T H E J O C R N A L O F I N D U S T R I A L A N D E iVGI LVE E RI N G C H E MI S T R Y
.5pr., 1914
TABLE I-DESCRIPTIOSOF SAMPLES OF SUGAR SAWD WASHEDA N D
SUMMARY
It has been shown t h a t very minute amounts of liter samples of air can be desulfur dioxide in 2 l termined b y direct titration with SI 1000 iodine. A correction factor of 1.3 for t h e apparent incompleteness of t h e reaction at t h e great dilution must be applied. On account of t h e gradual oxidation of t h e sulfur dioxide, t h e titrations must be made within a short time after t h e collection of t h e sample. The presence of moisture hast& t h e loss b y oxidation \-cry materially-.
.kNALYZED
KO. County 1
Argenteuil
By J . F. SSRLI, ASD
A. G. LOCHHEAD
Received January 7 , 1914
ISTRoDcCTIOS-ST’hen, in July, 191 I , Professor IT. H. K a r r e n ’ s article “Sugar Sand from I l a p l e S a p ; X Source of 1Ialic Xcid.”l appeared. N r . Lochhead h a d been engaged for some weeks in analyzing sugar sand a n d attempting t o prepare malic acid from i t . I n carrying out my suggestion t o treat t h e sand with dilute nitric acid, precipitate t h e malic acid as lead malate a n d liberate it b y treatment with hydrogen sulfide, he h a d found t h a t calcium bimalate could be crystallized out from t h e nitric acid solution, a n d transformed into free acid b y treatment with oxalic acid-essentially t h e process recommended by Warren. A h . Lochhead’s work was presented t o t h e Faculty of McGill University in 1912 as a thesis for t h e degree of M.Sc., b u t has not appeared i n print. T h e present article prepared during Mr. Lochhead’s absence is based upon his results. [ J . F. SNELL] P R E V I O U S L Y P U B L I S H E D Ah-ALYSES O F S U G A R S A N D
When t h e sap of t h e sugar maple has been concentrated t o a t h i n syrup b y boiling, a precipitate is deposited, which is known t o t h e sugarmaker as “sugar . s a n d ” or “niter.” T w o analyses of this precipitate,2 published previous t o Warren’s paper, indicated a content of 33.7 j a n d 40.10 per cent of calcium malate, respectively. These analyses included about 40 per cent of sugars a n d obviously referred t o t h e crude unwashed materials. Warren3 made a more detailed analysis of a single sample of washed sugar s a n d , which showed a calcium malate content of 68.64 per cent a n d a silica content of 7.74 per cent. ’
DESCRIPTION QF SAMPLES
We have analyzed six washed samples, all of Quebec origin, five being t h e product of single sugar bushes, t h e other ( S o . 5 ) a mixture. T h e sources of t h e samples a n d t h e descriptions of t h e unwashed material are given in Table I . T h e samples were washed b y mixing thoroughly \$-ith hot water a n d filtering with a Buchner filter, t h e p;ocess being repeated until t h e sweet taste disappeared. I n most instances four 11Varren. Jour. A n e r . C h e m . Soc., 33 (19111, 1205. 2 Bryan, U. S . Dept. Agriculture. Bureau of Chemistry, Bull. 154 (1910), 55. One of t h e analyses is original, t h e other is quoted f r o m I n diana 4 g r . Expt. Station, 12th Annual Report, 1899, p . 74. T h e latter is also quoted a n d commented upon b y Sy. Jonr. Franklin I n s f . , 1908. 3 Loc. c i l .
Remarks
Description
High land, shallow, gravelly soil, limestone bottom High gravelly soil High land, slate and loam
Light brown
2 ‘Shefford 3 Shefford
Light brown Darker t h a n I or 2
4
Shefford
5
Shefford
Dark brown containing much syrup Light colored
6
Brome
H Y G I E ~ LABORATORY IC \~4SHlVGTOV D c
THE ANALYSIS OF MAPLE PRODUCTS, IV The Composition of Maple Sugar Sand
301
Mixture from different parts of Shefford Co
1-ery dark, containing so much syrup a s t o make i t somewhat fluid
washings were sufficient. T h e 11-ashings invariably contained calcium as well as sugar. They readily underwent fermentation, liberating carbon dioxide a n d becoming acid in reaction. The mashed sugar sand was almost white and was non-hygroscopic, It h a d a specific gravity varying from 1.76 to 1.83 a n d averaging 1.80. T h e loss of d r y m a t t e r during mashing was determined in Samples I and j . I n four experiments TABLE 11-RESELTS OF
ASALYSIS OF WASHED
Sample
1 2 HzO . . . . . . , , . . . . 0.21 0.69 CaO . . . . . . . . . . . . 2 5 . 7 4 2 2 . 6 3 MnO.. . . .. . . . . . 1.87 1.38 MgO. . . . , , . . , . ... ... C;HaOd(a) . . . . . . . 5 3 . 7 3 4 6 . 4 9 6 . 1 6 18.55 SiOz . . . . . . . . . . . . ,...., ,.., 0.99
~
Total... . . . . . .
