Popular Science Monthly/Volume 26/February 1885/The Chemistry of Cookery XX
THE paternal tenderness with which wine is regarded, both by its producers and consumers, is amusing. They speak of it as being "sick," describe its "diseases" and their remedies as though it were a sentient being; and its diseases, like our own, are now attributed to bacilli, bacteria, or other microbia.
Pasteur, who has worked out this question of the origin of diseases in wine as he is so well known to have done in animals, recommends (in papers read before the French Academy in May and August, 1865) that these microbia be "killed" by filling the bottles close up to the cork, which is thrust in just with sufficient firmness to allow the wine on expanding to force it out a little, but not entirely, thus preventing any air from entering the bottle. The bottles are then placed in a chamber heated to temperatures ranging from 45° to 100° C. (113° to 212° Fahr.), where they remain for an hour or two. They are then set aside, allowed to cool, and the cork driven in. It is said that this treatment kills the microbia, gives to the wine an increased bouquet and improved color—in fact, ages it considerably. Both old and new wines may be thus treated.
I simply state this on the authority of Pasteur, having made no direct experiments or observations on these diseases, which he describes as resulting in acetification, ropiness, bitterness, and decay or decomposition.
There is, however, another kind of sickness which I have studied, both experimentally and theoretically. I refer to the temporary sickness which sometimes occurs to rich wines when they are moved from one cellar to another, and to wines when newly exported from their native climate to our own. The wines that are the most subject to such sickness are those that are the most genuine—the natural, unsophisticated wines, those that have not been subjected to "fortification," to "vinage," to "plastering," "sulphuring," etc.—processes of cookery to be presently described.
This sickness shows itself by the wine becoming turbid, or opalescent, then throwing down either a crust or a loose, troublesome sediment.
Those of my readers who are sufficiently interested in this subject to care to study it practically should make the following experiment:
Dissolve in distilled water, or, better, in water slightly acidulated with hydrochloric acid, as much cream of tartar as will saturate it. This is best done by heating the water, agitating an excess of cream of tartar in it, then allowing the water to cool, the excess of salt to subside, and pouring off the clear solution, Now add to this solution, while quite clear and bright, a little clear brandy, whisky, or other spirit, and mix them by shaking. The solution will become "sick," like the wine. Why is this?
It depends upon the fact that the bitartrate of potash, or cream of tartar, is soluble to some extent in water, but almost insoluble in alcohol. In a mixture of alcohol-and-water its solubility is intermediate —the more alcohol the smaller the quantity that can be held in solution (hydrochloric and most other acids, excepting tartaric, increase its solubility in water). Thus, if we have a saturated solution of this salt either in pure water or acidulated water or wine, the addition of alcohol throws some of it down in solid form, and this makes the solution sick, or turbid. When pure water or acidulated water is used, as in the above-described experiment, crystals of the salt are freely formed, and fall down readily; but with a complex liquid like wine, containing saccharine and mucilaginous matter, the precipitation takes place very slowly; the particles are excessively minute, and become entangled with the mucilage, etc., and thus remain suspended for a long time, maintaining the turbidity accordingly.
Now, this bitartrate of potash is the characteristic natural salt of the grape, and its unfermented juice is saturated with it. As fermentation proceeds, and the sugar of the grape-juice is converted into alcohol, the capacity of the juice for holding the salt in solution diminishes, and it is gradually thrown down. But it does not fall alone. It carries with it some of the coloring and extractive matter of the grape-juice. This precipitate, in its crude state called argol, or roher Weinstein, is the source from which we obtain the tartaric acid of commerce, the cream of tartar, and other salts of tartaric acid.
Now let us suppose that we have a natural, unsophisticated wine. It is evident that it is saturated with the tartrate, since only so much argol was thrown down during fermentation as it was unable to retain. It is further evident that if such a wine has not been exhaustively fermented, i. e., still contains some of the original grape-sugar, and, if any further fermentation of this sugar takes place, the capacity of the mixture for holding the tartrate in solution becomes diminished, and a further precipitation must occur. This precipitation will come down very slowly, will consist not merely of pure crystals of cream of tartar, but of minute particles carrying with it some coloring-matter, extractives, etc., and thus spoiling the brilliancy of the wine, making it more or less turbid.
