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17. THE CHEMISTRY OF THE COFFEE BEAN
Chemistry of the preparation and treatment of the green bean—Artificial aging—Renovating damaged coffees—Extracts—"Caffetannic acid"—Caffein, caffein-free coffee—Caffeol—Fats and oils—Carbohydrates—Roasting—Scientific aspects of grinding and packaging—The coffee brew—Soluble coffee—Adulterants and substitutes—Official methods of analysis
By Charles W. Trigg
Industrial Fellow of the Mellon Institute of Industrial Research, Pittsburgh, 1916–1920
WHEN the vast extent of the coffee business is considered, together with the intimate connection which coffee has with the daily life of the average human, the relatively small amount of accurate knowledge which we possess regarding the chemical constituents and the physiological action of coffee is productive of amazement.
True, a painstaking compilation of all the scientific and semi-scientific work done upon coffee furnishes quite a compendium of data, the value of which is not commensurate with its quantity, because of the spasmodic nature of the investigations and the non-conclusive character of the results so far obtained. The following general survey of the field argues in favor of the promulgation of well-ordered and systematic research, of the type now in progress at several places in the United States, into the chemical behavior of coffee throughout the various processes to which it is subjected in the course of its preparation for human consumption.
Green Coffee
One of the few chemical investigations of the growing tree is the examination by Graf of flowers from 20-year-old coffee trees, in which he found 0.9 percent caffein, a reducing sugar, caffetannic acid, and phytosterol. Power and Chestnut[102] found 0.82 percent caffein in air-dried coffee leaves, but only 0.087 percent of the alkaloid in the stems of the plant separated from the leaves. In the course of a study[103] instituted for the purpose of determining the best fertilizers for coffee trees, it developed that the cherries in different stages of growth show a preponderance of potash throughout, while the proportion of P2O5 attains a maximum in the fourth month and then steadily declines.
Experiments are still in progress to ascertain the precise mineral requirements of the crop as well as the most suitable stage at which to apply them. During the first five months the moisture content undergoes a steady decrease, from 87.13 percent to 65.77 percent, but during the final ripening stage in the last month there is a rise of nearly 1 percent. This may explain the premature falling and failure to ripen of the crop on certain soils, especially in years of low rainfall. Malnutrition of the trees may result also in the production of oily beans.[104]
The coffee berry comprises about 68 percent pulp, 6 percent parchment, and 26 percent clean coffee beans. The pulp is easily removed by mechanical means; but in order to separate the soft, glutinous, saccharine parchment, it is necessary to resort to fermentation, which loosens the skin so that it may be removed easily, after which the coffee is properly dried and aged. There is first a yeast fermentation producing alcohol; and then a bacterial action giving mainly inactive lactic acid, which is the main factor in loosening the parchment. For the production of the best coffee, acetic acid fermentation (which changes the color of the bean) and temperature above 60° should be avoided, as these inhibit subsequent enzymatic action.[105]
Various schemes have been proposed for utilizing the large amount of pulp so obtained in preparing coffee for market. Most of these depend upon using the pulp as fertilizer, since fresh pulp contains 2.61 percent nitrogen, 0.81 percent P2O5, 2.38 percent potassium, and 0.57 percent calcium. One procedure[106] in particular is to mix pulp with sawdust, urine, and a little lime, and then to leave this mixture covered in a pit for a year before using. In addition to these mineral matters, the pulp also contains about 0.88 percent of caffein and 18 to 37 percent sugars. Accordingly, it has been proposed[107] to extract the caffein with chloroform, and the sugars with acidulated water. The aqueous solution so obtained is then fermented to alcohol. The insoluble portion left after extraction can be used as fuel, and the resulting ash as fertilizer.
The pulp has been dried and roasted for use in place of the berry, and has been imported to England for this purpose. It is stated that the Arabs in the vicinity of Jiddah discard the kernel of the coffee berries and make an infusion of the husk.[108]
Quality of green coffee is largely dependent upon the methods used and the care taken in curing it, and upon the conditions obtaining in shipment and storage. True, the soil and climatic conditions play a determinative rôle in the creation of the characteristics of coffee, but these do not offer any greater opportunity for constructive research and remunerative improvement than does the development of methods and control in the processes employed in the preparation of green coffee for the market.
Cross-Section of the Endosperm or Hard Structure of the Green Bean
Storage prior and subsequent to shipment, and circumstances existing during transportation, are not to be disregarded as factors contributory to the final quality of the coffee. The sweating of mules carrying bags of poorly packed coffee, and the absorption of strong foreign aromas and flavors from odoriferous substances stored in too close proximity to the coffee beans, are classic examples of damage that bear iterative mention. Damage by sea water, due more to the excessive moisture than to the salt, is not so common an occurrence now as heretofore. However, a cheap and thoroughly effective means of ethically renovating coffee which has been damaged in this manner would not go begging for commercial application.
That green coffee improves with age, is a tenet generally accepted by the trade. Shipments long in transit, subjected to the effects of tropical heat under closely battened hatches in poorly ventilated holds, have developed into much-prized yellow matured coffee. Were it not for the large capital required and the attendant prohibitive carrying charges, many roasters would permit their coffees to age more thoroughly before roasting. In fact, some roasters do indulge this desire in regard to a portion of their stock. But were it feasible to treat and hold coffees long enough to develop their attributes to a maximum, still the exact conditions which would favor such development are not definitely known. What are the optimum temperature and the correct humidity to maintain, and should the green coffee be well ventilated or not while in storage? How long should coffee be stored under the most favorable conditions best to develop it? Aging for too long a period will develop flavor at the expense of body; and the general cup efficiency of some coffees will suffer if they be kept too long.
Portion of the Investing Membrane, Showing Its Structure
Drawn with the camera lucida, and magnified 140 diameters
The exact reason for improvement upon aging is in no wise certain, but it is highly probable that the changes ensuing are somewhat analogous to those occurring in the aging of grain. Primarily an undefined enzymatic and mold action most likely occurs, the nature of the enzymes and molds being largely dependent upon the previous treatment of the coffee. Along with this are a loss of moisture and an oxidation, all three actions having more evident effects with the passage of time.
Artificial Aging
In consideration of the higher prices which aged products demand, attempts have naturally been made to shorten by artificial means the time necessary for their natural production. Some of these methods depend upon obtaining the most favorable conditions for acceleration of the enzyme action; others, upon the effects of micro-organisms; and still others, upon direct chemical reaction or physical alteration of the green bean.
One of the first efforts toward artificial maturing was that of Ashcroft[109], who argued from the improved nature of coffee which had experienced a delayed voyage. His method consisted of inclosing the coffee in sweat-boxes having perforated bottoms and subjecting it to the sweating action of steam, the boxes being enclosed in an oven or room maintained at the temperature of steam.
Structure of the Green Bean
Showing thick-walled cells enclosing drops of oil
Timby[110] claimed to remove dusts, foreign odors, and impurities, while attaining in a few hours or days a ripening effect normally secured only in several seasons. In this process, the bagged coffee is placed in autoclaves and subjected to the action of air at a pressure of 2 to 3 atmospheres and a temperature of 40° to 100° F. The temperature should seldom be allowed to rise above 150° F. The pressure is then allowed to escape and a partial vacuum created in the apparatus. This alteration of pressure and vacuum is continued until the desired maturation is obtained. Desvignes[111] employs a similar procedure, although he accomplishes seasoning by treating the coffee also with oxygen or ozone.[112] First the coffee is rendered porous by storage in a hot chamber, which is then exhausted prior to admission of the oxygen. The oxygen can be ozonized in the closed vessel while in contact with the coffee. Complete aging in a few days is claimed.
Weitzmann[113] adopts a novel operation, by exposing bags of raw coffee to the action of a powerful magnetic field, obtained with two adjustable electro-magnets. The claim that a maturation naturally produced in several years is thus obtained in 1⁄2 to 2 hours is open to considerable doubt. A process that is probably attended with more commercial success is that of Gram[114] in which the coffee is treated with gaseous nitrogen dioxid.
By far the most notable progress in this field, both scientifically and commercially, has been made by Robison[115] with his "culturing" method. Here the green coffee is washed with water, and then inoculated with selected strains of micro-organisms, such as Ochraeceus or Aspergillus Wintii. Incubation is then conducted for 6 to 7 days at 90° F. and 85 percent relative humidity. Subsequent to this incubation, the coffee is stored in bins for about ten days; after which it is tumbled and scoured. With this process it is possible to improve the cupping qualities of a coffee to a surprising degree.
Renovating Damaged Coffees
Sophistication has often been resorted to in order ostensibly to improve damaged or cheap coffee. Glazing, coloring, and polishing of the green beans was openly and covertly practised until restricted by law. The steps employed did not actually improve the coffee by any means, but merely put it into condition for more ready sale. An apparently sincere endeavor to renovate damaged coffee was made by Evans[116] when he treated it with an aqueous solution of sulphuric acid having a density of 10.5° Baumé. After agitation in this solution, the beans were washed free from acid and dried. In this manner discolorations and impurities were removed and the beans given a fuller appearance.
