AUTHORITIES CITED IN PART FIRST.
[1] Sidersky: Traité d’Analyse des Matières Sucrées, p. 311.
[2] Die Agricultur-Chemische Versuchs-Station, Halle a/S., S. 34. (Read Dreef instead of Dree.)
[3] Report of Commissioner of Fish and Fisheries, 1888, p.686.
[4] Vid. op. cit. 2, p. 14.
[5] Journal of the American Chemical Society, Vol. 15, p. 83.
[6] Chemical Division, U. S. Department of Agriculture, Bulletin No. 28, p. 101.
[7] Not yet described in any publication. Presented at 12th annual meeting of the Association of Agricultural Chemists, Aug. 7th, 1895.
[8] Vid. op. cit. 6, p. 100.
[9] Cornell University Agricultural Experiment Station, Bulletin 12.
[10] (bis. p. 28). Vid. op. cit. 2, p. 15.
[11] Bulletin No. 13, Chemical Division, U. S. Department of Agriculture, Part First pp. 85-6.
[12] Bulletin de 1’ Association des Chimistes de Sucrerie, 1893, p. 656.
[13] Chemical News, Vol. 52, p. 280.
[14] Presented to 12th Annual Convention of the Association of Official Agricultural Chemists, Sept. 7th, 1895.
[15] Vid. Volume First, p. 411.
[16] Vid. op. cit. 2, p. 17.
[17] Dragendorff, Plant Analysis.
[18] Vid. op. cit. 6, p. 96.
[19] Journal of Analytical and Applied Chemistry, Vol. 7, p. 65, and Journal of the American Chemical Society, March 1893.
[20] Vid. op. cit. 16.
[21] Vid. op. cit. 6, p. 99.
[22] Vid. op. cit. 6, p. 103.
PART SECOND.
SUGARS AND STARCHES.
44. Introduction.—Carbohydrates, of which sugars and starches are the chief representatives, form the great mass of the results of vegetable metabolism. The first functions of the chlorophyll cells of the young plant are the condensation of carbon dioxid and water. The simplest form of the condensation is formaldehyd, CH₂O. There is no convincing evidence, however, that this is the product resulting from the functional activity of the chlorophyll cells. The first evidence of the condensation is found in more complex molecules; viz., those having six atoms of carbon. It is not the purpose of this work to discuss the physiology of this process, but the interested student can easily find access to the literature of the subject.[23] When a sample of a vegetable nature reaches the analyst he finds by far the largest part of its substance composed of these products of condensation of the carbon dioxid and water. The sugars, starches, pentosans, lignoses, and celluloses all have this common origin. Of many air-dried plants these bodies form more than eighty per cent.
In green plants the sugars exist chiefly in the sap. In plants cut green and quickly dried by artificial means the sugars are found in a solid state. They also exist in the solid state naturally in certain sacchariferous seeds. Many sugar-bearing plants when allowed to dry spontaneously lose all or the greater part of their sugar by fermentation. This is true of sugar cane, sorghum, maize stalks, and the like. The starches are found deposited chiefly in tubers, roots or seeds. In the potato the starch is in the tuber, in cassava the tuber holding the starch is also a root, in maize, rice and other cereals the starch is in the seeds. The wood-fibers; viz., pentosans, lignose, cellulose, etc., form the framework and support of the plant structure. Of all these carbohydrate bodies the most important as foods are the sugars and starches, but a certain degree of digestibility cannot be denied to other carbohydrate bodies with the possible exception of pure cellulose. In the following paragraphs the general principles of determining the sugars and starches will be given and afterwards the special processes of extracting these bodies from vegetable substances preparatory to quantitive determination.
45. Nomenclature.—In speaking of sugars it has been thought best to retain for the present the old nomenclature in order to avoid confusion. The terms dextrose, levulose, sucrose, etc., will therefore be given their commonly accepted significations.
A more scientific nomenclature has recently been proposed by Fischer, in which glucose is used as the equivalent of dextrose and fructose as the proper name for levulose. All sugars are further classified by Fischer into groups according to the number of carbon atoms found in the molecule. We have thus trioses, tetroses, pentoses, hexoses, etc. Such a sugar as sucrose is called hexobiose by reason of the fact that it appears to be formed of two molecules of hexose sugars. For a similar reason raffinose would belong to the hexotriose group.[24]
Again, the two great classes of sugars as determined by the structure of the molecule are termed aldoses and ketoses according to their relationship to the aldehyd or ketone bodies.
Since sugars may be optically twinned, that is composed of equal molecules of right and left-handed polarizing matter it may happen that apparently the same body may deflect the plane of polarization to the right, to the left, or show perfect neutrality.
Natural sugars, as a rule, are optically active, but synthetic sugars being optically twinned are apt to be neutral to polarized light.
To designate the original optical properties of the body therefore the symbols d, l, and i, meaning dextrogyratory, levogyratory, and inactive, respectively, are prefixed to the name. Thus we may have d, l, or i glucose, d, l, or i fructose, and so on.
The sugars that are of interest here belong altogether to the pentose and hexose groups; viz., C₅H₁₀O₅ and C₆H₁₂O₆, respectively. Of the hexobioses, sucrose, maltose, and lactose are the most important, and of the hexotrioses, raffinose. In this manual, unless otherwise stated, the term dextrose corresponds to d glucose, and levulose to d fructose. In this connection, however, it should be noted that the levulose of nature, or that which is formed by the hydrolysis of inulin or sucrose is not identical in its optical properties with the l fructose of Fischer.
