ANALYTICAL EDITION
January 15, 1935
41
TABLBI. (Continued) 2,6-DINITROANILINE 2-NAPHTHOL
Dry Sulfuric acid Water Alcohol Acid Alkali PH
Bri ht orange VinL
I&iible Very slightly soluble Yellow in alcohol Blue in alcohol
Bright red Red Insoluble Insoluble
..... ..... .....
2,4-DINITROANILINE-6BULFONIC ACID
2,6-DINITROANILINE4-BULFONIO ACID
Bri h t red viofet Very slightly soluble Insoluble Orange Blue 8.8 to >IO
Bright orange Blue-red Soluble Insoluble Orange Blue 8.4 to C10
Orange Orange
Insoluble Yellow Oreen 7.8 to 9.8
Orsnge Orange Very soluble Insoluble Orange Wine red 8.2 to 9.8
Could not be isolated
Could not be iaolated
R BALT
%uric acid Water Aloohol Acid Alkali PH
Bright red Bright urple Very soyuble Insoluble Red Dull violet
Bright red Bright red Soluble Insoluble Orange Red 8.8 to >10
Bright red Orange Very soluble Insoluble Orange Dull violet >10
Could not be
>10
Very soluble
0 BALT
%uric acid Water Alcohol Acid Alkali PH
iaolated
Bine yellow contains three sodium atoms. This salt can be isolated by precipitating the indicator from a strongly alkaline solution with alcohol; it forms a dark powder of metallic luster, is quite stable, can be dried a t 100" C., and has been analyzed. While in the dyes derived from 2,6-dinitroaniline it must be an ortho nitro group which becomes ionogen in alkaline
solution, it is an open question which of the two nitro groups assumes this function in the indicators derived from 2,4 dinitroaniline.
LITERATURE CITED ('1 Wenker*IN=*ENQ.
CaPM.* 26* 350 (1934)*
RSCEIVED August 14, 1934.
Baume-Purity-Moisture Tables for Corn Sirup W. R. FETZER AND J. W. EVANS, Union Starch and Refining Company, Granite City, Ill. Low purity 30 to 35 The moisture content of a corn sirup or corn Brewery use as "body sirups" of corn sirup are refined sugar for a given Baumk has beenfound dependent Regular Duritv 40 to 45 annually in the United Confectionery trade upon the purily of the sirup involved. Increasing States. Corn sirup is produced High purity 50 to 55 purity results in increasing dry substance for a Brewery and bakery trade from starch by acid hydrolysis given Baumk. in three purities-low, regular, The bulk of the sirup sold is of and high-and consists of dexThe dry substance values f o r corn sirup, as t r i n , m a l t o s e , and dextrose. regular or medium purity. found in several tables in use among the trade, In the mechanical separation Purity is defined within the inhave beenfound too high. A new table employing of starch from corn, a yield of 30 dustry as the amount of reducing purity as well as Baumi has been constructed sugars expressed as dextrose on a to 33 pounds per bushel is obfor the entire range of the usual starch hydrolytic dry substance basis. As the actained. I n the subsequent hytual dry substance in corn sirup d r o l y s i s of starch, there is a products. is difficult to determine, the cuschemical gain, the amount deSeveral corn sirups and corn sugars from diftom in the industry has been to pending upon whether sirup or ferent refineries have been analyzed for dry sube x p r e s s t h e purity on a Brix sugar is produced. Thus, the stance, with results which indicate that for equal solids basis as a matter of conyield in d r y s u b s t a n c e of the Baumk and purity the moisture content is the same. venience, even though the Brix various products produced on solids are not the actual solids. the basis of the dry substance The term "purity" is necessary, as the same sirup is sold corn used became an important measure of the efficiency of a a t different gravities. I n selling, gravity is used as a measure refinery. It was soon found that the Brix solids could not be of the dry substance contained in the sirup, and will run from used for the measure of dry