N T H E United States the two most inexpensive sources of energy-producing foods are cereal products and cane sugar I (6). In recent years workers have repeatedly demonstrated

that important B complex vitamins, which are found in un- processed cereal products, are greatly reduced in quantity during processing (1, 3, 4, 8, 1S, 18). The essential facts were recog- nized many years ago by those who advocated the advantages of whole-wheat flour (9, 10).

Investigators have clearly demonstrated that refined sugar is devoid of thiamine (6, 7, 11, 13, 19) and presumably of other vitamins. The present investigation of the water-soluble B complex vitamins of sugar cane and sugar cane juice was under- taken to discover to what extent the processes of sugar refining create this nutritional disparity by removing or destroying cer- tain vitamins naturally associated with sugar in the cane.

EXAMINATION OF SUGAR CANES AND JUICES

The samples of cane juices and canes used in the present in- vestigation were collected in Louisiana and Cuba. I n Louisiana ten samples of juices were taken from three varieties of cane- Le., Canal Point 28-19, Coimbatori 281, and Coimbatori 290; two additional samples were obtained from mixed canes direct from the crusher. The canes were freshly cut in the field, and the juices were immediately expressed in a laboratory crusher or in factory crushers. The juices were preserved by the addition of 2 0 3 0 % alcohol. Samples of whole sugar cane, consisting of two or three segments from both the top and bottom of several canes, were also taken directly from the field and preserved by

B COMPLEX VITAMINS

In Sugar Cane and Sugar Cane Juice

William I?. Jackson1 and Thomas J. Macek MERCK k COMPANY, INC., RAHWAY, N. J .

waxing. All samples were stored under refrigeration until assayed.

In Cuba a total of thirty-six different samples of juice were similarly collected from an equal number of different varieties of cane. I n addition, representative pieces of whole sugar cane were collected from thirty-nine different varieties. All juices and canes were preserved as described. I n both Louisiana and Cuba the samples were collected from plantations in different parts of the state and island, respectively, and thus are representa- tive of several types of soils. The age of the cane varied from 3 months to 2 years, and both plant and ratoon type were sampled. For the most part the Louisianan and Cuban canes were 9 and 11 months old, respectively.

On arrival at the laboratory the preserved juices were im- mediately assayed for sucrose, thiamine, riboflavin, niacin, pantothenic acid, and biotin. The pieces of whole cane were freed of their wax coating, and a portion of each piece was pulped with the aid of a mechanical saw, a knife, and finally a laboratory- type meat grinder. A weighed quantity of the fresh pulp was pressed on a Carver laboratory press, and the juice was col-

1 Present address, Wyeth Incorporated, Philadelphia, Pa.

TABLE I. SUCROSE AND VITAMIN CONTENTS O F JUrCES EXPRESSED FROM SUGAR CANE

No. of Vitamins, Micrograms/Gram of Juice Samples ' Thi- Panto-

Variety or Sucrose, amine Ribo- thenio of Cane Species HC1 flavin acid Niacin Biotin

Louisianan Cane Juiaes C.P. 28-19 Za 18.24 0.062 0.039 2.84 0.721 0.034 co. 281 6= 14.83 0.099 0.052 2.71 0.829 0.034 co. 290 Za 15.38 0.084 0.055 3.76 0.703 0.025 Mixed 1" 13.85 0.049 0,049 5.41 0,861 0.022 Mixed la 11.41 0.136 0.071 5.80 1.063 0.028 Minimum 11.41 0.049 0,038 2.53 0.657 0.022

Maximum . . . 18.24 0.136 0.077 5 80 1.063 0.038 Average i z h 14.76 o.mo 0.053 3.70 0.834 0.031

Cuban Cane Juices Badilla l b 20.19 0.179 0.112 1.65 0.975 0,030 Baragu& 35 18.66 0.229 0.070 1.76 0.814 0.033 Canalpoint 2b 16.41 0.259 0.070 2.28 0.768 0.038 Coimbatori 2) 16.66 0.197 0.110 3.04 0.797 0.042 Cristalina 2a 16.80 0.095 0.075 2.53 0.538 0.020 Fajardo l b 16.61 0.255 0.140 1.27 0.914 0.041 Mayaguez 6b 19.69 0.141 0.086 1.20 0.813 0,027 MediaLuna 20 17.23 0.180 0 081 1.38 0.956 0.028 Palma 1 b 19.67 0.103 0.059 1.60 0.697 0,025 POJ 158 17.27 0.186 0.082 1.53 0.720 0.029 SantaCruz l b 19 41 0.133 0.062 1.60 0.718 0.027 Minimum . . . 10.25 0.086 0.051 0.76 0.530 0.016 Average 36a 17.87 0.179 0.083 1.69 0.765 0.030 Maximum , , . 23.04 0.359 0.174 3.34 1.06 0.045

a Samples. b Species.