The addition of glucose, sucrose, lactose, or dextrin to green coffees is practised by von Niessen[117] and by Winter[118], with the object of giving a mild taste and strong aroma to "hard" coffees. The addition is accomplished by impregnating, with or without the aid of vacuum, the beans with a moderately concentrated solution of the sugar, the liquid being of insufficient quantity to effect extraction. When the solution has completely disseminated through the kernels, they are removed and dried. Upon subsequent roasting, a decided amelioration of flavor is secured.
Another method developed by von Niessen[119] comprises the softening of the outer layers of the beans by steam, cold or warm water, or brine, and then surrounding them with an absorbent paste or powder, such as china clay, to which a neutralizing agent such as magnesium oxid may be added. After drying, the clay can be removed by brushing or by causing the beans to travel between oppositely reciprocated wet cloths. In the development of this process, von Niessen evidently argued that the so-called "caffetannic acid" is the "harmful" substance in coffee, and that it is concentrated in the outer layers of the coffee beans. If these be his precepts, the question of their correctness and of the efficiency of his process becomes a moot one.
A procedure which aims at cleaning and refining raw coffee, and which has been the subject of much polemical discussion, is that of Thum[120]. It entails the placing of the green beans in a perforated drum; just covering them with water, or a solution of sodium chloride or sodium carbonate, at 65° to 70° C.; and subjecting them to a vigorous brushing for from 1 to 5 minutes, according to the grade of coffee being treated. The value of this method is somewhat doubtful, as it would not seem to accomplish any more than simple washing. In fact, if anything, the process is undesirable; as some of the extractive matters present in the coffee, and particularly caffein, will be lost. Both Freund[121] and Harnack[122] hold briefs for the product produced by this method, and the latter endeavors analytically to prove its merits; but as his experimental data are questionable, his conclusions do not carry much weight.
The Acids of Coffee
The study of the acids of coffee has been productive of much controversy and many contradictory results, few of which possess any value. The acid of coffee is generally spoken of as "caffetannic acid." Quite a few attempts have been made to determine the composition and structure of this compound and to assign it a formula. Among them may be noted those of Allen,[123] who gives it the empirical formula C14H16O7; Hlasiwetz,[124] who represents it as C15H18O8; Richter, as C30H18O16; Griebel,[125] as C18H24O10, and Cazeneuve and Haddon,[126] as C21H28O14. It is variously supposed to exist in coffee as the potassium, calcium, or magnesium salt. In regard to the physical appearance of the isolated substance there is also some doubt, Thorpe[127]describing it as an amorphous powder, and Howard[128] as a brownish, syrup-like mass, having a slight acid and astringent taste.
The chemical reactions of "caffetannic acid" are generally agreed upon. A dark green coloration is given with ferric chloride; and upon boiling it with alkalies or dilute acids, caffeic acid and glucose are formed. Fusion with alkali produces protocatechuic acid.
K. Gorter[129] has made an extensive and accurate investigation into the matter, and in reporting upon the same has made some very pertinent observations. His claim is that the name "caffetannic acid" is a misnomer and should be abandoned. The so-called "caffetannic acid" is really a mixture which has among its constituents chlorogenic acid (C32H38O19), which is not a tannic acid, and coffalic acid. Tatlock and Thompson[130] have expressed the opinion that roasted coffee contains no tannin, and that the lead precipitate contains mostly coloring matter. They found only 4.5 percent of tannin (precipitable by gelatin or alkaloids) in raw coffee.
Hanausek[131] demonstrated the presence of oxalic acid in unripe beans, and citric acid has been isolated from Liberian coffee. It also has been claimed that viridic acid, C14H20O11, is present in coffee. In addition to these, the fat of coffee contains a certain percentage of free fatty acids.
It is thus apparent that even in green coffee there is no definite compound "caffetannic acid," and there is even less likelihood of its being present in roasted coffee. The conditions, high heat and oxidation, to which coffee is subjected in roasting would suffice to decompose this hypothetical acid if it were present.
In the method of analysis for caffetannic acid (No. 24) given at the end of this chapter, there are many chances of error, although this procedure is the best yet devised. Lead acetate forms three different compounds with "caffetannic acid," so that this reagent must be added with extreme care in order to precipitate the compound desired. The precipitate, upon forming, mechanically carries down with it any fats which may be present, and which are removed from it only with difficulty. The majority of the mineral salts in the solution will come down simultaneously. All of the above-mentioned organic acids form insoluble salts with lead acetate, and there will also be a tendency toward precipitation of certain of the components of caramel, the acidic polymerization products of acrolein, glycerol, etc., and of the proteins and their decomposition products.
In view of this condition of uncertainty in composition, necessity for great care in manipulation, and ever-present danger of contamination, the significance of "caffetannic acid analysis" fades. It is highly desirable that the nomenclature relevant to this analytical procedure be changed to one, such as "lead number," which will be more truly indicative of its significance.
The Alkaloids of Coffee
In addition to caffein, the main alkaloid of coffee, trigonellin—the methylbetaine of nicotinic acid—sometimes known as caffearine, has been isolated from coffee.[132] This alkaloid, having the formula C14H16O4N2, is also found in fenugreek, Trigonella fœnum-græcum, in various leguminous plants, and in the seeds of strophanthus. When pure it forms colorless needles melting at 140° C., and, as with all alkaloids, gives a weak basic reaction. It is very soluble in water, slightly soluble in alcohol, and only very slightly soluble in ether, chloroform or benzol, so that it does not contaminate the caffein in the determination of the latter. Its effects on the body have not been studied, but they are probably not very great, as Polstorff obtained only 0.23 percent from the coffee which he examined.
Caffein, thein, trimethylxanthin, or C5H(CH3)3N4O2, in addition to being in the coffee bean is also found in guarana leaves, the kola nut, maté, or Paraguay tea, and, in small quantities, in cocoa. It is also found in other parts of these plants besides those commonly used for food purposes.
A neat test for detecting the presence of caffein is that of A. Viehoever,[133] in which the caffein is sublimed directly from the plant tissue in a special apparatus. The presence of caffein in the sublimate is verified by observing its melting point, determined on a special heating stage used in connection with a microscope.
The chief commercial source of this alkaloid is waste and damaged tea, from which it is prepared by extraction with boiling water, the tannin precipitated from the solution with litharge, and the solution then concentrated to crystallize out the caffein. It is further purified by sublimation or recrystallization from water. Coffee chaff and roaster-flue dust have been proposed as sources for medicinal caffein, but the extraction of the alkaloid from the former has not proven to be a commercial success. Several manufacturers of pharmaceuticals are now extracting caffein from roaster-flue dust, probably by an adaptation of the Faunce[134] process. The recovery of caffein from roaster-flue gases may be facilitated and increased by the use of a condenser such as proposed Ewé.[135]
Pure caffein forms long, white, silky, flexible needles, which readily felt together to form light, fleecy masses. It melts at 235–7° C. and sublimes completely at 178° C., though the sublimation starts at 120°. Salts of an unstable nature are formed with caffein by most acids. The solubility of caffein as determined by Seidell[136] is given in Table I.
| Table I—The Solubility of Caffein | ||||
| Solvent | Sp. Gr. of Solvent | Temperature of Solution | Solubility: Grm. Caffein per 100 Grm. of Saturated Solution | Sp. Gr. of Saturated Solution |
| Water | 0.997 | 25 | 2.14 | —— |
| Ether | 0.716 | 25 | 0.27 | —— |
| Chloroform | 1.476 | 25 | 11.0 | —— |
| Acetone | 0.809 | 30–1 | 2.18 | 0.832 |
| Benzene | 0.872 | 30–1 | 1.22 | 0.875 |
| Benzaldehyde | 1.055 | 30–1 | 11.62 | 1.087 |
| Amylacetate | 0.860 | 30–1 | 0.72 | 0.862 |
| Aniline | 1.02 | 30–1 | 22.89 | 1.080 |
| Amyl alcohol | 0.814 | 25 | 0.49 | 0.810 |
| Acetic acid | 1.055 | 21.5 | 2.44 | —— |
| Xylene | 0.847 | 32.5 | 1.11 | 0.847 |
| Toluene | 0.862 | 25 | 0.57 | 0.861 |
The similarity between caffein and theobromin (the chief alkaloid of cocoa), xanthin (one of the constituents of meat), and uric acid, is shown by the accompanying structural formulæ.
