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in grams to the volume desired, and add distilled water to counterbalance these weights. An excess of water, or water adhering to the neck of the flask, may be removed by means of a strip of clean filter paper. Stopper the flask, place it in a bath at 15.5°C. or 17.5°C. and, after an hour, mark the location of the lowest point of the meniscus, as described above.

[Note 1: The allowable error in counterbalancing the water and weights varies with the volume of the flask. It should not exceed one ten-thousandth of the weight of water.]

[Note 2: Other methods are employed which involve the use of calibrated apparatus from which the desired volume of water may be run into the dry flask and the position of the meniscus marked directly upon it. For a description of a procedure which is most convenient when many flasks are to be calibrated, the student is referred to the !Am. Chem J.!, 16, 479.]

GENERAL DIRECTIONS FOR VOLUMETRIC ANALYSES

It cannot be too strongly emphasized that for the success of analyses uniformity of practice must prevail throughout all volumetric work with respect to those factors which can influence the accuracy of the measurement of liquids. For example, whatever conditions are imposed during the calibration of a burette, pipette, or flask (notably the time allowed for draining), must also prevail whenever the flask or burette is used.

The student should also be constantly watchful to insure parallel conditions during both standardization and analyst with respect to the final volume of liquid in which a titration takes place. The value of a standard solution is only accurate under the conditions which prevailed when it was standardized. It is plain that the standard solutions must be scrupulously protected from concentration or dilution, after their value has been established. Accordingly, great care must be taken to thoroughly rinse out all burettes, flasks, etc., with the solutions which they are to contain, in order to remove all traces of water or other liquid which could act as a diluent. It is best to wash out a burette at least three times with small portions of a solution, allowing each to run out through the tip before assuming that the burette is in a condition to be filled and used. It is, of course, possible to dry measuring instruments in a hot closet, but this is tedious and unnecessary.

To the same end, all solutions should be kept stoppered and away from direct sunlight or heat. The bottles should be shaken before use to collect any liquid which may have distilled from the solution and condensed on the sides.

The student is again reminded that variations in temperature of volumetric solutions must be carefully noted, and care should always be taken that no source of heat is sufficiently near the solutions to raise the temperature during use.

Much time may be saved by estimating the approximate volume of a standard solution which will be required for a titration (if the data are obtainable) before beginning the operation. It is then possible to run in rapidly approximately the required amount, after which it is only necessary to determine the end-point slowly and with accuracy. In such cases, however, the knowledge of the approximate amount to be required should never be allowed to influence the judgment regarding the actual end-point.

STANDARD SOLUTIONS

The strength or value of a solution for a specific reaction is determined by a procedure called !Standardization!, in which the solution is brought into reaction with a definite weight of a substance of known purity. For example, a definite weight of pure sodium carbonate may be dissolved in water, and the volume of a solution of hydrochloric acid necessary to exactly neutralize the carbonate accurately determined. From these data the strength or value of the acid is known. It is then a !standard solution!.

NORMAL SOLUTIONS

Standard solutions may be made of a purely empirical strength dictated solely by convenience of manipulation, or the concentration may be chosen with reference to a system which is applicable to all solutions, and based upon chemical equivalents. Such solutions are called !Normal Solutions! and contain such an amount of the reacting substance per liter as is equivalent in its chemical action to one gram of hydrogen, or eight grams of oxygen. Solutions containing one half, one tenth, or one one-hundredth of this quantity per liter are called, respectively, half-normal, tenth-normal, or hundredth-normal solutions.

Since normal solutions of various reagents are all referred to a common standard, they have an advantage not possessed by empirical solutions, namely, that they are exactly equivalent to each other. Thus, a liter of a normal solution of an acid will exactly neutralize a liter of a normal alkali solution, and a liter of a normal oxidizing solution will exactly react with a liter of a normal reducing solution, and so on.

Beside the advantage of uniformity, the use of normal solutions simplifies the calculations of the results of analyses. This is particularly true if, in connection with the normal solution, the weight of substance for analysis is chosen with reference to the atomic or molecular weight of the constituent to be determined. (See problem 26.)

The preparation of an !exactly! normal, half-normal, or tenth-normal solution requires considerable time and care. It is usually carried out only when a large number of analyses are to be made, or when the analyst has some other specific purpose in view. It is, however, a comparatively easy matter to prepare standard solutions which differ but slightly from the normal or half-normal solution, and these have the advantage of practical equality; that is, two approximately half-normal solutions are more convenient to work with than two which are widely different in strength. It is, however, true that some of the advantage which pertains to the use of normal solutions as regards simplicity of calculations is lost when using these approximate solutions.

The application of these general statements will be made clear in connection with the use of normal solutions in the various types of volumetric processes which follow.

I. NEUTRALIZATION METHODS ALKALIMETRY AND ACIDIMETRY GENERAL DISCUSSION

!Standard Acid Solutions! may be prepared from either hydrochloric, sulphuric, or oxalic acid. Hydrochloric acid has the advantage of forming soluble compounds with the alkaline earths, but its solutions cannot be boiled without danger of loss of strength; sulphuric acid solutions may be boiled without loss, but the acid forms insoluble sulphates with three of the alkaline earths; oxalic acid can be accurately weighed for the preparation of solutions, and its solutions may be boiled without loss, but it forms insoluble oxalates with three of the alkaline earths and cannot be used with certain of the indicators.