46. Preparation of Pure Sugar.—In using the polariscope or in testing solutions for the chemical analysis of samples, the analyst will be required to keep always on hand some pure sugar. Several methods of preparing pure sugar have been proposed. The finest granulated sugar of commerce is almost pure. In securing samples for examination those should be selected which have had a minimum treatment with bluing in manufacture. The best quality of granulated sugar when pulverized, washed with ninety-five per cent and then with absolute alcohol and dried over sulfuric acid at a temperature not exceeding 50° will be found nearly pure. Such a sugar will, as a rule, not contain more than one-tenth per cent of impurities, and can be safely used for all analytical purposes. It is assumed in the above that the granulated sugar is made from sugar cane.
Granulated beet sugars may contain raffinose and so may show a polarization in excess of 100. This sugar may be purified by dissolving seventy parts by weight in thirty parts of water. The sugar is precipitated by adding slowly an equal volume of ninety-six per cent alcohol with constant stirring, the temperature of the mixture being kept at 60°. While still warm the supernatant liquor is decanted and the precipitated sugar washed by decantation several times with strong warm alcohol. The sugar, on a filter, is finally washed with absolute alcohol and dried in a thin layer over sulfuric acid at from 35° to 40°. By this process any raffinose which the sugar may have contained is completely removed by the warm alcohol. Since beet sugar is gradually coming into use in this country it is safer to follow the above method with all samples.[25] In former times it was customary to prepare pure sugar from the whitest crystals of rock candy. These crystals are powdered, dissolved in water, filtered, precipitated with alcohol, washed and dried in the manner described above.
47. Classification of Methods.—In the quantitive determination of pure sugar the various processes employed may all be grouped into three classes. In the first class are included all those which deduce the percentage of sugar present from the specific gravity of its aqueous solution. The accuracy of this process depends on the purity of the material, the proper control of the temperature, and the reliability of the instruments employed. The results are obtained either directly from the scale of the instruments employed or are calculated from the arbitrary or specific gravity numbers observed. It is evident that any impurity in the solution would serve to introduce an error of a magnitude depending on the percentage of impurity and the deviation of the density from that of sugar. The different classes of sugars, having different densities in solution, give also different readings on the instruments employed. It is evident, therefore, that a series of tables of percentages corresponding to the specific gravities of the solutions of different sugars would be necessary for exact work. Practically, however, the sugar which is most abundant, viz., sucrose, may be taken as a representative of the others and for rapid control work the densimetric method is highly useful.
In the second class of methods are grouped all those processes which depend upon the property of sugar solutions to rotate the plane of polarized light. Natural sugars all have this property and if their solutions be found neutral to polarized light it is because they contain sugars of opposite polarizing powers of equal intensity. Some sugars turn the polarized plane to the right and others to the left, and the degree of rotation in each case depends, at equal temperatures and densities of the solutions, on the percentages of sugars present. In order that the optical examination of a sugar may give correct results the solution must be of a known density and free of other bodies capable of affecting the plane of polarized light. In the following paragraphs an attempt will be made to give in sufficient detail the methods of practice of these different processes in so far as they are of interest to the agricultural analyst. The number of variations, however, in these processes is so great as to make the attempt to fully discuss them here impracticable. The searcher for additional details should consult the standard works on sugar analysis.[26]
In the third class of methods are included those which are of a chemical nature based either on the reducing power which sugar solutions exercise on certain metallic salts, upon the formation of certain crystalline and insoluble compounds with other bodies or upon fermentation. Under proper conditions solutions of sugar reduce solutions of certain metallic salts, throwing out either the metal itself or a low oxid thereof. In alkaline solutions of mercury and copper, sugars exercise a reducing action, throwing out in the one case metallic mercury and in the other cuprous oxid. With phenylhydrazin, sugars form definite crystalline compounds, quite insoluble, which can be collected, dried and weighed. There is a large number of other chemical reactions with sugars such as their union with the earthy bases, color reactions with alkalies, oxidation products with acids, and so on, which are of great use qualitively and in technological processes, but these are of little value in quantitive determinations.
THE DETERMINATION OF THE PERCENTAGE OF
SUGAR BY THE DENSITY OF ITS SOLUTION.
48. Principles of the Method.—This method of analysis is applied almost exclusively to the examination of one kind of sugar, viz., the common sugar of commerce. This sugar is derived chiefly from sugar cane and sugar beets and is known chemically as sucrose or saccharose. The method is accurate only when applied to solutions of pure sucrose which contain no other bodies. It is evident however, that other bodies in solution can be determined by the same process, so that the principle of the method is broadly applicable to the analyses of any body whatever in a liquid state or in solution. Gases, liquids and solids, in solution, can all be determined by densimetric methods.
Broadly stated the principle of the method consists in determining the specific gravity of the liquid or solution, and thereafter taking the percentage of the body in solution from the corresponding specific gravity in a table. These tables are carefully prepared by gravimetric determinations of the bodies in solution of known densities, varying by small amounts and calculation of the percentages for the intervening increments or decrements of density. This tabulation is accomplished at definite temperatures and the process of analysis secured thereby is rapid and accurate, with pure or nearly pure solutions.
49. Determination of Density.—While not strictly correct from a physical point of view, the terms density and specific gravity are here used synonymously and refer to a direct comparison of the weights of equal volumes of pure water and of the solution in question, at the temperature named. When not otherwise stated, the temperature of the solution is assumed to be 15°.5.
Figure 27. Common Forms of Pyknometers.
The simplest method of determining the density of a solution is to get the weight of a definite volume thereof. This is conveniently accomplished by the use of a pyknometer. A pyknometer is any vessel capable of holding a definite volume of a liquid in a form suited to weighing. It may be a simple flask with a narrow neck distinctly marked, or a flask with a ground perforated stopper, which, when inserted, secures always the same volume of liquid contents. A very common form of pyknometer is one in which the central stopper carries a thermometer and the constancy of volume is secured by a side tubulure of very small or even capillary dimensions, which is closed by a ground glass cap.