substance in corn sirup and sugar, 41" to 47" BB., being expressed a t 100" F. Sirups with a so special tables were constructed for the usual range of sirups gravity of 41" and 42' are more often termed "mixing sirups" produced, retaining the Brix solids for the basis of the purity and are largely used by manufacturers of mixed table sirups. determination. Each refinery either constructed a special Confectioners' sirup runs from 43" to 46" BB., the bulk being Baum6-moisture table or adopted one already in use a t another sold a t 43" BB., as this gravity represents the practical limit refinery. Once a table was in use, corrections became imat which this heavy viscous sirup may be handled economi- possible, as the management decreed that such a change would cally. In recent years considerable 42' BB. sirup has been render comparison with past factory performance impossible. sold to confectioners, as it is handled more easily in the piping If each factory was self-contained, this attitude might have systems which have been installed in candy factories. The been justified, but in selling sirups on the market, these purities produced by each refiner vary to a small degree, various moisture tables were given customers, who at once noticed that one table gave more dry substance for a given but the range and major use of the three types produced are:
0
VER one billion pounds
U
I
"
INDUSTRIAL AND ENGINEERING CHEMISTRY
42
Baume than another. The manufacturer whose table showed high moisture values soon'realized that he was at a sales disadvantage which was hard to explain, and took the easiest way out by adopting the table of the largest producer. The confusion to the customer was further enhanced by the use of the Old Dutch scale hydrometer of 144 modulus in the corn products industry. Thus, a salesman would quote data based on a 144 modulus spindle, which the customer would use with his hydrometer based on the Bureau of Standards modulus of 145. The relationship between the two hydrometers is shown in Table I, which also includes the moisture values in use by the largest producer in the industry, column I, and those in use by another refiner, column 11. TABLEI. HYDROMETER RELATIONSHIP M-144
MOISTURE
I
M-145
% 38.73 39.00 39.73 40.00 40.71 41.00 41.71 42.00 42.71 43,OO 43.69 44.00 44.69 45.00 45.68 46.00
39.00 39.27 40.00 40.27 41.00 41.29 42.00 42.29 43.00 43.29 44.00 44.31 45.00 45.31 46.00 46.32
26.0 25.5 24.0 23.5 22.1 21.5 20.9 19.5 18.2 17.7 16.6 16.1 15.0 14.5
.... .
,
.
I
I1 %
26.0 25.5 24.0 23.5 22.1 21.5 20.9 19.5 18.1 17.5 16.1 15.5 14.1 13.5 12.1 11.4
The errors in this table soon became apparent to the users Qf corn sirup. Candy makers claimed that from their yield figures the moisture of corn sirup was nearer 20 per cent than the 18.2 per cent of the table, making no allowance for 0.1"to 0.2" BB. overage which is always given. Gum makers, who use 45" BB. sirup, claimed that this sirup had over 15 per cent moisture by their yield figures. This confusion among the trade, and the discrepancy between various refiners who use their own tables, have prompted the work recorded in this paper. The authors have made a very careful study of the BaumB-moisture-purity values for sirups of their own manufacture and those of competitors. The table (Table 11)as originally constructed was for BaumB-moisture only, but it was found during the investigation that the moisture content decreased for a given Baume as the purity increased. Thus, in place of the limited corn sirup moistures originally planned, the work has been increased to cover the entire range of starch hydrolytic products.