_
_
3 4 0.69 0.57 24.27 2 4 . 0 7 1.80 1.63 0.27 0.84 4 7 . 1 4 44.32 1 3 . 7 4 15.03 0.70 0.82
_
_
_
SCGAR SAKD
5 0.17 25.33 1.49 0.45 50.73 10.65 0.33
0.88 44.88 13.82 0.29
_
_
6 0.11 23.06
..
.
~
_
_
87.71
90.73
88.61
87.28
89.15
83.04
Ca . . . . . . . . . . . . . 17.76 C I H I O J ( ~. ,) . . . . . 61.17 Ratio 1: , . . . . . . . 3.44 CaCiHaOj, calculated: ( 1 ) f r o m C a. . . 76.22 (2) fromCiHeOs 79.67
15.62 52.90 3.38
16.75 53.64 3.20
16.61 50.44 3.04
17.44 57.73 3.31
15.91 51.06 3.21
Average 16.68 54.49 3.26
67.03 68.91
71.88 69.87
71.28 65.73
T4.83 75.25
68.28 66.56
71.59 70.98
( a ) Malic acid anhydride.
( b ) Malate radical.
on No. I i t varied from j I t o j j per cent a n d averaged j 2 . 7 per cent. I n four experiments on No. j i t varied from 49.5 t o j 3 a n d averaged j z . 1 per cent. METHODS O F ANALYSIS
M o i s t u r e was determined b y drying IO grams a t 100’. T h e milteral constitueizts were determined in t h e air-dry ash a n d calculated over t o percentage of t h e original material. A trace of iron was found i n all t h e samples. M a l i c a c i d was determined by a method similar t o a n d suggested b y t h a t of Warren, whose work h a d been published before our malic acid determinations were undertaken: I g r a m sugar sand a n d 2 j cc. normal oxalic acid were heated on t h e water b a t h for a n hour a n d a half. T h e product was filtered a n d washed, a n d t h e filtrate made u p t o z j o cc. Total acidity was determined in one 5 0 cc. aliquot. I n another, t h e residual oxalic acid w a s determined b y neutralizing with ammonia, acidifying with acetic acid, precipitating with calcium chloride, dissolving the washed precipitate in sulfuric acid a n d titrating with standard permanganate. T h e difference between total acid a n d residual oxalic acid represents t h e liberated malic acid.
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
302
RESULTS
T h e results of our analyses are given in Table 11. F o r comparison with Warren’s analysis we give calcium ( C a ) a n d malate radicle (C4H40j), as well as lime a n d malic anhydride. An unsatisfactory feature of t h e analyses is t h e large percentage of undetermined matter. This appears also in Warren’s analysis, in spite of his determinations of sugar, ether extract, carbon dioxide a n d extraneous organic matter. Evidently constituents of some little q u a n t i t a t i r e importance are unreached both b y his methods of analysis a n d b y ours. T h e Indiana analysis, likewise, shows a b o u t I O per cent of undetermined matter. It is remarkable t h a t Bryan’s analysis shows only 1.66 per cent of “insoluble matter ”-apparently including silica-and totals 98.23 per cent (assuming “malic a c i d ” t o mean malate radicle). I n t w o of our samples t h e calcium content is higher t h a n in Warren’s, in four i t is lower. T h e average for all seven samples is 1 6 . 7 j per cent. I n malic acid four of our samples are higher a n d two lower t h a n Warren’s. T h e average for all seven is j4.06 per cent expressed as malate radicle. T h e ratio of malate t o calcium for our samples is given in Table 11. I t is in three cases higher, a n d in three lower than t h e theoretical ratio for normal calcium malate, uiz:., 3.29. T h e average for our six samples is 3.26. I n Warren’s analysis, this ratio is a little lower t h a n t h e lowest of ours, uiz., 3.00 as against 3.04. T h e average for all seven samples is 3.22. These results would indicate t h a t t h e calcium a n d malic acid, t h e chief constituents of sugar sand, are present almost wholly in t h e form of normal calcium malate, this salt constituting about 7 0 per cent of t h e washed material. Silica is t h e only other constituent of sugar sand of a n y prominence. I t s q u a n t i t y varies in t h e seven samples from a little over 6 t o a little over 18. j per cent. The q u a n t i t y of phosphoric acid present is always small. It is interestipg t o note in this connection t h a t in 1887 B. J . Harringtonl in boiling down t h e s a p of t h e ash-leaved maple ,(Negu?ido aceroides or A c e r n e g u f z d o ) obtained a deposit containing no less t h a n 64.91 per cent of t r i c a l c i u m plzos9hate. H e also found a large proportion of calcium phosphate in a similar deposit from t h e s a p of A c e r rubrzrm a n d based upon these results a n opinion on t h a t “if t h e nitre from t h e sap of Acer sacchasizi.m2 were examined for phosphoric acid, i t would here also be found t o be a prominent constituent.” S U BI M A R Y
T h e analyses of six Quebec samples of washed, air-dried maple sugar sand are reported. 2. This material contains from 6 5 t o 80 per cent of normal calcium malate, from 6 t o I 8 . j per cent of silica, minor quantities of manganese, magnesium a n d phosphorus, traces of iron a n d from I O t o 1 7 per cent of undetermined material. I.