The apparatus may not even be of flask form, but assume a quite different shape as in Sprengel’s tube. Pyknometers are often made to hold an even number of cubic centimeters, but the only advantage of this is in the ease of calculation which it secures. As a rule, it will be found necessary to calibrate even these, and then the apparent advantage will be easily lost. A flask which is graduated to hold fifty cubic centimeters, may, in a few years, change its volume at least slightly, due to molecular changes in the glass. Some of the different forms of pyknometers are shown in the accompanying figures.
In use the pyknometer should be filled with pure water of the desired temperature and weighed. From the total weight the tare of the flask and stopper, weighed clean and dry, is to be deducted. The remainder is the weight of the volume of water of the temperature noted, which the pyknometer holds. The weight of the solution under examination is taken in the same way and at the same temperature, and thus a direct comparison between the two liquids is secured.
| Example.—Let the weight of the pyknometer be | 15.2985 | grams. |
| and its weight with pure water at 15°.5 be | 26.9327 | ” |
| Then the weight of water is | 11.6342 | ” |
| The weight filled with the sugar solution is | 28.3263 | ” |
| Then the weight of the sugar solution is | 13.0278 | ” |
The specific gravity of the sugar solution is therefore, 13.0278 ÷ 11.6342 = 1.1198.
For strictly accurate results the weight must be corrected for the volume of air displaced, or in other words, be reduced to weights in vacuo. This however is unnecessary for the ordinary operations of agricultural analysis.
If the volume of the pyknometer be desired, it can be calculated from the weight of pure water which it holds, one cubic centimeter of pure water weighing one gram at 4°.
The weights of one cubic centimeter of water at each degree of temperature from 1° to 40°, are given in the following table:
Table Showing Weights of One
Cubic Centimeter of Pure Water
at Temperatures Varying from
1° To 40°.
| Temperature. | Weight, Gram. | Temperature. | Weight, Gram. |
|---|---|---|---|
| 0° | 0.999871 | 21° | 0.998047 |
| 1° | 0.999928 | 22° | 0.997826 |
| 2° | 0.999969 | 23° | 0.997601 |
| 3° | 0.999991 | 24° | 0.997367 |
| 4° | 1.000000 | 25° | 0.997120 |
| 5° | 0.999990 | 26° | 0.996866 |
| 6° | 0.999970 | 27° | 0.996603 |
| 7° | 0.999933 | 28° | 0.998331 |
| 8° | 0.999886 | 29° | 0.995051 |
| 9° | 0.999824 | 30° | 0.995765 |
| 10° | 0.999747 | 31° | 0.995401 |
| 11° | 0.999655 | 32° | 0.995087 |
| 12° | 0.999549 | 33° | 0.994765 |
| 13° | 0.999430 | 34° | 0.994436 |
| 14° | 0.999299 | 35° | 0.994098 |
| 15° | 0.999160 | 36° | 0.993720 |
| 16° | 0.999002 | 37° | 0.993370 |
| 17° | 0.998841 | 38° | 0.993030 |
| 18° | 0.998654 | 39° | 0.992680 |
| 19° | 0.998460 | 40° | 0.992330 |
| 20° | 0.998259 |
From the table and the weight of water found, the volume of the pyknometer is easily calculated.
Example.—Let the weight of water found be 11.72892 grams, and the temperature 20°. Then the volume of the flask is equal to 11.72892 ÷ 0.998259, viz., 11.95 cubic centimeters.
50. Use of Pyknometer at High Temperatures.—It is often found desirable to determine the density of a liquid at temperatures above that of the laboratory, e. g., at the boiling-point of water. This is easily accomplished by following the directions given below:
Weight of Flask.—Use a small pyknometer of from twenty-five to thirty cubic centimeters capacity. The stopper should be beveled to a fine edge on top and the lower end should be slightly concave to avoid any trapping of air. The flask is to be thoroughly washed with hot water, alcohol and ether, and then dried for some time at 100°. After cooling in a desiccator the weight of the flask and stopper is accurately determined.[27]
Figure 28. Bath for Pyknometers.
Weight of Water.—The flask in an appropriate holder, [Fig. 28], conveniently made of galvanized iron, is filled with freshly boiled and hot distilled water and placed in a bath of pure, very hot distilled water, in such a way that it is entirely surrounded by the liquid with the exception of the top.
The water of the bath is kept in brisk ebullition for thirty minutes, any evaporation from the flask being replaced by the addition of boiling distilled water. The stopper should be kept for a few minutes before use in hot distilled water and is then inserted, the flask removed, wiped dry, and, after it is nearly cooled to room temperature, placed in the balance and weighed when balance temperature is reached. A convenient size of holder will enable the analyst to use eight or ten flasks at once. The temperature at which water boils in each locality may also be determined; but unless at very high altitudes, or on days of unusual barometric disturbance the variations will not be great, and will not appreciably affect the results.
51. Alternate Method of Estimating the Weight of Water in Flasks.—Formulas for calculating the volume V, in cubic centimeters, of a glass vessel from the weight P of water at the temperature t contained therein, and the volume Vʹ at any other temperature t’ are given by Landolt and Börnstein.[28] They are as follows:
| V = P | p |
| d |
| Vʹ = P | p | [1 + γ (tʹ- t)]; |
| d |
in which p = weight (in brass weights) of one cubic centimeter H₂O in vacuo. This is so nearly one gram that it will not affect the result in the fifth place of decimals and may therefore be disregarded. Hence the formula stands:
| Vʹ = P | 1 | [1 + γ (tʹ- t)] |
| d |
d = density of water at temperature t.