METHODS OF ANALYSIS MOISTURE.The moisture values given in Table I1 were made according to the A. 0.A. C. method of drying on sand (1). Difficulties are encountered with this method on products containing dextrin, as it is almost impossible to remove the last traces of moisture. To overcome this difficulty, the present authors introduced the toluene distillation method with certain modifications for corn sirup (2) and this procedure has been used in the following work. However, it was difficult to be sure of the removal of the last trace of moisture from high gravity sirup, and it was necessary to adopt an increasing distillation time as the gravity increased, to secure accurate results. The schedule used was: 39" BB. for 6 hours' distillation time, with an increase of one hour for each degree increase in gravity. Thus, 47' BB. required 14 hours' distillation time. B A U M ~The . Baume was obtained according to the usual commercial practice. The sirup in a glass cylinder was placed in a water bath a t 140" * 5" F., and when free from air the hydrometer was introduced. Several hydrometer readings with corresponding temperature observations were
Vol. 7, No. 1
made. The data were corrected to 100" F., employing the correction of 4" F. = 0.1" BB., and averaged. The hydrometer used was based on a modulus of 145, standardized a t GO" F., with a Bureau of Standards certificate. This hydrometer was checked a t intervals, a t room temperature, against a similar hydrometer with a Bureau of Standards certificate. The thermometer used was a precision instrument. TABLE11. BAUM~-MOISTURE-PURITY RESULTS BAVMB PURITY CORRECT~D Botual Brix X 100 No. TO 100' F. MOISTURE solids solids PURITYAS 1 39.16 27.76 27.78 36.5 34.7 95.3 42.19 21.70 21.75 36.5 34.8 42.57 20.94 20.95 36.4 34.8 44.22 17.64 17.66 .. .. 2 39.32 27.34 27.39 37.8 35.8 95.2 23.64 41.17 23.68 37.8 35.9 42.44 21.08 21.12 37.9 36.0 42.67 20.62 36.0 20.64 44.79 16.41 16.44 36.0 45.04 15.90 15.97 11.71 47.14 11.77 3 28.02 38.95 28.08 39.3 37.4 95.2 23.90 37.5 41.02 23.90 39.4 43.11 19.65 19.61 39.5 37.6 45.48 14.95 37.5 14.98 .. 4 27.82 38.97 27.88 41.9 40.1 95.8 23.53 41.12 23.21 41.8 40.1 23.18 41.29 19.08 41.8 40.2 43.35 19.05 14.47 41.9 14.48 ... 45.64 26.01 5 39.84 26.05 43.2 41.3 95.4 22.71 41.47 22.73 43.3 41.3 13.28 46.16 13.31 43.3 41.4 27.34 6 39.19 27.38 43.3 41.6 96.1 22.74 41.47 22.75 43.4 41.7 18.33 43.65 18.37 43.5 41.7 14.20 14.19 45.72 43.5 45.3 27.64 27.66 43.3 7 38.97 95.8 45.3 23.95 23.99 43.4 40.80 45.4 19.87 19.91 43.4 42.82 15.82 15.86 44.83 13.41 13.49 46.02 27.70 27.78 54.6 52.7 98.5 S 38.63 22.51 41.20 54.7 52.8 22.55 20.14 42.38 54.8 52.9 20.15 14.29 14.32 45.26 10.95 11.02 46.95 .* 25.71 63.8 25.77 65.4 97.5 9 39.33 22.31 22.29 65.4 63.8 41.01 18.31 18.31 65.5 42.96 13.83 13.80 45.17 25.94 25.96 68.3 69.8 97.7 10 39.06 69.9 25.67 68.4 25.73 39.17 21.15 70.1 21.11 68.4 41.41 16.99 17.00 43.42 14.16 14.19 44.80 98.6 26.28 26.32 78.7 77.6 11 38.65 77.6 24.13 24.19 78.7 39.65 20.15 20.18 78.8 41.63 17.13 17.17 43.09 11.83 11.88 45.68 80.6 98.6 24.89 24.90 81.9 12 39.26 80.7 23.04 23.05 82.0 40.13 20.54 20.54 82.1 80.8 41.36 16.69 16.73 43.21 ,. 13.16 13.19 44.92 85.6 99.0 24.14 24.19 86.6 13 39.45 85.8 21.19 21.21 86.7 40.89 85.9 15.34 15.36 86.8 43.70 10.75 10.75 45.93 99.0 24.93 24.95 88.1 87.3 14 39.05 88.2 87.3 20.73 20.79 41.06 87.4 16.31 16.35 88.2 43.21 11.11 11.13 45.72 99.2 89.7 88.9 23.76 23.79 39.56 15 89.0 20.71 20.74 89.7 41.03 89.0 16.10 18.14 89.8 43.24 12.43 12.43 45.02 Nos 7 8 12 13 and 15 Union Starch & Refining Co factory production. Nos'io& 2' ddodddons. 9 'lo '11,Unibn Starch & Refining Co., ladoratory products; fao-
pm
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Nos. 1 and 14,manufactured by A. E. Stale Mfg. Co. No. 4, manufactured by Penlck.& Ford, L t z No. 5 manufactured by The Clmton Company.
No. 8: manufactured by Corn Produots Refining Company.
