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[REPRINTED FROM THE JOURNAL OF THE AMERICAN, CHEMICAL SOCIETY, VoL. XVIII., No. 2. FEBRUARY 1896.]

THE USE OF THE CALORIMETER IN DETECTING ADUL- TERATIONS OF BUTTER AND LARD.'

BY EK. A. DE SCHWEINITZ AND JAMES A. EMERY. ’

Received January 3, 1896.

HILE engaged in a study of the comparative value of butters and oleomargarines, it occurred to one of us

that possibly the determinations of their respective heats of combustion might be useful if taken in connection with other data. Prof. Atwater, who has for some time been conducting experiments with an improved calorimeter, very kindly con- sented to burn such samples as might be sent to him. The first results were so interesting that it occurred to us at once that this method might be useful in detecting the adulteration of but- ter with oleomargarine, and also perhaps in distinguishing between lards of different sources andcompound lards. Accord- ingly, some specially selected samples of which duplicates were kept in our laboratory, were sent to Prof. Atwater, and in the case of the butters and oleomargarines the results confirmed our first suppositions. In the use of the lards, however, the results were not so sharply distinctive, but taken in conjunction with other analytical data will prove, as we will endeavor to show,

1 Read at the Cleveland meeting, Dec. 31, 1895.

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CALORIMETER FOR BUTTER AND LARD. 3

exceedingly useful. The samples were forwarded to Prof. Atwater, prepared for combustion, without any description of their character being given except that they were fats. It is well understood that the estimation of the calories is of consider- able use in a determination of the molecular weights of complex molecules and the results which we will report will serve to show, we think, practical application of the use of the bomb calorimeter.

This is best seen by a study of the following tables, which give in detail the examinations that are ordinarily made for oleomargarine and butter (Table I.), and accompanying these examinations the calories per gram. The samples were pre- pared for these latter determinations by washing, melting, filter- ing, and drying the samples at 100° C.

The figures given by different authorities for butter fat, vary slightly. Stohman gives the heat equivalent as determined by the potassium chlorate method as 9.192 small calories per gram, while by the oxygen method it was 9.231 calories per gram. The three samples of pure butter burned were from the follow- ing sources: No. 28, the best butter used by Armour & Co., in the manufacture of butterine. No. 26, was Elgin Creamery butter, and No. 27, obtained from a Virginia gentleman, who sent it as a sample of the best butter made on his place. Nos. 31, 32, and 33, were mixtures of Elgin butter and oleomargarine. The figures obtained for butter fat are a little higher than those Stohman gives for pure butter.

Table IT, 'The steady increase in the calories of the mixtures is in proportion to the amount of oleomargarine added to the butter and this taken in conjunction with the iodine number gives additional confirmatory evidence of the character of the

sample. TABLE II.

MIXTURE COMPOSED OF DEFINITE PROPORTIONS OF ELGIN AND WOOD-

LAWN No. 2°. Actual Theoretical Actual Theoretical combustion combustion

iodine iodine calories calories

Sample. equivalent. equivalent. pergram. pergram. $ E and } W, No. 2°... 43.90 43.76 9-391 9.412 4 F and } W, No. 2°... 48.01 49-77 9.416 9.498

1 E and 2? W, No. 23..- 55.40 55-78 9.491 9.584

4 E. A. DE SCHWEINITZ AND JAMES A. EMERY.

The theoretical calories per gram for the above mixtures as compared with those found are,

Theory. Found. NO. 31 eee ce cc cece cree cece cece 9.412 9.391 NO. 320006 cece cece cece ccceccees 9.498 9.416 NO. 332222 - 20s codecs ccs scesicnsis 9.584 9.491

The actual combustion of the sample containing a small admixture of oleomargarine falls a little lower than theory requires, but is sufficiently high to indicate at once that there is adulteration of the normal butter. The other two samples give results still more distinctive and characteristic. The determina- tion of the calories would be sufficient, therefore, to detect oleo- margarine. If not relied upon entirely it still furnishes very satisfactory evidence. One point to which attention should be called is the exceedingly low temperature at which the oleomar- garines melted. They were purchased at the end of winter and probably made to suit the winter trade. If left in an open dish in the laboratory for a few hours they became soft and semi- fluid.