These formulæ show merely the relative position occupied by caffein in the purin group, and do not in any wise indicate, because of its similarity of structure to the other compounds, that it has the same physiological action. The presence and position of the methyl groups (CH3) in caffein is probably the controlling factor which makes its action differ from the behavior of other members of the series. The structure of these compounds was established, and their syntheses accomplished, in the course of various classic researches by Emil Fischer.[137]
Formula for Caffein, Showing Its Relation to the Purin Group
Gorter states that caffein exists in coffee in combination with chlorogenic acid as a potassium chlorogenate, C32H36O19, K2(C8H10O2N4)2·2H2O, which he isolated in colorless prisms. This compound is water-soluble, but caffein can not be extracted from the crystals with anhydrous solvents. To this behavior can probably be attributed the difficulty experienced in extracting caffein from coffee with dry organic solvents. However, the fact that a small percentage can be extracted from the green bean in this manner indicates that some of the caffein content exists therein in a free state. This acid compound of caffein will be largely decomposed during the process of torrefaction, so that in roasted coffee a larger percentage will be present in the free state. Microscopical examination of the roasted bean lends verisimilitude to this contention.
Planter's Bungalow with Coffee Trees in Flower, Mysore
Coolies Bagging Coffee on the Drying Grounds
COFFEE SCENES IN BRITISH INDIA
| Table II—Coffee Analyses | ||||||||
| Santos Green | Santos Roasted | Padang Green | Padang Roasted | Guatemala Green | Guatemala Roasted | Mocha Green | Mocha Roasted | |
| Moisture April 20th | 8.75 | 3.75 | 8.78 | 2.72 | 9.59 | 3.40 | 9.06 | 3.36 |
| Moisture September 20th | 8.12 | 6.45 | 8.05 | 6.03 | 8.68 | 6.92 | 8.15 | 7.10 |
| Ash | 4.41 | 4.49 | 4.23 | 4.70 | 3.93 | 4.48 | 4.20 | 4.43 |
| Oil | 12.96 | 13.76 | 12.28 | 13.33 | 12.42 | 13.07 | 14.04 | 14.18 |
| Caffein | 1.87 | 1.81 | 1.56 | 1.47 | 1.26 | 1.22 | 1.31 | 1.28 |
| Caffein, dry basis | 2.03 | —— | 1.69 | —— | 1.39 | —— | 1.44 | —— |
| Crude fiber | 20.70 | 14.75 | 21.92 | 14.95 | 22.23 | 15.23 | 22.46 | 15.41 |
| Protein | 9.50 | 12.93 | 12.62 | 14.75 | 10.43 | 11.69 | 8.56 | 9.57 |
| Protein, dry basis | 10.41 | —— | 13.68 | —— | 11.53 | —— | 9.41 | —— |
| Water extract | 31.11 | 30.30 | 30.83 | 30.21 | 31.04 | 30.47 | 31.27 | 30.44 |
| Specific gravity, 10 percent extract | 1.0109 | 1.0101 | 1.0107 | 1.0104 | 1.0105 | 1.0404 | 1.0108 | 1.0108 |
| Bushelweight | 47.0 | 28.2 | 45.2 | 27.8 | 52.2 | 27.2 | 48.8 | 30.2 |
| 1,000 kernel weight | 103.60 | 120.20 | 167.30 | 151.35 | 189.20 | 165.80 | 119.52 | 100.00 |
| 1,000 kernel weight, dry basis | 119.1 | 115.7 | 154.1 | 147.2 | 171.0 | 160.1 | 108.6 | 96.6 |
| Dextrose | —— | 0.72 | —— | 0.81 | —— | 0.54 | —— | 0.46 |
| Caffetannic acid | .58 | 17.44 | 15.37 | 16.93 | 16.27 | 17.13 | 15.61 | 16.89 |
| Acidity by titration apparent | 1.50 | 2.08 | 1.47 | 2.00 | 1.39 | 2.13 | 1.11 | 1.87 |
As may be seen in Table II,[138] the caffein content of coffee varies with the different kinds, a fair average of the caffein content being about 1.5 percent for C. arabica, to which class most of our coffees belong. However, aside from these may be mentioned C. canephora, which yields 1.97 percent caffein; C. mauritiana, which contains 0.07 percent of the alkaloid (less than the average "caffein-free coffee"); and C. humboltiana, which contains no caffein, but a bitter principle, cafemarin. Neither do the berries of C. Gallienii, C. Bonnieri, or C. Mogeneti contain any caffein; and there has also been reported[139] a "Congo coffee" which contained no crystallizable alkaloid whatever.
Apparently the variation in caffein content is largely due to the genus of the tree from which the berry comes, but it is also quite probable that the nature of the soil and climatic conditions play an important part. In the light of what has been accomplished in the field of agricultural research, it does not seem improbable that a man of Burbank's ability and foresight could successfully develop a series of coffees possessed of all the cup qualities inherent in those now used, but totally devoid of caffein. Whether this is desirable or not is a question to be considered in an entirely different light from the possibility of its accomplishment.
| Table III—Caffein in Different Roasts | |||
| Rio | Santos | Guatemala | |
| Green | 1.68% | 1.85% | 1.82% |
| Cinnamon | 1.70 | 1.72 | 1.80 |
| Medium | 1.66 | 1.66 | 1.56 |
| City | 1.36 | 1.66 | 1.46 |
The variation in the caffein content of coffee at different intensities of roasting, as shown in Table III[140] is, of course, primarily dependent upon the original content of the green. A considerable portion of the caffein is sublimed off during roasting, thus decreasing the amount in the bean. The higher the roast is carried, the greater the shrinkage; but, as the analyses in the above table show, the loss of caffein proceeds out of proportion to the shrinkage, for the percentage of caffein constantly decreases with the increase in color. If the roast be carried almost to the point of carbonization, as in the case of the "Italian roast," the caffein content will be almost nil. This is not a suitable coffee for one desiring an almost caffein-free drink, for the empyreumatic products produced by this excessive roasting will be more toxic by far than the caffein itself would have been.
Caffein-free Coffee
The demand for a caffein-free coffee may be attributed to two causes, namely: the objectionable effect which caffein has upon neurasthenics; and the questionable advertising of the "coffee-substitute" dealers, who have by this means persuaded many normal persons into believing that they are decidedly sub-normal. As a result of this demand, a variety of decaffeinated coffees have been placed on the market. Just why the coffee men have not taken advantage of naturally caffein-free coffees, or of the possibility of obtaining coffees low in caffein content by chemical selection from the lines now used, is a difficult question to answer.
In the endeavor to develop a commercial decaffeinated coffee the first method of procedure was to extract the caffein from roasted coffee. This method had its advantages and its disadvantages, of which the latter predominated. The caffein in the roasted coffee is not as tightly bound chemically as in the green coffee, and is, therefore, more easily extracted. Also, the structure of the roasted bean renders it more readily penetrable by solvents than does that of the green bean. However, the great objection to this method arises from the fact that at the same time as the caffein is extracted, the volatile aromatic and flavoring constituents of the coffee are removed also. These substances, which are essential for the maintenance of quality by the coffee, though readily separated from the caffein, can not be returned to the roasted bean with any degree of certainty. This virtually insurmountable obstacle forced the abandonment of this mode of attack.
In order to avoid this action, the attention of investigators was directed to extraction of the alkaloid in question from the green bean. Because of the difficulty of causing the solvent to penetrate the bean, recourse to grinding resulted. This greatly facilitated the desired extraction, but a difficulty was encountered when the subsequent roasting was attempted. The irregular and broken character of the ground green beans resisted all attempts to produce practically a uniformly roasted, highly aromatic product from the ground material.
Avoidance of this lack of uniformity in the product, and the great desirability to duplicate the normal bean as far as possible, necessitated the development of a method of extraction of the caffein from the whole raw bean without a permanent alteration of the shape thereof. The close structure of the green bean, and its consequent resistance to penetration by solvents, and the existence of the caffein in the bean as an acid salt, which is not easily soluble, offered resistance to successful extraction.
As a means of overcoming the difficulty of structure, the beans were allowed to stand in water in order to swell, or the cells were expanded by treatment with steam, or the beans were subjected to the action of some "cellulose-softening acids," such as acetic acid or sulphur dioxid. As a method of facilitating the mechanical side of extraction without deleterious effects, the treatment of the coffee with steam under pressure, as utilized in the patented process of Myer, Roselius, and Wimmer,[141] is probably the safest.
Many ingenious methods have been devised for the ready removal of the caffein from this point on. Several processes employ an alkali, such as ammonium hydroxid, to free the caffein from the acid; or an acid, such as acetic, hydrochloric, or sulphurous, is used to form a more soluble salt of caffein. Other procedures effect the dissociation of the caffein-acid salt by dampening or immersion in a liquid and subjecting the mass to the action of an electric current.
The caffein is usually extracted from the beans by benzol or chloroform, but a variety of solvents may be employed, such as petrolic ether, water, alcohol, carbon tetrachloride, ethylene chloride, acetone, ethyl ether, or mixtures or emulsions of these. After extraction, the beans may be steam distilled to remove and to recover any residual traces of solvent, and then dried and roasted. It is said[142] that by heating the beans before bringing them into contact with steam, not only is an economy of steam effected, but the quality of the resultant product is improved.
