Part 117

=630. Determination of Tartaric Acid.=—The determination of potassium bitartrate is necessary when an estimation of the free tartaric acid is desired.

Fifty cubic centimeters of wine are placed in a porcelain dish and evaporated to a sirupy consistence, a little quartz sand being added to render subsequent extraction easier. After cooling, seventy cubic centimeters of ninety-six per cent alcohol are added with constant stirring. After standing for twelve hours, at as low a temperature as practicable, the solution is filtered and the precipitate washed with alcohol until the filtrate is no longer acid. The alcoholic filtrate is preserved for the estimation of the tartaric acid. The filter and precipitate are returned to the porcelain dish and repeatedly treated with hot water, each extraction being filtered into a flask or beaker until the washings are neutral. The combined aqueous filtrates and washings are titrated with decinormal sodium hydroxid solution.

One cubic centimeter of decinormal sodium hydroxid solution = 0.0188 gram potassium bitartrate.

The alcoholic filtrate is made up to a definite volume with water and divided into two equal portions. One portion is exactly neutralized with decinormal sodium hydroxid solution, the other portion added, the alcohol evaporated, the residue washed into a porcelain dish and treated as above.

One cubic centimeter decinormal sodium hydroxid solution = 0.0075 gram tartaric acid.

As, however, only half of the free tartaric acid is determined by this method:

One cubic centimeter decinormal sodium hydroxid = 0.0150 gram of tartaric acid.

=631. Modified Berthelot-Fleury Method.=—Ten cubic centimeters of wine are neutralized with potassium hydroxid solution and mixed in a graduated cylinder with forty cubic centimeters of the same sample. To one-fifth of the volume, corresponding to ten cubic centimeters of wine, fifty cubic centimeters of a mixture of equal parts of alcohol and ether are added and allowed to stand twenty-four hours. The precipitated potassium bitartrate is separated by filtration, dissolved in water and titrated. The excess of potassium bitartrate over the amount of that constituent present in the wine corresponds to the free tartaric acid.

=632. Determination of Tartaric, Malic and Succinic Acids.=—Two hundred cubic centimeters of wine are evaporated to one-half, cooled and lead subacetate solution added until the reaction is alkaline. The precipitate is separated by filtration and washed with cold water until the filtrate shows only a slight reaction for lead. The precipitate is washed from the filter into a beaker, by means of hot water, and treated hot with hydrogen sulfid until all the lead is converted into sulfid. It is then filtered hot and the lead sulfid washed with hot water until the washings are no longer acid. The filtrate and washings are evaporated to fifty cubic centimeters and accurately neutralized with potassium hydroxid. An excess of a saturated solution of calcium acetate is added and the liquid allowed to stand from four to six hours with frequent stirring. It is then filtered and the precipitate washed until the filtrate amounts to exactly 100 cubic centimeters. The precipitate of calcium tartrate is converted into calcium oxid by igniting in a platinum crucible. After cooling, from ten to fifteen cubic centimeters of normal hydrochloric acid are added, the solution washed into a beaker and accurately titrated with normal potassium hydroxid solution. Every cubic centimeter of normal acid saturated by the calcium oxid is equivalent to 0.0750 gram tartaric acid. To the amount so obtained, 0.0286 gram must be added, representing the tartaric acid held in solution in the filtrate as calcium tartrate. The sum represents the total tartaric acid in the wine.

The filtrate from the calcium tartrate is evaporated to about twenty-five cubic centimeters, cooled and mixed with three times its volume of ninety-six per cent alcohol. After standing several hours, the precipitate is collected on a weighed filter, dried at 100° and weighed. It represents the calcium salts of malic, succinic and sulfuric acids and of the tartaric acid which remained in solution. This precipitate is dissolved in a minimum quantity of hydrochloric acid, filtered and the filter washed with hot water. Potassium carbonate solution is added to the hot filtrate, and the precipitated calcium carbonate separated by filtration and washed. The filtrate contains the potassium salts of the above named acids. It is neutralized with acetic acid, evaporated to a small volume and precipitated hot with barium chlorid. The precipitate of barium succinate and sulfate is separated by filtration, washed with hot water and treated on the filter with dilute hydrochloric acid. The barium sulfate remaining is washed, dried, ignited and weighed. In the filtrate, which contains the barium succinate, the barium is precipitated hot with sulfuric acid, washed, dried, ignited and weighed. Two hundred and twenty-three parts of barium sulfate equal 118 parts of succinic acid. The succinic and sulfuric acids, as well as the tartaric acid remaining in solution, which is equal to 0.0286 gram, are to be calculated as calcium salts and the result deducted from the total weight of the calcium precipitate. The remainder is the calcium malate, of which 172 parts equal 134 parts malic acid.

According to Macagno, succinic acid may be estimated in wines by the following process: One liter of the wine is digested with lead hydroxid, evaporated on the water bath and the residue extracted with strong alcohol. The residual salts of lead are boiled with a ten per cent solution of ammonium nitrate, which dissolves the salts of succinic acid. The solution is filtered, the lead removed by hydrogen sulfid, boiled, neutralized with ammonia and treated with ferric chlorid as long as a precipitate is formed. The ferric succinate is separated by filtration, washed and ignited. The succinic acid is calculated from the weight of ferric oxid obtained.

Malic acid in wines and ciders is determined by the method of Berthelot in the following manner: The sample is evaporated until reduced to a tenth of its volume. To the residue an equal volume of ninety per cent alcohol is added and the mixture set aside for some time. The tartaric acid and tartrates separate, together with the greater part of the salts of lime which may be present.

