride ion with 0.1000 M silver nitrate. Silver chloride, with its much larger solubility product, does not begin to precipitate until well into the titration

[i-] decreases to a tiny fraction of the [Cl-] before silver chloride begins to precipitate.

 Silver chloride forms only after 25.00 mL of titrant have been added in this titration.
At this point, the chloride ion concentration is approximately
OR

The percentage of iodide unprecipitated at this point

Within about 7.3 x 10-5 % of the equivalence point for iodide, no silver chloride forms.

 As chloride ion begins to precipitate:

OR

After 30.00 mL of titrant have been added,

Indicators for Argentometric Titrations

Chemical end point
Consists of a color change or, occasionally, the appearance or disappearance of turbidity in the solution being titrated. (1) the color change should occur over a limited range in pfunction of the reagent or the analyte and (2) the color change should take place within the steep portion of the titration curve for the analyte.

Potentiometric end point

Potential between a silver electrode and a reference electrode whose potential is constant is measured Independent of the added reagent

Amperometric end point

Current generated between a pair of silver microelectrodes in the solution of the analyte is measured Current plotted as a function of reagent volume

Chromate Ion; The Mohr Method

Sodium chromate can serve as an indicator for the argentometric determination of chloride, bromide, and cyanide ions by reacting with silver ion to form a brick-red silver chromate (Ag2CrO4) precipitate in the equivalence-point region. Ex:
At chemical equivalence: And

Adsorption Indicators: The Fajans Method

Adsorption indicator
An organic compound that tends to be adsorbed onto the surface of the solid in a precipitation titration. Ideally, the adsorption (or desorption) occurs near the equivalence point and results not only in a color change but also in a transfer of color from the solution to the solid (or the reverse). Fluorescein is a typical adsorption indicator that is useful for the titration of chloride ion with silver nitrate.
In aqueous solution, fluorescein partially dissociates into hydronium ions and negatively charged fluoresceinate ions are yellow-green. The fluoresceinate ions forms an intensely red silver salt. However, Its concentration is never large enough to precipitate as silver fluoresceinate.

Fluorescein

Iron(III) Ion; The Volhard Method

In the Volhard method, silver ions are titrated with a standard solution of thiocyanate ion:

Iron(III) serves as the indicator:

The titration must be carried out in acidic solution to prevent precipitation of iron (III) as the hydrated oxide. The most important application of the Volhard method is the indirect determination of halide ions.