One clever but expensive method[143] of preparing caffein-free coffee consists in heating the beans under pressure, with some substance, such as sodium salicylate, with the resultant formation of a more soluble and more easily steam-distillable compound of caffein. The beans are then steam distilled to remove the caffein, dried, and roasted.
Another process of peculiar interest is that of Hubner,[144] in which the coffee beans are well washed and then spread in layers and kept covered with water at 15° C. until limited germination has taken place, whereupon the beans are removed and the caffein extracted with water at 50° C. It is claimed by the inventor that sprouting serves to remove some of the caffein, but it is quite probable that the process does nothing more than accomplish simple aqueous extraction.
In the majority of these processes the flavor of the resultant product should be very similar to natural roasted coffee. However, in the cases where aqueous extraction is employed, other substances besides caffein are removed that are replaced in the bean only with difficulty. The resultant product accordingly is very likely to have a flavor not entirely natural. On the other hand, beans from which the caffein is extracted with volatile solvents, if the operation be conducted carefully, should give a natural-tasting roast. Any residual traces of the solvent left in the bean are volatilized upon roasting.
Some of the caffein-free coffees on the market show upon analysis almost as much caffein as the natural bean. Those manufactured by reliable concerns, however, are virtually caffein-free, their content of the alkaloid varying from 0.3 to 0.07 percent as opposed to 1.5 percent in the untreated coffee. Thus, although actually only caffein-poor, in order to get the reaction of one cup of ordinary coffee one would have to drink an unusual amount of the brew made from these coffees.
The Aromatic Principles of Coffee
To ascertain just what substance or substances give the pleasing and characteristic aroma to coffee has long been the great desire of both practical and scientific men interested in the coffee business. This elusive material has been variously called caffeol, caffeone, "the essential oil of coffee," etc., the terms having acquired an ambiguous and incorrect significance. It is now generally agreed that the aromatic constituent of coffee is not an essential oil, but a complex of compounds which usage has caused to be collectively called "caffeol."
These substances are not present in the green bean, but are produced during the process of roasting. Attempts at identification and location of origin have been numerous; and although not conclusive, still have not proven entirely futile. One of the first observations along this line was that of Benjamin Thompson in 1812. "This fragrance of coffee is certainly owing to the escape of a volatile aromatic substance which did not originally exist as such in the grain, but which is formed in the process of roasting it." Later, Graham, Stenhouse, and Campbell started on the way to the identification of this aroma by noting that "in common with all the valuable constituents of coffee, caffeone is found to come from the soluble portion of the roasted seed."[145]
Comparison of the aroma given off by coffee during the roasting process with that of fresh-ground roasted coffee shows that the two aromas, although somewhat different, may be attributed to the same substances present in different proportions in the two cases. Recovery and identification of the aromatic principles escaping from the roaster would go far toward answering the question regarding the nature of the aroma. Bernheimer[146] reported water, caffein, caffeol, acetic acid, quinol, methylamin, acetone, fatty acids and pyrrol in the distillate coming from roasting coffee. The caffeol obtained by Bernheimer in this work was believed by him to be a methyl derivative of saligenin. Jaeckle[147] examined a similar product and found considerable quantities of caffein, furfurol, and acetic acid, together with small amounts of acetone, ammonia, trimethylamin, and formic acid. The caffeol of Bernheimer could not be detected. Another substance was separated also, but in too small a quantity to permit complete identification. This substance consisted of colorless crystals, which readily sublimed, melted at 115° to 117° C., and contained sulphur. The crystals were insoluble in water, almost insoluble in alcohol, but readily soluble in ether.
By distilling roasted coffee with superheated steam, Erdmann[148] obtained an oil consisting of an indifferent portion of 58 percent and an acid portion of 42 percent, consisting mainly of a valeric acid, probably alphamethylbutyric acid. The indifferent portion was found to contain about 50 percent furfuryl alcohol, together with a number of phenols. The fraction containing the characteristic odorous constituent of coffee boiled at 93° C. under 13 mm. pressure. The yield of this latter principle was extremely small, only about 0.89 gram being procured from 65 kilos of coffee.
Pyridin was also shown to be present in coffee by Betrand and Weisweiller[149] and by Sayre.[150] As high as 200 to 500 milligrams of this toxic compound have been obtained from 1 kilogram of freshly roasted coffee.
As stated above, the empyreumatic volatile aromatic constituents of the coffee are without question formed during and by the roasting process. According to Thorpe,[151] the most favorable temperature for development of coffee odor and flavor is about 200° C. Erdmann claimed to have produced caffeol by gently heating together caffetannic acid, caffein, and cane sugar. Other investigators have been unable to duplicate this work. Another authority,[152] giving it the empirical formula C8H10O2, states that it is produced during roasting, probably at the expense of a portion of the caffein. These conceptions are in the main incomplete and inaccurate.
By means of careful work, Grafe[153] came closer to ascertaining the origin of the fugacious aromatic materials. His work with normal, caffein-free coffee and with Thum's purified coffee led him to state that a part of these substances was derived from the crude fiber, probably from the hemi-cellulose of the thick endosperm cells. Sayre[154] makes the most plausible proposal regarding the origin of caffeol. He considers the roasting of coffee as a destructive distillation process, summarizing the results, briefly, as the production of furfuraldehyde from the carbohydrates, acrolein from the fats, catechol and pyrogallol from the tannins, and ammonia, amins, and pyrrols from the proteins. The products of roasting inter-react to produce many compounds of varying degrees of complexity and toxicity.
The great difficulty which arises in the attempt to identify the aromatic constituents of coffee is that the caffeols of no two coffees may be said to be the same. The reason for this is apparent; for the green coffees themselves vary in composition, and those of the same constitution are not roasted under identical conditions. Therefore, it is not to be expected that the decomposition products formed by the action of the different greens would be the same. Also, these volatile products occur in the roasted coffee in such a small amount that the ascertaining of their percentage relationship and the recognition of all that are present are not possible with the methods of analysis at present at our disposal. Until better analytical procedures have been developed we can not hope to establish a chemical basis for the grading of coffees from this standpoint.
Coffee Oil and Fat
It is well to distinguish between the "coffee oils," as they are termed by the trade, and true coffee oil. In speaking of the qualities of coffee, connoisseurs frequently use erroneous terms, particularly when they designate certain of the flavoring and aromatic constituents of coffee as "oils" or "essential oils." Coffee does not contain any essential oils, the aromatic constituent corresponding to essential oil in coffee being caffeol, a complex which is water-soluble, a property not possessed by any true oil. True, the oil when isolated from roasted coffee does possess, before purification, considerable of the aromatic and flavoring constituents of coffee. They are, however, no part of the coffee fat, but are held in it no doubt by an enfleurage action in much the same way that perfumes of roses, etc., are absorbed and retained by fats and oils in the commercial preparation of pomades and perfumes. This affinity of the coffee oil for caffeol assists in the retention of aromatic substances by the whole roasted bean. However, upon extraction of ground roasted coffee with water, the caffeol shows a preferential solubility in water, and is dissolved out from the oil, going into the brew.
The true oil of coffee has been investigated to a fair degree and has been found to be inodorous when purified. Analysis of green and roasted coffees shows them to possess between 12 percent and 20 percent fat. Warnier[155] extracted ground unroasted coffee with petroleum ether, washed the extract with water, and distilled off the solvent, obtaining a yellow-brownish oil possessing a sharp taste. From his examination of this oil he reported these constants: d24–5, 0.942; refraction at 25°, 81.5; solidifying point, 6° to 5°; melting point, 8° to 9°; saponification number, 177.5; esterification number, 166.7; acid number, 6.2; acetyl number, 0; iodin number, 84.5 to 86.3. Meyer and Eckert[156] carefully purified coffee oil and saponified it with Li2O in alcohol. In the saponifiable portion, glycerol was the only alcohol present, the acids being carnaubic, 10 percent; daturinic acid, 1 to 1.5 percent; palmitic acid, 25 to 28 percent; capric acid, 0.5 percent; oleic acid, 2 percent, and linoleic acid, 50 percent. The unsaponifiable wax amounted to 21.2 percent, was nitrogen-free, gave a phytostearin reaction, and saponification and oxidation indicated that it was probably a tannol carnaubate. Von-Bitto[157] examined the fat extracted from the inner husk of the coffee berry and found it to be faint yellow in color, and to solidify only gradually after melting. Upon analysis, it showed: saponification value, 141.2; palmitic acid, 37.84 percent, and glycerids as tripalmitin, 28.03 percent.