TABLE 11. SUCROSE AND VITAMIN CONTENTS OF WHOLE SUGAR CANES

Vitamins, Micrograms/Gram of Cane Thi- Panto-

Variety No. ,of Sucrose, amine Ribo- thenic of Cane Species % HC1 flavin acid Niacin Biotin

Louisianan Whole Canes C.P. 28-19 .. 11.66 0.328 0.203 3.61 1.38 0.040 co . 281 . . 11.08 0.499 0.250 2.81 1.60 0.042 co. 290 . . 11.84 0.332 0.202 3.78 0.988 0.027 Minimum . . . . . 0.245 0.149 1.93 0.851 0.023 Average . . . . . 0.398 0.222 3.36 1.31 0.036 Maximum . . . . . 0.576 0.261 4.27 1.62 0.048

Cuban Whole Canes Badilla 1 BaraguB 3 Canal Point 2 Coimbatori 2

Fajardo 1 Mayaguez 6 Media Luna 2 Palma 3 POJ 15 Santa Crus 1 Uba 1

Cristalina 2

14.50 11.21 12.82 12.98 12.48 11.81 13.89 10.23 15.22 10.92 15.10 12.44

0.300 0.230 0.428 0.309 0.415 0.169 0.623 0.237 0.565 0.189 0.475 0.185 0.342 0.227 0.375 0.301 0.348 0.216 0.451 0.245 0.334 0.396 0.194 0.212

1.68 1.27 2.16 2.33 1.51 0.950 1.39 2.00 1.30 1.12 1.41 2.13

1.95 1.75 1.74 1.31 1.12 1.80 1.79 2.04 1.67 1.38 1.51 1.68

0.073 0.037 0.071 0.054 0.027 0.071 0.054 0.065 0.046 0.047 0.044 0.044

Minimum . . 5.30 0.194 0.129 0.543 0.888 0.009 Average 39 12.24 0.420 0.241 1.41 1.56 0.050 Maximum . . 18.95 0.793 0.396 3.47 3.03 0.106

d

261

262 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 36, No. 3

to a modification of the Snell and Wright method for niacin, The assays for sucrose and for the B complex vitamins were averaged and tabulated into groups accord- ing to the variety of cane. Averaged assays for juices and whole cane appear in Tables I and 11, respectively.

Variety of cane M ~ , % HC1 flavin Soid ~ i ~ ~ i ~ Biotin More complete data on the average assays for the in- Badilla 11 14.50 0,300 0.230 1 .e8 1.95 0.073 dividual varieties of Cuban cane, rather than for group- Baragu4 Baraguh 469 1.29 i j lg:ig g::!: ~:~~~ \;:; t:::: ings of similar varieties, appears in Table 111. Baragu4 470 11 9.91 0.202 0,389 1.74 2.52 0.038 Table IV compares the sucrose and vitamin contents

11 13.40 0.245 0.133 2.15 1.78 0.068 of the bottom and top portions of sugar cane in terms

TABLE 111. VITAMIN CONTENTS OF INDIVIDUAL VARIETIES O F CUBAN WHOLE SUGAR CANE

Av. Vitamin Content Micrograms/Gram of Chne

Thi- Panto- Age, Sucrose, amine Ribo- thenic

11 12.25 0.585 0.205 2.16 1.70 0.075 C.P. 29-116 C.P. 29-320

Co. 281 11 ll 12.95 12,55 0,595 o,713 0.129 o,208 3.47 1,68 1.32 1,35 0.063 o,026 The vitamin contents of Louisianan and Cuban juices Cristalina (Preston)

Fajardo 916 11 11.81 0.475 0.185 0.95 1.80 0.071

Co. 213 24 13.00 0.650 0.345 1.20 1.30 0.045 of averaged values.

Cristalina (Espana) 11 12.40 0.418 0.170 1.35 0.89 0.027 and canes are comparedin Table V.