In the case of the lards from various sources the results are somewhat different and are not so distinctive as compared with compound lard, as the butter and oleomargarine. (Table III.) Still even here the determination of the calories taken in con- junction with other determinations, as the iodine absorption, will also be of use. Should the determination of the calories show a low figure one could conclude that the lard was either a compound or a lard from the caul, intestines, or head of the ani- mals, while the determination of the iodine number and cotton- seed-oil test, would show at once whether the sample was a lard or a compound lard. The error of experiment in calorimetric work is usually counted at twenty-five calories per gram, but by careful work can be made less and a number of experiments in the same line as the above, would probably give data that would make the determination of the calories of still more practical value.

E. A. DE SCHWEINITZ AND JAMES A. EMERY. 5

TABLE III.

ANALYSES OF SPECIMENS FROM ARMOUR & Co. Combustion Cotton-seed oil,

Melting Iodine calories Bechi’s Quality. point. equivalent. per gram. test. Lard, leaf........ «.-- 56.85 9.621 none.

«* caul fat ---- 40.0° 58.61 9.573 Slightly darken ‘« intestinal fat 40.7° 54.74 9.581 <¢ be

‘« heads -.-... 29.5° 68.79 9.503 None. mixture of EMltiSace oooe 63.86 9.654 “s ‘“« trimmings. ..-- 65.57 9.606 ot ‘* compound,

Ist grade. .---- 86.18 9.583 Purple brown. «compound,

2nd grade .-.--. 86.57 9.530 os ss

shield ...-- tees 61.01 9-593 None.

“ce

‘ special pure 37.5° 63.63 9.617

-

In a recent number of this Journal, September, 1895, Wesson has very carefully reviewed the subject of the determination of the iodine absorption number in pure and compound lards, claiming that the figures heretofore given for pure lard were too low for the present methods of manufacture. This point also came up for incidental consideration in connection with our other examinations. We secured two sets of samples from Chi- cago, one sent direct from Armour & Co. (Table III), with the statement that the samples were what the namesindicated. The other set of samples was accompanied by a certificate from the inspector testifying to the character of the materialas forwarded.

TABLE IV. ANALYSES OF LARDS FROM ARMOUR & Co. Iodine Cotton-seed oil, Quality. equivalent. Bechi’s test.

Leaf ...cccecccccs cscs cence 55-60 No reaction. Garliitatse cle tsceesieiciste ote cree 58.08 a yu UnteStimalatatscmiereilsieretelaale 52.94 ‘ « Wf ead Slavs svetevstete’s'cr0.ccrle Soesa Gp 36 oe ae Trimmings --....--.+...-- 61.58 ‘ce 66 Special pure..-.........-. 60.87 6 “ Foreign shield............ 58.62 “ “ Exp. Ref. Comp.......... 69.79 Purple black. Prime steam ....--....... 65-97 No reactions

Dom. COMp.---++--+++++- 74.53 Purple black.

LIBRARY OF CONGRESS |

6 CALORIMETER FOR BUTTER AND LARD. TABLE V. Iodine Cotton-seed-oil, Combustion calo- Sample. equivalent. Bechi’s test. ries per gram. Lard No. 5 ---++-+eee-ee 58.98 share Lard Plains.....--...-.- 50.49 saiels 9.606 Cottolene «++ +--+ eeeeee 90.89 Purple black. cee

In addition two other samples of lard, one from Virginia, the other from Rhode Island, were examined. ‘The samples sent with the inspectors’ certificate were freshly made, while the other set was older material. There is a decided variation in the iodine equivalent and in deciding upon the character of the lard, the origin of the sample should undoubtedly be taken into consideration. As this is often not possible a check upon the other results may be secured by the determination of the calories.

=

BrClrEMIC LABORATORY, WASHINGTON, D. C December 14th, 1895.

Discussion.—Mr. A. H. Sabin: I am very decidedly of the opinion that in investigations as to fats and oils, conclusive and satisfactory results can only be obtained by a comparison of methods. Such a method as this seems to me to be of a good deal of practical value because it is definite and positive. We make a combustion in this way and get some results which can be depended upon, and which can be verified ; and the condi- tions are not difficult to duplicate. While I doubt if such a method will be of permanent value, because in such matters the ingenuity of the manufacturer is always pitted against the skill of the analyst, such a method always has weight, and must be taken in conjunction with other methods which also have weight and which also by themselves are not conclusive, but which have cumulative effect. I am certain that in regard to the vegetable fats it is only possible to arrive at just conclusions by a comparison of methods.

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