Carbohydrates of the Coffee Berry
There has been considerable diversity of opinion regarding the sugar of coffee. Bell believed the sugar to be of a peculiar species allied to melezitose, but Ewell,[158] G.L. Spencer, and others definitely proved the presence of sucrose in coffee. In fat-free coffee 6 percent of sucrose was found extractable by 70 percent alcohol. Baker[159] claimed that manno-arabinose, or manno-xylose, formed one of the most important constituents of the coffee-berry substance and yielded mannose on hydrolysis. Schultze and Maxwell state that raw coffee contains galactan, mannan, and pentosans, the latter present to the extent of 5 percent in raw and 3 percent in roasted coffee. By distilling coffee with hydrochloric acid Ewell obtained furfurol equivalent to 9 percent pentose. He also obtained a gummy substance which, on hydrolysis, gave rise to a reducing sugar; and as it gave mucic acid and furfurol on oxidation, he concluded that it was a compound of pentose and galactose. In undressed Mysore coffee Commaille[160] found 2.6 percent of glucose and no dextrin. This claim of the presence of glucose in coffee was substantiated by the work of Hlasiwetz,[161] who resolved a caffetannic acid, which he had isolated, into glucose and a peculiar crystallizable acid, C8H8O4, which he named caffeic acid.
The starch content of coffee is very low. Cereals may readily be detected and identified in coffee mixtures by the presence and characteristics of their starch, in view of the fact that coffee (chicory, too) is practically free from starch. On this score it is inadvisable for diabetics to use any of the many cereal substitutes for coffee. It is pertinent to note in this connection that persons suffering from diabetes may sweeten their coffee with saccharin (1⁄2 to 1 grain per cup) or glycerol, thus obtaining perfect satisfaction without endangering their health.
The cellulose in coffee is of a very hard and horny character in the green bean, but it is made softer and more brittle during the process of roasting. It is rather difficult to define under the microscope, particularly after roasting, even though the chief characteristics of the cellular tissue are more or less retained. Coffee cellulose gives a blue color with sulphuric acid and iodin, and is dissolved by an ammoniacal solution of copper oxid. Even after roasting, remnants of the silver skin are always present, the structure of which, a thin membrane with adherent, thick-walled, spindle-shaped, hollow cells, is peculiar to coffee.
The Chemistry of Roasting
The effect of the heat in the roasting of coffee is largely evidenced as a destructive distillation and also as a partial dehydration. At the same time, oxidizing and reducing reactions probably occur within the bean, as well as some polymerization and inter-reactions.
A loss of water is to be expected as the natural outcome of the application of heat; and analyses show that the moisture content of raw coffee varies from 8 to 14 percent, while after roasting it rarely exceeds 3 percent, and frequently falls as low as 0.5 percent. The loss of the original water content of the green bean is not the only moisture loss; for many of the constituents of coffee, notably the carbohydrates, are decomposed upon heating to give off water, so that analysis before and after roasting is no direct indication of the exact amount of water driven off in the process. If it be desired to ascertain this quantity accurately, catching of the products which are driven off and determination of their water content becomes necessary.
The carbohydrates both dehydrate and decompose. The result of the dehydration is the formation of caramel and related products, which comprise the principal coloring matters in coffee infusion. That portion of the carbohydrates known as pentosans gives rise to furfuraldehyde, one of the important components of caffeol.
The effect of roasting upon the fat content of the beans is to reduce its actual weight, but not to change appreciably the percentage present, since the decrease in quantity keeps pace fairly well with the shrinkage. Some of the more volatile fatty acids are driven off, and the fats break down to give a larger percentage of free fatty acids, some light esters, acrolein, and formic acid. If the roast be a very heavy one, or is brought up too rapidly, the fat will come to the surface, through breaking of the fat cells, with a decided alteration in the chemical nature of the fat and with pronounced expansion and cracking.
Decomposition of the caffein acid-salt and considerable sublimation of the caffein also occur. The majority of the caffein undergoes this volatilization unchanged, but a portion of it is probably oxidized with the formation of ammonia, methylamin, di-methylparabanic acid, and carbon dioxid. This reaction partly explains why the amount of caffein recovered from the roaster flues is not commensurate with the amount lost from the roasting coffee; although incomplete condensation is also an important factor. Microscopic examination of the roasted beans will show occasional small crystals of caffein in the indentations on the surface, where they have been deposited during the cooling process.
The compound, or compounds, known as "caffetannic acid" are probably the source of catechol, as the proteins are of ammonia, amins, and pyrrols. The crude fiber and other unnamed constituents of the raw beans react analogously to similar compounds in the destructive distillation of wood, giving rise to acetone, various fatty acids, carbon dioxid and other uncondensable gases, and many compounds of unknown identity.
During the course of roasting and subsequent cooling these decomposition products probably interact and polymerize to form aromatic tar-like materials and other complexes which play an important rôle among the delicate flavors of coffee. In fact, it is not unlikely that these reactions continue throughout the storage time after roasting, and that upon them the deterioration of roasted coffee is largely dependent. Speculation upon what complex compounds are thus formed offers much attraction. A notable one by Sayre[162] postulates the reaction between acrolein and ammonia to give methyl pyridin, which in turn with furfurol forms furfurol vinyl pyridin. This upon reduction would produce the alkaloid, conin, traces of which have been found in coffee.
Although furfuraldehyde is the natural decomposition product of pentosans, furfuryl alcohol is the main furane body of coffee aroma. This would indicate that active reducing conditions prevail within the bean during roasting; and the further fact that carbon monoxid is given off during roasting makes this seem quite probable. If one admits that caffetannic acid exists in the green bean; that upon oxidation it gives viridic acid; and that it is concentrated in the outer layers of the bean, as certain investigators have claimed, then there is chemical proof of the existence of oxidizing conditions about the exterior of the bean. In any event, however, the fact that oxidizing conditions predominate on the external portion of the bean is obvious. Accordingly, our meager knowledge of the chemistry of roasting indicates that while the external layers of the roasting beans are subjected to oxidizing conditions, reducing ones exist in the interior. Future experimentation will, no doubt, prove this to be the case.
Attempts have been made to retain in the beans the volatile products, which normally escape, both by coating previous to roasting[163] and by conducting the process under pressure.[164] However, the results so obtained were not practical, since the cup values were decreased in the majority of cases, and the physiological effects produced were undesirable. In cases where the quality was improved, the gain was not sufficient to recompense the roaster for the additional expense and difficulty of operation.
Various persons have essayed to control the roasting process automatically; but the extreme variance in composition of different coffees, the effect of changing atmospheric conditions, and the lack of constancy in the calorific power of fuels have conspired to defeat the automatic roasting machine.[165] It is even doubtful whether De Mattia's[166] process for roasting until the vapors evolved produce a violet color when passed into a solution of fuchsin decolorized with sulphur dioxid is commercially reliable.
Many patents have been granted for the treatment of coffees immediately prior to or during roasting with the object of thus improving the product. The majority of these depend upon adding solutions of sugar,[167] calcium saccharate,[168] or other carbohydrates,[169] and in the case of Eckhardt,[170] of small percentages of tannic acid and fat. In direct opposition to this latter practise, Jurgens and Westphal[171] apply alkali, ostensibly to lessen the "tannic acid" content. Brougier[172] sprays a solution containing caffein upon the roasting berries; and Potter[173]roasts the coffee together with chicory, effecting a separation at the end.
Ground Coffee Under the Microscope
The exact effect which roasting with sugars has upon the flavor is not well understood; but it is known that it causes the beans to absorb more moisture, due to the hygroscopicity of the caramel formed. For instance, berries roasted with the addition of glucose syrup hold an additional 7 percent of water and give a darker infusion than normally roasted coffee. When the green coffee is glazed with cane sugar prior to roasting, the losses during the process are much higher than ordinarily, on account of the higher temperature required to attain the desired results. Losses for ordinary coffee taken to a 16-percent roast are 9.7 percent of the original fat and 21.1 percent of the original caffein; while for "sugar glazed" coffee the losses were 18.3 percent of the original fat and 44.3 percent of the original caffein, using 8 to 9 percent sugar with Java coffee.
Grinding and Packaging
It is a curious fact that green coffee improves upon aging, whereas after roasting it deteriorates with time. Even when packed in the best containers, age shows to a disadvantage on the roasted bean. This is due to a number of causes, among which are oxidation, volatilization of the aroma, absorption of moisture and consequent hydrolysis, and alteration in the character of the aromatic principles. Doolittle and Wright[174] in the course of some extensive experiments found that roasted coffee showed a continual gain in weight throughout 60 weeks, this gain being mostly due to moisture absorption. An investigation by Gould[175] also demonstrated that roasted coffee gives off carbon dioxid and carbon monoxid upon standing. The latter, apparently produced during roasting and retained by the cellular structure of the bean, diffuses therefrom; whereas the former comes from an ante-roasting decomposition of unstable compounds present.[176]
The surface of the whole bean forms a natural protection against atmospheric influences, and as soon as this is broken, deterioration sets in. On this account, coffee should be ground immediately before extraction if maximum efficiency is to be obtained. The cells of the beans tend to retain the fugacious aromatic principles to a certain extent; so that the more of these which are broken in grinding, the greater will be the initial loss and the more rapid the vitiation of the coffee. It might, therefore, seem desirable to grind coarsely in order to avoid this as much as possible. However, the coarser the grind, the slower and more incomplete will be the extraction. A patent[177] has been granted for a grind which contains about 90 percent fine coffee and 10 percent coarse, the patentee's claim being that in his "irregular grind" the coarse coffee retains enough of the volatile constituents to flavor the beverage, while the fine coffee gives a very high extraction, thus giving an efficient brew without sacrificing individuality.