Mayaguez 7 11 12.45 0.363 0.150 0.78 1.25 0.068 Mayaguez 28 11 18.95 0.269 0.162 1.27 1.29 0.041 Mayagues 42 11 13.50 0.357 0 357 2.31 1.89 0 056 Mayaguez 49 11 10.82 0.223 0.223 0.58 1.53 0'070 Mayagues 62 11 11.40 0,360 0.220 1.88 1.72 0.056 Mayaguez 234 11 16.20 0.478 0.223 1.52 3.02 0.034 Medis Luna 318 12 9.60 0.470 0.230 2.18 2.08 0.045 Media Luna 4-17 11 10.85 0 Palma 19 11 15.70 0 Palma 32 (thin) Palma 32 (thick) POJ 22 POJ 2714 (Palma) POJ 2714 (Jatibonico) POJ 2714 (Rayada) POJ 2714 (Sport) POJ 2714 (Sport) POJ 2725 (Palma) POJ 2725 (Espana) POJ 2725 (Jatibonico) POJ 2727 (Preston) POJ 2727 (Jatibonico) POJ 2878 (Preston) POJ 2878 (Espana) POJ 2878 Preston) POJ 2883 {Violeta)

11 11 24 12 3 12 11 12 24 11 24 11 12 17 12

13.20 10.78 13.10 8.92 7.90 8.92 14.56 11.37 16.10 5.30 10.52 8.25 14.15 12.00 8.73

0.385 0.218 0.313 0.355 0.300 0.283 0.418 0.235 0.478 0.164 0.343 0.230 0.360 0.193 0.403 0.158 0.387 0.187 0.791 0.520 0.410 0.148 0.383 0.352 0.793 0.158 0.642 0.277 0.343 0.195

0.99 1.15 1.23 0.54 1.57 0.99 1.00 0.83 1.30 1.50 0.87 1.23 0.98 1.87 0.79

1.15 1.73 1.55 1.32 1.04 1.15 1.06 1.25 1.70 2.38 1.10 1.18 1.18 2.00 0.91

0.062 0.052 0.106 0.038 0,009 0.022 0.062 0.078 0.041 0.030 0.050 0.054 0.038 0.036 0.028

Santa Crus 124 11 15.10 0.334 0,396 1.41 1.51 0.044 U ba 11 12.44 0.194 0.212 2.13 1.68 0.044

TABLE IV. AVERAGE VITAMIN DISTRIBUTION IN TOP AND BOTTOM PORTIONS OF SUGAR CASES

-Louisianan Cane- -Cuban Can- TOP Bottom Top, Bottom

Microg;ams Microgra& Micrograms Micrograhs Per g. Per lb. Per g. Per lb.' Per g. Per lb. Perg. Per lb. cane sucro~e cane sucrose cane sucrose cane sucrose

ThiamineHC1 0.333 1491 0.498 1791 0.429 2274 0.394 1361 Riboflavin 0.258 1154 0.194 737 0.258 1284 0.223 850 Pantothenic

acid 3.99 17941 2.61 9367 1.51 7345 1.29 4653 Niacin 1.37 6164 1.21 4614 1.71 8224 1.45 5263 Biotin 0.034 154 0.035 138 0.051 224 0.050 179 Sucrase, % 10.09 12.82 11.32 13.16

RESULTS AND CONCLUSIONS

Sugar canes vary greatly in sucrose content in different countries, in different parts of the same country, and from time to time in the same locality. The maximum sucrose content of Louisianan cane is usually about 12%; the average content of Cuban cane is between 13 and 14q7,. In the present study the average sucrose content for the Louisianan samples was 11.5 and for the Cuban, 12.30J0. The bottom segments of the canes were generally richer in sucrose than the top segments. On the other hand, the top segments were generally richer in vitamins than the bottom ones (Table IV).

The results in Table I11 indicate that the vitamin content differs from one variety to another. This varia- tion likewise occurs between the groupings of Cuban varieties as shown in Table 11; between these group- ings no uniform correlation was apparent in respect to sucrose and vitamin content.

Except for pantothenic acid where the reverse is true, a comparison of the average vitamin values per pound sucrose (Table V) shows that Cuban cane is richer in the B complex vitamins than Louisianan. This was prob- ably true because the Cuban samples were more mature than the Louisianan. Because of climatic conditions Louisianan cane is usually cut before it reaches full maturity. From Table V it is b o evident that biotin and riboflavin occur in lesser amounts than does thiamine hydrochloride in sugar cane and juice, whereas niacin and pantothenic acid are found in greater amounts.

lected. The marc from the pressing was recovered, macerated with acidulated water for 30 minutes a t room temperature, again pressed, and the extract was collected. This process of macera- tion and pressing was repeated twice. In all, the pulp was sub- jected to four hydraulic pressings. Cbntrol tests showed that this treatment was sufficient to extract all the vitamins as well

TABLE V. VITAMIN CONTENTS OF LOUISIANAN AND CUBAN JUICES AND CANE (Mo. VITAMIN PER POUND SUCROSE)

Y L o u i s i a n a n Samples- -Cuban Samples- Whole Cane Juice Whole Cane Juice Av. Max. Av. Max. Av. Mas. Av. Max.