!Standard Alkali Solutions! may be prepared from sodium or potassium hydroxide, sodium carbonate, barium hydroxide, or ammonia. Of sodium and potassium hydroxide, it may be said that they can be used with all indicators, and their solutions may be boiled, but they absorb carbon dioxide readily and attack the glass of bottles, thereby losing strength; sodium carbonate may be weighed directly if its purity is assured, but the presence of carbonic acid from the carbonate is a disadvantage with many indicators; barium hydroxide solutions may be prepared which are entirely free from carbon dioxide, and such solutions immediately show by precipitation any contamination from absorption, but the hydroxide is not freely soluble in water; ammonia does not absorb carbon dioxide as readily as the caustic alkalies, but its solutions cannot be boiled nor can they be used with all indicators. The choice of a solution must depend upon the nature of the work in hand.

A !normal acid solution! should contain in one liter that quantity of the reagent which represents 1 gram of hydrogen replaceable by a base. For example, the normal solution of hydrochloric acid (HCl) should contain 36.46 grams of gaseous hydrogen chloride, since that amount furnishes the requisite 1 gram of replaceable hydrogen. On the other hand, the normal solution of sulphuric acid (H_{2}SO_{4}) should contain only 49.03 grams, i.e., one half of its molecular weight in grams.

A !normal alkali solution! should contain sufficient alkali in a liter to replace 1 gram of hydrogen in an acid. This quantity is represented by the molecular weight in grams (40.01) of sodium hydroxide (NaOH), while a sodium carbonate solution (Na_{2}CO_{3}) should contain but one half the molecular weight in grams (i.e., 53.0 grams) in a liter of normal solution.

Half-normal or tenth-normal solutions are employed in most analyses (except in the case of the less soluble barium hydroxide). Solutions of the latter strength yield more accurate results when small percentages of acid or alkali are to be determined.

INDICATORS

It has already been pointed out that the purpose of an indicator is to mark (usually by a change of color) the point at which just enough of the titrating solution has been added to complete the chemical change which it is intended to bring about. In the neutralization processes which are employed in the measurement of alkalies (!alkalimetry!) or acids (!acidimetry!) the end-point of the reaction should, in principle, be that of complete neutrality. Expressed in terms of ionic reactions, it should be the point at which the H^{+} ions from an acid[Note 1] unite with a corresponding number of OH^{-} ions from a base to form water molecules, as in the equation

H^{+}, Cl^{-} + Na^{+}, OH^{-} —> Na^{+}, Cl^{-} + (H_{2}O).

It is not usually possible to realize this condition of exact neutrality, but it is possible to approach it with sufficient exactness for analytical purposes, since substances are known which, in solution, undergo a sharp change of color as soon as even a minute excess of H^{+} or OH^{-} ions are present. Some, as will be seen, react sharply in the presence of H^{+} ions, and others with OH^{-} ions. These substances employed as indicators are usually organic compounds of complex structure and are closely allied to the dyestuffs in character.

[Note 1: A knowledge on the part of the student of the ionic theory as applied to aqueous solutions of electrolytes is assumed. A brief outline of the more important applications of the theory is given in the Appendix.]

BEHAVIOR OF ORGANIC INDICATORS

The indicators in most common use for acid and alkali titrations are methyl orange, litmus, and phenolphthalein.

In the following discussion of the principles underlying the behavior of the indicators as a class, methyl orange and phenolphthalein will be taken as types. It has just been pointed out that indicators are bodies of complicated structure. In the case of the two indicators named, the changes which they undergo have been carefully studied by Stieglitz (!J. Am. Chem. Soc.!, 25, 1112) and others, and it appears that the changes involved are of two sorts: First, a rearrangement of the atoms within the molecule, such as often occurs in organic compounds; and, second, ionic changes. The intermolecular changes cannot appropriately be discussed here, as they involve a somewhat detailed knowledge of the classification and general behavior of organic compounds; they will, therefore, be merely alluded to, and only the ionic changes followed.

Methyl orange is a representative of the group of indicators which, in aqueous solutions, behave as weak bases. The yellow color which it imparts to solutions is ascribed to the presence of the undissociated base. If an acid, such as HCl, is added to such a solution, the acid reacts with the indicator (neutralizes it) and a salt is formed, as indicated by the equation:

(M.o.)^{+}, OH^{-} + H^{+}, Cl^{-} —> (M.o.)^{+} Cl^{-} + (H_{2}O).

This salt ionizes into (M.o.)^{+} (using this abbreviation for the positive complex) and Cl^{-}; but simultaneously with this ionization there appears to be an internal rearrangement of the atoms which results in the production of a cation which may be designated as (M'.o'.)^{+}, and it is this which imparts a characteristic red color to the solution. As these changes occur in the presence of even a very small excess of acid (that is, of H^{+} ions), it serves as the desired index of their presence in the solution. If, now, an alkali, such as NaOH, is added to this reddened solution, the reverse series of changes takes place. As soon as the free acid present is neutralized, the slightest excess of sodium hydroxide, acting as a strong base, sets free the weak, little-dissociated base of the indicator, and at the moment of its formation it reverts, because of the rearrangement of the atoms, to the yellow form:

OH^{-} + (M'.o'.)^{+} —> [M'.o'.OH] —> [M.o.OH].

Phenolphthalein, on the other hand, is a very weak, little-dissociated acid, which is colorless in neutral aqueous solution or in the presence of free H^{+} ions. When an alkali is added to such a solution, even in slight excess, the anion of the salt which has formed from the acid of the indicator undergoes a rearrangement of the atoms, and

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