In packaging roasted coffee the whole bean is naturally the best form to employ, but if the coffee is ground first, King[178] found that deterioration is most rapid with the coarse ground coffee, the speed decreasing with the size of the ground particles. He explains this on the ground of "ventilation"—the finer the grind, the closer the particles pack together, the less the circulation of air through the mass, and the smaller the amount of aroma which is carried away. He also found that glass makes the best container for coffee, with the tin can, and the foil-lined bag with an inner lining of glassine, not greatly inferior.
Considerable publicity has been given recently to the method of packing coffee in a sealed tin under reduced pressure. While thus packing in a partial vacuum undoubtedly retards oxidation and precludes escape of aroma from the original package, it would seem likely to hasten the initial volatilizing of the aroma. Also, it would appear from Gould's[179] work that roasted coffee evolves carbon dioxid until a certain positive pressure is attained, regardless of the initial pressure in the container. Accordingly, vacuum-packing apparently enhances decomposition of certain constituents of coffee. Whether this result is beneficial or otherwise is not quite clear.
Brewing
The old-time boiling method of making coffee has gone out of style, because the average consumer is becoming aware of the fact that it does not give a drink of maximum efficiency. Boiling the ground coffee with water results in a large loss of aromatic principles by steam distillation, a partial hydrolysis of insoluble portions of the grounds, and a subsequent extraction of the products thus formed, which give a bitter flavor to the beverage. Also, the maintenance of a high temperature by the direct application of heat has a deleterious effect upon the substances in solution. This is also true in the case of the pumping percolator, and any other device wherein the solution is caused to pass directly into steam at the point where heat is applied. Warm and cold water extract about the same amount of material from coffee; but with different rates of speed, an increase in temperature decreasing the time necessary to effect the desired result.
It is a well known fact that re-warming a coffee brew has an undesirable effect upon it. This is very probably due to the precipitation of some of the water-soluble proteins when the solution cools, and their subsequent decomposition when heat is applied directly to them in reheating the solution. The absorption of air by the solution upon cooling, with attendant oxidation, which is accentuated by the application of heat in re-warming, must also be considered. It is likewise probable that when an extract of coffee cools upon standing, some of the aromatic principles separate out and are lost by volatilization.
The method of extracting coffee which gives the most satisfaction is practised by using a grind just coarse enough to retain the individualistic flavoring components, retaining the ground coffee in a fine cloth bag, as in the urn system, or on a filter paper, as in the Tricolator, and pouring water at boiling temperature over the coffee. During the extraction, a top should be kept on the device to minimize volatilization, and the temperature of the extract should be maintained constant at about 200° F. after being made. Whether a repouring is necessary or not is dependent upon the speed with which the water passes through the coffee, which in turn is controlled by the fineness of the grind and of the filtering medium.
The Water Extract
Although many analyses of the whole coffee bean are available, but little work has been reported upon the aqueous extracts. The total water extract of roasted coffee varies from 20 to 31 percent in different kinds of coffee. The following analysis of the extract from a Santos coffee may be taken as a fair average example of the water-soluble material.[180]
| Table IV—Analysis of Santos Coffee Extract (Dry Basis) | |
| Ether extract, fixed | 1.06% |
| Total nitrogen | 1.06% |
| Caffein | 1.06% |
| Crude fiber | 1.06% |
| Total ash | 1.06% |
| Reducing sugar | 1.06% |
| Caffetannic acid | 1.06% |
| Protein | 1.06% |
It is difficult to make the trade terms, such as acidity, astringency, etc., used in describing a cup of coffee, conform with the chemical meanings of the same terms. However, a fair explanation of the cause of some of these qualities can be made. Careful work by Warnier[181] showed the actual acidities of some East India coffees to be:
| Table V—Acidity of Some East India Coffees | |
| Coffee from | Acid Content |
| Sindjai | 0.033% |
| Timor | 0.028% |
| Bauthain | 0.019% |
| Boengei | 0.016% |
| Loewae | 0.021% |
| Waloe Pengenten | 0.018% |
| Kawi Redjo | 0.015% |
| Palman Tjiasem | 0.022% |
| Malang | 0.013% |
These figures may be taken as reliable examples of the true acid content of coffee; and though they seem very low, it is not at all incomprehensible that the acids which they indicate produce the acidity in a cup of coffee. They probably are mainly volatile organic acids, together with other acidic-natured products of roasting. We know that very small quantities of acids are readily detected in fruit juices and beer, and that variation in their percentage is quickly noticed, while the neutralization of this small amount of acidity leaves an insipid drink. Hence, it seems quite likely that this small acid content gives to the coffee brew its essential acidity. A few minor experiments on neutralization have proven that a very insipid beverage is produced by thus treating a coffee infusion.
The body, or what might be called the licorice-like character, of coffee, is due conceivably to the presence of bodies of a glucosidic nature and to caramel. Astringency, or bitterness, is dependent upon the decomposition products of crude fiber and chlorogenic acid, and upon the soluble mineral content of the bean. The degree to which a coffee is sweet-tasting or not is, of course, dependent upon its other characteristics, but probably varies with the reducing sugar content. Aside from the effects of these constituents upon cup quality, the influence of volatile aromatic and flavoring constituents is always evident in the cup valuation, and introduces a controlling factor in the production of an individualistic drink.
Coffee Extracts
The uncertainty of the quality of coffee brews as made from day to day, the inconvenience to the housewife of conducting the extraction, and the inevitable trend of the human race toward labor-saving devices, have combined their influences to produce a demand for a substance which will give a good cup of coffee when added to water. This gave rise to a number of concentrated liquid and solid "extracts of coffee," which, because of their general poor quality, soon brought this type of product into disrepute. This is not surprising; for these preparations were mainly mixtures of caramel and carelessly prepared extracts of chicory, roasted cereals, and cheap coffee.
Liquid extracts of coffee galore have appeared on the market only soon to disappear. Difficulty is experienced in having them maintain their quality over a protracted period of time, primarily due to the hydrolyzing action of water on the dissolved substances. They also ferment readily, although a small percentage of preservative, such as benzoate of soda, will halt spoilage.[182]
So much trouble is not encountered with coffee-extract powders—the so-called "soluble" or "instant" coffees. The majority of these powdered dry extracts do, however, show great affinity for atmospheric moisture. Their hygroscopicity necessitates packing and keeping them in air-tight containers to prevent them running into a solid, slowly soluble mass.
The general method of procedure employed in the preparation of these powders is to extract ground roasted coffee with water, and to evaporate the aqueous solution to dryness with great care. The major difficulty which seems to arise is that the heat needed to effect evaporation changes the character of the soluble material, at the same time driving off some volatile constituents which are essential to a natural flavor. Many complex and clever processes have been developed for avoiding these difficulties, and quite a number of patents on processes, and several on the resultant product, have been allowed; but the commercial production of a soluble coffee of freshly-brewed-coffee-duplicating-power is yet to be accomplished. However, there are now on the market several coffee-extract powders which dissolve readily in water, giving quite a fair approximation of freshly brewed coffee. The improvement shown since they first appeared augurs well for the eventual attainment of their ultimate goal.
Adulterants and Substitutes
There would appear to be three reasons why substitutes for coffee are sought—the high cost, or absence, of the real product; the acquiring of a preferential taste, by the consumer, for the substitute; and the injurious effects of coffee when used to excess. Makers of coffee substitutes usually emphasize the latter reason; but many substitutes, which are, or have been, on the market, seem to depend for their existence on the other two. Properly speaking, there are scarcely any real substitutes for coffee. The substances used to replace it are mostly like it only in appearance, and barely simulate it in taste. Besides, many of them are not used alone, but are mixed with real coffee as adulterants.
The two main coffee substitutes are chicory and cereals. Chicory, succory, Cichorium Intybus, is a perennial plant, growing to a height of about three feet, bearing blue flowers, having a long tap root, and possessing a foliage which is sometimes used as cattle food. The plant is cultivated generally for the sake of its root, which is cut into slices, kiln-dried, and then roasted in the same manner as coffee, usually with the addition of a small proportion of some kind of fat. The preparation and use of roasted chicory originated in Holland, about 1750. Fresh chicory[183] contains about 77 percent water, 7.5 gummy matter, 1.1 of glucose, 4.0 of bitter extractive, 0.6 fat, 9.0 cellulose, inulin and fiber, and 0.8 ash. Pure roasted chicory[184] contains 74.2 percent water-soluble material, comprised of 16.3 percent water, 26.1 glucose, 9.6 dextrin and inulin, 3.2 protein, 16.4 coloring matter, and 2.6 ash; and 25.8 percent insoluble substances, namely, 3.2 percent protein, 5.7 fat, 12.3 cellulose, and 4.6 ash. The effect of roasting upon chicory is to drive off a large percentage of water, increasing the reducing sugars, changing a large proportion of the bitter extractives and inulin, and forming dextrin and caramel as well as the characteristic chicory flavor.