The present authors believe that some of the confusion on Baum6-moisture determinations is caused by inaccurate gravity determinations. The error is introduced by the failure to remove all traces of air from the sirup. This is particularly true of routine determinations of gravities on factory shipments, which are usually required in a hurry. Common practice is to make all shipments 0.1" BB. heavy,
January 15, 1935
ANALYTICAL EDITION
but sirup has been procured on the open market which spindled as high as 0.7" BB. heavy. Samples which run 0.3 to 0.4' BB. heavy are fairly common. PURITY.The purity of corn sirup or sugar is controlled in the refinery by testing the liquor from the neutralizer, immediately after the conversion. The usual procedure is to obtain the Brix of the liquor and make a suitable dilution, after which the reducing sugars are determined as dextrose. The latter figure is then expressed on a Brix solids basis. Sugar liquor will run from 28 to 32 Brix, and sirup from 34 to 38 Brix. The procedure on the analysis of a finished sirup or sugar is to reduce it to the same Brix range, and employ the same method of analysis. For convenience, purity has been expressed in Table I1 on actual solids and on Brix solids. The titration method of Lane and Eynon (S),employing methylene blue as an indicator, was used for each method. The procedure for actual solids has already been described (2). For the Brix solids purity, a given quantity of sirup or sugar was diluted to fall within 30 to 36 Brix, on a precision instrument standardized a t 20" C. (68" F.). Twenty-five milliliters were taken, and diluted to 500 ml., from which point the procedure was the same as for actual solids. As the purity increased, the amount of sample used was decreased, so as to maintain a 12- to 15-ml. titration volume for 25 ml. of Fehling's solution. The actual solids purities in Table I1 are the average of duplicate titrations made on sirup of different densities, thus employing a different dry substance value in each case. The Brix solids purities are the average of duplicate titrations on different dilutions of the sirup to the Brix range indicated above. These data were plotted on millimeter graph paper of such aize that 0.02 per cent moisture and 0.02' BB. equaled 1 mm. A straight line fitted the plotted points with each purity. From this graph, purity-moisture values were obtained for the even Baume ' s and are given in Table 111. TABLP~ 111. PUR~TY-BAUM~-MOISTURE PURITY, ACTUAL SOLIDS39.0° 36.5 28.09 37.8 28.00 39.3 27.94 43.2 27.69 45.3 27.56 54.7 26.98 65.4 26.39 70.0 26.07 78.7 25.59 82.0 25.38 86.8 25.13 88.2 25.05 89.7 24.96
40.0' 26.09 26.00 25.93 25.68 25.55 24.96 24.35 24.02 23.53 23.32 23.05 22.98 22.88
41.0' 24.09 24.01 23.92 23.67 23.54 22.94 22.31 21.97 21.47 21.26 20.97 20.91 20.80
42.0° 22.09 22.01 21.91 21.66 21.54 20.92 20.27 19.92 19.41 19.20 18.89 18.83 18.72
43.0' 20.10 20.01 19.91 19.65 19.53 18.90 18.23 17.89 17.35 17.14 16.81 16.76 16.64
44.0' 18.10 18.02 17.90 17.65 17.53 16.89 16.19 15.84 15.30 15.08 14.74 14.68 14.56
45.0' 16.10 16.03 15.89 15.64 15.53 14.87 14.15 13.80 13.25 13.02 12.67 12.61 12.48
46.0' 14.11 14.03 13.88 13.63 13.63 12.85 12.11 11.76 11.20 10.96 10.60 10.54 10.40
47.0. 12.11 12.04 11.87 11.63 11.53 10.83
... ... ... ... ... ... ...
TABLEIV. PURITY-BAUM~-MOISTURE PURITY
43
Table IV has been prepared, giving moisture values for even purity-Baume values. . Brix solids purity The ratio X 100 was plotted and a actual solids purity straight line was found tc-fit the points. From this graph Table V has been prepared to show this relationship. PURITY ACTUA~ SOLIDS
TABLEV BRIXSOLIDS PURITY x 100 ACTUAL SOLIDS PURITY
% 35 40 50 60 70 80 90
95.0 95.4 96.2 96.9 97.7 98.4 99.2