Thiamine HC1 1. 57 2. 2o o. 29 o. 54 2. o5 17. 95 o. 46 1,

:;;$;

as all the sugar. The juice and extracts were combined and ad- Riboflavin 0.92 1.17 0.17 0.28 1.07 4.92 0.22 0.44 justed by the addition of acidulated water so that each gram 13.73 19.61 12.03 23.06 6.03 22.74 4.42 9.87

5.39 7.89 2.68 4.23 6.77 32.60 1.99 3.32 0.15 0.20 0.09 0.130.20 0.420.080.12

P a s , h e n i c

of combined extract represented a definite weight of fresh pulped cane. These extracts were then assayed for sucrose and the vitamins.

ASSAY METHODS ACKNOWLEDGMENT

Sucrose determinations were made following a modified Jack- son-Gillis method for Clerget sucrose (16). The values in the tables are given as per cent by weight.

Straub's modification (3) of the thiochrome method. Assay samples were treated with the enzyme claras? to hydrolyze any co-carboxylase that might be present. Riboflavin was deter- mined microbiologically by the method of Snell and Strong (IQ), pantothenic acid according to Strong, Feeney, and Earle (I?'), niacin according to Snell and Wright (16), and biotin according

So many people contributed to the success of this work that it is hardly possible to mention all. However, special thanks are due to the following members of the scientific staff of Merck & Company R. T. Major, Director of Research, E. H. Meiss, B.

Thiamine hydrochloride was determined by Connor and Martin, E. Benditt, M. Gunness, B. Moore, J. Cross, J. L. Stokes, J. A. Elder, W. C. Fulmer, and J. Young.

Walter Godchaux and W. Bondurant, Godchaux Sugars, Inc., H. J* Jacobs, South Coast Corporation, and J. T. Landry, Supreme Sugar Refinery, cooperated in providing samples and

George Deschapelle and Jose Maria Zayas, of Havana, made it possible for the material to be taken from Cuba with a mini-

for work on the Louisianan canes.

March, 1944 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 263

mum of trouble and delay. A. C. Matthews, Central Palma; E. Miller, Compafiia Arucarera Atlantica del Golfo; F. Adair Monroe, Compafiia Cubana; H. J. Schreiber, Ingenio Jatibon- NO; Percy A. Staples Hershey Corporation of Cuba; J. D. Stephenson, Central V)ioleta; N. N. Trinler, Central Preston; George T. Walker, Central Espana; and B. A. Sample, of Havana, provided facilities of all kinds and splendid hospitality. Special thanks are due F. A. Monroe, whose influence was of tre- mendous help in many difficult situations.

The Coca Cola Corporation of Havana made available, without chargel mobile refrigerating facilities which made possible the collection of samples from all over the island.

Leonard Wickenden, of New York, provided valuable connec- tions in Louisiana and Cuba.

LITERATURE CITED

(1) Andrews, J. S., Boyd, H. M., and Terry, D. E., Cereal Chem.,

(2) Baker, A. Z., Wright, M. D., and Drummond, J. C., J. SOC. 19, 55 (1942).

Chem. Id., 56, 191 (1937). (3) Connor, R. T., and Straub, G. J., IND. ENG. CEEM., ANAL. ED.,

(4) Copping, A. M., and Roscoe, M. H., ,Biochem. J., 31, 1879 13, 380 (1941).

(1937).

(6) Cowgill, 0. R., J. Am. Med. Assoc., 113, 2146 (1939). (6) Zbid., 122, 437 (1943). (7) Daniel, E. P., and Munsell, H. E., U. 8. Dept. Agr., iMisc. Pub.

(8) Harris, L. J., and Leong, P. C., J . SOC. C h m . Id., 56, 195

(9) Lapicque, L., and Chaussin, J., C m p t . rad., 166, 300 (1917). (10) Moore, C. V., and Brodie, J. L., Arch. Pediat., 42, 572 (1925). (11) Nelson, E. M., and Jones, D. B., J . Agr. Research, 41,749 (1930). (12) Pyke, M., J . SOC. Chem. Id., 58, 338 (1939). (13) Sherwood, R. C., Nordgren, R., and Andrews, J. S., Cered

(14) Snell, E. E., and Strong, F. M., IND. ENG. CHEM., ANAL. ED.,

(16) Snell, E. E., and Wright, L. D., J. Biol. Chem., 139, 676 (1941). (16) Spencer, G. L., and Meade, G. P., Handbook for Cane Sugar

Manufacturers and Their Chemists, 7th ed., p. 234, New York, John Wiley t Sons, 1929.