The cereal substitutes contain almost every type of grain, mainly wheat, rye, oats, buckwheat, and bran. They are prepared in two general ways, by roasting the grains, or the mixtures of grains, with or without the addition of such substances as sugar, molasses, tannin, citric acid, etc., or by first making the floured grains into a dough, and then baking, grinding, and roasting. Prior to these treatments, the grains may be subjected to a variety of other treatments, such as impregnation with various compounds, or germination. The effect of roasting on these grains and other substitutes is the production of a destructive distillation, as in the case of coffee; the crude fiber, starches, and other carbohydrates, etc., being decomposed, with the production of a flavor and an aroma faintly suggesting coffee.
The number, of other substitutes and imitations which have been employed are too numerous to warrant their complete description; but it will prove interesting to enumerate a few of the more important ones, such as malt, starch, acorns, soya beans, beet roots, figs, prunes, date stones, ivory nuts, sweet potatoes, beets, carrots, peas, and other vegetables, bananas, dried pears, grape seeds, dandelion roots, rinds of citrus fruits, lupine seeds, whey, peanuts, juniper berries, rice, the fruit of the wax palm, cola nuts, chick peas, cassia seeds, and the seeds of any trees and plants indigenous to the country in which the substitute is produced.
Aside from adulteration by mixing substitutes with ground coffee, and an occasional case of factitious molded berries, the main sophistications of coffee comprise coating and coloring the whole beans. Coloring of green and roasted coffees is practised to conceal damaged and inferior beans. Lead and zinc chromates, Prussian blue, ferric oxid, coal-tar colors, and other substances of a harmful nature, have been employed for this purpose, being made to adhere to the beans with adhesives. As glazes and coatings, a variety of substances have been employed, such as butter, margarin, vegetable oils, paraffin, vaseline, gums, dextrin, gelatin, resins, glue, milk, glycerin, salt, sodium bicarbonate, vinegar, Irish moss, isinglass, albumen, etc. It is usually claimed that coating is applied to retain aroma and to act as a clarifying agent; but the real reasons are usually to increase weight through absorption of water, to render low-grade coffees more attractive, to eliminate by-products, and to assist in advertising.
METHODS OF ANALYSIS OF COFFEES[185]
(Official and Tentative)
(Sole responsibility for any errors in compilation or printing of these methods is assumed by the author.)
Green Coffee
1. Macroscopic Examination—Tentative
A macroscopic examination is usually sufficient to show the presence of excessive amounts of black and blighted coffee beans, coffee hulls, stones, and other foreign matter. These can be separated by hand-picking and determined gravi-metrically.
2. Coloring Matters—Tentative
Shake vigorously 100 grams or more of the sample with cold water or 70 percent alcohol by volume. Strain through a coarse sieve and allow to settle. Identify soluble colors in the solution and insoluble pigments in the sediment.
Roasted Coffee
3. Macroscopic Examination—Tentative
Artificial coffee beans are apparent from their exact regularity of form. Roasted legumes and lumps of chicory, when present in whole roasted coffee, can be picked out and identified microscopically. In the case of ground coffee, sprinkle some of the sample on cold water and stir lightly. Fragments of pure coffee, if not over-roasted, will float; while fragments of chicory, legumes, cereals, etc., will sink immediately, chicory coloring the water a decided brown. In all cases identify the particles that sink by microscopical examination.
4. Preparation of Sample—Official
Grind the sample to pass through a sieve having holes 0.5 mm. in diameter and preserve in a tightly stoppered bottle.
5. Moisture—Tentative
Dry 5 grams of the sample at 105°—110°C. for 5 hours and subsequent periods of an hour each until constant weight is obtained. The same procedure may be used, drying in vacuo at the temperature of boiling water. In the case of whole coffee, grind rapidly to a coarse powder and weigh at once portions for the determination without sifting and without unnecessary exposure to the air.
6. Soluble Solids—Tentative
Place 4 grams of the sample in a 200-cc. flask, add water to the mark, and allow the mass to infuse for eight hours, with occasional shaking; let stand 16 hours longer without shaking, filter, evaporate 50 cc. of filtrate to dryness in a flat-bottomed dish, dry at 100° C., cool and weigh.
7. Ash—Official
Char a quantity of the substance, representing about 2 grams of the dry material, and burn until free of carbon at a low heat, not to exceed dull redness. If a carbon-free ash can not be obtained in this manner, exhaust the charred mass with hot water, collect the insoluble residue on a filter, burn till the ash is white or nearly so, and then add the filtrate to the ash and evaporate to dryness. Heat to low redness, until ash is white or grayish white, and weigh.
8. Ash Insoluble in Acid—Official
Boil the water-insoluble residue, obtained as directed under 9, or the total ash obtained as directed under 7, with 25 cc. of 10-percent hydrochloric acid (sp. gr. 1.050) for 5 minutes, collect the insoluble matter on a Gooch crucible or an ashless filter, wash with hot water, ignite and weigh.
9. Soluble and Insoluble Ash—Official
Heat 5 to 10 grams of the sample in a platinum dish of from 50 to 100 cc. capacity at 100° C. until the water is expelled, and add a few drops of pure olive oil and heat slowly over a flame until swelling ceases. Then place the dish in a muffle and heat at low redness until a white ash is obtained. Add water to the ash, in the platinum dish, heat nearly to boiling, filter through ash-free filter paper, and wash with hot water until the combined filtrate and washings measure to about 60 cc. Return the filter and contents to the platinum dish, carefully ignite, cool and weigh. Compute percentages of water-insoluble ash and water-soluble ash.
10. Alkalinity of the Soluble Ash—Official
Cool the filtrate from 9 and titrate with N/10 hydrochloric acid, using methyl orange as an indicator.
Express the alkalinity in terms of the number of cc. of N/10 acid per 1 gram of the sample.
11. Soluble Phosphoric Acid in the Ash—Official
Acidify the solution of soluble ash, obtained in 9, with dilute nitric acid and determine phosphoric acid (P2O5). For percentages up to 5 use an aliquot corresponding to 0.4 gram of substance, for percentages between 5 and 20 use an aliquot corresponding to 0.2 gram of substance, and for percentages above 20 use an aliquot corresponding to 0.1 gram of substance. Dilute to 75–100 cc., heat in a water-bath to 60°–65° C., and for percentages below 5 add 20–25 cc. of freshly filtered molybdate solution. For percentages between 5 and 20 add 30–35 cc. of molybdate solution. For percentages greater than 20 add sufficient molybdate solution to insure complete precipitation. Stir, let stand in the bath for about 15 minutes, filter at once, wash once or twice with water by decantation, using 25–30 cc. each time, agitate the precipitate thoroughly and allow to settle; transfer to the filter and wash with cold water until the filtrate from two fillings of the filter yields a pink color upon the addition of phenolphthalein and one drop of the standard alkali. Transfer the precipitate and filter to the beaker, or precipitating vessel, dissolve the precipitate in a small excess of the standard alkali, add a few drops of phenolphthalein solution, and titrate with the standard acid.
12. Insoluble Phosphoric Acid in the Ash—Official
Determine phosphoric acid (P2O5) in the Insoluble ash by the foregoing method.
13. Chlorides—Official
Moisten 5 grams of the substance in a platinum dish with 20 cc. of a 5-percent solution of sodium carbonate, evaporate to dryness and ignite as thoroughly as possible at a temperature not exceeding dull redness. Extract with hot water, filter and wash. Return the residue to the platinum dish and ignite to an ash; dissolve in nitric acid, and add this solution to the water extract. Add a known volume of N/10 silver nitrate in slight excess to the combined solutions. Stir well, filter and wash the silver chloride precipitate thoroughly. To the filtrate and washings add 5 cc. of a saturated solution of ferric alum and a few cc. of nitric acid. Titrate the excess silver with N/10 ammonium or potassium thiocyanate until a permanent light brown color appears. Calculate the amount of chlorin.