γ = 0.000025, the cubical expansion coefficient of glass.
From this volume the weight of the water may be readily obtained by referring to tables 13, 14 and 15a in Landolt and Börnstein’s book.
52. Example Showing Determination of Specific Gravity of a Fat.—The flask is emptied of its water, rinsed with alcohol and ether, and dried again for a few minutes at 100°. It is then filled with the dry, hot, fresh-filtered fat, which should be entirely free from air bubbles.
The stoppered flask is then replaced in the water-bath, kept for thirty minutes at the temperature of boiling water, removed, and treated as above. The weight of fat having been determined, the specific gravity is obtained by dividing it by the weight of water previously found.
| Example. | |
| Grams. | |
| Weight of flask, dry | 10.0197 |
| Weight of flask, plus water | 37.3412 |
| Weight of water | 27.3215 |
| Weight of flask, plus fat | 34.6111 |
| Weight of fat | 24.5914 |
| Specific gravity = 24.5914 ÷ 27.3215 = | 0.90008. |
The weight of the flask dry and empty and the weight of water at 99° to 100° contained therein may be used constantly if great care be taken in handling and cleaning the apparatus.
| Example. | |
| Grams. | |
| Weight of flask, dry and empty | 10.0028 |
| Weight of flask after three weeks’ use | 10.0030 |
Figure 29. Aereometers, Pyknometers, and Hydrostatic Balance.
53. Determination of Density by the Hydrostatic Balance.—While the pyknometer is useful in control work and in fixing standards of comparison, it is not used extensively in practical work. Quicker methods of determination are desired in such work, and these are found in the use of other forms of apparatus. A convenient method of operation consists in determining the weight of a sinker, whose exact weights in air and in pure water of a definite temperature, have been previously determined. The instrument devised by Mohr and modified by Westphal, is based upon that principle, and is extensively used in practical work. The construction of this apparatus and also that of the pyknometers and areometers is shown in the illustrations, figures [29] and [30].
Figure 30. Hydrostatic Balance.
The weight of the sinker is so adjusted that the index of the balance arm marks zero when the sinker is wholly immersed in pure water at the standard temperature. The density of a solution of sugar at the same temperature, is then determined by placing the rider-weights on the divided arm of the balance, until the index again marks zero. The density can then be read directly from the position of the weights in the arm of the balance or calculated therefrom.
54. The Areometric Method.—The most rapid method of determining the density of a solution and the one in most common use, is based on the distance to which a heavy bulb with a slender graduated stem will sink therein. An instrument of this kind is called an areometer. Many forms of this instrument are employed but they all depend on the same principle and differ only in the manner of graduation. The one of widest application has the stem graduated in such a manner as to give directly the specific gravity of the solution in which it is placed.
Others are made with a special graduation giving directly the percentage of solid matter in the solution. These instruments can be used only for the special purposes for which they are constructed. Other forms are provided with an arbitrary graduation, the numbers of which by appropriate tables can be converted into expressions of specific gravity or of per cents of dissolved matters. It is not practicable to give here, a discussion of the principles of the construction of areometers.[29] The two which are commonly used, are the baumé hydrometer and the balling or brix spindle.
In the baumé instrument the zero of the scale is fixed at the point marked by the surface of distilled water at 15°, and the point to which it sinks in pure monohydrated sulfuric acid at the same temperature is marked 66, corresponding to a specific gravity of 1.8427.
The specific gravity corresponding to any degree of the scale, may be calculated in the absence of a table giving it, by the following formula
| P = | 144.3 | . |
| 144.3 - d |
In this formula P is the density and d the degree of the scale.[30] In former times the baumé instruments were graduated with a solution of common salt and a different formula was employed for calculating specific gravity, but these older instruments are no longer in common use.
The following table shows the specific gravities of solutions corresponding to baumé degrees from 1° to 75° consecutively[31]:
| Degree baumé | Specific gravity | Degree baumé | Specific gravity | Degree baumé | Specific gravity | Degree baumé | Specific gravity |
|---|---|---|---|---|---|---|---|
| 0 | 1.0000 | 19 | 1.1516 | 38 | 1.3574 | 57 | 1.6527 |
| 1 | 1.0069 | 20 | 1.1608 | 39 | 1.3703 | 58 | 1.6719 |
| 2 | 1.0140 | 21 | 1.1702 | 40 | 1.3834 | 59 | 1.6915 |