(17) Strong, F. M., Feeney, R. E., and Esrle, A., IND. ENG. CHE~M., ANAL. ED., 13, 566 (1941).

(18) Thomas, J. M., Bina, A. F., and Brown, E. B., Cereal Chem., 19, 173 (1942).

(19) Williams, R. R., IND. ENG. CREM., 33, 718 (1941). PRSSS~NTBIII before the Division of Sugar Chemistry and Technology a t the 106th Meeting of the AMERICAN CHEMICAL SOCIIITY, Pittsburgh, Pa.

275 (1937).

(1937).

Chem., 18, 811 (1941).

11, 346 (1939).

Corrosivity of Lubricating Oils EXISTENT AND POTENTIAL

GEORGE W. WATERS‘ AND HUGH D. BURNHAM* Shell Oil Company, Inc., Wood River, Ill.

H E f u n d a m e n t a l Bearing corrosion is analyzed into two concepts: ‘‘ex- On the other hand requ&tes for cor- istent corrosivity” which occurs by virtue of the instan- every lubricant can cause rosion are a corrodi- taneous chemical state of a lubricant, and “potential cor- immediate corrosion to: a

rosivity” which occurs under conditions, representative degree, varying from zero ble and vulnerable metal surface, and the presence of those of service, which lead to the simultaneous oxida- to relatively great magni- of corrosive bodies, gener- tion of the oil. The effects upon both types of corrosivity tude. This “existent corro- ally acidic. of temperature, time, nature of oil, concentration of react- sivity” (EC) is defined as

Corrosion of the bear- ants, and physical factors of tests are described. The im- the corrosion caused by ings of an internal corn- portant functioh of protective lacquer films in preventing a lubricant under con- bustion engine by lubricat- corrosion and the interference with their action by de- ditions which lead to ing oil occurs in service tergents are demonstrated. no, or insignificant, change under conditions which ef- either chemically or physi- fect simultaneously other cally, other than that chemical changes in the lubricant. In general, an unused oil con- directly associated with the occurrence of corrosion. Thus, tains no corrosive bodies; however, when an oil-metal system is an undoped, fresh oil would be expected to have very low aged under conditions representative of service, corrosion will EC, whereas the same oil after a period of service may have occur to a degree dependent upon the oil and the severity of the developed an appreciable EC. Existent corrosivity is expressed fundamental factors. This tendency of an oil to become corro- in the same units as potential corrosivity; however, the appara- sive, called “potential corrosivity” (PC), is defined the ex- tus and conditions of memurement necessarily differ markedly. tent of corrosion which occurs during the service life of the oil. Although the potential corrosivity of a lubricant is influenced Some liberty is taken in this definition since the corrosion which by the initial characteristics of the oil, i t win depend to a major occurs in service is a function of the conditions, and varies not degree upon the conditions of aging. In service, corrosion is only with type of engine but Over different units of the same inseparable from and dependent upon the oxidation of the oil. type. However, standard engine tests have been devised and Hence, in the laboratory, conditions of test for potential corrosiv-

T

limits assigned to permissible corrosion; potential corrosivity, therefore, is not an imaginary concept. Potential corrosivity pertains to fresh oils and is most accurately measured in the en- &e. Laboratory tests, however, which age an oil under the conditions representative of service, predict with reasonable accuracy its potential COrrOSiVity. Potential COrrOSiVity is ex- pressed as the milligram weight loss per square centimeter BUS- tained by the metal under the selected conditions.

ity should promote the oxidation of the lubricant. Herein lies a fundamental difference between potential corrosivity and existent corrosivity; for the latter the maximum separation of variables is sought. Although existent corrosivity is useful in a fundamental study, potential corrosivity remains more im- portant practically since the quality of a lubricant is determined by its performance in service,

* Present address, Shell Oil Company, Inc., 50 West 50th Street, New

3 Present address, Lieutenant, Ordnance Department, The Proving Center,

APPARATUS FOR MEASURING CORROSIVITY

The corrosion and stability (C and 5) apparatus and test used to evaluate potential corrosivity were described elsewhere (8) ;

York 20, N. Y.

Aberdeen Proving Ground, Md.