But this is not all. Boiling water dissolves 1 of its weight of cream of tartar, cold water only 1 and, at intermediate temperatures, intermediate quantities. Therefore, if we lower the temperature of a saturated solution, precipitation occurs. Hence, the sickening of wine due to change of cellars or change of climate, even when no further fermentation occurs. The lighter the wine, i. e., the less alcohol it contains naturally, the more tartrate it contains, and the greater the liability to this source of sickness.
This, then, is the temporary sickness to which I have referred. I have proved the truth of this theory by filtering such sickened wine through laboratory filtering-paper, thereby rendering it transparent, and obtaining on the paper all the guilty disturbing matter. I found it to be a kind of argol, but containing a much larger proportion of extractive and coloring matter, and a smaller proportion of tartrate, than the argol of commerce. I operated upon rich new Catalan wine.
This brings me at once to the source or origin of a sort of wine-cookery by no means so legitimate as the Pasteuring already described, as it frequently amounts to serious adulteration.
The wine-merchants are here the victims of their customers, who demand an amount of transparency that is simply impossible as a permanent condition of unsophisticated grape-wine. To anybody who has any knowledge of the chemistry of wine, nothing can be more ludicrous than the antics of the pretending connoisseur of wine who holds his glass up to the light, shuts one eye (even at the stage before double vision commences), and admires the brilliancy of the liquid, this very brilliancy being, in nineteen samples out of twenty, the evidence of adulteration, cookery, or sophistication of some kind. Genuine wine made from pure grape-juice without chemical manipulation is a liquid that is never reliably clear, for the reasons above stated. Partial precipitation, sufficient to produce opalescence, is continually taking place, and therefore the brilliancy demanded is obtained by substituting the natural and wholesome tartrate by salts of mineral acids, and even by the free mineral acid itself. At one time I deemed this latter adulteration impossible, but have been convinced by direct examination of samples of high-priced (mark this, not cheap) dry sherries that they contained free sulphuric and sulphurous acid.
The action of this free mineral acid on the wine will be understood by what I have already explained concerning the solubility of the bitartrate of potash. This solubility is greatly increased by a little of such acid, and therefore the transparency of the wine is by such addition rendered stable, unaffected by changes of temperature.
But what is the effect of such mineral acid on the drinker of the wine? If he is in any degree predisposed to gout, rheumatism, stone, or any of the lithic-acid diseases, his life is sacrificed, with preceding tortures of the most horrible kind. It has been stated, and probably with truth, that the late Emperor Napoleon III drank dry sherry, and was a martyr of this kind, I repeat emphatically that high-priced dry sherries are far worse than cheap Marsala, both as regards the quantity they contain of sulphates and free acid.
Anybody who doubts this may convince himself by simply purchasing a little chloride of barium, dissolving it in distilled water, and adding to the sample of wine to be tested a few drops of this solution.
Pure wine, containing its full supply of natural tartrate, will become cloudy to a small extent, and gradually. A small precipitate will be formed by the tartrate. The wine that contains either free sulphuric acid or any of its compounds will yield immediately a copious white precipitate like chalk, but much more dense. This is sulphate of baryta. The experiment may be made in a common wineglass, but better in a cylindrical test-tube, as, by using in this a fixed quantity in each experiment, a rough notion of the relative quantity of sulphate may be formed by the depth of the white layer after all has come down. To determine this accurately, the wine, after applying the test, should be filtered through proper filtering-paper, and the precipitate and paper burned in a platinum or porcelain crucible and then weighed; but this demands apparatus not always available, and some technical skill. The simple demonstration of the copious precipitation is instructive, and those of my readers who are practical chemists, but have not yet applied this test to such wines, will be astonished, as I was, at the amount of precipitation.
I may add that my first experience was upon a sample of dry sherry, brought to me by a friend who bought his wine of a most respectable wine-merchant, and paid a high price for it, but found that it disagreed with him; since that I have tested scores of samples, some of the finest in the market, sent to me by a thoroughly conscientious importer as the best he could obtain, and these contained sulphate of potash instead of bitartrate.
My friend, the sherry-merchant, could not account for it, though he was most anxious to do so. This was about three years ago. By dint of inquiry and cross-examination of experts in the wine-trade, I have, I believe, discovered the origin of the sulphate of potash that is contained in the samples that the British wine-merchant sells as he buys, and conscientiously believes to be pure. I will state particulars in my next.