| 3 | 1.0212 | 22 | 1.1798 | 41 | 1.3968 | 60 | 1.7115 |
| 4 | 1.0285 | 23 | 1.1895 | 42 | 1.4104 | 61 | 1.7321 |
| 5 | 1.0358 | 24 | 1.1994 | 43 | 1.4244 | 62 | 1.7531 |
| 6 | 1.0433 | 25 | 1.2095 | 44 | 1.4386 | 63 | 1.7748 |
| 7 | 1.0509 | 26 | 1.2197 | 45 | 1.4530 | 64 | 1.7968 |
| 8 | 1.0586 | 27 | 1.2301 | 46 | 1.4678 | 65 | 1.8194 |
| 9 | 1.0665 | 28 | 1.2407 | 47 | 1.4829 | 66 | 1.8427 |
| 10 | 1.0744 | 29 | 1.2514 | 48 | 1.4983 | 67 | 1.8665 |
| 11 | 1.0825 | 30 | 1.2624 | 49 | 1.5140 | 68 | 1.8909 |
| 12 | 1.0906 | 31 | 1.2735 | 50 | 1.5301 | 69 | 1.9161 |
| 13 | 1.0989 | 32 | 1.2849 | 51 | 1.5465 | 70 | 1.9418 |
| 14 | 1.1074 | 33 | 1.2964 | 52 | 1.5632 | 71 | 1.9683 |
| 15 | 1.1159 | 34 | 1.3081 | 53 | 1.5802 | 72 | 1.9955 |
| 16 | 1.1246 | 35 | 1.3201 | 54 | 1.5978 | 73 | 2.0235 |
| 17 | 1.1335 | 36 | 1.3323 | 55 | 1.6157 | 74 | 2.0523 |
| 18 | 1.1424 | 37 | 1.3447 | 56 | 1.6340 | 75 | 2.0819 |
55. Correction for Temperature.—The baumé hydrometer should be used at the temperature for which it is graduated, usually 15°. In this country the mean temperature of our working rooms is above 15°. The liquid in the hydrometer flask should therefore be cooled to a trifle below 15°, or kept in a bath exactly at 15° while the observation is made. When this is not convenient, the observation may be made at any temperature, and the reading corrected as follows: When the temperature is above 15° multiply the difference between the observed temperature and fifteen, by 0.0471 and add the product to the observed reading of the baumé hydrometer; when the temperature on the other hand, is below fifteen, the corresponding product is subtracted.[32]
56. The Balling or Brix Hydrometer.—The object of the balling or brix instrument is to give in direct percentages the solid matter in solution. It is evident that for this purpose the instrument must be graduated for a particular kind of material, since ten per cent of sugar in solution, might have a very different specific gravity from a similar quantity of another body. Instruments of this kind graduated for pure sugar, find a large use in technical sugar analysis. To attain a greater accuracy and avoid an instrument with too long a stem, the brix hydrometers are made in sets. A convenient arrangement is to have a set of three graduated as follows; one from 0° to 30°, one from 25° to 50°, and one from 45° to 85°. When the percentage of solid matter dissolved is over seventy the readings of the scale are not very reliable.
57. Correction for Temperature.—The brix as the baumé scale is graduated at a fixed temperature. This temperature is usually 17°.5. The following table shows the corrections to be applied to the scale reading when made at any other temperature:[33]
Per Cent of Sugar in Solution.
| 0. | 5. | 10. | 15. | 20. | 25. | 30. | 35. | 40. | 50. | 60. | 70. | 75. | |
| Temp. | To be subtracted from the degree read. | ||||||||||||
| 0° | 0.17 | 0.30 | 0.41 | 0.52 | 0.62 | 0.72 | 0.82 | 0.92 | 0.98 | 1.11 | 1.22 | 1.25 | 1.29 |
| 5° | 0.23 | 0.30 | 0.37 | 0.44 | 0.52 | 0.59 | 0.65 | 0.72 | 0.75 | 0.80 | 0.88 | 0.91 | 0.94 |
| 10° | 0.20 | 0.26 | 0.29 | 0.33 | 0.36 | 0.39 | 0.42 | 0.45 | 0.48 | 0.50 | 0.54 | 0.58 | 0.61 |
| 11° | 0.18 | 0.23 | 0.26 | 0.28 | 0.31 | 0.34 | 0.36 | 0.39 | 0.41 | 0.43 | 0.47 | 0.50 | 0.53 |
| 12° | 0.16 | 0.20 | 0.22 | 0.24 | 0.26 | 0.29 | 0.31 | 0.33 | 0.34 | 0.36 | 0.40 | 0.42 | 0.46 |
| 13° | 0.14 | 0.18 | 0.19 | 0.21 | 0.22 | 0.24 | 0.26 | 0.27 | 0.28 | 0.29 | 0.33 | 0.35 | 0.39 |
| 14° | 0.12 | 0.15 | 0.16 | 0.17 | 0.18 | 0.19 | 0.21 | 0.22 | 0.22 | 0.23 | 0.26 | 0.28 | 0.32 |
| 15° | 0.09 | 0.11 | 0.12 | 0.14 | 0.14 | 0.15 | 0.16 | 0.16 | 0.17 | 0.17 | 0.19 | 0.21 | 0.25 |
| 16° | 0.06 | 0.07 | 0.08 | 0.09 | 0.10 | 0.10 | 0.11 | 0.12 | 0.12 | 0.12 | 0.14 | 0.16 | 0.18 |
| 17° | 0.02 | 0.02 | 0.03 | 0.03 | 0.03 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.05 | 0.05 | 0.06 |
| To be added to the degree read. | |||||||||||||
| 18° | 0.02 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.02 |
| 19° | 0.06 | 0.08 | 0.08 | 0.09 | 0.09 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.08 | 0.06 |
| 20° | 0.11 | 0.14 | 0.15 | 0.17 | 0.17 | 0.18 | 0.18 | 0.18 | 0.19 | 0.19 | 0.18 | 0.15 | 0.11 |
| 21° | 0.16 | 0.20 | 0.22 | 0.24 | 0.24 | 0.25 | 0.25 | 0.25 | 0.26 | 0.26 | 0.25 | 0.22 | 0.18 |
| 22° | 0.21 | 0.26 | 0.28 | 0.31 | 0.31 | 0.32 | 0.32 | 0.32 | 0.33 | 0.34 | 0.32 | 0.29 | 0.25 |
| 23° | 0.27 | 0.32 | 0.35 | 0.37 | 0.38 | 0.39 | 0.39 | 0.39 | 0.40 | 0.42 | 0.39 | 0.36 | 0.33 |
| 24° | 0.32 | 0.38 | 0.41 | 0.43 | 0.44 | 0.46 | 0.46 | 0.47 | 0.47 | 0.50 | 0.46 | 0.43 | 0.40 |
| 25° | 0.37 | 0.44 | 0.47 | 0.49 | 0.51 | 0.53 | 0.54 | 0.55 | 0.55 | 0.58 | 0.54 | 0.51 | 0.48 |
| 26° | 0.43 | 0.50 | 0.54 | 0.56 | 0.58 | 0.60 | 0.61 | 0.62 | 0.62 | 0.66 | 0.62 | 0.58 | 0.55 |
| 27° | 0.49 | 0.57 | 0.61 | 0.63 | 0.65 | 0.68 | 0.68 | 0.69 | 0.70 | 0.74 | 0.70 | 0.65 | 0.62 |
