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The standardized sodium hydroxide solution secondary standard may be used to standardize solutions. Standard solution Standard solution is the reagent of exactly known concentration that is used in titrimetric analysis.

Standard solutions play a central role in all titrimetric method of analysis. Therefore we need to consider the desirable properties for such solutions, how they are prepared and how their concentration are expressed.

Few reagents meet all these ideal perfectly. Methods for establishing the concentration of standard solutions Two basic methods are used to establish the concentration of such solutions. The first is the direct method in which a carefully weighed quantity of primary standard is dissolved in a suitable solvent and diluted to an exactly known volume in a volumetric flask.

The second is by standardization the process whereby the concentration of a reagent is determined by reaction with a known quantity of a second reagent. A titrant that is standardized against another standard solution is some times referred as a secondary standard solution. If there is a choice, then solution are prepared by the direct method. On the other hand , many reagents lack the properties required for a primary standard and therefore required standardization.

Method for expressing the concentration of standard solution The concentrations of standard solution are generally expressed in units of either molarity or normality. The first gives the number of moles of reagents contained in 1L of solution, and the second gives the number of equivalents of reagent in the same volume.

Direct titration and back titration When a titrant reacts directly with an analyte, the procedure is termed a direct titration. It is some times necessary to add an excess of standard titrant and then determine the excess amount by back titration with a second standard titrant.

In other wards back titration is a process in which the excess of standard solution used to react with an analyte is determined by titration with a second standard solution. Back — titration are often required when the rate of reaction between the analyte and reagent is slow or when the standard solution lacks stability.

In back — titration, the equivalence point corresponds to the point when the amount of initial titrant is chemically equivalent to the amount af analyte plus the amount of back titrant. Classification of reaction in titrimetric analysis The reaction employed in titrmetric analysis fall into four main classes.

The first three of these involve no change in oxidation state as they are dependent upon the combination of ions. But the fourth class, oxidation-reduction reactions, involves a change of oxidation state or, expressed another, a transfer of electron. These include the titration of free bases, or those formed from salts of weak acids by hydrolysis with a standard acid acidimetry , and the titration of free acids, or those formed by the hydrolysis of salts or weak bases, with a standard base alkalimrtry.

The reaction involve the combination of hydrogen and hydroxide ions to form water. Also under this heading must be included titrations in non-aqueous solvents, most of which involve organic compounds. Analytical Chemistry Lecture Notes ……………………………………………………………… 10 2- Precipitation reaction.

These depend upon the combination of ions to form a simple precipitate as in the titration of silver ion with solution of chloride. No change in oxidation state occurs. These depend upon the combination of ions, other than hydrogen or hydroxide ion, to form a soluble slightly dissociated ion or compound, as in the titration of a solution af a cyanide with silver nitrate.

Ethylendiaminetera-acetic acid, largely as the disodium salt of EDTA, is a very important reagent for complex formation titration and has become on of the most important reagents used in titrimetric analysis. Under this heading are included all reactions involving change in oxidation number or transfer of electrons among the reactive substance. The standard solutions are either oxidizing or reducing agents. Titration Curves To find the end point we monitor some property of the titration reaction that has a well- defined value at the equivalence point.

We can find the end point, therefore, by monitoring the pH with a pH electrode or by adding an indicator that changes color at a pH of 7. Acid-base titration curve for Suppose that the only available indicator changes color at a pH of 6. Is this end point close enough to the equivalence point that the titration error may be safely ignored? To answer this question we need to know how the pH changes during the titration.

A titration curve provides us with a visual picture of how a property, such as pH, changes as we add titrant. We can measure this titration curve experimentally by suspending a pH electrode in the solution containing the analyte, monitoring the pH as titrant is added. We can also calculate the expected titration curve by considering the reactions responsible for the change in pH.

However we arrive at the titration curve, we may use it to evaluate an indicator's likely titration error. For example, the titration curve in the above figure shows us that an end point pH of 6. Stopping the titration at an end point pH of A titration curve is a plot of reagent volume added versus some function of the analyte concentration. Volume of added reagent is generally plotted on the x axis. The measured parameter that is a function of analyte concentration is plotted on the y axis.

Analytical Chemistry Lecture Notes ……………………………………………………………… 11 Two general titration curve types are seen: 1. Sigmoidal curve - a "z" or "s"-shaped curve where the y axis is a p-function of the analyte or the reagent reacted with the analyte during titration or the potential of an ion-specific electrode. The equivalent point is observed in the middle of the "middle" segment of the "z" or "s.

Linear-segment curve - a curve generally consisting of two line segments that intersect at an angle. Analytical Chemistry Lecture Notes ……………………………………………………………… 12 Applications of Titrimetry in Pharmaceutical Analysis Titrimetric methods are still widely used in pharmaceutical analysis because of their robustness, cheapness and capability for high precision. The only requirement of an analytical method that they lack is specificity. Suppliers of raw materials may provide these materials at a specified purity which has been assayed titrimetrically to a pharmacopoeial standard.

Typical instrumentation for performing an automatic titration automatic titrator. Analytical Chemistry Lecture Notes ……………………………………………………………… 13 Titrations Based on Acid-Base Reactions The earliest acid-base titrations involved the determination of the acidity or alkalinity of solutions, and the purity of carbonates and alkaline earth oxides.

Various acid-base titration reactions, including a number of scenarios of base in the burette, acid in the reaction flask, and vice versa, as well as various monoprotic and polyprotic acids titrated with strong bases and various weak monobasic and polybasic bases titrated with strong acids.

A monoprotic acid is an acid that has only one hydrogen ion or proton to donate per fomula. A polyprotic acid is an acid that has two or more hydrogen ions to donate per formula.



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