A correspondent writes to the editor asking whether I class cocoa among the stimulants. So far as I am able to learn, it should not be so classed, but I can not speak absolutely. Mere chemistry supplies no answer to this question. It is purely a physiological subject, to be studied by observation of effects. Such observations may be made by anybody whose system has not become "tolerant" of the substance in question. My own experience of cocoa in all its forms is that it is not stimulating in any sensible degree. I have acquired no habit of using it, and yet I can enjoy a rich cup or bowl of cocoa or chocolate just before bed-time without losing any sleep. When I am occasionally betrayed into taking a late cup of coffee or tea, I repent it for some hours after going to bed. My inquiries among other people, who are not under the influence of that most powerful of all arguments, the logic of inclination, have confirmed my own experience.
I should, however, add that some authorities have attributed exhilarating properties to the theobromine or nitrogenous alkaloid of cocoa. Its composition nearly resembles that of theine, as the following (from Johnstone) shows:
It exists in the cocoa-bean in about the same proportion as the theine in tea, but in making a cup of cocoa we use a much greater weight of cocoa than of tea in a cup of tea. If, therefore, the properties of theobromine were similar to those of theine, we should feel the stimulating effects much more decidedly.
The alkaloid of tea and coffee in its pure state has been administered to animals, and found to produce paralysis, but I am not aware that theobromine has acted similarly.
Another essential difference between cocoa and tea or coffee is that cocoa is, strictly speaking, a food. We do not merely make an infusion of the cacao-bean, but eat it bodily in the form of a soup. It is highly nutritious, one of the most nutritious foods in common use. When traveling on foot in mountainous and other regions, where there was a risk of spending the night al fresco and supperless, I have usually carried a cake of chocolate in my knapsack, as the most portable and unchangeable form of concentrated nutriment, and have found it most valuable. On one occasion I went astray on the Kjolenfjeld, in Norway, and struggled for about twenty-four hours without food or shelter. I had no chocolate then, and sorely repented my improvidence. Many other pedestrians have tried chocolate in like manner, and all I know have commended its great "staying" properties, simply regarded as food. I therefore conclude that Linnæus was not without strong justification in giving it the name of theobroma (food for the gods), but to confirm this practically the pure nut, the whole nut, and nothing but the nut (excepting the milk and sugar added by the consumer), should be used. Some miserable counterfeits are offered — farinaceous paste, flavored with cocoa and sugar. The best sample I have been able to procure is the ship cocoa prepared for the navy. This is nothing but the whole nut unsweetened, ground, and crushed to an impalpable paste. It requires a little boiling, and when milk alone is used, with due proportion of sugar, it is a theohroma. Condensed milk diluted and without further sweetening may be used.
In my last I promised the results of my investigations concerning the source of the sulphate of potash that I found replacing the natural tartrate in so many samples of sherry.
At first I hunted up all the information I could obtain from books concerning the manufacture of sherry, and learned that the grapes are usually sprinkled with a little powdered sulphur as they are placed in the vats prior to stamping. The quantity thus added, however, is quite insufficient to account for the sulphur compounds in the samples of wine I examined. Another source is described in the books—that from the sulphuring the casks. This process consists simply of burning sulphur inside a partially-filled or empty cask, until the exhaustion of free oxygen and its replacement by sulphurous acid renders further combustion impossible. The cask is then filled with the wine. This would add a little of sulphurous acid, but still not sufficient.
Then comes the "plastering," or intentional addition of gypsum (plaster of Paris). This, if largely carried out, is sufficient to explain the complete conversion of the natural tartrates into sulphates of potash, but such plastering is admitted to be an adulteration or sophistication, and the best makers deny their use of it. I obtained samples of sherry from a reliable source, which I have no doubt the shipper honestly believed to have been subjected to no such deliberate plastering; still, from these came down an extravagantly excessive precipitate on the addition of chloride-of-barium solution.
At last I learned that "Spanish earth" was used in the fining. Why Spanish earth in preference to isinglass or white of egg, which are quite unobjectionable and very efficient? To this question I could get no satisfactory answer directly, but learned vaguely that the fining produced by the white of egg, though complete at the time, was not permanent, while that effected by Spanish earth, containing much sulphate of lime, is permanent. The brilliancy thus obtained is not lost by age or variations of temperature, and the dry sherries thus cooked are preferred by English wine-drinkers.