| 28° | 0.56 | 0.64 | 0.68 | 0.70 | 0.72 | 0.76 | 0.76 | 0.78 | 0.78 | 0.82 | 0.78 | 0.72 | 0.70 |
| 29° | 0.63 | 0.71 | 0.75 | 0.78 | 0.79 | 0.84 | 0.84 | 0.86 | 0.86 | 0.90 | 0.88 | 0.80 | 0.78 |
| 30° | 0.70 | 0.78 | 0.82 | 0.87 | 0.87 | 0.92 | 0.92 | 0.94 | 0.94 | 0.98 | 0.94 | 0.88 | 0.86 |
| 35° | 1.10 | 1.17 | 1.22 | 1.24 | 1.30 | 1.32 | 1.33 | 1.35 | 1.36 | 1.39 | 1.34 | 1.27 | 1.25 |
| 40° | 1.50 | 1.61 | 1.67 | 1.71 | 1.73 | 1.79 | 1.79 | 1.80 | 1.82 | 1.83 | 1.78 | 1.69 | 1.65 |
| 50° | — | 2.65 | 2.71 | 2.74 | 2.78 | 2.80 | 2.80 | 2.80 | 2.80 | 2.79 | 2.70 | 2.56 | 2.51 |
| 60° | — | 3.87 | 3.88 | 3.88 | 3.88 | 3.88 | 3.88 | 3.88 | 3.90 | 3.82 | 3.70 | 3.43 | 3.41 |
| 70° | — | — | 5.18 | 5.20 | 5.14 | 5.13 | 5.10 | 5.08 | 5.06 | 4.90 | 4.72 | 4.47 | 4.35 |
| 80° | — | — | 6.62 | 6.59 | 6.54 | 6.16 | 6.38 | 6.30 | 6.26 | 6.06 | 5.82 | 5.50 | 5.33 |
According to observations of Gerlach, the correction for temperature varies with the concentration of the solution and the range of temperature as shown in the table.
58. Comparison of Brix and Baumé Degrees.—The following table shows the degree baumé and the specific gravity of a sugar solution for each degree brix (per cent of sugar in solution) from zero to ninety-five:[34]
59. Error Due to Impurities.—The fact that equal per cents of solid bodies in solution affect the specific gravity in different degrees has already been noted. The specific gravities of the solutions of the common sugars, however, are so nearly the same for equal per cents of solid matter in solution as to render the use of a brix hydrometer quite general for technical purpose. For the mineral salts which often occur in sugar solutions the case is quite different. A twenty per cent solution of cane sugar at 17°.5 has a specific gravity 1.08329 and of dextrose 1.08310, practically identical. But a solution of calcium acetate of similar strength has a specific gravity of 1.0874; of sodium sulfate 1.0807, and of potassium nitrate 1.1359. This latter number would correspond to a sugar content of nearly twenty-seven per cent. The brix scale can, therefore, be regarded as giving only approximately the percentage of solid matter in sugar solutions and, while useful in technical work, should never be relied upon for exact analytical data.
THE DETERMINATION OF SUGAR
WITH POLARIZED LIGHT.
60. Optical Properties of Natural Sugars.—The solutions of all natural sugars have the property of deflecting the plane of polarized light and the degree of deflection corresponds to the quantity of sugar in solution. By measuring the amplitude of the rotation produced the percentage of sugar in the solution can be determined. In order to secure accuracy in the determinations it is necessary that only one kind of sugar be present, or, if more than one, that the quantities of all but one be determined by other means, and the disturbances produced thereby in the total rotation be properly arranged. In point of fact the process in practice is applied chiefly to cane and milk sugars, both of which occur in nature in an approximately pure state. The process is also useful in determining cane sugar when mixed with other kinds, by reason of the fact that this sugar after hydrolysis by treatment with a weak acid for a long or a strong acid for a short time, definitely changes its rotating power. Since, by the same treatment, the rotating power of other sugars which may be present is only slightly altered, the total disturbance produced is approximately due to the inversion of the cane sugar.
Dextrose and maltose arising from the hydrolysis of starch may also be determined with a fair degree of accuracy by their deportment with polarized light. When a solution of natural sugars shows negative results when examined with polarized light, it is due to an admixture of two or more sugars of opposite polarizing powers in such proportions as to produce neutrality. This condition often occurs in the examination of honeys or in submitting artificial sugars to polarimetric observations. In the latter case the neutrality is caused by the tendency manifested by artificially produced sugars to form twin compounds of optically opposite qualities.
The instrument used for measuring the degree of deflection produced in a plane of polarized light is called a polariscope, polarimeter, or optical saccharimeter. For a theoretical discussion of the principles of polarization and the application of these principles in the construction of polariscopes, the reader is referred to the standard works on optics and the construction of optical instruments.[35] For the purposes of this work a description of the instruments commonly employed and the methods of using them will be sufficient.
61. Polarized Light.—When a ray of light has been repeatedly reflected from bright surfaces or when it passes through certain crystalline bodies it acquires peculiar properties and is said to be polarized.