14. Caffein—The Fendler and Stüber Method—Tentative
Pulverize the coffee to pass without residue through a sieve having circular openings 1 mm. in diameter. Treat a 10-gram sample with 10 grams of 10-percent ammonium hydroxid and 200 grams of chloroform in a glass-stoppered bottle and shake continuously by machine or hand for one-half hour. Pour the entire contents of the bottle on a 12.5-cm. folded filter, covering with a watch glass. Weigh 150 grams of the filtrate into a 250-cc. flask and evaporate on the steam bath, removing the last chloroform with a blast of air. Digest the residue with 80 cc. of hot water for ten minutes on a steam bath with frequent shaking, and let cool. Treat the solution with 20 cc. (for roasted coffee) or 10 cc. (for unroasted coffee) of 1-percent potassium permanganate and let stand for 15 minutes at room temperature. Add 2 cc. of 3-percent hydrogen peroxid (containing 1 cc. of glacial acetic acid in 100 cc.). If the liquid is still red or reddish, add hydrogen peroxid, 1 cc. at a time, until the excess of potassium permanganate is destroyed. Place the flask on the steam bath for 15 minutes, adding hydrogen peroxid in 0.5-cc. portions until the liquid becomes no lighter in color. Cool and filter into a separatory funnel, washing with cold water. Extract four times with 25 cc. of chloroform. Evaporate the chloroform extract from a weighed flask with aid of an air blast and dry at 100° C. to constant weight (one-half hour is usually sufficient). Weigh the residue as caffein and calculate on 7.5 grams of coffee. Test the purity of the residue by determining nitrogen and multiplying by 3.464 to obtain caffein.
15. Caffein—Power-Chestnut Method—Official
Moisten 10 grams of the finely powdered sample with alcohol, transfer to a Soxhlet, or similar extraction apparatus, and extract with alcohol for 8 hours. (Care should be exercised to assure complete extraction.) Transfer the extract with the aid of hot water to a porcelain dish containing 10 grams of heavy magnesium oxid in suspension in 100 cc. of water. (This reagent should meet the U.S.P. requirements.) Evaporate slowly on the steam bath with frequent stirring to a dry, powdery mass. Rub the residue with a pestle into a paste with boiling water. Transfer with hot water to a smooth filter, cleaning the dish with a rubber-tipped glass rod. Collect the filtrate in a liter flask marked at 250 cc. and wash with boiling water until the filtrate reaches the mark. Add 10 cc. of 10-percent sulphuric acid and boil gently for 30 minutes with a funnel in the neck of the flask. Cool and filter through a moistened double paper into a separatory funnel and wash with small portions of 0.5-percent sulphuric acid. Extract with six successive 25-cc. portions of chloroform. Wash the combined chloroform extracts in a separatory funnel with 5 cc. of 1-percent potassium hydroxid solution. Filter the chloroform into an Erlenmeyer flask. Wash the potassium hydroxid with 2 portions of chloroform of 10 cc. each, adding them to the flask together with the chloroform washings of the filter paper. Evaporate or distil on the steam bath to a small volume (10–15 cc.), transfer with chloroform to a tared beaker, evaporate carefully, dry for 30 minutes in a water oven, and weigh. The purity of the residue can be tested by determining nitrogen and multiplying by the factor 3.464.
16. Crude Fiber—Official
Prepare solutions of sulphuric acid and sodium hydroxid of exactly 1.25-percent strength, determined by titration. Extract a quantity of the substance representing about 2 grams of the dry material with ordinary ether, or use residue from the determination of the ether extract. To this residue in a 500-cc. flask add 200 cc. of boiling 1.25-percent sulphuric acid; connect the flask with a reflux condenser, the tube of which passes only a short distance beyond the rubber stopper into the flask, or simply cover a tall conical flask, which is well suited for this determination, with a watch glass or short stemmed funnel. Boil at once and continue boiling gently for thirty minutes. A blast of air conducted into the flask may serve to reduce the frothing of the liquid. Filter through linen, and wash with boiling water until the washings are no longer acid; rinse the substance back into the flask with 200 cc. of the boiling 1.25-percent solution of sodium hydroxid free, or nearly so, of sodium carbonate; boil at once and continue boiling gently for thirty minutes in the same manner as directed above for the treatment with acid. Filter at once rapidly, wash with boiling water until the washings are neutral. The last filtration may be performed upon a Gooch crucible, a linen filter, or a tared filter paper. If a linen filter is used, rinse the crude fiber, after washing is completed, into a flat-bottomed platinum dish by means of a jet of water; evaporate to dryness on a steam bath, dry to constant weight at 110° C., weigh, incinerate completely, and weigh again. The loss in weight is considered to be crude fiber. If a tared filter paper is used, weigh in a weighing bottle. In any case, the crude fiber after drying to constant weight at 110° C., must be incinerated and the amount of the ash deducted from the original weight.
17. Starch—Tentative
Extract 5 grams of the finely pulverized sample on a hardened filter with five successive portions (10 cc. each) of ether, wash with small portions of 95-percent alcohol by volume until a total of 200 cc. have passed through, place the residue in a beaker with 50 cc. of water, immerse the beaker in boiling water and stir constantly for 15 minutes or until all the starch is gelatinized; cool to 55° C., add 20 cc. of malt extract and maintain at this temperature for an hour. Heat again to boiling for a few minutes, cool to 55° C., add 20 cc. of malt extract and maintain at this temperature for an hour or until the residue treated with iodin shows no blue color upon microscopic examination. Cool, make up directly to 250 cc., and filter. Place 200 cc. of the filtrate in a flask with 20 cc. of hydrochloric acid (sp. gr. 1.125); connect with a reflux condenser and heat in a boiling water bath for 2.5 hours. Cool, nearly neutralize with sodium hydroxid solution, and make up to 500 cc. Mix the solution well, pour through a dry filter and determine the dextrose in an aliquot. Conduct a blank determination upon the same volume of the malt extract as used upon the sample, and correct the weight of reduced copper accordingly. The weight of the dextrose obtained multiplied by 0.90 gives the weight of starch.
18. Sugars—Tentative
See original.[186]
19. Petroleum Ether Extract—Official
Dry 2 grams of coffee at 100° C., extract with petroleum ether (boiling point 35° to 50° C.) for 16 hours, evaporate the solvent, dry the residue at 100° C., cool, and weigh.
20. Total Acidity—Tentative
Treat 10 grams of the sample, prepared as directed under 4, with 75 cc. of 80-percent alcohol by volume in an Erlenmeyer flask, stopper, and allow to stand 16 hours, shaking occasionally. Filter and transfer an aliquot of the filtrate (25 cc. in the case of green coffee, 10 cc. in the case of roasted coffee) to a beaker, dilute to about 100 cc. with water and titrate with N/10 alkali, using phenolphthalein as an indicator. Express the result as the number of cc. of N/10 alkali required to neutralize the acidity of 100 grams of the sample.
21. Volatile Acidity—Tentative
Into a volatile acid apparatus introduce a few glass beads, and over these place 20 grams of the unground sample. Add 100 cc. of recently boiled water to the sample, place a sufficient quantity of recently boiled water in the outer flask and distil until the distillate is no longer acid to litmus paper. Usually 100 cc. of distillate will be collected. Titrate the distillate with N/10 alkali, using phenolphthalein as an indicator. Express the result as the number of cc. of N/10 alkali required to neutralize the acidity of 100 grams of the sample.
Unofficial Methods
22. Protein
Determine nitrogen in 3 grams of the sample by the Kjeldahl or Gunning method. This gives the total nitrogen due to both the proteids and the caffein. To obtain the protein nitrogen, subtract from the total nitrogen the nitrogen due to caffein, obtained by direct determination on the separated caffein or by calculation (caffein divided by 3.464 gives nitrogen). Multiply by 6.25 to obtain the amount of protein.
23. Ten Percent Extract—McGill Method
Weigh into a tared flask the equivalent of 10 grains of the dried substance, add water until the contents of the flask weigh 110 grams, connect with a reflux condenser and heat, beginning the boiling in 10 to 15 minutes. Boil for 1 hour, cool for 15 minutes, weigh again, making up any loss by the addition of water, filter, and take the specific gravity of the filtrate at 15° C.
According to McGill, a 10-percent extract of pure coffee has a specific gravity of 1.00986 at 15° C., and under the same treatment chicory gives an extract with a specific gravity of 1.02821. In mixtures of coffee and chicory the approximate percentage of chicory may be calculated by the following formula:
(1.02821 – sp. gr.)
Percent of chicory = 100 —————————
0.01835
Percent of chicory = 100 —————————
0.01835
The index of refraction of the above solution may be taken with the Zeiss immersion refractometer or with the Abbe refractometer.
With a 10-percent coffee extract, nd 20° = 1.3377.
With a 10-percent chicory extract, nd 20° = 1.3448.
Determinations of the solids, ash, sugar, nitrogen, etc., may be made in the 10-percent extract, if desired.
24. Caffetannic Acid—Krug's Method[187]
Treat 2 grains of the coffee with 10 cc. of water and digest for 36 hours; add 25 cc. of 90-percent alcohol and digest 24 hours more, filter, and wash with 90-percent alcohol. The filtrate contains tannin, caffein, color, and fat. Heat the filtrate to the boiling point and add a saturated solution of lead acetate. If this is carefully done, a caffetannate of lead will be precipitated containing 49 percent of lead. As soon as the precipitate has become flocculent, collect on a tared filter, wash with 90-percent alcohol until free from lead, wash with ether, dry and weigh. The precipitate multiplied by 0.51597 gives the weight of the caffetannic acid.