Here, then, is a solution of the mystery. The sulphate of potash which is thus made to replace bitartrate is so readily soluble that neither changes of temperature nor increase of alcohol, due to further fermentation, will throw it down; and thus the wine-merchant, without any guilty intent, and ignorant of what he is really doing, sophisticates the wine, alters its essential composition, and adds an impurity in doing what he supposes to be a mere clarification or removal of impurities.
I have heard of genuine sherries being returned as bad to the shipper because they were genuine, and had been fined without sophistication. Are we to blame the wine-merchant for this? I think not.
My own experience of genuine wines in wine-growing countries teaches me that such wines are rarely brilliant; and the variations of solubility of the natural salt of the grape, which I have already explained, shows why this is the case. If the drinkers of sherry and other white and golden wines would cease to demand the conventional brilliancy, they would soon be supplied with the genuine article, which really costs the wine-merchant less than the cooked product they now insist upon having. This foolish demand of his customers merely gives him a large amount of unnecessary trouble.
So far, the wine-merchant; but how about the consumer? Simply that the substitution of a mineral acid—the sulphuric for a vegetable acid (the tartaric)—supplies him with a precipitant of lithic acid in his own body; that is, provides him with the source of gout, rheumatism, gravel, stone, etc., with which English wine-drinkers are proverbially tortured.
I am the more urgent in propounding this view of the subject because I see plainly that not only the patients, but too commonly their medical advisers, do not understand it. When I was in the midst of these experiments I called upon a clerical neighbor, and found him in his study with his foot on a pillow, and groaning with gout. A decanter of pale, choice, very dry sherry was on the table. He poured out a glass for me and another for himself. I tasted it, and then perpetrated the unheard-of rudeness of denouncing the wine for which my host had paid so high a price. He knew a little chemistry, and I accordingly went home forthwith, brought back some chloride of barium, added it to his choice sherry, and showed him a precipitate which made him shudder. He drank no more dry sherry, and has had no serious relapse of gout.
In this case his medical adviser prohibited port and advised dry sherry.
The following from "The Brewer, Distiller, and Wine Manufacturer," by John Gardner (Churchill's "Technological Handbooks," 1883), supports my view of the position of the wine-maker and wine merchant: "Dupré and Thudicum have shown by experiment that this practice of plastering, as it is called, also reduces the yield of the liquid, as a considerable part of the wine mechanically combines with the gypsum and is lost." When an adulteration—justly so called—is practiced, the object is to enable the perpetrator to obtain an increased profit on selling the commodity at a given price. In this case an opposite result is obtained. The gypsum, or Spanish earth, is used in considerable quantity, and leaves a bulky residuum, which carries away some of the wine with it, and thus increases the cost to the seller of the salable result.
Having referred so often to dry wines, I should explain the chemistry of this so-called dryness. The fermentation of wine is the result of a vegetable growth, that of the yeast, a microscopic fungus (Pencillium glaucum). The must, or juice of the grape, obtains the germ spontaneously—probably from the atmosphere. Two distinct effects are produced by this fermentation or growth of fungus: first, the sugar of the must is converted into alcohol; second, more or less of the albuminous or nitrogenous matter of the must is consumed as food by the fungus. If uninterrupted, this fermentation goes on either until the supply of sufficient sugar is stopped, or until the supply of sufficient albuminous matter is stopped. The relative proportions of these determine which of the two shall be first exhausted.
If the sugar is exhausted before the nitrogenous food of the fungus, a dry wine is produced; if the nitrogenous food is first consumed, the remaining unfermented sugar produces a sweet wine. If the sugar is greatly in excess, a vin de liqueur is the result, such as the Frontignac, Lunel, Rivesaltes, etc., made from the Muscat grape.
The varieties of grape are very numerous. Rusby, in his "Visit to the Vineyards of Spain and France," gives a list of five hundred and seventy varieties, and as far back as 1827 Cavalow enumerated more than fifteen hundred different wines in France alone.
From the above it will be understood that, cœteris paribius, the poorer the grape the drier the wine; or that a given variety of grape will yield a drier wine if grown where it ripens imperfectly, than if grown in a warmer climate. But the quantity of wine obtainable from a given acreage in the cooler climate is less than where the sun is more effective, and thus the naturally dry wines cost more to produce than the naturally sweet wines.
This has promoted a special cookery or artificial drying, the mysteries of which will be discussed in my next.