Polarization is therefore a term applied to a phenomenon of light, in which the vibrations of the ether are supposed to be restricted to a particular form of an ellipse whose axes remain fixed in direction. If the ellipse become a straight line it is called plane polarization. This well-known phenomenon is most easily produced by a nicol prism, consisting of a cut crystal of calcium carbonate (Iceland spar). This rhombohedral crystal, the natural ends of which form angles of 71° and 109°, respectively, with the opposite edges of its principal section, is prepared as follows:
The ends of the crystals are ground until the angles just mentioned become 68° and 112°. The crystal is then divided diagonally at right angles with the planes of the ends and with the principal section, and after the new surfaces are polished they are joined again by canada balsam. The principal section of this prism passes through the shorter diagonal of the two rhombic ends. If now a ray of light fall on one of the ends of this prism, parallel with the edge of its longer side, it suffers double refraction, and each ray is plane polarized, the one at right angles with the other. That part of the entering ray of light which is most refracted is called the ordinary and the other the extraordinary ray. The refractive index of the film of balsam being intermediate between those of the rays, permits the total reflection of the ordinary ray, which, passing to the blackened sides of the prism, is absorbed. The extraordinary ray passes the film of balsam without deviation and emerges from the prism in a direction parallel with the incident ray, having, however, only half of its luminous intensity.
Two such prisms, properly mounted, furnish the essential parts of a polarizing apparatus. They are called the polarizer and the analyzer, respectively.
If now the plane of vibration in each prism be regarded as coincident with its principal section, the following phenomena are observed: If the prisms are so placed that the principal sections lie in the prolongation of the same plane, then the extraordinary polarized ray from the polarizer passes into the analyzer, which practically may be regarded in this position as a continuation of the same prism. It happens, therefore, that the extraordinary polarized ray passes through the analyzer exactly as it did through the polarizer, and is not reflected by the film of balsam, but emerges from the analyzer in seemingly the same condition as from the polarizer. If now the analyzer be rotated 180°, bringing the principal section again in the same plane, the same phenomenon is observed. But if the rotation be in either direction only 90°, then the polarized ray from the first prism, incident on the second, deports itself exactly as the ordinary ray, and on meeting the film of balsam is totally reflected. The field of vision, therefore, is perfectly dark.
In all other inclinations of the planes of the principal sections of the two prisms the ray incident in the analyzer is separated into two, an ordinary and extraordinary, varying in luminous intensity in proportion to the square of the cosine of the angle of the two planes.
Figure 31. Course
of Rays of Light
In a Nicol.
Thus, by gradually turning the analyzer, the field of vision passes slowly from maximum luminosity to complete obscurity. The expression crossed nicols refers to the latter condition of the field of vision.
62. Description of the Prism.—In a nicol made as described above, [Fig. 31], suppose a ray of light parallel with the longer side of the prism be incident to the end a b at m. By the double refracting power of the spar the ray is divided into two, which traverse the first half of the prism. The two rays are polarized at right angles to one another. The less refracted ray when it strikes the film of Canada balsam passes through it without interference. The more refracted ray strikes the balsam at o at such an angle as to be totally reflected and made to pass out of the prism in the direction o r. If the prism be blackened at the surface the ray will be entirely absorbed. The other ray passes on through the other half of the prism and emerges in the direction of qs. It is evident that the emergent light from a nicol has only half the illuminating power possessed by the immergent rays.
The polarized plane of light from the nicol just described may be regarded as passing also into a second nicol of essentially the same construction as the first.
This second nicol, called the analyzer, is so constructed as to revolve freely about its longitudinal axis, and is attached to a graduated circle in such a way that the degree of rotation can be accurately read. If the planes of polarization of the two nicols are coincident when prolonged, the ray of light passing from the first nicol will pass through the second practically unchanged in character or intensity. If, however, the analyzing nicol be turned until the plane of polarization is at right angles to that of the polarizer the immergent ray will suffer refraction in such a manner as to be totally reflected when reaching the film of balsam and will be thus entirely lost. In making a complete revolution of the analyzer, therefore, two positions of maximum intensity of light and two of darkness will be observed. In intermediate positions the ray immergent to the analyzer will be separated as in the first instance into two rays g p varying intensities, one of which will be always totally reflected.
Figure 32. Theory of
the Nicol.