The supernatant liquid is decanted and a small quantity of lime added to it until in slight excess of that required to neutralize the acidity. Calcium malate is separated mixed with lime. The solid matters are separated by filtration, dissolved in a ten per cent solution of nitric acid, from which the lime bimalate will separate in a crystalline form. The weight of calcium bimalate multiplied by 0.59 gives that of the malic acid.

=633. Polarizing Bodies in Fermented Beverages.=—The study of the nature of the carbohydrates, which constitute an important part of the solid matters dissolved in fermented beverages, is of the greatest importance. These bodies consist of grape sugars, sucrose, tartaric acid and the unfermented hydrolytic products derived from starch. A natural grape sugar (chiefly dextrose) is found in wines. Sucrose is also a very important constituent of sweet wines. The hydrolytic products of starch are found in beers, either as a residue from the fermentation of malt or from the rice, glucose, hominy grits etc., added in brewing. The character and quantities of these residues can be determined by the methods already given in the parts of this volume relating to sugars and starches. For convenience, however, and for special application to the investigation of fermented beverages a résumé of the methods adopted by the official chemists follows:

=634. Determination of Reducing Sugars.=—The reducing sugars are estimated as dextrose, and may be determined by any of the methods given for the estimation thereof (=113-140=).

=635. Polarization.=—All results are to be stated as the polarization of the undiluted sample. The triple field shadow saccharimeter is recommended, and the results are expressed in the terms of the sugar scale of this instrument. If any other instrument be used, or if it be desirable to convert to angular rotation, the following factors may be employed:

1° Schmidt and Haensch = 0°.3468 angular rotation D. 1° angular rotation D = 2°.8835 Schmidt and Haensch. 1° Schmidt and Haensch = 2°.6048 Wild (sugar scale). 1° Wild (sugar scale) = 0°.3840 Schmidt and Haensch. 1° Wild (sugar scale) = 0°.1331 angular rotation D. 1° angular rotation D = 0°.7511 Wild (sugar scale). 1° Laurent (sugar scale) = 0°.2167 angular rotation D. 1° angular rotation D = 4°.6154 Laurent (sugar scale).

In the above table D represents the angular rotation produced with yellow monochromatic light.

(a) In White Wines or Beers.—Sixty cubic centimeters of wine are decolorized with three cubic centimeters of lead subacetate solution and filtered. Thirty cubic centimeters of the filtrate are treated with one and five-tenths cubic centimeters of a saturated solution of sodium carbonate, filtered and polarized. This gives a solution of nearly ten to eleven, which must be considered in the calculation, and the polariscope reading must accordingly be increased one-tenth.

(b) In Red Wines.—Sixty cubic centimeters of wine are decolorized with six cubic centimeters of lead subacetate solution and filtered. To thirty cubic centimeters of the filtrate, three cubic centimeters of a saturated solution of sodium carbonate are added, filtered and the filtrate polarized. The dilution in this case is nearly five to six, and the polariscope reading must accordingly be increased one-fifth.

(c) In Sweet Wines. (1) Before Inversion.—One hundred cubic centimeters are decolorized with two cubic centimeters of lead subacetate solution and filtered after the addition of eight cubic centimeters of water. One-half cubic centimeter of a saturated solution of sodium carbonate and four and five-tenths cubic centimeters of water are added to fifty-five cubic centimeters of the filtrate, the liquids mixed, filtered and polarized. The polariscope reading is multiplied by 1.2.

(2) After Inversion.—Thirty-three cubic centimeters of the filtrate from the lead subacetate in (1) are placed in a flask with three cubic centimeters of strong hydrochloric acid. After mixing well, the flask is placed in water and heated until a thermometer, placed in the flask with the bulb as near the center of the liquid as possible, marks 68°, consuming about fifteen minutes in the heating. It is then removed, cooled quickly to room temperature, filtered and polarized, the temperature being noted. The polariscope reading is multiplied by 1.2. Because of the action of lead subacetate on invert sugar (=87=) it is advisable to decolorize the samples with other reagents (=87-89=).

(3) After Fermentation.—Fifty cubic centimeters of wine, which have been dealcoholized by evaporation and made up to the original volume with water, are mixed, in a small flask, with well washed beer yeast and kept at 30° until fermentation has ceased, which requires from two to three days. The liquid is washed into a 100 cubic centimeter flask, a few drops of a solution of acid mercuric nitrate and then lead subacetate solution, followed by sodium carbonate, added. The flask is filled to the mark with water, shaken, the solution filtered and polarized and the reading multiplied by two.

=636. Application of Analytical Methods.=—(1) There is no rotation.—This may be due to the absence of any rotatory body, to the simultaneous presence of the dextrorotatory nonfermentable constituents of commercial dextrose and levorotatory sugar, or to the simultaneous presence of dextrorotatory cane sugar and levorotatory invert sugar.

(a) The Wine is Inverted.—A levorotation shows that the sample contains cane sugar.

(b) The Wine is Fermented.—A dextrorotation shows that both levorotatory sugar and the unfermentable constituents of commercial dextrose are present.

If no change take place in either (a) or (b) in the rotation, it proves the absence of unfermented cane sugar, the unfermentable constituents of commercial dextrose and of levorotatory sugar.

(2) There is right rotation.—This may be caused by unfermented cane sugar, the unfermentable constituents of commercial dextrose or both.