For the convenience of the chemists in the confectionery, bakery, brewing, and rayon industries, and as a means of standardizing a table within the corn products industry itself the authors present Table VI. TABLEVI. PURITY-BAUM~MOISTURE, CORNSIRUPAND CORNSUGAR (Table a t 100' F.; hydrometer, 145 M, 60° F.) PURITY BAT@ AS BS 39O 40" 41° 42' 43 44O 45O 40 38.2 27.9 25.9 23.9 21.9 19.9 17.9 15.9 41 39.1 27.8 25.8 23.8 21.8 19.8 17.8 15.8 42 40.1 27.8 25.8 23.8 21.7 19.7 17.7 15.7 43 41.1 27.7 25.7 23.7 21.7 19.7 17.7 15.7 44 42.1 27.6 25.6 23.6 21.6 19.6 17.6 15.6 45 43.1 27.6 25.6 23.6 21.6 19.6 17.5 15.6 46 44.1 27.5 25.5 23.5 21.5 19.5 17.5 15.5 47 45.1 27.5 25.5 23.4 21.4 19.4 17.4 15.4 48 46.1 27.4 25.4 23.4 21.4 19.4 17.3 15.3 49 47.1 27.4 25.3 23.3 21.3 19.3 17.3 15.3 17.2 15.2 50 51 17.1 15.1 52 17.1 15.1 53 17.0 15.0 64 16.9 14.9 55 16.9 14.8 16.8 14.8 66 16.7 14.7 57 5s 16.7 14.6 59 16.6 14.6 60 58.1 26.7 24.7 22.6 20.6 18.6 16.5 14.5 65 63.3 26.4 24.4 22.3 20.3 18.2 16.2 14.2 70 68.4 26.1 24.1 22.0 20.0 17.9 15.9 13.8 75 73.5 25.8 23.8 21.7 19.7 17.6 15.5 13.6 78.7 25.5 23.5 21.4 19.3 17.3 15.2 13.1 80 79.7 25.5 23.4 21.3 19.3 17.2 15.1 13.1 81 80.8 25.4 23.3 21.3 19.2 17.1 15.1 13.0 82 83 81.9 25.4 23.3 21.2 19.2 17.1 15.0 12.9 83.0 25.3 23.2 21.2 19.1 17.0 14.9 12.9 84 84.0 25.2 23.2 21.1 19.0 16.9 14.9 12.8 85 85.1 25.2 23.1 21.0 19.0 16.9 14.8 12.7 86 86.1 25.1 23.0 21.0 18.9 16.8 14.7 12.7 87 87.2 25.1 23.0 20.9 18.8 16.8 14.7 12.6 88 88.2 25.0 22.9 20.8 18.8 16.7 14.6 12.5 89 89.3 24.9 22.9 20.8 18.7 16.6 14.5 12.5 90 90.4 24.9 22.8 20.7 18.6 16.6 14.5 12.4 91 92 91.4 24.8 22.7 20.6 18.6 16.5 14.4 12.3 Lb. er 11.33 11.43 11.54 11.66 11.77 11.89 12.01 gJ. Water, 8.279 I
46O 13.9 13.8 13.7 13.7 13.6 13.5 13.4 13.4 13.3 13.2 13.2 13.1 13.0 13.0 12.9 12.8 12.8 12.7 12.6 12.5 12.5 12.1 11.8 11.4 11.1 11.0 10.9 10.9 10.8 10.7 10.7 10.6 10.5 10.4 10.4 10.3 10.2
47O 11.9 11.8 11.7 11.7 11.6 11.5 11.4 11.4 11.3 11.2 11.2 11.1 11.0 10.9 10.9 10.8 10.7 10.7 10.8 10.5 10.4
..
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.. .... ..
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..
12.1312.25
AOTUA~
SOLIDS39.0° 35 28.18 40 27.88 50 27.29 60 26.70 70 26.12 SO 25.53 90 24.94
40.0' 26.18 25.88 25.27 24.67 24.07 23.47 22.86
41.0° 24.18 23.87 23.25 22.64 22.02 21.40 20.78
42.0° 22.18 21.87 21.24 20.61 19.97 19.34 18.70
43.0' 20.19 19.87 19.22 18.57 17.92 17.27 16.62
44.0' 18.20 17.87 17.20 16.54 15.87 15.21 14.54
45.0' 16.19 15.86 15.18 14.51 13.82 13.14 12.46
46.0' 14.21 13.86 13.17 12.47 11.77 11.08 10.38
47.0' 12.21 11.86 11.15 10.44
... ... ...
LITERATURE CITED (1) Assoc. Official Agr. Chem., Official and Tentative Methods,
p.
364 (1930).
Evans, J. W., and Longeneoker, J. B., IND.ENG. C H ~ MAnal. ., Ed., 5, 81 (1933). (3) Lane, J. H., and Eynon, L., J . SOC.Chem. Ind.,42, 32T (1923). (2) Fetzer, W. R.,
These data were plotted on the same size of graph paper, with purity and moisture as abscissas. A straight line was found to fit the points for each Baume. From this graph,
RECEIVBD November 7, 1934. Presented before the Division of Sugar Chemiatry a t the 88th Meeting of the American Chemioal Society, Clereland, Ohio, September 10 t o 14, 1934.
CARBON PAPERAND TYPEWRITER RIBBONS. The National Bureau of Standards has prepared Letter Circular 424, in which it is shown how anybody can make writing tests of carbon paper and typewriter ribbons, and select for himself the kinds that are best adapted to his special needs. Brief accounts are also given of the manufacture of these materials, and it is pointed out how
their physical properties and composition are related to their writing qualities. A serviceability or wear-down test and a manifolding test for carbon paper are described, as well as a wear-down test for typewriter ribbons, and a method for testing ribbons for the clogging of type.