In [Fig. 32] is given a more detailed illustration of the action of the rays of light. The film of balsam is represented as enlarged and of the thickness bb. Draw the perpendiculars represented by the dotted lines n₁ nʹ₁, n₂ nʹ₂, n₃ nʹ₃ and n₄ nʹ₄. In passing into the prism at m both refracted rays are bent towards the normal m nʹ₁. The degree of deflection depends on the refractive index of the two rays 1.52 and 1.66 respectively. The refractive index of the extraordinary ray in calcspar being 1.52, and in Canada balsam 1.54, it suffers but little disturbance in passing from one to the other. On the other hand the balsam, being considerably less refractive for the ordinary ray than the calcspar, causes that ray to diverge outwards from the normal o nʹ₂, and to such a degree as to suffer total reflection. The critical angle, that is the angle at which a ray issuing from a more refractive into a less refractive medium, emerges just parallel to the bounding surfaces, depends on the relative index of refraction. In the case under consideration the ratio for balsam and spar is 1.54/1.66 = 0.928 = sin 68°. Therefore the limiting value of m o n₃ so that m o may just emerge in the direction od is 68°. If now mo were parallel to o d the angle m o n, would be just 68°, being opposite b a d. which has been ground to 68° in the construction of the prism. But in passing into the prism, m o is refracted so that the angle m o n₃ is greater than b a d. It is therefore always certain that by grinding b a d to 68° the ordinary ray m o will be with certainty entirely thrown out in every case. In respect of the analyzing nicol the following additional observations will be found useful. In all uniaxial crystals there are two directions at right angles to each other, one of greatest and one of least resistance to the propagation of luminous vibrations. These planes are in the direction of the principal axis and at right angles thereto. Only light vibrating in these two directions can be transmitted through calcspar; and all incident light propagated by vibrations in a plane at any other angle to the principal section is resolved into two such component rays. But the velocities of transmission in the two directions are unequal, that is, the refractive index of the spar for the two rays is different. If the analyzing nicol be so adjusted as to receive the emergent light from the polarizer when the corresponding planes of the two prisms are coincident when extended, the emergent extraordinary ray falling into a plane of the same resistance as that it had just left is propagated through the second nicol with the same velocity that it passed the first one. It is therefore similarly refracted. If, however, the two prisms be so arranged that corresponding planes cross then the extraordinary ray falls into a plane which it traverses with greater velocity than it had before and is accordingly refracted and takes the course which ends in total reflection at the film of balsam. No light therefore can pass through the prism in that position. If any other substance, as for instance a solution of sugar, capable of rotating a plane of polarized light, be interposed between the two nicols the effect produced is the same as if the analyzer had been turned to a corresponding degree. When the analyzer is turned to that degree the corresponding planes again coincide and the light passes. This is the principle on which the construction of all polarizing instruments is based.[36]
63. The Polariscope.—A polariscope for the examination of solutions of sugar consists essentially of a prism for polarizing the light, called a nicol, a tube of definite length for holding the sugar solution, a second nicol made movable on its axis for adjustment to the degree of rotation and a graduated arc for measuring it. Instead of having the second nicol movable, many instruments have an adjusting wedge of quartz of opposite polarizing power to the sugar, by means of which the displacement produced on the polarized plane is corrected. A graduated scale and vernier serve to measure the movement of the wedges and give in certain conditions the desired reading of the percentage of sugar present. Among the multitude of instruments which have been devised for analytical purposes, only three will be found in common use, and the scope of this volume will not allow space for a description of a greater number. For a practical discussion of the principles of polarization and their application to optical saccharimetry, the reader may conveniently refer to the excellent manuals of Sidersky, Tucker, Landolt, and Wiechmann.[37]
64. Kinds of Polariscopes.—The simplest form of a polarizing apparatus consists of two nicol prisms, one of which, viz., the analyzer, is capable of rotation about its long axis. The prolongation of this axis is continuous with that of the other prism, viz., the polarizer. The two prisms are sufficiently removed from each other to allow of the interposition of the polarizing body whose rotatory power is to be measured.
For purposes of description three kinds of polarimeters may be mentioned.
1. Instruments in which the deviation of the plane of polarization is measured by turning the analyzer about its axis.
Instruments of this kind conform to the simple type first mentioned, and are coeteris paribus the best. The Laurent, Wild, Landolt-Lippich, etc., belong to this class.
2. Instruments in which both nicols are fixed and the direction of the plane of polarized light corrected by the interposition of a wedge of a solid polarizing body.
Belonging to this class are the apparatus of Soleil, Duboscq, Scheibler, and the compensating apparatus of Schmidt and Haensch.
3. Apparatus in which the analyzer is set at a constant angle with the polarizer, and the compensation secured by varying the length or concentration of the interposed polarizing liquid.
The apparatus of Trannin belongs to this class.
65. Appearance of Field of Vision.—Polarimeters are also classified in respect of the appearance of the field of vision.
1. Tint Instruments.—The field of vision in these instruments in every position of the nicols, except that on which the plane of vibration of the polarized light is coincident with the three principal sections, is composed of two semi-disks of different colors.
2. Shadow Instruments.—The field of vision in this class of polarimeters in all except neutral positions, is composed of two semi-disks, one dark and one yellow. As the neutral position is approximated the two disks gradually assume a light yellow color, and when neutrality is reached they appear to be equally colored.
The Laurent, Schmidt and Haensch shadow and Landolt-Lippich instruments, are of this class.
3. Striated Instruments.—In this class the field of vision is striated. The lines may be tinted as in Wild’s polaristrobometer or black, as in the Duboscq and Trannin instruments. The neutral position is indicated either by the disappearance of the striae (Wild) or by the phenomenon of their becoming continuous. (Duboscq, Trannin.)
66. Character of Light Used.—Polariscopes may be further divided into two classes, based on the kind of light employed.
1. Instruments which Use Ordinary White Light.—(Oil lamp, etc.) Scheibler, Schmidt and Haensch.
2. Instruments Employing Monochromatic Light.—(Sodium flame, etc.) Laurent, Landolt-Lippich, etc.
67. Interchangeable Instruments.—Some of the instruments in common use are arranged to be used either with ordinary lamp or gas light, or with a monochromatic flame. Laurent’s polarimeter is one of this kind. The compensating instruments also may have the field of vision arranged for tints or shadows. Theoretically the best instrument would be one in which the light is purely monochromatic, the field of vision a shadow, and the compensation secured by the rotation of the second nicol.
The accuracy of an instrument depends, however, on the skill and care with which it is constructed and used. With quartz wedges properly ground and mounted, and with ordinary white light, polariscopes may be obtained which give readings as accurate as can be desired.
Since many persons are more or less affected with color-blindness, the shadow are to be preferred to the tint fields of vision.
For practical use in sugar analysis the white light is much more convenient than the monochromatic light.
For purposes of general investigation the polarimeters built on the model of the laurent are to be preferred to all others. Such instruments are not only provided with a scale which shows the percentage of sucrose in a solution, but also with a scale and vernier by means of which the angular rotation which the plane of vibration has suffered, can be accurately measured in more than one-quarter of the circle.