MACDONALD COLLCGE, QUEBEC, CANADA 1
2
Harrington, Trans Roy SOL.C a n . , 5, Sec. 3 , p. 39 (1887). Evidently referring t o the hard or sugar maple, now designated Acer
saccharum.
Vol. 6, NO. 4
MANUFACTURE OF UNFERMENTED GRAPE JUICE IN CALIFORNIA By
\V V. C R U E S A~X D C J HINTZE Received December 1, 1913
T h e present o u t p u t of unfermented grape juice in California is estimated at 80,000 t o I O O , O O O gallons yearly. Considering t h e size of t h e Viticulture indust r y in t h e state, this a m o u n t is very small in comparison with t h e production in t h e Eastern states. On t h e other h a n d , t h e possibilities are almost unlimited because California produces 5 j-60 million gallons of wine a n d a great quantity of table a n d raisin grapes. With t h e growth of t h e temperance movement, t h e popularity of grape juice will undoubtedly increase. California will be t h e logical source of supply because of its adaptability t o t h e production of large quantities of grapes of high quality. T h e varieties of grapes t o be selected may either be t h e American varieties, which produce a juice with t h e well known “ f o x y ) ’ flavor, a n d which would satisfy the demand already created by such juices now on t h e m a r k e t ; or, as is t h e general rule in California, t h e European varieties of high flavor, such as are grown in t h e s t a t e a t t h e present time, m a y be utilized. Among t h e former, California produces t h e Isabella a n d Concord, chiefly. Of t h e European varieties, t h e Muscat of Alexandria, Semillon, a n d Franken Riesling are suitable highly flavored white grapes, while t h e Cabernet is a suitable black grape of pronounced flavor. Besides high flavor, high acid is necessary. For white juice. Muscat m a y be taken t o give flavor a n d blended with Burger or West’s White Prolific ivhich are high in acid b u t lacking in distinctive flavor. Both color a n d acid, as well as high flavor, are needed in red juice. For flavor Isabella grapes m a y be used; t h e acid a n d color m a y be obtained b y mixing with t h e m slightly underripe Alicante Bouschet or Alicante Ganzin juice, or b y heating Zinfandel or other common black juice on t h e skins t o 180’ F. for a short time t o extract t h e color. T h e acidity of t h e juice in a n y case should be between 0 . 8 a n d I . I per cent as tartaric acid. T h e total solids (Brix or Balling) should be not higher t h a n 2 0 per cent. T h e desired composition can usually be obtained by judicious blending. It m a y be said t h a t one of t h e chief defects of a great deal of t h e juice a t present is t h a t due to t h e use of grapes too high in sugar a n d defective in acid. T h e objects in t h e manufacture of grape juice are t h e a t t a i n m e n t of high a n d agreeable flavor a n d perfect a n d permanent brightness in bottle. An outline of present commercial methods is given below a n d is followed b y a s u m m a r y of experimental results. O U T L I I i E O F P R E S E N T JIETHODS
T h e grapes a r e picked without a n y special regard t o t h e proper degree of ripeness for grape juice making, usually a t about 2 2 per cent Balling or more a n d crushed as soon as possible t o prevent mold growth. The juice is drained from t h e crushed grapes a n d t h e pomace is pressed in a hydraulic press. T h e free r u n a n d press juice are mixed a n d pasteurized at once a t a temperature of 185’ F. into 5 0 gallon
